阅读说明：本技术 复合活性物质粒子、正极、全固体锂离子电池及它们的制造方法 (Composite active material particle, positive electrode, all-solid-state lithium ion battery, and methods for producing same ) 是由 三木成章 于 2017-12-06 设计创作，主要内容包括：本发明涉及复合活性物质粒子、正极、全固体锂离子电池及它们的制造方法。[课题]公开在制得全固体锂离子电池时可降低电池电阻的复合活性物质粒子。[解决手段]采用这样的复合活性物质粒子,其具有活性物质粒子和被覆该活性物质粒子表面的至少一部分的锂离子传导性氧化物,水分量为319ppm以下。(The present invention relates to composite active material particles, a positive electrode, an all-solid lithium ion battery, and methods for producing the same. [ problem ] to disclose composite active material particles that can reduce the battery resistance when an all-solid lithium ion battery is produced. [ solution ] composite active material particles having active material particles and a lithium ion conductive oxide coating at least a part of the surfaces of the active material particles, wherein the water content is 319ppm or less are used.)

1. A positive electrode comprising a positive electrode mixture layer containing composite active material particles and a sulfide solid electrolyte,

the composite active material particle comprises active material particles and a lithium ion conductive oxide coating at least a part of the surface of the active material particles, and has a water content of 319ppm or less.

2. The positive electrode according to claim 1, wherein the water content is 119ppm or less.

3. The positive electrode according to claim 1, wherein the water content is 70ppm or less.

4. The positive electrode as claimed in any one of claims 1 to 3, wherein the lithium ion-conductive oxide is at least one selected from the group consisting of lithium niobate, lithium titanate, lanthanum lithium zirconate, lithium tantalate, and lithium tungstate.

5. An all-solid lithium ion battery comprising the positive electrode according to any one of claims 1 to 3, a solid electrolyte layer, and a negative electrode.

6. A method for producing composite active material particles, comprising:

a step 1 of coating at least a part of the surface of active material particles with a lithium ion conductive oxide, drying and firing the coated active material particles to obtain composite active material particles; and

a 2 nd step of vacuum-drying the composite active material particles obtained in the 1 st step at a temperature of 120 ℃ to 300 ℃ for 1 hour or more,

the lithium ion conductive oxide is at least one selected from lithium niobate, lithium titanate, lanthanum lithium zirconate, lithium tantalate and lithium tungstate,

the composite active material particle is used for a positive electrode of an all-solid-state lithium ion battery provided with a sulfide solid electrolyte.

7. A method for manufacturing a positive electrode, comprising: a step of mixing the composite active material particles produced by the production method according to claim 6 with a sulfide solid electrolyte to obtain a positive electrode mixture; and a step of molding the positive electrode mixture.

8. A method for manufacturing an all-solid lithium ion battery, comprising: a step of laminating the positive electrode manufactured by the manufacturing method according to claim 7, the solid electrolyte layer, and the negative electrode.

Technical Field

Disclosed are composite active material particles, a positive electrode, an all-solid-state lithium ion battery, and methods for producing the same.

Background

Patent document 1 discloses the following problems: in an all-solid-state lithium ion battery using a sulfide solid electrolyte, a high resistance layer is formed at a contact interface between the sulfide solid electrolyte and a positive electrode active material, and the output characteristics of the battery are reduced; as a means for solving the problem, disclosed is a method for producing composite active material particles by coating the surface of a positive electrode active material with a lithium ion conductive oxide. In patent document 1, a solution containing an element constituting a coating layer of a lithium ion conductive oxide is applied to the surface of a positive electrode active material, and the resultant is heated at a temperature of 400 ℃.

Patent document 2 discloses the following problems: in the case where the composite active material particles are produced by coating the surface of the positive electrode active material with lithium niobate, which is a lithium ion conductive oxide, the electrical resistance value of the composite active material particles themselves increases even if the formation of a high resistance layer at the contact interface between the sulfide solid electrolyte and the positive electrode active material can be suppressed; as a means for solving this problem, reduction of the carbon content of the composite active material particles is disclosed. In patent document 2, a positive electrode active material is mixed with an aqueous solution containing a niobium compound and a lithium compound, the niobium compound and the lithium compound are allowed to adhere to the surface of the positive electrode active material, and then heat treatment is performed at 300 ℃ to 700 ℃ inclusive, thereby obtaining composite active material particles.

