JP6121110B2 - Solid electrolyte particles and composition thereof - Google Patents

Description

  The present invention relates to a sulfide-based solid electrolyte particle that does not use lithium as a conductive species, a composition thereof, and a battery using the same.

In recent years, demand for secondary batteries used in portable information terminals, portable electronic devices, small household electric power storage devices, motor-driven motorcycles, electric vehicles, hybrid electric vehicles, and the like has increased.
Here, there is a lithium ion battery as a high-capacity secondary battery. Since the lithium ion battery is an electrolytic solution containing an organic solvent, there is a risk of liquid leakage or fire.

In order to solve such a problem, various studies have been conducted on sulfide-based solid electrolytes, and sulfide-based solid electrolytes having high ionic conductivity have been developed (Patent Document 1).
However, since the sulfide-based solid electrolyte described in Patent Document 1 contains lithium as an essential component, there is a risk that the lithium source as a raw material will be insufficient with an increase in demand for lithium ion batteries.

Therefore, a sodium-based solid electrolyte using sodium, which is abundant in raw materials, as a conductive species has been developed (Patent Document 2). Further, a sodium battery manufactured using a sodium-based solid electrolyte described in Patent Document 2 has been developed (Non-Patent Document 1).
However, the sodium battery described in Non-Patent Document 1 has a drawback of low battery performance.

JP 2005-228570 A JP 2012-121789 A

The world's first successful operation of an all-solid-state sodium storage battery in the world-a big step in the research and development of a highly safe next-generation storage battery-(Professor Kazuna's presentation) (released May 23, 2012, Osaka Prefecture University and Science) Technical Promotion Organization)

  It is an object to obtain solid electrolyte particles having high battery performance and capable of producing a battery that does not use lithium as a conductive species.

According to the present invention, the following solid electrolyte particles and the like are provided.
1. A volume that includes at least one component selected from sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, and radium, and phosphorus and sulfur, and is measured by a laser diffraction particle size distribution measurement method. Solid electrolyte particles having a standard average particle size of 0.01 μm or more and 50 μm or less.
2. 2. The solid electrolyte particle according to 1, wherein the at least one component is sodium.
3. 3. The solid electrolyte particle according to 1 or 2, wherein the volume reference average particle diameter is 0.1 μm or more and 10 μm or less, and the volume reference particle diameter of 90% or more of the particles is 20 μm or less.
The composition containing the solid electrolyte particle in any one of 4.1-3.
5). 5. The composition according to 4, comprising a nitrile compound.
6. An electrolyte layer comprising the solid electrolyte particles according to any one of 1 to 3 and / or the composition according to 4 or 5.
7. An electrode layer comprising the solid electrolyte particles according to any one of 1 to 3 and / or the composition according to 4 or 5.
A battery comprising the solid electrolyte particles according to any one of 8.1 to 3 and / or the composition according to 4 or 5.
An electrolyte layer produced using the solid electrolyte particles according to any one of 9.1 to 3 and / or the composition according to 4 or 5.
10. An electrode layer produced using the solid electrolyte particles according to any one of 10.1 to 3 and / or the composition according to 4 or 5.
11. A battery produced using the solid electrolyte particles according to any one of 11.1 to 3 and / or the composition according to 4 or 5.

  Solid electrolyte particles capable of producing a battery having high battery performance and not using lithium as a conductive species could be obtained.

It is a figure which shows an example of the manufacturing apparatus used with a slurry method.

[Solid electrolyte particles]
(1) Solid electrolyte The solid electrolyte particles of the present invention comprise at least one component selected from sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium and radium, phosphorus, and sulfur. Including.
Preferred are sodium, potassium, rubidium, cesium, francium and beryllium, more preferred are sodium and potassium, and still more preferred is sodium.

As other elements, Ge, Si, Al, Ga, Al, B, and In can be included.
Further, fluorine, chlorine, bromine and iodine may be included as the halogen element. When the halogen element is included, chlorine, bromine and iodine are preferable, and chlorine and bromine are more preferable.

A solid electrolyte represented by the formula (1) is preferable.
_{L a M b P c S d} X e ... (1)
L is sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, or radium.
L is preferably sodium, potassium, rubidium, cesium, francium or beryllium, more preferably sodium or potassium, still more preferably sodium.

  M is B, Al, Si, Ge, Ga, In, As, Se, Sn, Sb, Te, Pb, Bi, or a combination thereof. B, Si, Ge, and Al are preferable, and Ge, Si, and B are more preferable.

  X is a halogen element, and may be a combination of halogen elements, preferably fluorine, chlorine, bromine, iodine, more preferably chlorine, bromine, iodine, and still more preferably chlorine, bromine. is there.

0.1 <a ≦ 15, preferably 0.2 ≦ a ≦ 13, and more preferably 0.3 ≦ a ≦ 12.
0.1 ≦ b ≦ 3, preferably 0.2 ≦ b ≦ 3, more preferably 0.2 ≦ b ≦ 2, and most preferably b is 0.
0.5 <c ≦ 5, preferably 0.5 ≦ c ≦ 4, more preferably 0.8 ≦ c ≦ 4, and most preferably c is 1.
0 <d ≦ 15, preferably 1 ≦ d ≦ 15, more preferably 1 ≦ d ≦ 13, and most preferably 0.5 ≦ d ≦ 12.
0 ≦ e ≦ 3, preferably 0 ≦ e ≦ 2, more preferably 0 ≦ e ≦ 2.
Alternatively, 0.1 <e ≦ 3 is preferable, 0.1 ≦ e ≦ 2 is more preferable, and 0.2 ≦ e ≦ 2 is still more preferable.

The solid electrolyte may be crystallized or amorphous. If the crystal has higher ionic conductivity than amorphous, the ionic conductivity of the electrolyte layer and electrode layer can be increased by crystallization. If amorphous, the crystal is softer than the crystal. The contact state between the solid electrolytes and the contact state with the active material and the conductive auxiliary agent can be improved.
Here, the crystal structure is preferably a Na ₃ PS ₄ crystal structure. This is because the ionic conductivity can be increased.

(2) Manufacturing method of solid electrolyte Hereinafter, the manufacturing method of a solid electrolyte is illustrated, However, it cannot be overemphasized that a solid electrolyte is not limited to the solid electrolyte manufactured by the following manufacturing method.

