JP2013143338A - Sulfide-based solid electrolyte composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sulfide-based solid electrolyte composition, having high ionic conductivity, and capable of reducing a generation amount of hydrogen sulfide of a sulfide-based solid electrolyte.SOLUTION: A sulfide-based solid electrolyte containing composition contains a sulfide-based solid electrolyte, halide containing an alkali metal or an alkali earth metal, or a compound containing an alkali metal or an alkali earth metal and sulfur, where a generation amount of a hydrogen sulfide is 1000 ppm or less, and ionic conductivity is 1×10S/cm or over.

Description

  The present invention relates to a sulfide-based solid electrolyte composition.

In the current lithium ion battery, an organic electrolyte is mainly used as an electrolyte.
Although organic electrolytes exhibit high ionic conductivity, the electrolytes are liquid and flammable, so there are concerns about risks such as leakage and ignition when used as batteries. Therefore, development of a safer solid electrolyte is expected as an electrolyte for next-generation lithium ion batteries.

In order to solve the above problem, a sulfide-based solid electrolyte containing sulfur element, lithium element and phosphorus element as main components has been proposed (for example, Patent Document 1). Since this electrolyte is a solid, there is no problem of leakage or the like unlike a liquid electrolyte.
However, the sulfide-based solid electrolyte has a problem that hydrogen sulfide is generated by contact with moisture and the battery is deteriorated.

Japanese Patent Laid-Open No. 11-134937

  An object of the present invention is to provide a sulfide-based solid electrolyte composition having high ionic conductivity and capable of reducing the amount of hydrogen sulfide generated in the sulfide-based solid electrolyte.

According to the present invention, the following sulfide-based solid electrolyte composition and the like are provided.
1. A sulfide-based solid electrolyte;
A halide containing an alkali metal or an alkaline earth metal, or a compound containing an alkali metal or an alkaline earth metal and sulfur,
A sulfide-based solid electrolyte-containing composition having an ionic conductivity of 1 × 10 ⁻⁴ S / cm or more,
0.1 g was weighed into a 100 cc two-necked flask, and once passed through water at a flow rate of 500 ml / min, the gas that passed through the two-necked flask with a cock was collected, and the sulfur content was measured by ultraviolet fluorescence. A sulfide-based solid electrolyte-containing composition in which the amount of generated hydrogen sulfide measured by quantification is 1000 ppm or less.
2. 2. The sulfide solid electrolyte composition according to 1, wherein the sulfide electrolyte satisfies the following formula (1).
Li _a M _b P _c S _d (1)
(In the formula, M represents one or more elements selected from B, Zn, Si, Cu, Ga and Ge.
a to d indicate the composition ratio of each element, and a: b: c: d satisfies 1 to 12: 0 to 0.5: 1: 2 to 9. )
3. 3. The sulfide solid electrolyte composition according to 1 or 2 that satisfies the following formula (2).
0.001 ≦ x / y ≦ 0.6 (2)
Wherein x represents the weight [g] of the halide containing the alkali metal or alkaline earth metal, or the compound containing alkali metal or alkaline earth metal and sulfur, and y is the weight of the sulfide solid electrolyte. [G] is shown.)
The electrode material containing the sulfide type solid electrolyte composition in any one of 4.1-3.
The electrode material manufactured from the sulfide type solid electrolyte composition in any one of 5.1-3.
A battery provided with at least one of the electrode and electrolyte layer containing the sulfide type solid electrolyte composition in any one of 6.1-3.
A battery comprising at least one of an electrode and an electrolyte layer manufactured from the sulfide-based solid electrolyte composition according to any one of 7.1 to 3.

  ADVANTAGE OF THE INVENTION According to this invention, the ionic conductivity is high and can provide the sulfide type solid electrolyte composition which can reduce the generation amount of the hydrogen sulfide of sulfide type solid electrolyte.

[Sulfide-based solid electrolyte composition]
The sulfide-based solid electrolyte composition of the present invention is a composition comprising a sulfide-based solid electrolyte and a halide containing an alkali metal or alkaline earth metal, or a compound containing an alkali metal or alkaline earth metal and sulfur. is there.
The composition includes a halide containing an alkali metal or an alkaline earth metal, or a compound containing an alkali metal or an alkaline earth metal and sulfur, thereby suppressing generation of hydrogen sulfide from the sulfide-based solid electrolyte. it can.

The amount of hydrogen sulfide generated in the composition of the present invention is 1000 ppm by weight or less per 0.1 g of the composition, preferably 950 ppm by weight or less,
More preferably, it is 900 weight ppm or less, More preferably, it is 90 weight ppm or less, Most preferably, it is 70 weight ppm or less.
The lower limit of the amount of hydrogen sulfide generated is not particularly limited, but is, for example, 0 ppm by weight.

The amount of hydrogen sulfide generated is measured by the following method.
Under a nitrogen atmosphere, 0.1 g of the composition of the present invention was weighed into a two-neck flask with a cock, and air (humidity 80-90%) once passed through water was circulated at 500 ml / min and a two-neck with a cock. The hydrogen sulfide gas concentration is calculated by collecting the gas that has passed through the flask and quantifying the sulfur content by ultraviolet fluorescence.

