JP2013125697A - Lithium particle-containing composition, electrode and battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which lithium can be introduced into a battery with good handleability.SOLUTION: A composition includes: at least one of an active material and an electrode composite material; and a lithium particle.

Description

  The present invention relates to a composition containing lithium particles, an electrode, and a battery.

In recent years, there has been a strong demand for a secondary battery that can be used for a long time, is small in size and light in weight, and has a high level of safety, as mobile phones, PDAs, notebook personal computers, and the like become more sophisticated. In these devices, lithium ion secondary batteries are used because they are excellent in energy density, power density, and the like.
Many lithium ion secondary batteries use flammable organic solvents, and there is a risk of liquid leakage or ignition during overcharge or abuse. Therefore, ensuring the safety has been an important issue as the energy density of batteries increases.

  Research and development of all-solid-state lithium ion batteries using inorganic solid electrolytes as electrolytes that are chemically stable and have no leakage or ignition problems compared to organic electrolytes have been conducted as batteries that solve these problems. (For example, refer to Patent Document 1).

By the way, in general, a lithium ion battery has a positive electrode layer, a solid electrolyte, and a negative electrode as main components, and has a structure in which these are laminated. As positive electrode active materials used for the positive electrode layer, active materials not containing lithium and active materials containing lithium have been studied.
Examples of the active material not containing lithium include sulfur, metal sulfides (TiS ₂ , MoS ₂ , FeS, FeS ₂ , CuS, Ni ₃ S _2, etc.), MnO ₂ , V ₂ O _{5, and the} like.

As the active material containing lithium, Li ₂ S, 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 Examples include Co _Z O ₄ (where 0 <Z <2), LiCoPO ₄ , and LiFePO ₄ .
Examples of the negative electrode active material include carbon, silicon, and tin.

  When using an active material that does not contain lithium as the positive electrode active material, for example, sulfur, a positive electrode mixture is prepared by mixing sulfur, a conductive additive, and a solid electrolyte. Lithium that contributes to the reaction is not included. Therefore, it is necessary to introduce a lithium source into the electrochemical system. As a method for introducing a lithium source, a thin lithium foil is applied to a negative electrode mixture layer or a positive electrode mixture layer.

However, since the lithium foil is soft, it is very difficult to apply it evenly over the positive electrode mixture layer and the negative electrode mixture layer. Therefore, generation | occurrence | production of the wrinkles, the air approach to a sticking surface, etc. arise. Moreover, there was a problem that handling property was very poor and adhesion with the composite layer was not stable.
Further, as the capacity of the lithium ion battery increases, the amount of lithium required in the battery increases. However, when the lithium foil becomes thicker, the handling property becomes worse. For this reason, there is a problem that the adhesion is further deteriorated, particularly when a lithium foil is applied to an electrode mixture containing a solid electrolyte.

On the other hand, when a material containing lithium such as Li ₂ S or LiCoO ₂ is used as the positive electrode active material, for example, a carbon material such as graphite or hard carbon, silicon, tin, or the like is used as the negative electrode active material. These materials have irreversible capacity during initial discharge. For this reason, a method (hereinafter referred to as “pre-dope”) in which lithium for an irreversible capacity is introduced into the electrochemical system in advance has been studied.
One method of lithium pre-doping is a method of attaching a lithium foil, but it is difficult to attach a lithium foil to a composite material containing a solid electrolyte as described above.

  In addition, in the manufacture of batteries, a pressing step for consolidating the constituent members is necessary. However, when lithium foil is used, the lithium foil is stretched. There were problems such as wrapping of lithium metal at the electrode edge and short-circuiting between the electrodes. This problem becomes conspicuous as the thickness of the lithium foil increases.

JP 2002-109955 A

  An object of the present invention is to provide a method capable of introducing lithium with good handleability when manufacturing battery cells.

According to the present invention, the following compositions and the like are provided.
1. A composition comprising at least one of an active material and an electrode composite material, and lithium particles.
2. An electrode comprising at least one of an active material and an electrode composite material, and lithium particles.
3. An electrode using the composition according to 1 above as a raw material.
4). A battery comprising the electrode according to 2 or 3 above.
5. A battery comprising a layer containing lithium particles, a positive electrode layer, a negative electrode layer, and an electrolyte layer.

  According to the present invention, lithium can be introduced into a battery with good handling properties.

The composition of the present invention includes at least one of an active material and an electrode composite material, and lithium particles.
(1) Lithium particles (powder)
In the present application, the lithium particles mean a powder in which metallic lithium is finely pulverized. The shape of the lithium powder is not particularly limited, and may take any structure such as a spherical shape, a rod shape, a needle shape, a plate shape, a column shape, an indefinite shape, a flake shape, and a spindle shape.
Although there is no restriction | limiting in particular about the average particle diameter of lithium particle, Preferably it is 0.1-200 micrometers, More preferably, it is 1-50 micrometers. An average particle size of 1 μm or more is preferable because it is easy to handle. On the other hand, an average particle size of 200 μm or less is preferable in that the in-plane dispersion state of the electrode becomes good.
The average particle diameter of the lithium particles is a value measured by laser diffraction particle size distribution measurement (laser diffraction scattering method).

The lithium particles have a function (pre-doping) to compensate for the irreversible capacity of the electrode generated at the first charge / discharge, and a function of adding lithium to the positive electrode.
The lithium particles may be a single lithium metal or may be particles whose surface is stabilized. For example, surface stabilization includes a method of forming a film on the surface of lithium metal particles. In the case of lithium particles having a coating, the average particle size of only lithium particles before stabilization (core) is used as the average particle size of lithium particles.

Examples of the lithium particle stabilization treatment include materials having good environmental stability on the surface of the lithium metal powder, for example, organic rubber such as NBR (nitrile butadiene rubber) and SBR (styrene butadiene rubber), EVA (ethylene vinyl alcohol copolymer resin). ), Organic resin such as PVDF (polyvinylidene fluoride) and PEO (polyether), metal carbonates such as Li ₂ CO ₃ and Li ₂ O, and inorganic compounds such as metal oxides. Can be mentioned.

  Examples of the stabilized lithium powder include LctroMax Powder (SLMP) manufactured by FMC, lithium powder (# 5905884) manufactured by Aldrich, and China Energy Lithium Co. , Ltd., Ltd. There are passivated lithium powders manufactured by the company. These may be used individually by 1 type and may use 2 or more types together.

  By stabilizing the lithium particles, the lithium particles can be stabilized in the air or in a solvent such as xylene, and the deterioration of lithium can be prevented even in a dry room having a dew point of about −40 ° C. Therefore, it is excellent in that highly reactive metallic lithium does not react with water or a solvent in the atmosphere or the dispersion medium or deactivate. Moreover, when an insulating film exists on the surface of the lithium metal particles, it is possible to suppress the direct contact between lithium and the negative electrode active material. Thereby, since the excessive reaction between lithium and a negative electrode active material is suppressed at the time of pre dope, the emitted-heat amount which arises by this reaction can be reduced. As a result, since the binder and the like are not melted, lithium for the irreversible capacity can be supplemented to the battery without increasing the internal resistance of the negative electrode.

(2) Active material The active material includes a positive electrode active material and a negative electrode active material.
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 (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 (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 (0 <Z <2), LiCoPO ₄ , LiFePO ₄ , bismuth oxide (Bi ₂ O ₃ ), bismuth leadate (Bi ₂ Pb ₂ O ₅ ), copper oxide (CuO), vanadium oxide (V ₆ O ₁₃ ), Li _x CoO ₂ , Li _x NiO ₂ , Li _x Mn ₂ O ₄ , Li _x Examples thereof include oxides such as FePO ₄ , Li _x CoPO ₄ , Li _x Mn _1/3 Ni _1/3 Co _1/3 O ₂ , and Li _x Mn _1.5 Ni _0.5 O ₂ .

Examples of positive electrode active materials other than those described above include, for example, elemental sulfur (S), titanium sulfide (TiS ₂ ), molybdenum sulfide (MoS ₂ ), iron sulfide (FeS, FeS ₂ ), and 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. S and Li ₂ S having a high theoretical capacity are preferable.