(I) Raw material The raw material is a compound represented by the following formula (3) and phosphorus sulfide, sulfur and phosphorus, phosphorus sulfide and sulfur, or phosphorus sulfide and sulfur and phosphorus.
L _y S (3)
L is sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, or radium.
L is preferably sodium, potassium, rubidium, cesium, francium or beryllium, more preferably sodium or potassium, still more preferably sodium.
In addition, S means sulfur.

y is 0.5 or more and 3 or less, preferably 0.7 or more and 2.5 or less, more preferably 1 or more and 2 or less, and even more preferably 2.
For example, Na ₂ S (sodium sulfide), K ₂ S, Rb ₂ S, BeS, MgS, CaS, SrS, BaS, or the like can be used. You may use these in mixture of 2 or more types.
A compound that reduces the glass transition temperature (vitrification accelerator) may be added. Examples of the vitrification promoter include inorganic compounds such as Na ₃ PO ₄ , Na ₄ SiO ₄ , Na ₄ GeO ₄ , Na ₃ BO ₃ , Na ₃ AlO ₃ , Na ₃ CaO ₃ , and Na ₃ InO _3. .

Furthermore, a compound represented by the following formula (2) may be used as a raw material.
M _w X _x (2)
M is sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, B, Al, Si, P, S, Ge, As, Se, Sn, Sb, Te, Pb, Bi Or a combination of these.
M is preferably sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, phosphorus or combinations thereof, more preferably sodium, potassium, phosphorus or combinations thereof. More preferably sodium, phosphorus or a combination thereof.
w is 0.5 or more and 5 or less, preferably 0.5 or more and 4 or less, more preferably 3 or less, and most preferably 1.

X may be a halogen element or a combination of halogen elements, preferably fluorine, chlorine, bromine or iodine, more preferably chlorine, bromine or iodine, still more preferably chlorine or bromine.
x is an arbitrary integer selected from an integer of 1 to 10, preferably an integer of 0.5 to 6, more preferably an integer of 1 to 5 It is an integer, most preferably 1 or 3.

For example, sodium halide (NaI, NaBr, NaCl, NaF, etc.), phosphorus halide (PBr ₃ , PCl ₃ , PCl ₅ , P ₂ Cl ₄ , PI ₃ , P ₂ I ₄ , PF ₅ , PF ₃ etc.) AlF ₃ , AlBr ₃ , AlI ₃ , AlCl ₃ , SiF ₄ , SiCl ₄ , SiCl ₃ , Si ₂ Cl ₆ , SiBr ₄ , SiBrCl ₃ , SiBr ₂ Cl ₂ , SiI ₄ , POCl ₃ , POBr ₃ F, SF _{2 S 4} , SF ₆ , S ₂ F ₁₀ , SCl ₂ , S ₂ Cl ₂ , S ₂ Br ₂ , GeF ₄ , GeCl ₄ , GeBr ₄ , GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , AsF ₃ , AsCl ₃ , AsBr ₃ , AsI ₃ , AsF ₅ , SeF ₄ , SeF ₆ , SeCl ₂ , SeCl ₄ , Se _{2 Br 2, SeBr 4, SnF 4} , SnCl 4, SnBr 4, SnI 4, SnF 2, SnCl 2, SnBr 2, SnI 2, SbF 3, SbCl 3, SbBr 3, SbI 3, SbF 5, SbCl 5, PbF 4 _{, PbCl 4, PbF 2, PbCl} 2, PbBr 2, PbI 2, BiF 3, BiCl 3, BiBr 3, BiI 3, TeF 4, Te 2 F 10, TeF 6, TeCl 2, TeCl 4, TeBr 2, TeBr 4 , TeI _{4 and the} like, preferably sodium halide (NaI, NaBr, NaCl, NaF, etc.), phosphorus halide (PBr ₃ , PCl ₃ , PCl ₅ , P ₂ Cl ₄ , PI ₃ , P ₂ I _4, a _PF 5 ,, PF _3, etc.), more preferably, NaBr, NaCl, Br _3, is PCl _3.

(Ii) Amorphous Production Method Hereinafter, a method for producing a solid electrolyte (glass) using sodium sulfide and diphosphorus pentasulfide as raw materials will be described.
The ratio (molar ratio) of sodium sulfide to diphosphorus pentasulfide is, for example, 60:40 to 90:10, preferably 65:35 to 85:15 or 70:30 to 90:10, and more preferably 67:33. It is -83: 17 or 72: 28-88: 12, More preferably, it is 67: 33-80: 20 or 74: 26-86: 14. Most preferably, it is 70: 30-80: 20 or 75: 25-85: 15. Most preferably, the ratio (molar ratio) between sodium sulfide and diphosphorus pentasulfide is 72:28 to 78:22, or 77:23 to 83:17.
A solid electrolyte (glass) can be produced by the following method using the above raw materials.

(A) Melting and quenching method The melting and quenching method is a method in which a predetermined amount of P ₂ S ₅ and Na ₂ S are mixed, reacted at a predetermined temperature, and then rapidly cooled to obtain a solid electrolyte (glass). .
For example, a mixture of pellets in a mortar is placed in a carbon-coated quartz tube and vacuum-sealed. After reacting at a predetermined reaction temperature, the solid electrolyte (glass) is obtained by putting it in ice and quenching.
The reaction temperature is preferably 400 ° C to 1000 ° C, more preferably 800 ° C to 900 ° C.
The reaction time is preferably 0.1 hour to 12 hours, more preferably 1 to 12 hours.
The quenching temperature of the reactant is usually 10 ° C. or less, preferably 0 ° C. or less, and the cooling rate is usually about 1 to 10,000 K / sec, preferably 10 to 10,000 K / sec.

(B) Mechanical milling method (MM method)
The MM method is a method of obtaining a solid electrolyte (glass) by mixing a predetermined amount of P ₂ S ₅ and Li ₂ S and applying mechanical energy.
A method for applying mechanical energy is not particularly limited, and various ball mills can be exemplified.
For example, a solid electrolyte (glass) can be obtained by mixing P ₂ S ₅ and Na ₂ S in a predetermined amount in a mortar and reacting them for a predetermined time using, for example, various ball mills.
The MM method using the above raw materials can be reacted at room temperature. Therefore, there is an advantage that a solid electrolyte (glass) having a charged composition can be obtained without thermal decomposition of the raw material.
Further, the MM method has an advantage that it can be finely powdered simultaneously with the production of the solid electrolyte (glass).
Various types such as a rotating ball mill, a rolling ball mill, a vibrating ball mill, and a planetary ball mill can be used for the MM method.
As conditions for the MM method, for example, when a planetary ball mill is used, the rotational speed may be set to several tens to several hundreds of revolutions / minute, and the treatment may be performed for 0.5 hours to 100 hours.
The balls of the ball mill may be used by mixing balls having different diameters.
Moreover, you may adjust the temperature in the mill in the case of MM processing.
It is preferable that the raw material temperature during the MM treatment be 60 ° C. or higher and 160 ° C. or lower.