The ionic conductivity of the composition of the present invention is 1 × 10 ⁻⁴ S / cm or more, preferably 1.5 × 10 ⁻⁴ S / cm or more, and more preferably 2.0 × 10 ⁻⁴ S. / Cm or more. The battery performance of the all-solid-state lithium battery manufactured using the composition can be improved because the ionic conductivity of the composition is 1 × 10 ⁻⁴ S / cm or more.
The ionic conductivity of the composition is, for example, 5 MPa so that 0.1 g of the composition is press-molded into a tablet having a diameter of 1 cm at 5 MPa, and 0.01 g of graphite is attached to both sides of the obtained pellet as an electrode. It can be understood by pressure molding to form a pellet-shaped solid electrolyte sheet and measuring the sheet by an alternating current impedance method (measurement frequency: 10 Hz to 5 MHz).

Hereinafter, each component of the composition of the present invention will be described.
[Sulfide-based solid electrolyte]
The sulfide-based solid electrolyte is an ion conductive material containing a sulfur atom (S), preferably has an ionic conductivity of 1.0 × 10 ⁻⁴ S / cm or more, and more preferably 1.5 × 10 ^{−. 4} S / cm or more.

The sulfide-based solid electrolyte is preferably a sulfide-based solid electrolyte containing an alkali metal or an alkaline earth metal and having ionic conductivity of the alkali metal or alkaline earth metal.
Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, barium, and radium.
The alkali metal or alkaline earth metal is preferably lithium or sodium, and more preferably lithium.
Examples of lithium contained in the sulfide-based solid electrolyte include LiBr, LiI, LiCl, LiF, and LiSH. The purity of these lithium compounds is preferably 90% or more.

The sulfide-based solid electrolyte may be either an amorphous sulfide-based solid electrolyte glass or a crystallized sulfide-based solid electrolyte glass ceramic, but Li ₇ P ₃ S ₁₁ from the viewpoint of increasing ionic conductivity. Glass ceramics having a crystal structure are preferred, and glass having a Li ₃ PS ₄ structure or glass ceramics having a Li ₃ PS ₄ structure is preferred from the viewpoint of reducing the amount of hydrogen sulfide generated.

The glass particles and / or glass ceramic particles which are sulfide-based solid electrolytes are preferably lithium ion conductive inorganic solid electrolytes that satisfy the composition represented by the following formula (1).
Li _{a Mb} P _c S _d (1)
In the formula (1), M represents an element selected from B, Zn, Si, Cu, Ga, or Ge.
a to d indicate the composition ratio of each element, and a: b: c: d satisfies 1-12: 0 to 0.5: 1: 2-9.
Preferably b is 0, more preferably the ratio of a, c and d (a: c: d) is a: c: d = 1 to 9: 1: 3-7, more preferably a: c: d. = 1.5-4: 1: 3.25-4.5.

  The composition ratio of each element can be controlled by adjusting the compounding amount of the raw material compound when producing glass particles and glass ceramic particles.

The sulfide-based solid electrolyte contains at least lithium (Li), phosphorus (P), and sulfur (S). For example, lithium sulfide and diphosphorus pentasulfide, or lithium sulfide and simple phosphorus and simple sulfur, and further lithium sulfide, It can be produced from raw materials such as diphosphorus pentasulfide, simple phosphorus and / or simple sulfur.
The sulfide-based solid electrolyte may be further subjected to a flame retardant treatment.

The sulfide-based solid electrolyte is preferably a sulfide-based solid electrolyte glass ceramic having a crystallinity of 50% or more from the viewpoint of improving ionic conductivity. This is because when the crystallization degree of the sulfide-based solid electrolyte is 50% or more, the ionic conductivity can be improved by crystallization.
Further, a mixture of a sulfide-based glass ceramic solid electrolyte and a sulfide-based glass solid electrolyte may be used.
The degree of crystallinity can be measured by using an NMR spectrum apparatus. Specifically, a solid ³¹ P-NMR spectrum of a sulfide-based solid electrolyte was measured, and the resonance line observed at 70-120 ppm was separated into a Gaussian curve using a nonlinear least square method. It can be measured by determining the area ratio of each curve.

The sulfide-based solid electrolyte is preferably produced from raw materials such as lithium sulfide, diphosphorus pentasulfide, simple phosphorus and / or simple sulfur.
As lithium sulfide, those commercially available without particular limitation can be used, but those having high purity are preferred.
Preferably, the lithium sulfide has a total content of lithium salts of sulfur oxides of 0.15% by mass or less, more preferably 0.1% by mass or less, and a content of lithium N-methylaminobutyrate of 0.1%. It is 15 mass% or less, More preferably, it is 0.1 mass% or less. When the total content of the lithium salt of sulfur oxide is 0.15% by mass or less, the solid electrolyte obtained by the melt quenching method or the mechanical milling method becomes a glassy electrolyte (fully amorphous). On the other hand, if the total content of the lithium salt of sulfur oxide exceeds 0.15% by mass, the obtained electrolyte may become a crystallized product from the beginning, and the ionic conductivity of this crystallized product is low. Further, even if this crystallized product is subjected to a heat treatment, the crystallized product is not changed, and there is a possibility that a sulfide-based solid electrolyte having high ion conductivity cannot be obtained.