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. Moreover, the mixture containing these 2 types may be sufficient. Preferably, it is artificial graphite.
Also, an alloy in combination with a metal itself such as metal indium, metal aluminum, or metal silicon, or another element or compound can be used as the negative electrode material. Of these, silicon and tin having a high theoretical capacity are preferable.

(3) Electrode composite material The electrode composite material is a composite of an active material and another substance.
The other substance may be an ion conductive substance or a conductive substance. Further, the other substance may be both an ion conductive substance and a conductive substance.
Examples of the composite material include a composite of an active material and a conductive material, and a composite of an active material, a conductive material, and an ion conductive material.

  For example, the active material is deposited on the surface of the conductive material, the active material is dissolved and the conductive material is brought into contact with the surface and solidified, and the active material is made of the conductive material. Examples include those synthesized in the presence and integrated with a conductive material, and those obtained by integrating an active material and a conductive material by a mechanical action such as mechanical milling.

As the active material, the above-described positive electrode active material and negative electrode active material can be used.
As the conductive substance, a substance having an electric conductivity of 1.0 × 10 ³ S / m or more can be used. The substance is preferably 1.0 × 10 ⁴ S / m or more, and more preferably 1.0 × 10 ⁵ S / m or more.

  The conductive substance preferably has pores. By having pores, for example, sulfur and sulfur-based compounds can be included in the pores, and the contact area between sulfur and the conductive material can be increased, and the specific surface area of sulfur and the like can be increased. it can.

  Examples of the conductive substance include carbon, metal powder, metal compound, and the like, and preferably carbon. When the electrode material of the present invention contains carbon as a conductive substance, since carbon has high conductivity and is light, a battery having a high energy density per mass can be obtained.

The shape of the conductive material is not particularly limited, and examples thereof include a particulate conductive material, a plate-shaped conductive material, and a rod-shaped conductive material.
Examples of the plate-like conductive material include graphene. Examples of the rod-like conductive substance include carbon nanotubes. Examples of the particulate conductive material include ketjen black and activated carbon having a large surface area, a large pore volume, and a high electron conductivity.

More preferably, the conductive material is porous carbon having pores.
Examples of porous carbon include carbon black such as ketjen black, acetylene black, denka black, thermal black, and channel black; carbon such as graphite, carbon fiber, and activated carbon. These may be used alone or in combination of two or more.

The conductive material preferably has pores. When the conductive substance has pores, for example, it can be combined with a compound containing sulfur and / or a sulfur atom, and the electron conductivity of the electrode material can be increased.
The pore volume of the conductive material is preferably 0.5 cc / g or more and 4.0 cc / g or less, more preferably 0.6 cc / g or more and 3.95 cc / g or less, particularly preferably 0.75 cc. / G to 3.9 cc / g. When the pore capacity is less than 0.5 cc / g, the content of the sulfur compound inside the conductive material may be reduced, and it may be difficult to obtain a lithium ion battery having a high electric capacity. On the other hand, when the pore volume of the conductive substance is more than 4.0 cc / g, there is a possibility that sufficient electron conductivity cannot be ensured even if it is combined with a sulfur compound.

  The average pore diameter of the conductive substance is preferably 100 nm or less, more preferably 1 nm or more and 100 nm or less, still more preferably 1 nm or more and 18 nm or less, and particularly preferably 2 nm or more and 17 nm or less. When the average pore diameter is less than 1 nm, it may be difficult to impregnate the pores with a sulfur compound. On the other hand, when the average pore diameter of the conductive material is more than 100 nm, the sulfur compound impregnated in the pores may not function sufficiently as an active material.

  The particle size of the conductive substance is preferably 1 nm to 500 μm, more preferably 5 nm to 250 μm, and still more preferably 10 nm to 200 μm.

The composition of the present invention preferably contains a solid electrolyte in addition to the above-described lithium particles and the active material and / or composite material. Thereby, the energy density of the battery manufactured using this composition can be made high.
Examples of the solid electrolyte include a polymer solid electrolyte, an oxide solid electrolyte, and a sulfide solid electrolyte. In the present invention, an oxide solid electrolyte or a sulfide solid electrolyte is preferable, and a sulfide solid electrolyte is more preferable. In the composition of the present invention, a plurality of solid electrolytes may be used.

  The polymer-based solid electrolyte is not particularly limited, and as disclosed in JP 2010-262860, as a polymer electrolyte such as a fluororesin, polyethylene oxide, polyacrylonitrile, polyacrylate, derivatives thereof, and copolymers thereof. The material used 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, Thio-LISICON, La _0.55 Li _0.35 TiO ₃ , LiTi ₂ P ₃ O ₁₂ having a NASICON type structure, These crystallized electrolytes can be used.

The sulfide-based solid electrolyte, the following equation (1) is preferably one having a composition shown in _{Li a M b P c S d} ... (1)

In the formula (1), M represents an element 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 0.2: 1: 2 to 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 blending amount of the raw material compound when producing the sulfide-based solid electrolyte.

The sulfide-based solid electrolyte may be amorphous (vitrified), crystallized (glass ceramics), or only partially crystallized. Here, when crystallized, the ion conductivity may be higher than that of glass. In that case, it is preferable to crystallize.
As the crystal structure, for example, Li ₇ PS ₆ structure, Li ₄ P ₂ S ₆ structure, Li ₃ PS ₄ structure, Li ₄ SiS ₄ structure, Li ₂ SiS ₃ structure, disclosed in JP 2002-109955 A, JP The Li ₇ P ₃ S ₁₁ structure disclosed in 2005-228570 and WO 2007/065539 is preferred.

Here, the Li ₇ P ₃ S ₁₁ structure has 2θ = 17.8 ± 0.3 deg, 18.2 ± 0.3 deg, 19.8 ± 0. 0 in X-ray diffraction (CuKα: λ = 1.5418４). It has diffraction peaks at 3 deg, 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.
This is because the above-described crystal structure has higher ionic conductivity than the amorphous body.

Note that the crystallized portion of the sulfide-based solid electrolyte may be composed of only one crystal structure or may have a plurality of crystal structures. As the crystal structure, Li ₇ P ₃ S ₁₁ is most preferable because of its high ionic conductivity.

The degree of crystallinity of the sulfide-based solid electrolyte (the degree of crystallinity of the crystal structure having higher ionic conductivity than that of the amorphous body) is preferably 50% or more, and more preferably 60% or more.
This is because when the crystallinity of the sulfide-based solid electrolyte is less than 50%, the effect of increasing the ionic conductivity by crystallization is reduced.
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.

About the manufacturing method of sulfide solid electrolyte, the raw material of sulfide solid electrolyte includes Li ₂ S (lithium sulfide), P ₂ S ₃ (phosphorus trisulfide) _, P ₂ S ₅ (phosphorus pentasulfide), SiS ₂ (silicon sulfide), Li ₄ SiO ₄ (lithium orthosilicate), Al ₂ S ₃ (aluminum sulfide), simple phosphorus (P), simple sulfur (S), silicon (Si), GeS ₂ (germanium sulfide) , B ₂ S ₃ (diarsenic trisulfide), Li ₃ PO ₄ (lithium phosphate), Li ₄ GeO ₄ (lithium germanate), LiBO ₂ (lithium metaborate), LiAlO ₃ (lithium aluminate) or the like is used. be able to.

Preferred raw materials for sulfide-based solid electrolytes are Li ₂ S and P ₂ S ₅ .
Hereinafter, a sulfide-based solid electrolyte using Li ₂ S and P ₂ S ₅ as a raw material for the sulfide-based solid electrolyte will be described.

  As lithium sulfide, those commercially available without particular limitation can be used, but those having high purity are preferred. Lithium sulfide can be produced, for example, by the methods described in JP-A-7-330312, JP-A-9-283156, JP-A 2010-163356, and Japanese Patent Application No. 2009-233892.