(C) Solid phase method The solid phase method is a method of obtaining a solid electrolyte (glass) by mixing raw materials and heating at a predetermined temperature. Specifically, a predetermined amount of P ₂ S ₅ and Na ₂ S are mixed in a mortar and heated at a temperature of 100 to 900 ° C., whereby a solid electrolyte (glass) is obtained.

(D) Wet mechanical milling method (wet MM method)
In this method, the raw material is manufactured by mechanical milling in a hydrocarbon solvent.

As the hydrocarbon solvent, saturated hydrocarbon, unsaturated hydrocarbon, or aromatic hydrocarbon can be used.
Examples of the saturated hydrocarbon include hexane, pentane, 2-ethylhexane, heptane, decane, and cyclohexane.
Examples of the unsaturated hydrocarbon include hexene, heptene, cyclohexene and the like.
Aromatic hydrocarbons include toluene, xylene, decalin, 1,2,3,4-tetrahydronaphthalene and the like.
As the hydrocarbon solvent, toluene and xylene are preferable.

  The hydrocarbon solvent is preferably dehydrated in advance. Specifically, the water content is preferably 100 ppm by weight or less, particularly preferably 30 ppm by weight or less.

  In addition, you may add another solvent to a hydrocarbon type solvent as needed. Specifically, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, alcohols such as ethanol and butanol, esters such as ethyl acetate, dichloromethane, chlorobenzene, heptane fluoride, fluorinated benzene 2,3- Halogenated hydrocarbons such as fluorine-based compounds such as dihydroperfluoropentane and 1,1,2,2,3,3,4-heptafluorocyclopentane.

  The amount of the hydrocarbon-based solvent is preferably such that the raw material becomes a solution or slurry by the addition of the solvent. Usually, the amount of the raw material (total amount) added to 1 liter of solvent is about 0.01 kg to 1 kg.

  Various types of grinding methods can be used for the mechanical milling treatment. A planetary ball mill and a bead mill are preferred.

The rotation speed and rotation time of the mechanical milling treatment are not particularly limited, but the higher the rotation speed, the higher the glassy electrolyte generation rate, and the longer the rotation time, the higher the conversion rate of the raw material into the glassy electrolyte.
For example, when a planetary ball mill is used, the rotational speed may be 250 rpm / min to 300 rpm / min, and the treatment may be 5 minutes to 50 hours.

  In this method, since the mechanical milling process is performed in the presence of the hydrocarbon solvent, the processing time can be shortened. You may heat from room temperature to 200 degreeC as needed.

(E) Slurry method Mechanical energy supply means for imparting dynamic energy to the raw material in a hydrocarbon solvent, contact means for bringing the raw material into contact with the hydrocarbon solvent, and the dynamic energy supply means And a connecting means for connecting the contacting means, and a circulating means for circulating the raw material and / or reactants of the raw material between the mechanical energy supply means and the contacting means through the connecting means. This is a method for producing a solid electrolyte. As the hydrocarbon solvent, the same solvents as described above can be used.

FIG. 1 is a diagram showing an example of a manufacturing apparatus that can be used in this method.
When manufacturing a solid electrolyte using this apparatus 1, a hydrocarbon solvent and a raw material are supplied to the pulverizer 10 and the temperature holding tank 20, respectively. Hot water (HW) enters and exits the heater 30 (RHW). While maintaining the temperature in the pulverizer 10 with the heater 30, the raw material is reacted while being pulverized in a hydrocarbon solvent to synthesize a solid electrolyte. While keeping the temperature in the temperature holding tank 20 by the oil bath 40, the raw materials are reacted in a hydrocarbon solvent to synthesize a solid electrolyte. The temperature in the temperature holding tank 20 is measured with a thermometer (Th). At this time, the stirring blade 24 is rotated by the motor (M) to stir the reaction system so that the slurry composed of the raw material and the solvent does not precipitate. Cooling water (CW) enters and exits the cooling pipe 26 (RCW). The cooling pipe 26 cools and liquefies the vaporized solvent in the container 22 and returns it to the container 22. While the solid electrolyte is synthesized in the pulverizer 10 and the temperature holding tank 20, the raw material in the reaction is circulated between the pulverizer 10 and the temperature holding tank 20 by the pump 54 through the connecting pipes 50 and 52. The temperature of the raw material and the solvent fed into the pulverizer 10 is measured by a thermometer (Th) provided in the second connecting pipe before the pulverizer 10.

  Examples of the pulverizer 10 include a rotary mill (rolling mill), a swing mill, a vibration mill, and a bead mill. A bead mill is preferable in that the raw material can be finely pulverized. When the pulverizer includes balls, the balls are preferably made of zirconium, reinforced alumina, or alumina.

  Moreover, in order to prevent mixing of the ball | bowl from the grinder 10 to the temperature holding tank 20, you may provide the filter which isolate | separates a ball | bowl, a raw material, and a solvent in the grinder 10 or the 1st connection pipe 50 as needed.

  The pulverization temperature in the pulverizer is usually 20 ° C. or higher and 80 ° C. or lower, preferably 20 ° C. or higher and 60 ° C. or lower. The reaction temperature in the container 22 is usually 60 ° C. or higher and 300 ° C. or lower, preferably 80 ° C. or higher and 200 ° C. or lower.

  The amount of the hydrocarbon-based solvent is preferably such that the raw material becomes a solution or slurry by the addition of the solvent. Usually, the amount of raw material (total amount) added to 1 kg of solvent is about 0.03 kg to 1 kg.

(F) Improved slurry method
In this method, the raw material is contacted in a hydrocarbon solvent. As the hydrocarbon solvent, the same solvents as described above can be used.

  The amount of the hydrocarbon-based solvent is preferably such that the raw material becomes a solution or slurry by the addition of the solvent. Usually, the addition amount of the raw material (total amount) with respect to 1 liter of solvent is about 0.001 kg to 1 kg.