  In addition, when the content of lithium N-methylaminobutyrate is 0.15% by mass or less, a deteriorated product of lithium N-methylaminobutyrate does not deteriorate the cycle performance of the lithium ion battery. When lithium sulfide with reduced impurities is used, a high ion conductive electrolyte can be obtained.

The method for producing lithium sulfide is not particularly limited as long as it can reduce at least the above impurities. For example, it can be obtained by purifying lithium sulfide produced by the following methods ac. Among the following production methods, the method a or b is particularly preferable.
a. A method in which lithium hydroxide and hydrogen sulfide are reacted at 0 to 150 ° C. in an aprotic organic solvent to produce lithium hydrosulfide, and then this reaction solution is dehydrosulfurized at 150 to 200 ° C. 7-330312 gazette).
b. A method in which lithium hydroxide and hydrogen sulfide are reacted at 150 to 200 ° C. in an aprotic organic solvent to directly produce lithium sulfide (see JP-A-7-330312).
c. A method of reacting lithium hydroxide and a gaseous sulfur source at a temperature of 130 to 445 ° C. (see JP-A-9-283156).

There is no restriction | limiting in particular as a purification method of the lithium sulfide obtained as mentioned above. As a preferable purification method, for example, a purification method described in International Publication No. WO2005 / 40039 and the like can be mentioned. Specifically, the lithium sulfide obtained as described above is washed at a temperature of 100 ° C. or higher using an organic solvent.
The organic solvent used for washing is preferably an aprotic polar solvent, and more preferably, the aprotic organic solvent used for lithium sulfide production and the aprotic polar organic solvent used for washing are the same. .

  Examples of the aprotic polar organic solvent preferably used for washing include aprotic polar organic compounds such as amide compounds, lactam compounds, urea compounds, organic sulfur compounds, cyclic organophosphorus compounds, Or it can use suitably as a mixed solvent. In particular, N-methyl-2-pyrrolidone (NMP) is selected as a good solvent.

  The amount of the organic solvent used for washing is not particularly limited, and the number of times of washing is not particularly limited, but is preferably 2 or more. Cleaning is preferably performed under an inert gas such as nitrogen or argon.

  The washed lithium sulfide is dried at a temperature equal to or higher than the boiling point of the organic solvent used for washing for 5 minutes or more, preferably about 2 to 3 hours or more under an inert gas stream such as nitrogen under normal pressure or reduced pressure. Thus, lithium sulfide used in the present invention can be obtained.

As long as diphosphorus pentasulfide (P ₂ S ₅ ) is industrially manufactured and sold, it can be used without particular limitation. In place of P ₂ S ₅ , elemental phosphorus (P) and elemental sulfur (S) in a corresponding molar ratio can also be used. Simple phosphorus (P) and simple sulfur (S) can be used without particular limitation as long as they are industrially produced and sold.

The mixing molar ratio of lithium sulfide to diphosphorus pentasulfide or simple phosphorus and simple sulfur is usually 50:50 to 80:20, preferably 60:40 to 75:25.
Particularly preferably, it is about Li ₂ S: P ₂ S ₅ = 68: 32 to 74:26 (molar ratio).

As a method for producing a sulfide-based glass solid electrolyte, there are a melt quenching method and a mechanical milling method (MM method).
In the case of the melt quenching method, P ₂ S ₅ and Li ₂ S mixed in a predetermined amount in a mortar and pelletized are placed in a carbon-coated quartz tube and vacuum-sealed. After reacting at a predetermined reaction temperature, a sulfide-based glass solid electrolyte is obtained by putting it in ice and rapidly cooling it.

The reaction temperature at this time is preferably 400 ° C to 1000 ° C, more preferably 800 ° C to 900 ° C.
Moreover, reaction time becomes like this. Preferably it is 0.1 to 12 hours, More preferably, it is 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.

In the case of the MM method, a sulfide-based glass solid electrolyte is obtained by mixing a predetermined amount of P ₂ S ₅ and Li ₂ S 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. According to the MM method, since a glass solid electrolyte can be produced at room temperature, there is an advantage that a glass solid electrolyte having a charged composition can be obtained without thermal decomposition of raw materials.
Further, the MM method has an advantage that the glass solid electrolyte can be made into fine powder simultaneously with the production of the glass solid electrolyte.

  In the MM method, various types such as a rotating ball mill, a rolling ball mill, a vibrating ball mill, and a planetary ball mill can be used.

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.
Although specific examples of the sulfide-based glass solid electrolyte by the melt quenching method and the MM method have been described above, manufacturing conditions such as temperature conditions and processing time can be appropriately adjusted according to the equipment used.

Thereafter, the obtained sulfide-based glass solid electrolyte is heat-treated at a predetermined temperature to produce a sulfide-based crystallized glass (glass ceramic) solid electrolyte.
The heat treatment temperature for producing the sulfide-based crystallized glass solid electrolyte is preferably 180 ° C to 330 ° C, more preferably 200 ° C to 320 ° C, and particularly preferably 210 ° C to 310 ° C. When the temperature is lower than 180 ° C., it may be difficult to obtain a crystallized glass having a high degree of crystallinity.