Specifically, lithium hydroxide and hydrogen sulfide are reacted at 70 ° C. to 300 ° C. in a hydrocarbon-based organic solvent to produce lithium hydrosulfide, and then the reaction solution is dehydrosulfurized to form lithium sulfide. Can be synthesized (Japanese Patent Laid-Open No. 2010-163356).
In addition, lithium hydroxide and hydrogen sulfide are reacted at 10 ° C. to 100 ° C. in an aqueous solvent to produce lithium hydrosulfide, and then the reaction liquid is dehydrosulfurized to synthesize lithium sulfide (special feature). Application 2009-238952).

  The lithium sulfide preferably has a total lithium oxide lithium salt content of 0.15% by mass or less, more preferably 0.1% by mass or less, and a lithium N-methylaminobutyrate content. The content is preferably 0.15% by mass or less, more preferably 0.1% by 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, when 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.

  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.

When lithium sulfide is produced based on the above-mentioned JP-A-7-330312 and JP-A-9-283156, it is preferable to purify the lithium sulfide because it contains a lithium salt of a sulfur oxide.
On the other hand, lithium sulfide produced by the method for producing lithium sulfide described in JP-A-2010-163356 may be used without purification because it contains a very small amount of sulfur oxide lithium salt or the like.
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.

  As long as diphosphorus pentasulfide is manufactured and sold industrially, it can be used without particular limitation.

The ratio (molar ratio) of lithium sulfide to diphosphorus pentasulfide is usually 50:50 to 90:10, preferably 65:35 to 78:22. Particularly _{preferably, Li 2 S: P 2 S} 5 = 67: 33~77: is 23 (molar ratio).

  As a method for producing a sulfide-based glass solid electrolyte, there are a melt quenching method, a mechanical milling method (MM method), a slurry method in which raw materials are reacted in an organic solvent, and the like.

(A) Melting and quenching method The melting and quenching method is described, for example, in JP-A-6-279049 and WO2005 / 119706. Specifically, a mixture of P ₂ S ₅ and Li ₂ S in a predetermined amount in a mortar and pelletized is 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 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 described in, for example, JP-A-11-134937, JP-A-2004-348972, and JP-A-2004-348993.
Specifically, a predetermined amount of P ₂ S ₅ and Li ₂ S are mixed in a mortar and reacted for a predetermined time using, for example, various ball mills to obtain a sulfide-based glass solid electrolyte.
The MM method using the above raw materials can be reacted at room temperature. Therefore, there is an advantage that a glass solid electrolyte having a charged composition can be obtained without thermal decomposition of the raw material.
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 is set to several tens to several hundreds of revolutions / minute, and the treatment may be performed for 0.5 hours to 100 hours.
Further, as described in JP 2010-90003 A, balls of a ball mill may be used by mixing balls having different diameters.
Further, as described in JP2009-110920A or JP2009-2111950, an organic solvent may be added to the raw material to form a slurry, and this slurry may be subjected to MM treatment.
Further, as described in JP 2010-30889 A, the temperature in the mill during MM processing may be adjusted.
It is preferable that the raw material temperature during MM treatment be 60 ° C. or higher and 160 ° C. or lower.

(C) Slurry method The slurry method is described in WO2004 / 093099 and WO2009 / 047977.
Specifically, a sulfide-based glass solid electrolyte is obtained by reacting a predetermined amount of P ₂ S ₅ particles and Li ₂ S particles in an organic solvent for a predetermined time.
Here, as described in JP-A-2010-140893, in order to advance the reaction, the slurry containing the raw material may be reacted while being circulated between the bead mill and the reaction vessel.
Further, as described in WO2009 / 047977, when the raw material lithium sulfide is pulverized in advance, the reaction can proceed efficiently.
Further, as described in Japanese Patent Application No. 2010-270191, in order to increase the specific surface area of the raw material lithium sulfide, it is predetermined in a polar solvent (for example, methanol, diethyl carnate, acetonitrile) having a solubility parameter of 9.0 or more. You may soak for hours.

The reaction temperature is preferably 20 ° C. or higher and 80 ° C. or lower, more preferably 20 ° C. or higher and 60 ° C. or lower.
The reaction time is preferably 1 hour or longer and 16 hours or shorter, more preferably 2 hours or longer and 14 hours or shorter.

  It is preferable that the raw materials lithium sulfide and phosphorous pentasulfide be in a solution or slurry form by the addition of an organic solvent. Usually, the amount of the raw material (total amount) added to 1 liter of the organic solvent is about 0.001 kg or more and 1 kg or less. Preferably they are 0.005 kg or more and 0.5 kg or less, Most preferably, they are 0.01 kg or more and 0.3 kg or less.

The organic solvent is not particularly limited, but an aprotic organic solvent is particularly preferable.
Examples of the aprotic organic solvent include aprotic apolar organic solvents (for example, hydrocarbon-based organic solvents), aprotic polar organic compounds (for example, amide compounds, lactam compounds, urea compounds, organic sulfur compounds, cyclic compounds) An organic phosphorus compound or the like) can be suitably used as a single solvent or a mixed solvent.

As the hydrocarbon-based organic solvent, saturated hydrocarbons, unsaturated hydrocarbons, or aromatic hydrocarbons can be used as the hydrocarbon-based solvent that is the solvent.
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.
Of these, toluene and xylene are particularly preferable.

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

  In addition, you may add another solvent to a hydrocarbon type solvent as needed. Specific examples include ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, alcohols such as ethanol and butanol, esters such as ethyl acetate, and halogenated hydrocarbons such as dichloromethane and chlorobenzene.

  Manufacturing conditions such as temperature conditions, processing time, and charge for the melt quenching method, MM method and slurry method can be appropriately adjusted according to the equipment used.

A method for producing a sulfide-based solid electrolyte (glass ceramics) is disclosed in JP-A-2005-228570, WO2007 / 065539, and JP-A-2002-109955.
Specifically, the sulfide-based solid electrolyte (glass) obtained above is heat-treated at a predetermined temperature to generate sulfide-based crystallized glass (glass ceramics).
The heating is preferably performed in an environment having a dew point of −40 ° C. or less, and more preferably in an environment having a dew point of −60 ° C. or less.
Moreover, the pressure at the time of a heating may be a normal pressure, and may be under pressure reduction.
The atmosphere may be air or an inert atmosphere.
Furthermore, you may heat in a solvent as it describes in Unexamined-Japanese-Patent No. 2010-186744.

The heat treatment temperature for producing the glass ceramic having the Li ₇ P ₃ S ₁₁ structure is preferably 180 ° C. or higher and 330 ° C. or lower, more preferably 200 ° C. or higher and 320 ° C. or lower, and particularly preferably 210 ° C. or higher and 310 ° C. or lower. When the temperature is lower than 180 ° C., it may be difficult to obtain a crystallized glass having a high degree of crystallinity.

  In the case of a temperature of 180 ° C. or higher and 210 ° C. or lower, the heat treatment time is preferably 3 hours or longer and 240 hours or shorter, and particularly preferably 4 hours or longer and 230 hours or shorter. When the temperature is higher than 210 ° C. and lower than or equal to 330 ° C., it is preferably 0.1 hours or longer and 240 hours or shorter, particularly preferably 0.2 hours or longer and 235 hours or shorter, and more preferably 0.3 hours or longer and 230 hours or shorter. .

  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 production of Li ₇ PS ₆ crystal structure, Li ₄ P ₂ S ₆ crystal structure, Li ₃ PS ₄ crystal structure, Li ₄ SiS ₄ crystal structure and Li ₂ SiS ₃ crystal structure may be performed by a known method.
For example, crystallized glass having the above crystal structure can be produced by a method disclosed in JP-A No. 2002-109955.

  The shape of the solid electrolyte is not particularly limited, and may be a particle shape or a sheet shape.