The method for contacting the raw material in the hydrocarbon solvent is not particularly limited. For example, the method of stirring the mixture of a raw material and a hydrocarbon-type solvent in the container which has a stirring apparatus is mentioned. It is preferable to stir at the time of contact.
The temperature during the contact (reaction) step is usually 50 ° C. or higher and 300 ° C. or lower, preferably 60 ° C. or higher and 250 ° C. or lower, more preferably 70 ° C. or higher and 200 ° C. or lower.
Moreover, the time at the time of a contact process is 5 minutes or more and 200 hours or less normally, Preferably, they are 10 minutes or more and 100 hours or less.
Note that the temperature and time may be combined using several conditions as steps. For example, contact is made at 100 ° C. for 1 hour from the start of contact, and heating is carried out at 150 ° C. for 10 hours after 1 hour.

  The contacting step is preferably carried out in an inert gas atmosphere such as nitrogen or argon. The dew point of the inert gas is preferably −20 ° C. or less, particularly preferably −40 ° C. or less. The pressure is usually normal pressure to 100 MPa, preferably normal pressure to 20 MPa.

(Iii) Crystallization method A solid electrolyte (glass ceramic) can be obtained by heat-treating the solid electrolyte (glass) (sulfide glass). Heating is preferably performed in an environment with a dew point of −40 ° C. or lower, more preferably in an environment with a dew point of −60 ° C. or lower.
The pressure at the time of heating may be a normal pressure or a reduced pressure.
The atmosphere may be in the air or an inert atmosphere.
Furthermore, you may heat in a solvent (For example, a hydrocarbon type organic solvent and a hydrocarbon type organic solvent are the same as the above).
The heating temperature is preferably not less than the glass transition temperature (Tg) of the solid electrolyte (glass) and not more than the crystallization temperature (Tc) of the electrolyte precursor 1 + 100 ° C. or less. If the heating temperature is lower than the Tg of the solid electrolyte (glass), the production time may be very long. On the other hand, when it exceeds (Tc + 100 ° C.), impurities or the like may be contained in the obtained solid electrolyte (glass ceramic), and the ionic conductivity may be lowered.
The heating temperature is more preferably (Tg + 5 ° C.) or more and (Tc + 90 ° C.) or less, and further preferably (Tg + 10 ° C.) or more and (Tc + 80 ° C.) or less.
For example, the heating temperature is 150 ° C. or higher and 360 ° C. or lower, preferably 160 ° C. or higher and 350 ° C. or lower, more preferably 180 ° C. or higher and 310 ° C. or lower, more preferably 180 ° C. or higher and 290 ° C. or lower, Especially preferably, it is 190 degreeC or more and 270 degrees C or less. Further, when there are two temperature peaks in the thermophysical property, the peak temperature on the low temperature side is defined as Tc in this case, and heat treatment is performed between Tc on the low temperature side and the second crystallization peak on the high temperature side (Tc2). preferable.

  The crystallization temperature of the solid electrolyte (glass) is measured using a thermogravimetric apparatus (TGA / DSC1 manufactured by METTLER TOLEDO) and about 20 mg of the solid electrolyte (glass) at 10 ° C./min. It should be noted that the crystallization temperature or the like may change depending on the temperature rising rate or the like, and should be selected based on Tc measured at a rate close to the temperature rising rate for heat treatment.

  The heating time is preferably 0.005 minutes or more and 10 hours or less. More preferably, it is 0.005 minutes or more and 5 hours or less, and particularly preferably 0.01 minutes or more and 3 hours or less. If it is less than 0.005 minutes, the electrolyte of the present invention contains a large amount of an electrolyte precursor, and the ionic conductivity may be lowered. If it exceeds 10 hours, impurities or the like may be generated in the solid electrolyte of the present invention, and the ionic conductivity may be lowered.

(3) Average particle diameter The solid electrolyte particles of the present invention have a volume-based average particle diameter of 0.01 μm or more and 50 μm or less measured by a laser diffraction particle size distribution measuring method.
If the volume-based average particle diameter is 0.01 μm or more, handling becomes easy, and if the volume-based average particle diameter is 50 μm or less, the pores in the electrolyte layer and the electrode layer manufactured using the electrolyte particles are reduced. And more contact with the electrode active material in the electrode layer. An all-solid battery with improved energy density and power density can be obtained.

The volume-based average particle diameter is preferably 0.05 μm or more and 20 μm or less, and the volume-based average particle diameter is more preferably 0.1 μm or more and 10 μm or less.
Further, the volume-based average particle diameter is preferably 2.5 μm or less, particularly preferably 0.5 μm or less. When the volume-based average particle diameter is so small, a uniform layer can be formed when the layer is formed using a slurry containing solid electrolyte particles.

The volume reference particle diameter (Dp90) of 90 % of the particles measured by the laser diffraction particle size distribution measuring method is preferably 100 μm or less, more preferably 40 μm or less, and even more preferably 20 μm or less, Particularly preferably, it is 5 μm or less.

The laser diffraction particle size distribution measurement method can measure the particle size distribution without drying the composition, and measures the particle size distribution by irradiating a particle group in the composition with laser and analyzing the scattered light. be able to.
A measurement example in the case where the laser diffraction particle size distribution measuring device is a master sizer 2000 manufactured by Malvern Instruments Ltd. is as follows.

  First, 110 ml of dehydrated toluene (Wako Pure Chemicals, product name: special grade) was placed in the dispersion tank of the apparatus, and 6% of dehydrated tertiary butyl alcohol (Wako Pure Chemicals, special grade) was added as a dispersant. Added. Here, the addition of a dispersant to toluene is not to make the “aggregated solid electrolyte particles” in the solid electrolyte-containing composition primary particles (disperse), but in the solid electrolyte-containing composition to be measured. This is to prevent the solid electrolyte particles from aggregating.

After sufficiently mixing the mixture, the solid electrolyte-containing composition is added and the particle size is measured. The amount of the solid electrolyte-containing composition added is adjusted so that the laser scattering intensity corresponding to the particle concentration falls within the specified range (10 to 20%) on the operation screen specified by Mastersizer 2000. If this range is exceeded, multiple scattering may occur, and an accurate particle size distribution may not be obtained. On the other hand, when the amount is less than this range, the SN ratio is deteriorated, and there is a possibility that accurate measurement cannot be performed. In Mastersizer 2000, the laser scattering intensity is displayed on the basis of the addition amount of the solid electrolyte-containing composition. Therefore, it is preferable to find the addition amount that falls within the laser scattering intensity.
Although the optimum amount of the solid electrolyte-containing composition varies depending on the concentration of the composition, it is generally about 10 μL to 200 μL.

[Composition]
The composition of this invention contains said solid electrolyte particle. Furthermore, a solvent and / or a nitrile compound can be included.