The heat treatment time is preferably from 3 to 240 hours, particularly preferably from 4 to 230 hours, when the temperature is from 180 ° C to 210 ° C. Moreover, in the case of temperature higher than 210 degreeC and 330 degrees C or less, 0.1 to 240 hours are preferable, 0.2 to 235 hours are especially preferable, Furthermore, 0.3 to 230 hours are preferable.
When the heat treatment time is shorter than 0.1 hour, it may be difficult to obtain a crystallized glass with a high degree of crystallinity, and when it is longer than 240 hours, a crystallized glass with a low degree of crystallinity may be generated.

The sulfide-based crystallized glass solid electrolyte is obtained by 2θ = 17.8 ± 0.3 deg, 18.2 ± 0.3 deg, 19.8 ± 0.3 deg, in X-ray diffraction (CuKα: λ = 1.5418４). It is preferable to have diffraction peaks at 21.8 ± 0.3 deg, 23.8 ± 0.3 deg, 25.9 ± 0.3 deg, 29.5 ± 0.3 deg, 30.0 ± 0.3 deg.
A solid electrolyte having such a crystal structure has extremely high lithium ion conductivity.

[Additional halogen / sulfur metal salts]
Halide containing alkali metal or alkaline earth metal contained in the composition of the present invention, or compound containing alkali metal or alkaline earth metal and sulfur (hereinafter, these may be collectively referred to as added halogen / sulfur metal salt) It is necessary that the sulfide-based solid electrolyte does not react and change into another substance. This is because if the added halogen / sulfur metal salt becomes a different substance due to the reaction, the amount of hydrogen sulfide generated cannot be reduced. On the other hand, in the case of an alkali metal or alkaline earth metal hydroxide such as lithium hydroxide (LiOH) instead of an added halogen / sulfur metal salt, there is a problem in redox stability because it has an active proton itself. May occur.
When the additive halogen / sulfur metal salt particles and sulfide solid electrolyte particles are mixed to produce the composition of the present invention, the added halogen / sulfur metal salt particles and sulfide solid electrolyte The particles may be complexed or may exist as separate particles.

Examples of the alkali metal constituting the added halogen / sulfur metal salt include lithium, sodium, potassium, rubidium, and cesium. Examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, barium, and radium.
The alkali metal or alkaline earth metal constituting the added halogen / sulfur metal salt is preferably lithium or sodium, more preferably lithium.
Moreover, it is preferable that the alkali metal or alkaline earth metal contained in the above-mentioned sulfide-based solid electrolyte and the alkali metal or alkaline earth metal constituting the added halogen / sulfur metal salt are the same.

  The halogen constituting the added halogen metal salt is fluorine, chlorine, bromine, iodine, astatine or ununseptium, preferably fluorine, chlorine, bromine or iodine, more preferably chlorine, bromine or iodine.

Specific examples of halides containing alkali metal or alkaline earth metal that are added halogen metal salts include LiCl, LiBr, LiI, NaCl, NaBr, and NaI.
Specific examples of the compound containing an alkali metal or alkaline earth metal and sulfur, which are added sulfur metal salts, include NaSH, KSH, RbSH, and CsSH.

The content of the added halogen / sulfur metal salt in the composition of the present invention preferably satisfies the following formula (2), more preferably satisfies the following formula (3).
0.001 ≦ x / y ≦ 0.6 (2)
0.2 ≦ x / y ≦ 0.5 (3)
(In the formula, x represents the weight [g] of a halide containing an alkali metal or alkaline earth metal, or an alkali metal or alkaline earth metal and a compound containing sulfur, and y represents the weight [g of a sulfide-based solid electrolyte] ]

[Method for producing sulfide-based solid electrolyte composition]
The sulfide-based solid electrolyte composition of the present invention can be produced by mixing a sulfide-based solid electrolyte that generates hydrogen sulfide and an added halogen / sulfur metal salt.
The mixing method is not particularly limited, and examples thereof include a mixing method using a mortar or the like, and a mixing method using a planetary ball mill, a vibration mill, or the like.

For example, when a planetary ball mill is used for mixing a sulfide-based solid electrolyte and an added halogen / sulfur metal salt, ten alumina 10 mmφ balls are put in a 45 ml capacity alumina pot per pot, and 100 rpm to 500 rpm. Mixing may be performed at a rotational speed for 1 to 1200 minutes.
If a planetary ball mill or the like is used for mixing, the sulfide-based solid electrolyte may react with the added halogen / sulfur metal salt. In the present invention, the sulfide-based solid electrolyte and the “halide containing an alkali metal or alkaline earth metal” do not react, and the “halide containing an alkali metal or alkaline earth metal” itself is present, so that hydrogen sulfide is present. In order to reduce the generation amount of the above, it is necessary to mix under the condition that the sulfide-based solid electrolyte and the “halide containing alkali metal or alkaline earth metal” do not react.
In the mixed state, the sulfide-based solid electrolyte and the added halogen / sulfur metal salt may be integrated to form a composite, or may exist as separate particles.

[battery]
Since the sulfide-based solid electrolyte composition of the present invention generates a small amount of hydrogen sulfide, it can suppress battery deterioration and is suitable as a battery material.
The battery of the present invention includes the sulfide-based solid electrolyte composition of the present invention, for example, a battery including an electrode layer, an electrolyte layer, and a current collector, and the electrolyte layer may include the composition of the present invention. The layer may contain the composition of the present invention, and both the electrolyte layer and the electrode layer may contain the composition of the present invention.
Similarly, the battery of the present invention is a battery using the sulfide-based solid electrolyte composition of the present invention, and the battery includes, for example, an electrode layer, an electrolyte layer, and a current collector. A composition may be used, the composition of this invention may be used for an electrode layer, and the composition of this invention may be used for both an electrolyte layer and an electrode layer.