Although not relating to all-solid-state batteries, patent document 3 discloses the following technique: in order to achieve both a low self-discharge rate and a high recovery rate in a nonaqueous electrolyte secondary battery, positive electrode active material particles having a predetermined specific surface area and a moisture content of not more than a predetermined amount are used.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2007/004590

Patent document 2: japanese laid-open patent publication No. 2012-074240

Patent document 3: japanese laid-open patent publication No. 10-149832

Disclosure of Invention

Problems to be solved by the invention

As described above, various studies have been made on composite active material particles of all-solid lithium ion batteries, and the performance of all-solid lithium ion batteries has been increasingly improved. However, even when the composite active material particles as disclosed in patent documents 1 and 2 are used, the battery resistance of the all-solid lithium ion battery is still high, and it is difficult to say that the all-solid lithium ion battery has sufficient performance.

Disclosed are composite active material particles that can reduce the battery resistance when an all-solid lithium ion battery is manufactured.

Means for solving the problems

The present inventors have intensively studied the main cause of increasing the battery resistance of an all-solid lithium ion battery, and as a result, they have found that the resistance of an all-solid lithium ion battery increases due to the fact that a minute amount of water contained in the composite active material particles reacts with the sulfide solid electrolyte to deteriorate the sulfide solid electrolyte. Based on this knowledge, the present inventors have considered that a treatment for greatly reducing the amount of water in the composite active material particles is necessary when producing the particles, and have conducted further studies. As a result, it was found that the amount of water contained in the composite active material particles can be greatly reduced by performing vacuum drying under predetermined conditions when the composite active material particles are produced. When an all-solid-state lithium ion battery is produced using the composite active material particles thus produced, an all-solid-state lithium ion battery having a low battery resistance can be obtained.

Based on the above findings, the present application discloses, as one of means for solving the above problems, composite active material particles having active material particles and a lithium ion conductive oxide coating at least a part of the surfaces of the active material particles, the composite active material particles having a moisture content of 319ppm or less.

The "active material particles" may be particles having a normal size that can be used as an active material of an all-solid lithium ion battery.

The "lithium ion conductive oxide" refers to an oxide that has lithium ion conductivity and functions as a protective material for suppressing a reaction between active material particles and a sulfide solid electrolyte. That is, it means an oxide having lithium ion conductivity and relatively low reactivity with respect to a sulfide solid electrolyte as compared with active material particles.

The "moisture content is 319ppm or less" means that the mass% concentration of moisture contained in the composite active material particles is 319ppm or less. The "water content" of the composite active material particles can be measured by karl fischer titration.

In the composite active material particle of the present disclosure, it is preferable that the lithium ion conductive oxide is at least one selected from the group consisting of lithium niobate, lithium titanate, lanthanum lithium zirconate, lithium tantalate, and lithium tungstate.

As one means for solving the above problems, the present application discloses a positive electrode including a positive electrode mixture layer containing the negative electrode active material particles of the present disclosure and a sulfide solid electrolyte.

As one means for solving the above problems, the present application discloses an all-solid-state lithium ion battery including the positive electrode, the solid electrolyte layer, and the negative electrode of the present disclosure.

As one of means for solving the above problems, the present application discloses a method for producing composite active material particles, comprising: a step 1 of coating at least a part of the surface of active material particles with a lithium ion conductive oxide to obtain composite active material particles; and a 2 nd step of vacuum-drying the composite active material particles obtained in the 1 st step at a temperature of 120 ℃ to 300 ℃ for 1 hour or more.

The term "vacuum drying" means that water is extracted from the composite active material particles by reducing the pressure to 100kPa or less.

In the step 1 of the method for producing composite active material particles according to the present disclosure, it is preferable that the composite active material particles are produced by drying an aqueous solution of a peroxide complex containing an element constituting a lithium ion conductive oxide on the surface of the active material particles to obtain a precursor, and firing the precursor.

As one of means for solving the above problems, the present application discloses a method for manufacturing a positive electrode, including: a step of mixing the composite active material particles produced by the method for producing composite active material particles of the present disclosure with a sulfide solid electrolyte to obtain a positive electrode mixture; and a step of molding the positive electrode mixture.