  Since the composition of this invention contains the solid electrolyte particle which has said volume reference | standard average particle diameter, the performance of the battery manufactured using this improves. Moreover, it is easy to maintain the state of the slurry (composition) containing the solvent, and it is easy to handle.

  In the composition containing the solid electrolyte particles of the present invention, the sedimentation volume fraction is preferably 20% or more and 95% or less, more preferably 30% or more and 90% or less, and further preferably 50% or more and 90% or less. And most preferably 50% or more and 80% or less.

The sedimentation volume fraction is expressed by “volume of solid electrolyte particles settled / total slurry volume × 100”, and is an index related to the aggregation state of primary particles. If the sedimentation volume fraction is less than 20%, the pulverization energy is used to re-agglomerate the agglomerates, so there is a risk that the atomization will not be sufficiently performed. When the coating is applied, the solid electrolyte membrane can be formed only in part, and there is a possibility that a uniform membrane cannot be formed. On the other hand, when the sedimentation volume fraction exceeds 95%, the solvent may not be sufficiently dried when the composition is dried to obtain a solid electrolyte powder or a solid electrolyte membrane.
The sedimentation volume fraction can be evaluated by the method described in Examples described later.

(1) Solvent The solvent is preferably an organic solvent, more preferably a hydrocarbon-based organic solvent that is less reactive with the solid electrolyte.
Examples of the hydrocarbon organic solvent include hexane, heptane, cyclohexane, toluene, xylene, decalin and the like. In consideration of the drying process after the formation of the coating, hexane, toluene and xylene having a low boiling point can be preferably used.
The solvent may be a nitrile compound. The nitrile compound will be described later.

The composition of the present invention preferably contains solid electrolyte particles and a solvent in a ratio of 5:95 to 50:50 (weight ratio), more preferably 5:95 to 5:30 (weight ratio).
If the solid electrolyte particle content is less than 5:95 (weight ratio), in the production method described later, the amount of pulverization of the solid electrolyte may be small, and the production efficiency may be deteriorated. There is a risk that the viscosity of the product slurry will increase and it will be difficult to handle in terms of transfer and the like.

(2) Nitrile Compound The composition of the present invention can contain a nitrile compound as a solvent. When the solvent is not a nitrile compound, it preferably further contains a nitrile compound. When the nitrile compound is included, the solid electrolyte particles are well dispersed.

A nitrile compound is a compound represented, for example by a following formula.
R-CN
(In the formula, R is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 ring carbon atoms, or a group having an aromatic ring having 6 to 18 ring carbon atoms. Yes, preferably an alkyl group having 3 to 6 carbon atoms having a branched structure, and more preferably an alkyl group having 3 to 5 carbon atoms having a branched structure.

  Examples of the nitrile compound include acetonitrile, benzonitrile, tertiary butyronitrile, isobutyronitrile, and the like, preferably isobutyronitrile.

When a solvent (not a nitrile compound) and a nitrile compound are included, the nitrile compound and the solvent are preferably included at 0.1: 99.9 to 50:50 (weight ratio), more preferably 1:99 to 30:70 ( (Weight ratio), more preferably 3:97 to 15:85 (weight ratio).
If the content of the nitrile compound is small and less than 0.1: 99.9 (weight ratio), the dispersion effect of the solid electrolyte particles may be reduced. If the content of the nitrile compound is large and more than 50:50, the solid electrolyte particles There is a possibility that the dispersion effect of the material is not improved.

[Production method]
Although the manufacturing method of the solid electrolyte particle of this invention and the composition of this invention is not ask | required in particular, For example, it can manufacture by grind | pulverizing the solid electrolyte particle with a large particle size in the composition containing a solvent. Moreover, it can manufacture by grind | pulverizing the solid electrolyte particle with a large particle size in the composition containing a nitrile compound and a solvent.
Moreover, it can also manufacture by grind | pulverizing a solid electrolyte particle with a large particle size, without adding a solvent.

The composition and structure of the solid electrolyte particles to be pulverized, the nitrile compound, the solvent, and the mixing ratio (weight ratio) thereof are the same as described above.
In particular, when the content of the nitrile compound with respect to the solvent is small, and the nitrile compound: solvent = less than 0.1: 99.9 (weight ratio), the aggregation of the solid electrolyte particles during dispersion may not be prevented, and the solid electrolyte There is a possibility that the particles cannot be atomized.

The method for pulverizing the solid electrolyte particles is not particularly limited. For example, the solid electrolyte particles are pulverized using a pulverizer.
The pulverizer is preferably a ball mill, a bead mill, a water jet mill, a homogenizer, or the like, and more preferably an apparatus including balls or beads inside a reaction vessel such as a ball mill or a bead mill.

The average particle diameter of the solid electrolyte particles to be pulverized is 10% or less of the diameter of the ball such as beads because the particle diameter that can be efficiently pulverized by a bead mill or the like is usually one tenth or less of the diameter of the beads to be used. It is preferable that it is 1 or less. Accordingly, since beads having a diameter of 1 mm to 0.1 mm are generally used in a bead mill or the like, the average particle diameter of the solid electrolyte particles to be pulverized is preferably 100 μm or less.
In addition, it is preferable to use the multistage grinding | pulverization which uses together the bead etc. from which a particle size differs as needed for the grinding | pulverization by a bead mill.

The solid electrolyte particles of the present invention can be suitably used for an electrolyte layer, and can also be suitably used for an electrode layer (positive electrode layer and / or negative electrode layer) by mixing with an active material.
By using the electrolyte fine particles of the present invention, the electrolyte layer and the electrode layer can be made very thin, and the ionic conductivity of the electrolyte layer itself can be increased. For example, the thickness of the electrolyte layer and electrode layer containing the electrolyte fine particles of the present invention can be 10 μm or less.

[Electrolyte layer]
The electrolyte layer of the present invention includes the solid electrolyte particles and / or the composition described above, or is manufactured using the solid electrolyte particles and / or the composition described above.

  The thickness of the electrolyte layer is preferably in the range of 1 to 500 μm. More preferably, it is 3-300 micrometers. Most preferably, it is 5-100 micrometers.

  The electrolyte layer of the present invention can be produced by using the composition of the present invention, and for example, can be produced by drying the composition of the present invention by electrostatic screen printing or electrostatic spray printing.

The composition used for manufacturing the electrolyte layer may further contain a binder.
The binder is not particularly limited, but for example, vinylidene fluoride is suitable, and polyvinylidene fluoride, polyethylene glycol, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polysiloxy acid, vinylidene fluoride-hexafluoropropylene copolymer Examples include coalescence.