  The solid electrolyte composition of the present invention may further contain a binder (binder), a positive electrode active material, a negative electrode active material, a conductive additive, an organic solvent, and the like. The positive electrode, the electrolyte layer, the negative electrode, etc. It can be used as a material and a material for forming a member (layer) constituting a battery.

Hereinafter, examples of other constituent materials will be described.
Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine-containing resins such as fluorine rubber, thermoplastic resins such as polypropylene and polyethylene, ethylene-propylene-dienemer (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.

As the positive electrode active material, a material capable of inserting and desorbing lithium ions, and a material known as a positive electrode active material in the battery field can be used.
For example, V ₂ O ₅ , LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , LiMn ₂ O ₄ , Li (Ni _a Co _b Mn _c ) O ₂ (where 0 <a <1, 0 <b <1, 0 < c <1, a + b + c = 1), LiNi _1-Y Co _{Y 2} O ₂ , LiCo _1-Y Mn _{Y 2} O ₂ , LiNi _1-Y Mn _{Y 2} O ₂ (where 0 ≦ Y <1), Li (Ni _{a Co b Mn c) O 4 (} 0 <a <2,0 <b <2,0 <c <2, a + b + c = 2), LiMn 2-Z Ni Z O 4, LiMn 2-Z Co Z O 4 ( wherein 0 <Z <2), LiCoPO ₄ , LiFePO ₄ , bismuth oxide (Bi ₂ O ₃ ), bismuth lead acid (Bi ₂ Pb ₂ O ₅ ), copper oxide (CuO), vanadium oxide (V ₆ O ₁₃ ) _{, Li x CoO 2, Li x} NiO 2, Li Mentioned _{Mn 2 O 4, Li x FePO} 4, Li x CoPO 4, Li x Mn 1/3 Ni 1/3 Co 1/3 O 2, oxides such as Li _x Mn _{1.5 Ni} 0.5 _{O 2} is It is done. Other positive electrode active materials include, for example, elemental sulfur (S), titanium sulfide (TiS ₂ ), molybdenum sulfide (MoS ₂ ), iron sulfide (FeS, FeS ₂ ), copper sulfide (CuS) in the sulfide system. Nickel sulfide (Ni ₃ S ₂ ), lithium sulfide (Li ₂ S), niobium selenide (NbSe ₃ ), organic disulfide compounds, carbon sulfide compounds, sulfur, metal indium, and the like can be used. Preferably, S and Li ₂ S having a high theoretical capacity can be used.

  Organic disulfide compounds and carbon sulfide compounds are exemplified below.

  In formulas (A) to (C), X is a substituent, n and m are each independently an integer of 1 to 2, and p and q are each independently an integer of 1 to 4.

  In formula (D), Z is -S- or -NH-, respectively, and n is an integer of 2 to 300 repetitions.

As the negative electrode active material, a material capable of inserting and desorbing lithium ions, and a material known as a negative electrode active material in the battery field can be used.
For example, carbon materials, specifically 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 Examples thereof include fibers, vapor-grown carbon fibers, natural graphite, and non-graphitizable carbon. Or it may be a mixture thereof. Preferably, it is artificial graphite.

  Also, an alloy in combination with a metal itself such as metallic lithium, metallic indium, metallic aluminum, metallic silicon, or another element or compound can be used as the negative electrode material. Among these, silicon, tin, and lithium metal having a high theoretical capacity are preferable.

The conductive auxiliary agent only needs to have conductivity. For example, the conductivity is preferably 1 × 10 ³ S / cm or more, more preferably 1 × 10 ⁵ S / cm or more.
Examples of the conductive aid include substances selected from carbon materials, metal powders and metal compounds, and mixtures thereof.
Specific examples of conductive aids include carbon, nickel, copper, aluminum, indium, silver, cobalt, magnesium, lithium, chromium, gold, ruthenium, platinum, beryllium, iridium, molybdenum, niobium, osnium, rhodium, tungsten and zinc. A substance containing at least one element selected from the group consisting of: More preferably, it is a simple substance of carbon, carbon, nickel, copper, silver, cobalt, magnesium, lithium, ruthenium, gold, platinum, niobium, osnium or rhodium having a high conductivity, simple substance, mixture or compound.

Specific examples of the carbon material include carbon black such as ketjen black, acetylene black, denka black, thermal black and channel black, graphite, carbon fiber, activated carbon and the like. These can be used alone or in combination of two or more.
Among these, acetylene black, denka black, and ketjen black having high electron conductivity are preferable.

  The electrolyte layer (sheet) may include the above-described composition of the present invention. In addition to the composition of the present invention, the above-described binder or the like may be contained depending on the purpose of use, and other electrolytes may be contained.

The other electrolyte is at least one of a polymer-based solid electrolyte, an oxide-based solid electrolyte, or the electrolyte precursor 1 or 2 described above.
The polymer-based solid electrolyte is not particularly limited. For example, as disclosed in Japanese Patent Application Laid-Open No. 2010-262860, materials used as a polymer electrolyte such as a fluororesin, polyethylene oxide, polyacrylonitrile, polyacrylate, derivatives thereof, and copolymers thereof can be used.