When it is particulate, the average particle size of the solid electrolyte is preferably in the range of 0.01 to 100 μm. More preferably, it is 0.05-50 micrometers.
Note that the average particle diameter of the solid electrolyte particles is a volume-based average particle diameter (referred to as Mean Volume Diameter). The method for measuring solid electrolyte particles of the present invention is preferably performed by a laser diffraction particle size distribution measuring method.
Here, the laser diffraction particle size distribution measurement method can measure the particle size distribution without drying the composition. The particle size distribution is obtained by irradiating a particle group in the composition with laser and analyzing the scattered light. Can be measured.
In the present invention, the average particle diameter of the ion conductive material is measured using dried solid electrolyte particles.
A measurement example when the laser diffraction type 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.
After sufficiently mixing the above mixture, “dry solid electrolyte particles” are added and the particle size is measured. The amount of “dry solid electrolyte particles” 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. Add. 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 based on the added amount of “dried solid electrolyte particles”. Therefore, it is preferable to find the added amount that falls within the laser scattering intensity.
The optimum amount of the “dried solid electrolyte particles” is about 0.01 g to 0.05 g, although the optimum amount varies depending on the type of the ion conductive substance.

You may mix | blend a conductive support agent, a binder, a solvent, etc. with the composition of this invention as needed.
Examples of the conductive assistant include carbon blacks such as Denka black and Ketjen black, conductive oxide particles, silver particles, and conductive polymers.

Examples of binders 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.
By using the binder, the adhesion to the current collector and the electrolyte layer is improved.

The solvent is not particularly limited as long as it does not adversely affect the solid electrolyte. For example, aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, n-heptane, octane, and rubber volatile oil; mineral spirit, high boiling point Aromatic hydrocarbon solvents such as petroleum solvent (ink oil), toluene, xylene, trimethylbenzene, solvent naphtha, tetralin and dipentene; chain carbonate solvents such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; propylene carbonate, ethylene Cyclic carbonate solvents such as carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate; tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,3-dioxane Cyclic ether solvents such as orchid; chain ether solvents such as 1,2-dimethoxyethane and 1,2-diethoxyethane; methyl acetate, ethyl acetate, methyl difluoroacetate, ethyl trifluoroacetate, methyl propionate, ethyl Ester solvents such as propinate, methyl formate and ethyl formate; Lactone solvents such as γ-butyrolactone and γ-valerolactone; Phosphate ester solvents such as trimethyl phosphate, triethyl phosphate and trioctyl phosphate; N-methyl- Amido solvents such as 2-pyrrolidone, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacetate; sulfolane, dimethyl sulfoxide, 1,3-propane sultone, 1, 4-butansa Sulfur solvents such as tons and ethylene sulfites; Nitrile solvents such as acetonitrile, isobutyronitrile, propionitrile and benzonitrile; Glycol solvents such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol Glycol glycol solvents such as ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether (butyl carbitol); ethylene glycol monobutyl ether acetate (butyl cellosolve acetate) ), Propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate (butyl carbitol acetate) glycol ether ester such as solvents, fluorobenzene, trifluoromethyl benzene, fluorine-based solvents such as Fluorinert.
By using a solvent, an electrode layer can be formed by coating.

  The composition of the present invention substantially consists of the above-described lithium particles, an active material and / or a composite material, and optionally one or more selected from a solid electrolyte, a conductive additive, a binder and a solvent. Moreover, it may consist only of these components. “Substantially” means that the composition mainly comprises lithium particles, an active material and / or composite material, and optionally a solid electrolyte, a conductive aid, a binder, and a solvent. In addition to known additives.

In the composition of the present invention, the total amount of the active material and the electrode composite material in the entire composition excluding lithium particles and the solvent is 20% by mass to 100% by mass. Preferably, they are 30 mass%-90 mass%, Most preferably, they are 40 mass%-85 mass%.
If there are few active materials and electrode composite materials, the performance of the active materials may not be fully exhibited. On the other hand, when too much, the energy density as a battery may fall.

The compounding amount of the lithium particles is determined by the amount [g] of the active material contained in the composite material (electrode layer) and the theoretical capacity [Ah · g ⁻¹ ]. Here, the lithium particles themselves are not blended for the purpose of functioning as an active material.
For example, when manufacturing an all-solid battery using an active material that is not a lithium supply source for both the positive electrode and the negative electrode, {(theoretical capacity of the active material contained in the positive electrode) × (amount of active material contained in the positive electrode) } And {(theoretical capacity of the active material contained in the negative electrode) × (the amount of active material contained in the negative electrode)} is a value obtained by dividing the smaller value by the theoretical capacity of the lithium particles as the blending amount of the lithium particles Be ideal.
However, when the entire theoretical capacity of the active material is not used, it may be an amount obtained by dividing the capacity of the active material to be used by the theoretical capacity of the lithium particles. As will be described below, the upper limit of the amount of lithium particles is preferably the following upper limit of the amount of lithium particles because all lithium in the lithium particles is not occluded by the active material.
・ Lithium particle blending amount {(theoretical capacity of active material contained in positive electrode) × (amount of active material contained in positive electrode)} and {(theoretical capacity of active material contained in negative electrode) × (active capacity contained in negative electrode) (The amount of the substance)} is less than 5 times the value obtained by dividing the smaller value by the theoretical capacity of the lithium particles (hereinafter referred to as “X1”). X1 is more preferably 3 times or less, and even more preferably 1 .5 times or less.
The lower limit of X1 is not particularly limited, and examples thereof include 0.01 times or more, 0.02 times or more, 0.03 times or more, 0.1 times, and 0.2 times.

There is no restriction | limiting in particular in the upper limit of the compounding quantity of lithium particle, It can adjust according to the use of a composition.
For example, in the case of a lithium ion battery that uses an active material that does not contain lithium for the positive electrode, the blending amount of the lithium particles is not more than 5 times, preferably not more than 3 times, more preferably not more than 1.5 times the negative electrode capacity as the counter electrode Most preferably, the amount corresponds to a capacity of 1.2 times or less.
The negative electrode capacity is obtained by the following formula.
Negative electrode capacity = “theoretical capacity of negative electrode active material contained in negative electrode [Ah · g ⁻¹ ]” × “weight of negative electrode active material contained in negative electrode (g)”
For example, assuming that the capacity of the negative electrode is X2, the blending amount of lithium particles is the theoretical capacity of X2 / lithium particles.
The theoretical capacity of the lithium particles is 2000 to 3863 mAh / g, preferably 2500 to 3800 mAh / g.
The high theoretical capacity of the lithium particles means that the content of lithium metal contained in the lithium particles is large.
From the viewpoint of reducing the amount of lithium particles to be blended, it is better that the theoretical capacity of the lithium particles is higher.
On the other hand, as described above, in order to stabilize the lithium particles, it is better that the theoretical capacity of the lithium particles is slightly lower than the “theoretical capacity of lithium metal”. For example, when a film is formed on the surface of lithium metal particles, the theoretical capacity of the film is 0 or lower than the theoretical capacity of lithium metal, and thus is slightly lower than the “theoretical capacity of lithium metal” as described above.
The layer made of the composition of the present invention may be formed on either the positive electrode side or the negative electrode side of the lithium ion battery.

In the case of a lithium ion battery using an active material containing lithium for the positive electrode, the amount of lithium particles is 10 times or less, preferably 5 times or less, more preferably 1.5 times or less the initial irreversible capacity of the negative electrode as the counter electrode. Is equivalent to the capacity of. The initial irreversible capacity can be measured by preparing a battery that does not contain lithium particles.
The layer made of the composition of the present invention may be formed on either the positive electrode side or the negative electrode side of the lithium ion battery.

The compounding quantity of the other containing material which occupies for the whole composition except a lithium particle and a solvent is 0 mass%-80 mass%. Preferably, they are 0.1 mass%-60 mass%, Most preferably, they are 0.5 mass%-55 mass%.
The other contained substances mean the above-described solid electrolyte and binder.
The blending amount of the solid electrolyte is preferably 0% by weight to 80% by weight, more preferably 10% by weight to 70% by weight, and particularly preferably 15% by weight to the total composition excluding lithium particles and the solvent. 60% by mass.
The amount of the solvent used is preferably 20 parts by mass to 90 parts by mass, particularly preferably 30 parts by mass to 80 parts by mass, when the entire composition excluding the solvent is 100 parts by mass.