[Electrode layer]
The electrode layer of the present invention includes the above-described solid electrolyte particles and / or composition, or is manufactured using the above-described solid electrolyte particles and / or composition.

  What is necessary is just to adjust the thickness of an electrode layer suitably according to the shape and use of a battery, and it is preferable that they are 1 micrometer-500 micrometers. More preferably, it is 10-300 micrometers. Especially preferably, it is 20-150 micrometers.

(1) Positive electrode layer When the active material is a positive electrode active material, any compound that can dope and dedope sodium ions may be used, and an inorganic compound is preferably used.
Examples of the sulfide system include sulfur (S), titanium sulfide (TiS ₂ ), molybdenum sulfide (MoS ₂ ), iron sulfide (FeS, FeS ₂ ), copper sulfide (CuS), nickel sulfide (Ni ₃ S ₂ ), and the like. It is done. TiS ₂ is preferable.
Examples of the oxide system include bismuth oxide (Bi ₂ O ₃ ), bismuth lead acid (Bi ₂ Pb ₂ O ₅ ), copper oxide (CuO), and vanadium oxide (V ₆ O ₁₃ ).

The inorganic sodium _compound, NaFeO _2, NaMnO 2, NaNiO ₂ and NaCoO oxide represented by NaM _a O _2, such as _2, oxide represented by _{Na 0.44 Mn 1-a M1 a} O 2, Na 0 _.7 Mn _1-a M1 oxide represented by _{a O 2.05} (M1 is one or more transition metal _{elements, 0 ≦ a <1),} Na 6 Fe 2 Si 12 O 30 and _Na 2 _Fe 5 Si An oxide represented by Na _b M2 _c Si ₁₂ O ₃₀ such as ₁₂ O ₃₀ (M2 is one or more transition metal elements, 2 ≦ b ≦ 6, 2 ≦ c ≦ 5), Na ₂ Fe ₂ Si ₆ O ₁₈ and _Na 2 MnFeSi ₆ oxide represented by O in ₁₈ such _{Na d M3 e Si 6 O 18} (M3 is one or more transition metal elements, 3 ≦ d ≦ 6,1 ≦ e ≦ 2), Na 2 Na _f M4 _g Si such as FeSiO ₆ Oxide represented by ₂ O ₆ (M4 is one or more elements selected from the group consisting of transition metal elements, Mg and Al, 1 ≦ f ≦ 2, 1 ≦ g ≦ 2), NaFePO ₄ , Na ₃ Fe ₂ (PO ₄ ) ₃ or the like; NaFeBO ₄ , Na ₃ Fe ₂ (BO ₄ ) ₃ or the like borate; Na ₃ FeF _{6 or} Na ₂ MnF ₆ or any other Na _h M5F ₆ Compound (M5 is one or more transition metal elements, 2 ≦ h ≦ 3) and the like.
Examples thereof include organic disulfide compounds and carbon sulfide compounds.

The positive electrode active material can be used by mixing the sulfide system and the oxide system. In addition to the above sulfides and oxides, niobium selenide (NbSe ₃ ) can also be used.
As the positive electrode active material, a positive electrode active material whose surface is coated with an oxide, sulfide or the like can be suitably used as necessary.
Examples of the shape of the positive electrode active material include a particle shape, and are preferably spherical or elliptical. Moreover, when it is a particulate form, it is preferable that the average particle diameter exists in the range of 0.1-100 micrometers. If it deviates from this range, a dense positive electrode layer may not be obtained.
More preferably, it is the range of 1-50 micrometers, Most preferably, it is the range of 1-25 micrometers.

  The positive electrode layer is preferably a mixture of a positive electrode active material and a solid electrolyte, and the content of the positive electrode active material is preferably in the range of 50 to 90% by weight, and in the range of 60 to 80% by weight. More preferably.

  The thickness of the positive electrode layer may be appropriately selected depending on the kind of the all-solid battery intended, but it is usually preferably in the range of 1 μm to 200 μm.

  The solid electrolyte used for the positive electrode layer is preferably sodium ion solid electrolyte glass, sodium ion solid electrolyte glass ceramic or a mixture thereof among the above solid electrolyte particles, and is preferably glass before being pressed and heated to form a battery. Good.

  Further, the positive electrode layer may contain a conductive substance. Examples of the conductive substance include a carbon material, a metal powder, a metal compound, and the like, and preferably a carbon material.

(2) Negative electrode layer When the active material is a negative electrode active material, a negative electrode active material known in the field of batteries capable of inserting and releasing sodium ions can be used as the negative electrode active material.
Specifically, sodium metal, a sodium alloy, or a carbon material can be used.
Examples of the sodium alloy include Na—Sn, Na—Zn, and Na—Al.
Carbon materials include artificial graphite, graphite carbon fiber, resin-fired carbon, pyrolytic vapor-grown carbon, coke, mesocarbon microbeads (MCMB), furfuryl alcohol resin-fired carbon, polyacene, pitch-based carbon fiber, vapor-phase growth Examples include carbon fiber, natural graphite, and non-graphitizable carbon. Or it may be a mixture thereof. Preferably, it is artificial graphite.

  The negative electrode layer is preferably a mixture of a negative electrode active material and a solid electrolyte, and the content of the negative electrode active material is preferably in the range of 50 to 90% by weight, and in the range of 60 to 80% by weight. More preferably.

  The thickness of the negative electrode layer may be appropriately selected depending on the kind of the all-solid battery intended, but it is usually preferably in the range of 1 μm to 200 μm.

  The solid electrolyte used for the negative electrode layer is preferably sodium ion solid electrolyte glass, sodium ion solid electrolyte glass ceramic or a mixture thereof among the above solid electrolyte particles, and is a glass in the case of forming a battery by pressurization and heating. Is good.

  The positive electrode layer and the negative electrode layer may further contain a binder. As the binder, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), fluorine-containing resins such as fluorine rubber, or thermoplastic resins such as polypropylene and polyethylene, ethylene-propylene-diene rubber (EPDM), sulfonated EPDM, Natural butyl rubber (NBR) or the like can be used alone or as a mixture of two or more. In addition, an aqueous dispersion of cellulose or styrene butadiene rubber (SBR), which is an aqueous binder, can also be used.