As one of means for solving the above problems, the present application discloses a method for manufacturing an all-solid-state lithium-ion battery, comprising: a step of laminating the positive electrode manufactured by the positive electrode manufacturing method of the present disclosure, the solid electrolyte layer, and the negative electrode.

Effects of the invention

The composite active material particles of the present disclosure have a very small water content. Thus, when applied to an all-solid lithium ion battery, the sulfide solid electrolyte can be inhibited from being deteriorated by moisture contained in the composite active material particles, and the sulfide solid electrolyte can maintain high conductivity. Thus, an all-solid lithium ion battery having a low battery resistance can be obtained.

Drawings

Fig. 1 is a schematic diagram for explaining the structure of the composite active material particle 10.

Fig. 2 is a schematic diagram for explaining the structure of positive electrode 20.

Fig. 3 is a schematic diagram for explaining the structure of the all-solid lithium ion battery 100.

Fig. 4 is a diagram for explaining the flow of the method (S10) for producing composite active material particles.

Fig. 5 is a diagram for explaining the flow of the positive electrode manufacturing method (S20).

Fig. 6 is a diagram for explaining the flow of the method (S100) for manufacturing the all-solid lithium ion battery.

Description of the reference numerals

1 active substance particles

2 lithium ion conductive oxide

10 composite active material particles

11 sulfide solid electrolyte

12 conductive material

13 adhesive

20 positive electrode

20a positive electrode mixture layer

20b positive electrode collector

30 solid electrolyte layer

40 negative electrode

41 negative electrode active material

42 solid electrolyte

43 adhesive

100 all-solid lithium ion battery

Detailed Description

1. Composite active material particles

Fig. 1 schematically shows the structure of the composite active material particle 10. In fig. 1, 1 piece of the composite active material particle 10 is extracted, and the composite active material particle 10 is shown in a simplified manner. As shown in fig. 1, the lithium ion conductive oxide coating material comprises active material particles 1 and a lithium ion conductive oxide 2 that covers at least a part of the surface of the active material particles 1. Here, the composite active material particle 10 is characterized in that the water content is 319ppm or less.

1.1. Active substance particles

The composite active material particle 10 is characterized in that the amount of water is very small, and if this condition is satisfied, a desired effect can be exhibited to solve the above-described problem. Therefore, the type of the active material particles 1 is not particularly limited, and any particles containing a material that can be used as an active material of an all-solid lithium ion battery can be used. As such a material, LiCoO may be mentioned₂、LiNi_xCo_1-xO₂(0＜x＜1)、LiNi_1/3Co_1/3Mn_1/3O₂、LiMnO₂Replacement of Li-Mn spinel (LiMn) by a dissimilar element_1.5Ni_0.5O₄、LiMn_1.5Al_0.5O₄、LiMn_1.5Mg_0.5O₄、LiMn_1.5Co_0.5O₄、LiMn_1.5Fe_0.5O₄、LiMn_1.5Zn_0.5O₄) Lithium titanate (e.g. Li)₄Ti₅O₁₂) Lithium metal phosphate (LiFePO)₄、LiMnPO₄、LiCoPO₄、LiNiPO₄) Transition metal oxide (V)₂O₅、MoO₃)、TiS₂Carbon materials such as graphite and hard carbon, LiCoN, Si and SiO₂、Li₂SiO₃、Li₄SiO₄Lithium metal (Li), lithium alloys (LiSn, LiSi, LiAl, LiGe, LiSb, LiP), lithium-storing intermetallic compounds (e.g. Mg₂Sn、Mg₂Ge、Mg₂Sb、Cu₃Sb), and the like. Here, two kinds of substances having different potentials (charge/discharge potentials) for occluding and releasing lithium ions can be selected from the above materials, and a substance exhibiting a high potential can be used for the positive electrode active material and a substance exhibiting a low potential can be used for the negative electrode active material. By such an arrangement, an all-solid lithium ion battery of an arbitrary voltage can be constructed. In particular, the active material particles 1 are preferably positive electrode active material particles, and more preferably selected from LiCoO₂、LiNi_xCo_1-xO₂(0＜x＜1)、LiNi_1/3Co_1/3Mn_{1/ 3}O₂、LiMnO₂And particles of lithium-containing composite oxide such as lithium-Mn spinel and lithium metal phosphate substituted with a different element. The form of the active material particles 1 is not particularly limited as long as the composite active material particles 10 can be formed, and the primary particle diameter thereof is preferably 1nm to 100 μm. The lower limit is more preferably 10nm or more, still more preferably 100nm or more, particularly preferably 500nm or more, and the upper limit is more preferably 30 μm or less, still more preferably 3 μm or less. The active material particles 1 may be secondary particles formed by aggregating such primary particles.