  The composition of the present invention can be suitably used as a material for introducing lithium into a lithium ion battery. It can also be used as a material for various battery electrodes.

Next, the electrode of the present invention will be described.
The electrode of the present invention includes lithium particles and at least one of an active material and a composite material. The lithium particles, the active material, and the composite material are the same as those used in the above-described composition of the present invention.
The blending amount of the active material and the electrode composite material in the entire component excluding lithium particles from the electrode of the present invention is 20% by mass to 100% by mass. Preferably, they are 30 mass%-90 mass%, Most preferably, they are 40 mass%-85 mass%. When there are few active materials and electrode composite materials, there exists a possibility that the performance of an active material cannot fully be exhibited. On the other hand, when too much, the energy density as a battery will fall.

The electrode of the present invention may contain a solid electrolyte, a binder, and the like in addition to the above-described lithium particles and the active material and / or composite material.
The compounding quantity of the solid electrolyte which occupies for the whole component except lithium particles from the electrode of this invention is 0 mass%-80 mass%. Preferably, they are 10 mass%-70 mass%, Most preferably, they are 15 mass%-60 mass%.

  The compounding quantity of the binder which occupies for the whole component except lithium particles from the electrode of this invention is 0 mass%-20 mass%. Preferably, they are 0.5 mass%-15 mass%, Most preferably, they are 1 mass%-10 mass%.

The electrode of the present invention preferably contains lithium particles in an amount such that the theoretical capacity is 2000 to 3863 mAh / g, and particularly preferably contains lithium particles corresponding to 2500 to 3800 mAh / g.
More specifically, when the active material not containing lithium is used as the positive electrode active material, the amount of lithium particles is 5 times or less, preferably 3 times or less, more preferably 1.5 times the negative electrode capacity as the counter electrode. Hereinafter, the amount is most preferably an amount corresponding to a capacity of 1.2 times or less.
When the active material containing lithium is used as the positive electrode active material, the amount of lithium particles is 10 times or less, preferably 5 times or less, more preferably 1.5 times or less the initial irreversible capacity of the negative electrode as the counter electrode. Is equivalent to The initial irreversible capacity can be measured by preparing a battery that does not contain lithium particles.

  The electrode of this invention can be manufactured by using the composition of this invention mentioned above, for example.

The battery of this invention should just have the layer obtained from the composition of this invention mentioned above, or the electrode of this invention, and can use a well-known thing in this technical field about another structural member.
For example, in the case of a lithium ion battery using the electrode of the present invention, a battery including a current collector, a positive electrode layer, a solid electrolyte layer, and a negative electrode layer can be exemplified. At least one of the positive electrode layer and the negative electrode layer may be the electrode of the present invention.
As the positive electrode layer, an electrode containing a positive electrode active material is used. As the negative electrode layer, an electrode containing a negative electrode active material is used. A known electrode that does not contain lithium particles may be used for one of the positive electrode layer and the negative electrode layer.

A known current collector can be used as the current collector. 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.
As the solid electrolyte layer, a solid electrolyte used in the above-described composition of the present invention, for example, a polymer-based solid electrolyte, an oxide-based solid electrolyte, or a sulfide-based solid electrolyte can be used.
The solid electrolyte layer may contain a binder, and a plurality of types of solid electrolytes may be used.

In the case of a lithium ion battery having a layer containing lithium particles, that is, a layer formed using the composition of the present invention as a member other than an electrode, the layer containing lithium particles introduces metallic lithium into the electrochemical system. Formed. Specifically, the layer containing lithium particles is used for the purpose of introducing lithium when the positive electrode active material of the positive electrode layer does not contain lithium, or for the purpose of pre-doping.
For the current collector, the positive electrode layer, the solid electrolyte layer, and the negative electrode layer, as described above, known materials can be used.

Hereinafter, an example of a layer configuration of a lithium ion battery having a layer containing lithium particles will be described. Note that a known layer such as a current collector can be added to the exemplified configuration as necessary.
Layer configuration example of lithium ion battery in which one layer containing lithium particles is formed 1. Positive electrode layer / layer containing lithium particles / electrolyte layer / negative electrode layer 2. positive electrode layer / electrolyte layer / layer containing lithium particles / negative electrode layer 3. Layer containing lithium particles / positive electrode layer / electrolyte layer / negative electrode layer Positive electrode layer / electrolyte layer / negative electrode layer / layer containing lithium particles

A plurality of layers containing lithium particles may be formed. An example of a configuration in which two layers containing lithium particles are formed is shown below.
Layer configuration example of lithium ion battery in which two layers containing lithium particles are formed 5. Layer containing lithium particles / positive electrode layer / layer containing lithium particles / electrolyte layer / negative electrode layer 6. Layer containing lithium particles / positive electrode layer / electrolyte layer / layer containing lithium particles / negative electrode layer 7. Positive electrode layer / layer containing lithium particles / electrolyte layer / negative electrode layer / layer containing lithium particles Positive electrode layer / electrolyte layer / layer containing lithium particles / negative electrode layer / layer containing lithium particles

  In addition, you may use the electrode (electrode containing lithium particle) of this invention for a positive electrode layer or a negative electrode layer. Moreover, the manufacturing method of each layer is well-known, and it does not restrict | limit in particular. For example, the electrode can be manufactured by applying and drying an electrode mixture slurry.

[Production of solid electrolyte]
Production Example 1
(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 at 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, the temperature of the reaction solution was raised under a nitrogen stream (200 cc / min), and a part of the reacted hydrogen sulfide was dehydrosulfurized. 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 increased, 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 under normal pressure at 230 ° C. (temperature higher than the boiling point of NMP) for 3 hours to obtain purified lithium sulfide.
When the impurity content of the obtained purified lithium sulfide was measured by an ion chromatography method, lithium sulfite (Li ₂ SO ₃ ), lithium sulfate (Li ₂ SO ₄ ), and lithium thiosulfate (Li ₂ S ₂ O ₃ ) The total content of each sulfur oxide was 0.13% by mass, and the content of lithium N-methylaminobutyrate (LMAB) was 0.07% by mass.

(3) Production of solid electrolyte with Li ₂ S: P ₂ S ₅ [molar ratio] = 70: 30 The molar ratio of Li ₂ S produced above and P ₂ S ₅ (manufactured by Aldrich) is 70:30. About 1 g of the obtained mixture was put in a 45 mL alumina container together with 10 alumina balls having a diameter of 10 mm and sealed.
The sealed alumina container is subjected to mechanical milling treatment for 20 hours with a planetary ball mill (manufactured by Fritsch: Model No. P-7) in nitrogen at room temperature (25 ° C.) at a rotation speed of 370 rpm. As a result, a lithium / phosphorous sulfide glass solid electrolyte was obtained. Furthermore, the crushing process was performed and the coarse particle was removed by sieving. The recovery rate at this time was 83%.
It was 220 degreeC when the glass transition temperature of the obtained solid electrolyte glass particle was measured by DSC (differential scanning calorimetry). Further, as a result of X-ray diffraction measurement (CuKα: λ = 1.5418４) of the 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 were sealed in a SUS tube under an Ar atmosphere in a glove box, subjected to heat treatment at 300 ° C. for 2 hours, and Li ₂ S: P ₂ S ₅ [molar ratio] = 70: 30. An electrolyte glass ceramic (sulfide-based solid electrolyte: average particle size of 14.52 μm) was obtained. In the X-ray diffraction measurement of the glass ceramic particles, peaks were observed at 2θ = 17.8, 18.2, 19.8, 21.8, 23.8, 25.9, 29.5, 30.0 deg. .
The ionic conductivity of the glass ceramic particles was 1.3 × 10 ⁻³ S / cm. The ionic conductivity was calculated from the result measured by the AC impedance method.