[battery]
The battery of the present invention includes the solid electrolyte particles and / or the composition described above, or is produced using the solid electrolyte particles and / or the composition described above, or includes at least one of the electrolyte layer and the electrode layer.
As the electrolyte layer other than the electrolyte layer, a known electrolyte layer (polymer electrolyte, non-aqueous electrolyte, etc.) can be used. Moreover, a well-known electrode layer can be used for electrode layers other than the said electrode layer, for example, there exists an electrode using the compound material of the said active material and electrolyte.

Example 1
[Production of solid electrolyte glass coarse particles 1]
Na ₂ S (manufactured by High Purity Chemical Laboratory) and P ₂ S ₅ (manufactured by Aldrich) were used as starting materials. Na ₂ S 25.72 g (75 mol%) and P ₂ S ₅ 24.288 g (25 mol%) are put in a 500 ml alumina container containing 175 10 mmφ alumina balls, and dehydrated toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 68 ml was added and sealed. The above weighing, addition and sealing operations were all carried out in the glove box, and all the used instruments were dehydrated in advance with a dryer. In addition, dehydrated toluene was 8.4 ppm as measured by the Karl Fischer method.
The sealed alumina container was mechanically milled at 290 rpm at room temperature with a planetary ball mill (PM400 manufactured by Lecce) for 18 hours to obtain a white-yellow powder slurry (cream).
This was filtered and air-dried, and then dried with a tube heater at 160 ° C. for 2 hours to obtain solid electrolyte glass coarse particles 1 (powder).

This operation was performed 20 times to obtain 800 g of solid electrolyte glass coarse particles 1.
The volume standard average diameter was 110 μm. The volume standard average diameter was measured with a laser diffraction type particle size distribution analyzer (manufactured by Malvern Instruments Ltd., model number: Mastersizer 2000).
As a result of X-ray diffraction measurement (CuKα: λ = 1.5418４) of this powder, no peak was observed other than the halo pattern derived from amorphous, and it was confirmed that the powder was solid electrolyte glass.

[Production of solid electrolyte glass ceramic coarse particles 1]
The solid electrolyte glass coarse particles (powder) were sealed in a SUS tube in a glow box under an argon atmosphere, and heat-treated at 280 ° C. for 2 hours. As a result of X-ray diffraction measurement of the treated powder, it was confirmed that the powder had a cubic Na ₃ PS ₄ structure, and it was found to be solid electrolyte glass ceramic coarse particles 1.
The volume standard average diameter was 137 μm.
The ionic conductivity of the solid electrolyte glass ceramic coarse particles 1 was 2 × 10 ⁻⁴ S / cm.

In addition, the measurement of ion conductivity was performed with the following method.
The solid electrolyte was filled in a tablet molding machine, and a molded body was obtained by applying a pressure of 4 to 6 MPa. Next, a mixture obtained by mixing carbon and a solid electrolyte at a weight ratio of 1: 1 as an electrode is placed on both sides of the molded body, and pressure is applied again with a tablet molding machine, thereby forming a molded body for conductivity measurement (diameter 10 mm). , 1 mm thick). About this molded object, ion conductivity measurement was implemented by alternating current impedance measurement. The conductivity value was a value at 25 ° C.

The above weighing and sealing operations were all carried out in the glove box, and all the equipment used was previously used after removing moisture with a dryer.
As a result of X-ray diffraction measurement (CuKα: λ = 1.5418４) of the obtained coarse particles, the peak of the raw material Na 2 S was not observed, and it was an XRD pattern of the solid electrolyte glass ceramic.

[Production of solid electrolyte particles 1]
A container with a stirrer was connected to a bead mill LMZ015 manufactured by Ashizawa Finetech, and the resulting slurry containing the solid electrolyte glass ceramic coarse particles 1 was pulverized by a method of circulating with a pump.
Specifically, 440 g of 0.5φZrO ₂ beads are charged in a bead mill, and a slurry composed of 1031.9 g of anhydrous toluene solvent, 102.1 g of isobutyronitrile, and 126.0 g of solid electrolyte glass ceramic coarse particles 1 is placed in a vessel equipped with a stirrer. Prepared. While circulating the slurry at 200 mL / min, the slurry was treated at a blade tip speed of 10 m / s rpm for 2 hours, and the slurry containing the solid electrolyte particles was recovered. Next, the ZrO ₂ beads of the bead mill were replaced with 0.1φZrO ₂ beads, and the recovered slurry containing the solid electrolyte particles was treated again in the same manner as described above to obtain a slurry containing the solid electrolyte particles 1.

As a result of measuring the particle size of the obtained solid electrolyte particles 1 with the laser diffraction particle size distribution measuring apparatus, the volume standard average particle size is 0.13 μm, and the volume standard particle size is 0.29 μm or less of 90%. Met.
Further, after the slurry containing the solid electrolyte particles 1 thus obtained was well stirred, the slurry was allowed to stand for 24 hours, and the sedimentation volume fraction (volume of solid electrolyte particles 1 sedimented / total slurry volume × 100) was measured. %Met. In addition, when a coating film (film thickness 70 μm) was formed by the doctor blade method using the obtained slurry, a uniform film was obtained visually. The results are shown in Table 1.

The sedimentation volume fraction was measured as follows.
While stirring the slurry containing the solid electrolyte particles 1, 20 ml was extracted, and the total slurry volume was measured with a graduated cylinder. After thoroughly stirring the slurry, the slurry was allowed to stand for 24 hours, and the volume of the portion where the solid electrolyte particles 1 settled was measured. Using each value, the sedimentation volume fraction was determined from the volume of solid electrolyte particles 1 sedimented / total slurry volume × 100. All operations were performed under an inert gas atmosphere so that the sample did not touch the atmosphere.

Example 2
In the production of the solid electrolyte particles 1, a slurry containing solid electrolyte particles was prepared in the same manner as in Example 1 except that the amount of anhydrous toluene solvent charged was 1088.6 g and the amount of isobutyronitrile charged was 45.4 g. Prepared and evaluated.

  As a result, the volume-based average particle diameter of the obtained solid electrolyte particles was 0.32 μm, and the volume-based particle diameter of 1.12 μm or less was 90%. Moreover, the sedimentation volume fraction was 50%. When a coating film was formed in the same manner as in Example 1, a uniform film was obtained visually. The results are shown in Table 1.

Example 3
In the production of the solid electrolyte particles 1, a slurry containing the solid electrolyte particles was prepared and evaluated in the same manner as in Example 1 except that the solid electrolyte glass coarse particles 1 were used instead of the solid electrolyte glass ceramic coarse particles 1.