  As a fluororesin, what contains vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), these derivatives, etc. as a structural unit is mentioned, for example. Specifically, a homopolymer such as polyvinylidene fluoride (PVdF), polyhexafluoropropylene (PHFP), polytetrafluoroethylene (PTFE), or a copolymer of VdF and HFP (hereinafter, this copolymer is referred to as “ P (VdF-HFP) ”may be used, and binary copolymers and ternary copolymers.

Examples of the oxide-based solid electrolyte include crystals having a perovskite structure such as LiN, LISICON, La _0.55 Li _0.35 TiO ₃ , LiTi ₂ P ₃ O ₁₂ having a NASICON type structure, and further crystallizing these. An electrolyte or the like can be used.

The electrolyte layer of another aspect is an electrolyte layer produced using the composition of the present invention.
The electrolyte layer may be produced, for example, by applying a slurry containing the composition of the present invention, a binder and a solvent, or by an electrostatic screen printing method using a granular solid electrolyte.

The positive electrode layer preferably contains a positive electrode active material, an electrolyte, and a conductive additive. Moreover, the binder may be included. These specific examples are the same as those described above.
In the positive electrode layer, the ratios of the positive electrode active material, the electrolyte, the conductive auxiliary agent and the like are not particularly limited, and known ratios can be used.
The thickness of the positive electrode layer is preferably 0.01 mm or more and 10 mm or less.
The positive electrode layer can be produced by a known method. For example, it can be produced by a coating method or an electrostatic method (electrostatic spray method, electrostatic screen method, etc.).

  It is preferable that a negative electrode layer contains a negative electrode active material, an electrolyte, and a conductive support agent. Moreover, the binder may be included. These specific examples are the same as those described above. The formation method and thickness are the same as in the case of the positive electrode.

The electrolyte layer includes an electrolyte and may also include a binder. These specific examples are the same as those described above.
The solid electrolyte of the electrolyte layer is preferably fused. Here, the fusion means that a part of the solid electrolyte particles is dissolved, and the dissolved part is integrated with other solid electrolyte particles.

The electrolyte layer may be a solid electrolyte plate. In addition, the case where part or all of the solid electrolyte particles are dissolved to form a plate-like body is included.
The thickness of the electrolyte layer is preferably 0.001 mm or more and 1 mm or less.
Since the electrolyte and binder are the same as those of the positive electrode layer, description thereof is omitted.

  The battery of the present invention preferably uses a current collector in addition to the positive electrode layer, the electrolyte layer, and the negative electrode layer. A known current collector can be used. For example, a layer coated with Au or the like that reacts with a sulfide-based solid electrolyte such as Au, Pt, Al, Ti, or Cu can be used.

  In addition, about the battery of this invention, although the example which mainly used lithium type electrolyte was demonstrated, this invention is not limited to a lithium ion battery. For example, an alkali metal electrolyte such as sodium or a divalent cation electrolyte such as magnesium may be used. In these cases, the effects of the present invention can be obtained.

Production Example 1 [Production of lithium sulfide]
(1) Production of lithium sulfide (Li ₂ S) Lithium sulfide was produced according to the method of the first aspect (two-step method) of JP-A-7-330312. Specifically, N-methyl-2-pyrrolidone (NMP) 3326.4 g (33.6 mol) and lithium hydroxide 287.4 g (12 mol) were charged into a 10 liter autoclave equipped with a stirring blade, and 300 rpm, 130 The temperature was raised to ° C. After the temperature rise, hydrogen sulfide was blown into the liquid for 2 hours at a supply rate of 3 liters / minute.
Subsequently, this reaction solution was heated in a nitrogen stream (200 cc / min) to dehydrosulfide a part of the reacted hydrogen sulfide. As the temperature increased, water produced as a by-product due to the reaction between hydrogen sulfide and lithium hydroxide started to evaporate, but this water was condensed by the condenser and extracted out of the system. While water was distilled out of the system, the temperature of the reaction solution rose, but when the temperature reached 180 ° C., the temperature increase was stopped and the temperature was kept constant. After the dehydrosulfurization reaction was completed (about 80 minutes), the reaction was completed to obtain lithium sulfide.

(2) Purification of lithium sulfide After decanting NMP in the 500 mL slurry reaction solution (NMP-lithium sulfide slurry) obtained in (1) above, 100 mL of dehydrated NMP was added and stirred at 105 ° C. for about 1 hour. . NMP was decanted at that temperature. Further, 100 mL of NMP was added, stirred at 105 ° C. for about 1 hour, NMP was decanted at that temperature, and the same operation was repeated a total of 4 times. After completion of the decantation, lithium sulfide was dried at 230 ° C. (temperature higher than the boiling point of NMP) under a nitrogen stream for 3 hours under normal pressure. The impurity content in the obtained lithium sulfide was measured.

Incidentally, lithium sulfite _(Li 2 _SO 3), the content of each sulfur oxide lithium sulfate _(Li 2 SO ₄₎ and lithium thiosulfate _{(Li 2 S 2 O 3)} , and N- methylamino acid lithium (LMAB) Was quantified by ion chromatography. As a result, the total content of sulfur oxides was 0.13% by mass, and LMAB was 0.07% by mass.