Production Example 2
Except that Li ₂ S and P ₂ S ₅ (manufactured by Aldrich) manufactured in Production Example 1 (2) were mixed at a molar ratio of 75:25, and heat treatment was not performed at 300 ° C. for 2 hours. In the same manner as in Production Example 1, solid electrolyte glass particles were produced. (Average particle size 15 μm).
Note that the recovery rate of the solid electrolyte glass particles is 82%, and the peak of the raw material Li ₂ S is not observed in the X-ray diffraction measurement (CuKα: λ = 1.5418 、), and the halo pattern is attributed to the solid electrolyte glass. there were. Moreover, the ionic conductivity of the obtained glass particle was 0.3 * 10 < ^-3 > S / cm.

Production Example 3
Except that Li ₂ S and P ₂ S ₅ (manufactured by Aldrich) manufactured in Production Example 1 (2) were mixed at a molar ratio of 80:20, and heat treatment was not performed at 300 ° C. for 2 hours. In the same manner as in Production Example 1, solid electrolyte glass particles were produced (average particle size of 35 μm).
Note that the recovery rate of the solid electrolyte glass particles was 87%, and in the X-ray diffraction measurement (CuKα: λ = 1.5418 回 折), the peak of the raw material Li ₂ S was not observed, and the halo pattern originated from the solid electrolyte glass there were. Moreover, the ionic conductivity of the obtained glass particles was 1.7 × 10 ⁻⁴ S / cm.

Example 1
(1) Manufacture of a composite of sulfur and porous carbon 0.700 g of sulfur (manufactured by Aldrich, purity 99.998%) and 0.300 g of porous carbon (Ketjen Black (KB) EC600JD, manufactured by Lion Corporation) in a mortar After mixing, the mixture was placed in an airtight stainless steel container and heat-treated in an electric furnace. The heating conditions were from room temperature to 150 ° C. at 10 ° C./minute, held at 150 ° C. for 6 hours, then heated to 300 ° C. at 10 ° C./minute, held for 2.75 hours, then naturally cooled, A complex was obtained.

(2) Production of positive electrode material (composition) containing lithium particles 0.5 g of the composite produced in (1) above and 0.5 g of the sulfide-based solid electrolyte powder produced in Production Example 1 are placed in a mill pot, A mechanical ball milling process was performed for 10 hours at room temperature (25 ° C.) with argon in a mold ball mill (Fritchch: Model No. P-7) at room temperature (25 ° C.).
After the treatment, 0.5 g of the mixture was taken out from the mill pot, and mixed with 0.152 g of lithium particles in a mortar to obtain a positive electrode material.

(3) Production of negative electrode material 0.700 g of Si powder (manufactured by High Purity Chemical Laboratory, 99.9%, D ₅₀ diameter: 4.5 μm) and 0.300 g of the sulfide-based solid electrolyte powder produced in Production Example 1 A negative electrode material was obtained by mixing.

(4) Production of Lithium Ion Battery 60 mg of the sulfide-based solid electrolyte produced in Production Example 1 was put into a plastic cylinder having a diameter of 10 mm, and pressure-molded to form a solid electrolyte layer.
Thereafter, 9.0 mg of the positive electrode material produced in the above (2) was put into a cylinder and again pressure-molded to form a laminate of a solid electrolyte layer and a positive electrode.
On the surface side of the solid electrolyte layer where the positive electrode is not formed, 4.3 mg of the negative electrode material prepared in (3) above is charged into a cylinder and is again pressure-molded to form a three-layer structure of the positive electrode, the solid electrolyte layer, and the negative electrode A lithium ion battery having

Example 2
(1) Production of positive electrode material A positive electrode material was obtained in the same manner as in Example 1 (2) except that it was not mixed with lithium particles after mechanical milling.

(2) Production of negative electrode material (composition) containing lithium particles Si powder (manufactured by High Purity Chemical Laboratory, 99.9%, D ₅₀ diameter: 4.5 μm) 0.700 g and sulfide produced in Production Example 1 A negative electrode material was obtained by mixing 0.300 g of the solid electrolyte powder and 0.304 g of lithium particles in a mortar.

(3) Manufacture of lithium ion battery Except having used 6.9 mg of positive electrode materials produced by said (1), and 6.4 mg of negative electrode materials produced by said (2), it carried out similarly to Example 1 (4). A lithium ion battery was produced.

Example 3
(1) Preparation of positive electrode material 1.0 g of lithium sulfide obtained in Production Example 1 (2), 0.300 g of Denka Black (DB, manufactured by Denki Kagaku Kogyo), and sulfide-based solid electrolyte produced in Production Example 1 0 g was put in a mill pot, and a positive electrode material was produced by a mechanical milling treatment for 10 hours at a rotation speed of 370 rpm at room temperature (25 ° C.) in argon using a planetary ball mill (manufactured by Fritsch: Model No. P-7).

(2) Production of negative electrode material (composition) containing lithium particles Manufactured with 0.700 g of Si powder (manufactured by High Purity Chemical Laboratory, 99.9%, D ₅₀ diameter: 4.5 μm) and Production Example 1 (Li7P3S11) The sulfide solid electrolyte powder 0.300 g and lithium particles 0.122 g were mixed to obtain a negative electrode material.

(3) Manufacture of lithium ion battery Except having used 7.9 mg of positive electrode materials produced by said (1), and 4.8 mg of negative electrode materials produced by said (2), it carried out similarly to Example 1 (4). A lithium ion battery was produced.

Example 4
(1) Production of positive electrode material (composition) containing lithium particles Manufactured in Production Example 1 with 1.0 g of lithium sulfide obtained in Production Example 1 (2) and 0.300 g of Denka Black (DB, manufactured by Denki Kagaku Kogyo) 1.0 g of the sulfide-based solid electrolyte was put into a mill pot and subjected to mechanical milling for 10 hours at a rotation speed of 370 rpm at room temperature (25 ° C.) in argon with a planetary ball mill (manufactured by Fritsch: Model No. P-7). .
Thereafter, 1.15 g of the mixture was taken out from the mill pot and mixed with 0.061 g of lithium particles in a mortar to obtain a positive electrode material.

(2) Production of negative electrode material 0.700 g of Si powder (manufactured by High-Purity Chemical Laboratory, 99.9%, D ₅₀ diameter: 4.5 μm) and 0.300 g of the sulfide-based solid electrolyte powder produced in Production Example 1 Were mixed to obtain a negative electrode material.

(3) Manufacture of lithium ion battery Except having used 8.4 mg of positive electrode materials produced by said (1), and 4.3 mg of negative electrode materials produced by said (2), it carried out similarly to Example 1 (4). A lithium ion battery was produced.

Example 5
(1) Production of positive electrode material (composition) containing lithium particles 70 mg of LiNi _0.80 Co _0.15 Al _0.05 O ₂ particles, 30 mg of the sulfide solid electrolyte powder produced in Production Example 1, and lithium particles 1 0.098 mg was mixed with a mortar to prepare a positive electrode material.

(2) Production of negative electrode material 60 mg of graphite and 40 mg of the sulfide-based solid electrolyte powder produced in Production Example 1 were mixed in a mortar to produce a negative electrode material.

(3) Manufacture of lithium ion battery Except having used 14.432 mg of positive electrode materials produced by said (1), and 12.1 mg of negative electrode materials produced by said (2), it carried out similarly to Example 1 (4). A lithium ion battery was produced.

Example 6
(1) Production of positive electrode material 70 mg of LiNi _0.80 Co _0.15 Al _0.05 O ₂ particles and 30 mg of the sulfide-based solid electrolyte powder produced in Production Example 1 were mixed in a mortar to produce a positive electrode material.

(2) Production of negative electrode material containing lithium particles 60 mg of graphite, 40 mg of the sulfide solid electrolyte powder produced in Production Example 1 and 1.098 mg of lithium particles were mixed in a mortar to produce a negative electrode material.

(3) Manufacture of lithium ion battery Except having used 14.3 mg of positive electrode materials produced by said (1), and 12.232 mg of negative electrode materials produced by said (2), it carried out similarly to Example 1 (4). A lithium ion battery was produced.