  As a result, the volume-based average particle diameter of the obtained solid electrolyte particles was 0.14 μm, and 90% of the particles had a particle diameter of 0.44 μm or less. The sedimentation volume fraction was 79%. When a coating film was formed in the same manner as in Example 1, a uniform film was obtained visually. The results are shown in Table 1.

Example 4
[Production of solid electrolyte glass coarse particles 2]
In the production of the solid electrolyte glass coarse particles 1, 690 g of Na ₂ S and 9.2 g of P ₂ S ₅ (manufactured by Aldrich) were sealed in an alumina container except that 20.8 g was put in an alumina container and sealed. Solid electrolyte glass coarse particles 2 were obtained. The molar ratio of the raw materials was Na ₂ S: P ₂ S ₅ = 80: 20 (molar ratio). The obtained solid electrolyte glass coarse particles 2 had a volume-based average particle diameter of 126 μm and were subjected to X-ray diffraction measurement (CuKα: λ = 1.5418１．５). As a result, the peak of the raw material Na ₂ S was not observed, and the solid It was a halo pattern resulting from the electrolyte glass.

[Production of solid electrolyte particles 2]
In the production of the solid electrolyte particles 1, a slurry containing the solid electrolyte particles was prepared and evaluated in the same manner as in Example 1 except that the solid electrolyte glass coarse particles 2 were used instead of the solid electrolyte glass ceramic coarse particles 1.

  As a result, the volume-based average particle size of the obtained solid electrolyte particles 2 was 0.26 μm, and 90% of the particles had a particle size of 0.88 μm or less. The sedimentation volume fraction was 78%. When a coating film was formed in the same manner as in Example 1, a uniform film was obtained visually. The results are shown in Table 1.

Reference Example 5
In the production of the solid electrolyte particles 1, a slurry containing solid electrolyte particles was prepared and evaluated in the same manner as in Example 1 except that the amount of dehydrated toluene charged was 1134.0 g and no isobutyronitrile was added. .

  As a result, the volume-based average particle size of the obtained solid electrolyte particles was 2.60 μm, and 90% of the particles had a particle size of 10.0 μm or less. Moreover, the sedimentation volume fraction was 15%. When a coating film was formed in the same manner as in Example 1, a film having a part of the hole was obtained. The results are shown in Table 1.

Reference Example 6
Reference Example 5, except for using the solid electrolyte glass grit 2 instead of the solid electrolyte glass ceramics coarse particles 1 in the same manner as in Reference Example 5, to prepare a slurry containing the solid electrolyte particles was evaluated.

As a result, the volume-based average particle size of the obtained solid electrolyte particles was 2.75 μm, and 90% of the particles had a particle size of 12.0 μm or less. Moreover, the sedimentation volume fraction was 13%. When a coating film was formed in the same manner as in Example 1, a film having a part of the hole was obtained. The results are shown in Table 1.

Reference Example 7
The solid electrolyte glass coarse particles 1 were pulverized using a jet mill (manufactured by Seishin Enterprise Co., Ltd.).
As processing conditions, nitrogen having a throughput of 90 g / hr and a pressure of 0.7 MPa was used as a grinding fluid.

  As a result, the volume-based average particle size of the obtained solid electrolyte particles was 1.5 μm, and 90% of the particles had a particle size of 8 μm or less. Moreover, the sedimentation volume fraction was 35%. When a coating film was formed in the same manner as in Example 1, a uniform film was obtained.

Reference Example 8
The same procedure as in Reference Example 7 was performed except that the solid electrolyte glass coarse particles 1 were changed to the solid electrolyte glass coarse particles 2.

  As a result, the volume-based average particle size of the obtained solid electrolyte particles was 2 μm, and 90% of the particles had a particle size of 10 μm or less. Moreover, the sedimentation volume fraction was 30%. When a coating film was formed in the same manner as in Example 1, a substantially uniform film was obtained.

Reference Example 9
The same procedure as in Reference Example 7 was performed except that the solid electrolyte glass coarse particles 1 were changed to the solid electrolyte glass ceramic 1.

  As a result, the volume-based average particle diameter of the obtained solid electrolyte particles was 1.2 μm, and 90% of the particles had a particle diameter of 7 μm or less. The sedimentation volume fraction was 40%. When a coating film was formed in the same manner as in Example 1, a uniform film was obtained.

Comparative Example 1
To a slurry prepared by adding 123.7 g of dehydrated toluene to 13.7 g of solid electrolyte glass ceramic coarse particles 1 as a solvent, 545 g of 0.2 mm diameter zirconia beads are added, and a rotational speed of 2000 rpm using a batch type bead mill (manufactured by Imex). For 1 hour. The volume-based average particle diameter was 55% and 90% of the particles having a size of 90 μm or less. Moreover, the sedimentation volume fraction was 5%. When the coating film was formed, holes were partially formed in the film. It cannot be used as a sheet for a solid electrolyte layer.

  The solid electrolyte particles and composition of the present invention can be used for an electrolyte layer and an electrode layer of a battery.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus 10 Crusher 20 Temperature holding tank 22 Container 24 Stirring blade 26 Cooling pipe 30 Heater 40 Oil bath 50 1st connecting pipe 52 2nd connecting pipe 54 Pump

Claims (10)

Containing at least one component selected from sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium and radium, phosphorus and sulfur,
Volume-based average particle diameter of more than 0.01μm, as measured by a laser diffraction particle size distribution measuring method 2.5 [mu] m Ri der below,
Solid electrolyte particles having a volume reference particle diameter (Dp90) of 90% of particles measured by a laser diffraction particle size distribution measuring method of 5 μm or less .   The solid electrolyte particle according to claim 1, wherein the at least one component is sodium. Compositions comprising the solid electrolyte particles according to claim 1 or 2. The composition of claim 3 comprising a nitrile compound. The electrolyte layer containing the solid electrolyte particle of Claim 1 or 2 , and / or the composition of Claim 3 or 4 . The electrode layer containing the solid electrolyte particle of Claim 1 or 2 , and / or the composition of Claim 3 or 4 . Battery comprising a composition according to claim 1 or 2 solid electrolyte particles according to, and / or claim 3 or 4. The electrolyte layer manufactured using the solid electrolyte particle of Claim 1 or 2 , and / or the composition of Claim 3 or 4 . The electrode layer manufactured using the solid electrolyte particle of Claim 1 or 2 , and / or the composition of Claim 3 or 4 . The battery manufactured using the solid electrolyte particle of Claim 1 or 2 , and / or the composition of Claim 3 or 4 .

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