Production Example 2
[Sulfide-based solid electrolyte glass ceramics with Li ₂ S: P ₂ S ₅ (molar ratio) = 70: 30]
Li ₂ S and P ₂ S ₅ (manufactured by Aldrich) produced in Production Example 1 were used as starting materials. About 1 g of a mixture adjusted to a molar ratio of 70:30 and 10 alumina balls having a diameter of 10 mm were placed in a 45 mL alumina container, and nitrogen was measured using a planetary ball mill (manufactured by Fritsch: Model No. P-7). A lithium / phosphorous sulfide solid electrolyte glass, which is a white yellow powder, was obtained by performing mechanical milling treatment for 20 hours at room temperature (25 ° C.) with a rotational speed of 370 rpm.
It was 220 degreeC when the glass transition temperature of the obtained sulfide type solid electrolyte glass was measured by DSC (differential scanning calorimetry).

The obtained solid electrolyte glass particles are sealed in a SUS tube under an Ar atmosphere in a glove box, and subjected to heat treatment at 300 ° C. for 2 hours to obtain sulfide-based solid electrolyte glass ceramics (sulfide-based solid electrolyte: average particle size 14 .52 μm). With respect to the obtained glass ceramic particles, a peak was observed at 2θ = 17.8, 18.2, 19.8, 21.8, 23.8, 25.9, 29.5, 30.0 deg by X-ray diffraction measurement. It was done.
It was 3.0 * 10 < ^-3 > S / cm when the ionic conductivity of this glass ceramic particle was measured by the alternating current impedance method.

Production Example 3
[Sulfide-based solid electrolyte glass with Li ₂ S: P ₂ S ₅ (molar ratio) = 75: 25]
Sulfide-based solid in the same manner as in Production Example 2 except that 0.766 g of Li ₂ S having an average particle diameter of about 30 μm obtained in Production Example 1 and 1.22 g of P ₂ S ₅ (Aldrich) were used. Electrolyte glass particles (sulfide-based solid electrolyte: average particle size 50 μm) were obtained. The recovery rate at this time was 82%.
As a result of X-ray diffraction measurement (CuKα: λ = 1.5418４) of the obtained sulfide-based solid electrolyte glass, the peak of the raw material Li ₂ S was not observed, and the halo pattern was attributed to the solid electrolyte glass. .
The ionic conductivity of the solid electrolyte glass particles was 0.3 × 10 ⁻³ S / cm.

Production Example 4
[Sulfide-based solid electrolyte glass ceramics of Li ₂ S: P ₂ S ₅ (molar ratio) = 80: 20]
Solid electrolyte glass particles obtained in the same manner as in Production Example 2, except that 0.906 g of Li ₂ S having an average particle size of about 30 μm obtained in Production Example 1 and 1.092 g of P ₂ S ₅ (Aldrich) were used. Got. The recovery rate at this time was 85%. As a result of X-ray diffraction measurement (CuKα: λ = 1.5418４) of the obtained solid electrolyte glass particles, the peak of the raw material Li ₂ S was not observed, and it was a halo pattern resulting from the solid electrolyte glass.

The obtained solid electrolyte glass particles are sealed in a SUS tube under an Ar atmosphere in a glove box, and subjected to heat treatment at 280 ° C. for 2 hours to obtain sulfide-based solid electrolyte glass ceramics (sulfide-based solid electrolyte: average particle diameter 50 μm) was obtained.
The ionic conductivity of the glass ceramic particles was 0.7 × 10 ⁻³ S / cm.

Example 1
1.9 g of the sulfide-based solid electrolyte glass ceramics (Li ₂ S: P ₂ S ₅ (molar ratio) = 70: 30) prepared in Production Example 2 and 0.1 g of LiBr were mixed in a mortar. The mixture was put into a 45 ml planetary ball mill. The mill was mixed at 150 rpm for 2 hours to produce a sulfide-based solid electrolyte-containing composition.
The ionic conductivity of the obtained composition was 3.0 × 10 ⁻³ S / cm. The maximum value of the hydrogen sulfide concentration generated by the composition was calculated and found to be 800 ppm.

The hydrogen sulfide concentration (generated amount) of the composition was evaluated by the following method.
Under a nitrogen atmosphere, 0.1 g of the composition was weighed into a two-necked flask equipped with a cock, and air once passed through water was circulated at 500 ml / min. The humidity in the air was 80-90%. The gas that passed through the two-necked flask with a cock was collected, and the sulfur content was quantified by an ultraviolet fluorescence method to calculate the hydrogen sulfide gas concentration.
When the collected gas sample was subjected to qualitative analysis by gas chromatography, it was confirmed that the sulfur content was all hydrogen sulfide gas.

Example 2
A sulfide-based solid electrolyte-containing composition was produced and evaluated in the same manner as in Example 1 except that 1.8 g of glass ceramics and 0.2 g of LiBr were used.
The ionic conductivity of the obtained composition was 2.5 × 10 ⁻³ S / cm. The maximum value of the hydrogen sulfide concentration generated by the composition was calculated to be 400 ppm.

Example 3
A sulfide-based solid electrolyte-containing composition was produced and evaluated in the same manner as in Example 1 except that LiI was used instead of LiBr.
The resulting composition had an ionic conductivity of 2.4 × 10 ⁻³ S / cm. The maximum value of the hydrogen sulfide concentration generated by the composition was calculated to be 400 ppm.