Example 7
Except for using the sulfide solid electrolyte powder produced in Production Example 2 instead of the sulfide solid electrolyte (glass ceramic) powder produced in Production Example 1, in the production of the positive electrode material and the negative electrode material, Similarly, a lithium ion battery was produced.

Example 8
In the production of the positive electrode material and the negative electrode material, lithium ions were obtained in the same manner as in Example 2 except that the sulfide solid electrolyte powder produced in Production Example 2 was used instead of the sulfide solid electrolyte powder produced in Production Example 1. A battery was produced.

Example 9
In the production of the positive electrode material and the negative electrode material, lithium ions were obtained in the same manner as in Example 3 except that the sulfide solid electrolyte powder produced in Production Example 2 was used instead of the sulfide solid electrolyte powder produced in Production Example 1. A battery was produced.

Example 10
In the production of the positive electrode material and the negative electrode material, lithium ions were obtained in the same manner as in Example 4 except that the sulfide solid electrolyte powder produced in Production Example 2 was used instead of the sulfide solid electrolyte powder produced in Production Example 1. A battery was produced.

Example 11
In the production of the positive electrode material and the negative electrode material, lithium ion was used in the same manner as in Example 5 except that the sulfide solid electrolyte powder produced in Production Example 2 was used instead of the sulfide solid electrolyte powder produced in Production Example 1. A battery was produced.

Example 12
In the production of the positive electrode material and the negative electrode material, lithium ions were obtained in the same manner as in Example 6 except that the sulfide solid electrolyte powder produced in Production Example 2 was used instead of the sulfide solid electrolyte powder produced in Production Example 1. A battery was produced.

Example 13
In the production of the positive electrode material and the negative electrode material, Example 1 was used except that the sulfide-based solid electrolyte powder produced in Production Example 3 was used instead of the sulfide-based solid electrolyte (glass ceramics) powder produced in Production Example 1. Similarly, a lithium ion battery was produced.

Example 14
In the production of the positive electrode material and the negative electrode material, lithium ions were obtained in the same manner as in Example 2 except that the sulfide solid electrolyte powder produced in Production Example 3 was used instead of the sulfide solid electrolyte powder produced in Production Example 1. A battery was produced.

Example 15
In the production of the positive electrode material and the negative electrode material, lithium ions were obtained in the same manner as in Example 3 except that the sulfide solid electrolyte powder produced in Production Example 3 was used instead of the sulfide solid electrolyte powder produced in Production Example 1. A battery was produced.

Example 16
In the production of the positive electrode material and the negative electrode material, lithium ions were obtained in the same manner as in Example 4 except that the sulfide solid electrolyte powder produced in Production Example 3 was used instead of the sulfide solid electrolyte powder produced in Production Example 1. A battery was produced.

Example 17
In the production of the positive electrode material and the negative electrode material, lithium ions were obtained in the same manner as in Example 5 except that the sulfide solid electrolyte powder produced in Production Example 3 was used instead of the sulfide solid electrolyte powder produced in Production Example 1. A battery was produced.

Example 18
In the production of the positive electrode material and the negative electrode material, lithium ion was used in the same manner as in Example 6 except that the sulfide solid electrolyte powder produced in Production Example 3 was used instead of the sulfide solid electrolyte powder produced in Production Example 1. A battery was produced.

About the lithium ion battery produced in Examples 1-18, the constant current charging / discharging test was done with the current density of 0.500 mA / cm < ² > of charging / discharging, and the charging / discharging temperature of 25 degreeC.
For Examples 1-2, 7-8, and 13-14, the charge / discharge potential range was 0.6-2.65 V, and for Examples 3-4, 9-10, 15-16, the charge / discharge potential range. The charge / discharge potential range was set to 2.5-4.2V for Examples 5-6, 11-12, and 17-18.

The results of the initial discharge capacity are shown in Table 1. In addition, all discharge capacity was shown by the capacity | capacitance of 1 g of positive electrode active materials.
When the solid electrolytes of Production Examples 1 and 2 were used, it was possible to discharge to near the theoretical capacity of each active material. Further, the operation was confirmed also in the solid electrolyte of Production Example 3.

[Manufacture of electrode composite materials]
Production Example 4
The following composites (A-1) to (A-4) were produced.
(A-1) Sulfur / carbon / solid electrolyte composite After premixing 70 parts by weight of sulfur powder and 30 parts by weight of ketjen black powder (EC600JD, manufactured by Lion Corporation), the same conditions as in Example 1 (1) were obtained. Then, a heat treatment was performed to obtain a sulfur / carbon composite.
Next, 50 parts by weight of this sulfur / carbon composite and 50 parts by weight of the sulfide-based solid electrolyte powder produced in Production Example 1 were mixed with a zirconia ball having a diameter of 10 mm, and a planetary ball mill (LP-4 manufactured by ITO Corporation) was mixed. Then, mechanical milling treatment was performed at 220 rpm for 10 hours to obtain a sulfur / carbon / solid electrolyte composite.

(A-2) Production of Sulfur / Carbon / Solid Electrolyte Complex Sulfur / carbon was produced in the same manner as (A-1) except that the solid electrolyte powder was changed to the solid electrolyte (75:25) produced in Production Example 2. A carbon / solid electrolyte composite was obtained.

(A-3) Li ₂ S / carbon / solid electrolyte composite 100 parts by weight of lithium sulfide prepared in Production Example 1 (2), 30 parts by weight of Denka Black (manufactured by Denki Kagaku Kogyo), sulfide produced in Production Example 1 100 parts by weight of a physical solid electrolyte is mixed with zirconia balls having a diameter of 10 mm, and subjected to mechanical milling treatment at 220 rpm for 20 hours with a planetary ball mill (LP-4 manufactured by Ito Seisakusho Co., Ltd.) to obtain a lithium sulfide / carbon / solid electrolyte composite. Got the body.

(A-4) Li ₂ S / carbon / solid electrolyte composite Lithium sulfide in the same manner as (A-3) except that the solid electrolyte powder was changed to the solid electrolyte (75:25) prepared in Production Example 2. A carbon / solid electrolyte composite was obtained.

[Production of positive electrode mixture slurry containing electrode composite material]
Production Example 5
The following positive electrode mixture slurries (B-1) to (B-4) were produced.
(B-1) Sulfur-based positive electrode mixture slurry 100 parts by weight of the composite (A-1) produced in Production Example 4, PVDF-HFP (20) resin solution (in isobutyronitrile solvent, “Kynar 2500-20 (manufactured by Arkema) ) "5 wt% dissolved) 106 parts by weight of T.P. K. Using a film mix type 56-50 (manufactured by Primix), a dispersion treatment was performed at a peripheral speed of 30 m / s for 30 seconds to produce a positive electrode mixture slurry.

(B-2) Sulfur-based positive electrode mixture slurry A slurry was produced in the same manner as the composite (B-1) except that the composite (A-1) was changed to the composite (A-2).

(B-3) Li ₂ S-based positive electrode mixture slurry A slurry was produced in the same manner as the composite (B-1) except that the composite (A-1) was changed to the composite (A-3).

(B-4) Li ₂ S-based positive electrode composite slurry A slurry was produced in the same manner as the composite (B-1) except that the composite (A-1) was changed to the composite (A-4).

Example 19
Production of lithium particle-containing sulfur-based positive electrode mixture slurry (B-5) 100 parts by weight of composite (A-1), 30.4 parts by weight of lithium powder, PVDF-HFP (20) resin solution (in isobutyronitrile solvent) “Kynar 2500-20” was dissolved in 5 wt%). K. Dispersion treatment was performed for 60 seconds at a peripheral speed of 30 m / s using a film mix type 56-50 (manufactured by Primix) to produce a positive electrode mixture slurry.

Example 20
Production of lithium particle-containing Li ₂ S-based positive electrode mixture slurry (B-6) Except for changing composite (A-1) to composite (A-3), the same as composite (B-5) A slurry was produced.

[Production of negative electrode mixture slurry]
Production Example 6
The following silicon-based negative electrode mixture slurry (C-1) was produced.
70 parts by weight of Si powder, 30 parts by weight of the sulfide-based solid electrolyte powder prepared in Production Example 1, and 3 wt% of PVDF-HFP (15) resin solution (“Kynar 2751-00 (manufactured by Arkema)” in isobutyronitrile solvent) ) 100 parts by weight was mixed, and the mixture was dispersed at 220 rpm for 2 hours using a planetary ball mill to produce a negative electrode mixture slurry.

Example 21
Production of lithium particle-containing silicon-based negative electrode mixture slurry (C-2) 100 parts by weight of negative electrode mixture slurry (C-1), 12.9 parts by weight of lithium powder, and 10 parts by weight of isobutyronitrile solvent were mixed. . K. Using a film mix type 56-50 (manufactured by PRIMIX Co., Ltd.), a dispersion treatment was performed at a peripheral speed of 20 m / s for 10 seconds to produce a negative electrode mixture slurry.

Example 22
Production of lithium particle-containing silicon-based negative electrode mixture slurry (C-3) 100 parts by weight of negative electrode mixture slurry (C-1), 5.2 parts by weight of lithium powder, and 5 parts by weight of isobutyronitrile solvent were mixed. . K. Using a film mix type 56-50 (manufactured by PRIMIX Co., Ltd.), a dispersion treatment was performed at a peripheral speed of 20 m / s for 10 seconds to produce a negative electrode mixture slurry.

[Production of solid electrolyte slurry]
Production Example 7
A solid electrolyte slurry (D-1) was produced. Specifically, 40 parts by mass of the sulfide-based solid electrolyte prepared in Production Example 1 and 60 parts by mass of toluene are put into a planetary ball mill container, and a zirconia ball having a diameter of 10 mm is placed therein, and dispersion treatment is performed at 200 rpm for 2 hours. A solid electrolyte slurry was obtained.

[Manufacture and manufacture of aluminum current collector]
Production Example 8
An aluminum current collector (E-1) with an undercoat layer was produced. Specifically, using a doctor blade (application width: 150 mm, application thickness: 50 μm), an aluminum foil (width: 200 mm, thickness: 30 μm) and conductive paint (trade name: Bunny Height UCC-2, manufactured by Nippon Graphite Co., Ltd.) And dried under reduced pressure at 150 ° C. for 2 hours to form an undercoat layer having a thickness of 5 μm.

[Production of electrode sheet]
(Preparation of positive electrode mixture sheet)
Production Example 9
Using a doctor blade (application width: 50 mm, application thickness: 250 μm), the positive electrode mixture slurry (B-1) was applied to the aluminum collector (E-1) with an undercoat layer, and then at 100 ° C. for 6 hours. It dried under reduced pressure and the positive mix sheet was obtained. The basis weight of the positive electrode mixture was 9.7 mg / cm ² . Here, the weight per unit area represents the amount of all materials constituting the positive electrode mixture per unit area.

Production Examples 10 and 11
A positive electrode mixture sheet was produced in the same manner as in Production Example 9 except that the positive electrode mixture slurry was changed to (B-2) or (B-3), respectively. The basis weight of each positive electrode mixture was 9.7 g / cm ² and 11.1 g / cm ² .

Example 23
A positive electrode mixture sheet was produced in the same manner as in Production Example 9 except that the positive electrode mixture slurry was changed to (B-5). The basis weight of the positive electrode mixture was 12.6 mg / cm ² .

(Preparation of negative electrode composite sheet)
Production Example 12
Using a doctor blade (application width: 50 mm, application thickness: 250 μm), the negative electrode mixture slurry (C-1) was applied to the aluminum current collector (E-1) with an undercoat layer, and then at 100 ° C. for 6 hours. It dried under reduced pressure and the negative electrode compound material sheet was obtained. The basis weight of the negative electrode mixture was 6.0 g / cm ² .

Examples 24 and 25
A negative electrode mixture sheet was produced in the same manner as in Production Example 12 except that the negative electrode mixture slurry was changed to (C-2) or (C-3), respectively. The basis weight of each negative electrode mixture was 9.0 g / cm ² and 6.7 g / cm ² .

[Manufacture of lithium ion secondary batteries]
Example 26
A PET sheet (thickness: 200 μm) provided with an opening of 20 × 20 mm was placed on the negative electrode composite sheet prepared in Example 24, and the sulfide-based solid electrolyte slurry (D-1) was poured into the squeegee spatula. Conditioned and air dried. Thereafter, the PET sheet was removed, and after drying under reduced pressure at 100 ° C. for 2 hours, a two-layer sheet comprising a negative electrode layer and a solid electrolyte layer was produced.
The two-layer sheet and the positive electrode mixture sheet produced in Production Example 9 were each cut out to a size of 20 × 20 mm, and then bonded together so as to sandwich the electrolyte layer. Using a hydraulic press, the pressure was 500 MPa. Integrally molded. Thereafter, an electrode tab was attached to each current collector and sealed with an aluminum laminate film to form a battery cell. In the obtained battery, there was no internal short circuit.

Example 27
A battery cell was produced in the same manner as in Example 26 except that the positive electrode mixture sheet was changed to the electrode sheet of Example 23 and the negative electrode mixture sheet was changed to the electrode sheet described in Production Example 12.

Example 28
A battery cell was produced in the same manner as in Example 26 except that the positive electrode mixture sheet was changed to the electrode sheet described in Production Example 10 and the negative electrode mixture sheet was changed to the electrode sheet described in Example 24.

Example 29
A battery cell was produced in the same manner as in Example 26 except that the positive electrode mixture sheet was changed to the electrode sheet described in Production Example 11 and the negative electrode mixture sheet was changed to the electrode sheet described in Example 25.

Comparative Example 1
A copper punching sheet (opening hole: 500 μm, opening ratio: 30%, thickness: 30 μm) was used as a porous current collector to dope lithium into the electrode from the back side of the current collector. Using a doctor blade (application width: 50 mm, application thickness: 250 μm), the negative electrode mixture slurry (C-1) was applied on the punching sheet described above, and then dried under reduced pressure at 100 ° C. for 6 hours to obtain a negative electrode mixture sheet. Got. The basis weight of the negative electrode mixture was 6.8 g / cm ² .
Furthermore, a PET sheet (thickness: 200 μm) provided with an opening of 20 × 20 mm was placed on the negative electrode mixture layer side, and a sulfide-based solid electrolyte slurry (D-1) was poured in, smoothed with a squeegee spatula, and air-dried. . Thereafter, the PET sheet was removed, and after drying under reduced pressure at 100 ° C. for 2 hours, a two-layer sheet comprising a negative electrode layer and a solid electrolyte layer was produced.
The above-mentioned two-layer sheet and the positive electrode mixture sheet produced in Production Example 9 were cut out to a size of 20 × 20 mm, and bonded together so as to sandwich the electrolyte layer. Then, using a hydraulic press, 500 MPa Integrally molded with pressure.
Next, the lithium foil was pasted on the punching sheet on the side opposite to the negative electrode composite material layer, and pasted at 10 MPa with a press. However, since the lithium foil was peeled off, a battery cell could not be formed.

Comparative Example 2
A battery cell was tried to be formed by the same method as in Comparative Example 1 except that the press pressure during lithium bonding was changed to 300 MPa. However, since a short circuit occurred, a battery cell could not be formed.

  The composition of the present invention is suitable for materials for various batteries, particularly lithium ion batteries. Specifically, it can be used as a material for introducing lithium into the positive electrode, the negative electrode, and the periphery thereof.

Claims (5)

At least one of an active material and an electrode composite material;
Lithium particles,
A composition comprising At least one of an active material and an electrode composite material;
Lithium particles,
Including electrodes.   An electrode using the composition according to claim 1 as a raw material.   A battery comprising the electrode according to claim 2.   A battery comprising a layer containing lithium particles, a positive electrode layer, a negative electrode layer, and an electrolyte layer.