Example 4
A sulfide-based solid electrolyte-containing composition was produced and evaluated in the same manner as in Example 2 except that LiI was used instead of LiBr.
The obtained composition had an ionic conductivity of 2.6 × 10 ⁻³ S / cm. The maximum value of the hydrogen sulfide concentration generated by the composition was calculated to be 400 ppm.

Example 5
A sulfide-based solid electrolyte in the same manner as in Example 1 except that the glass ceramic of Production Example 4 (Li ₂ S: P ₂ S ₅ (molar ratio) = 80: 20) was used instead of the glass ceramic of Production Example 2. The containing composition was manufactured and evaluated.
The ionic conductivity of the obtained composition was 7.0 × 10 ⁻⁴ S / cm. The maximum value of the hydrogen sulfide concentration generated by the composition was calculated and found to be 100 ppm.

Example 6
A sulfide-based solid electrolyte in the same manner as in Example 2 except that the glass ceramic of Production Example 4 (Li ₂ S: P ₂ S ₅ (molar ratio) = 80: 20) was used instead of the glass ceramic of Production Example 2. The containing composition was manufactured and evaluated.
The resulting composition had an ionic conductivity of 6.0 × 10 ⁻⁴ S / cm. The maximum value of the hydrogen sulfide concentration generated by the composition was calculated and found to be 80 ppm.

Example 7
Sulfide-based solid electrolyte contained in the same manner as in Example 1 except that the glass of Production Example 3 (Li ₂ S: P ₂ S ₅ (molar ratio) = 75: 25) was used instead of the glass ceramic of Production Example 2 Compositions were made and evaluated.
The ionic conductivity of the obtained composition was 2.0 × 10 ⁻⁴ S / cm. Further, the maximum value of the hydrogen sulfide concentration generated by the composition was calculated and found to be 30 ppm.

Comparative Example 1
Without using LiBr, only the sulfide-based solid electrolyte glass ceramics of Production Example 2 (Li ₂ S: P ₂ S ₅ (molar ratio) = 70: 30) were evaluated.
The glass ceramic after milling had an ionic conductivity of 3.0 × 10 ⁻³ S / cm. The maximum value of the hydrogen sulfide concentration of the glass ceramics was calculated to be 1200 ppm.

Comparative Example 2
Without using LiBr, only the glass ceramic of Production Example 4 (Li ₂ S: P ₂ S ₅ (molar ratio) = 80: 20) was milled in the same manner as in Example 5 and evaluated.
The glass ceramic after milling had an ionic conductivity of 7.0 × 10 ⁻⁴ S / cm. Moreover, it was 200 ppm when the maximum value of the hydrogen sulfide density | concentration of glass ceramics was computed.

Comparative Example 3
Without using LiBr, only the glass of Production Example 3 (Li ₂ S: P ₂ S ₅ (molar ratio) = 75: 25) was milled in the same manner as in Example 7 and evaluated.
The glass ceramic after milling had an ionic conductivity of 3.0 × 10 ⁻⁴ S / cm. Moreover, it was 70 ppm when the maximum value of the hydrogen sulfide density | concentration of glass ceramics was computed.

The sulfide-based solid electrolyte composition of the present invention is suitable as a battery constituent material such as a positive electrode layer, an electrolyte layer, and a negative electrode.

Claims (7)

A sulfide-based solid electrolyte;
A halide containing an alkali metal or an alkaline earth metal, or a compound containing an alkali metal or an alkaline earth metal and sulfur,
A sulfide-based solid electrolyte-containing composition having an ionic conductivity of 1 × 10 ⁻⁴ S / cm or more,
0.1 g was weighed into a 100 cc two-necked flask, and once passed through water at a flow rate of 500 ml / min, the gas that passed through the two-necked flask with a cock was collected, and the sulfur content was measured by ultraviolet fluorescence. A sulfide-based solid electrolyte-containing composition in which the amount of generated hydrogen sulfide measured by quantification is 1000 ppm or less. The sulfide-based solid electrolyte composition according to claim 1, wherein the sulfide-based electrolyte satisfies the following formula (1).
Li _a M _b P _c S _d (1)
(In the formula, M represents one or more elements selected from B, Zn, Si, Cu, Ga and Ge.
a to d indicate the composition ratio of each element, and a: b: c: d satisfies 1 to 12: 0 to 0.5: 1: 2 to 9. ) The sulfide solid electrolyte composition according to claim 1 or 2, wherein the following formula (2) is satisfied.
0.001 ≦ x / y ≦ 0.6 (2)
Wherein x represents the weight [g] of the halide containing the alkali metal or alkaline earth metal, or the compound containing alkali metal or alkaline earth metal and sulfur, and y is the weight of the sulfide solid electrolyte. [G] is shown.)   The electrode material containing the sulfide type solid electrolyte composition in any one of Claims 1-3.   The electrode material manufactured from the sulfide type solid electrolyte composition in any one of Claims 1-3.   A battery provided with at least one of the electrode and electrolyte layer containing the sulfide type solid electrolyte composition in any one of Claims 1-3. A battery comprising at least one of an electrode and an electrolyte layer produced from the sulfide-based solid electrolyte composition according to claim 1.