1.2. Lithium ion conductive oxide

The lithium ion conductive oxide 2 has lithium ion conductivity and functions as a protective material for suppressing a reaction between the active material particles 1 and a sulfide solid electrolyte 11 described later. As long as it has such a function, any kind of the lithium ion conductive oxide 2 can exhibit a desired effect, and the above problem can be solved. Examples of the lithium ion conductive oxide 2 include a composite oxide containing a lithium metal and a metal element. Specifically, lithium niobate, lithium titanate, lanthanum lithium zirconate, lithium tantalate, lithium tungstate, and the like can be given. Wherein. Lithium niobate is preferable from the viewpoint of further reducing the reaction resistance between the active material particles 1 and the sulfide solid electrolyte 11 described later. In the composite active material particles 10, the coating layer of the lithium ion conductive oxide 2 preferably contains 90 mass% or more of such a lithium ion conductive oxide. The upper limit is not particularly limited, and is, for example, 99 mass% or less. The thickness of the coating layer is not particularly limited, and is preferably 3nm to 100nm from the viewpoint of further reducing the reaction resistance.

1.3. Amount of water

It is important that the water content of the composite active material particle 10 is 319ppm or less. The water content of the composite active material particle 10 is preferably 119ppm or less, and more preferably 70ppm or less. By thus making the amount of water in the particles extremely small, when applied to an all-solid lithium ion battery, the deterioration of the sulfide solid electrolyte 11 described later due to the water contained in the composite active material particles 10 can be suppressed, and the sulfide solid electrolyte 11 can maintain high conductivity. That is, by using the composite active material particles 10, an all-solid lithium ion battery having a low battery resistance can be obtained.

2. Positive electrode

Fig. 2 schematically shows the structure of the positive electrode 20. As shown in fig. 2, the positive electrode 20 includes a positive electrode mixture layer 20a containing the composite active material particles 10 and the sulfide solid electrolyte 11. The positive electrode mixture layer 20a may contain the conductive material 12 and the binder 13 as optional components. Further, the positive electrode 20 may include a positive electrode current collector 20b electrically connected to the positive electrode mixture layer 20 a.

2.1. Composite active material particles

The positive electrode mixture layer 20a of the positive electrode 20 contains the composite active material particles 10 as a positive electrode active material. Two types of substances having different potentials (charge/discharge potentials) for occluding and releasing lithium ions can be selected from the above-described substances described as specific examples of the active material particles 1, and a substance exhibiting a high potential is used as the active material particles 1, and a substance exhibiting a low potential is used as a negative electrode active material described later. The content of the composite active material particles 10 in the positive electrode mixture layer 20a is not particularly limited, and is preferably 40% to 99% by mass, for example.

2.2. Sulfide solid electrolyte

The positive electrode mixture layer 20a of the positive electrode 20 contains the sulfide solid electrolyte 11. A part of the sulfide solid electrolyte 11 is in contact with the composite active material particles 10. The sulfide solid electrolyte 11 that may be contained in the positive electrode mixture layer 20a includes, for example, Li₂S－SiS₂、LiI－Li₂S－SiS₂、LiI－Li₂S－P₂S₅、LiI－Li₂O－Li₂S－P₂S₅、LiI－Li₂S－P₂O₅、LiI－Li₃PO₄－P₂S₅、Li₂S－P₂S₅、Li₃PS₄And the like. The sulfide solid electrolyte 11 may be amorphous or crystalline. The content of the sulfide solid electrolyte 11 in the positive electrode mixture layer 20a is not particularly limited.

2.3. Other ingredients

The positive electrode mixture layer 20a of the positive electrode 20 may contain the conductive material 12 as an arbitrary component. Examples of the conductive material 12 that can be contained in the positive electrode mixture layer 20a include carbon materials such as vapor-grown carbon fibers, Acetylene Black (AB), Ketjen Black (KB), Carbon Nanotubes (CNT), and Carbon Nanofibers (CNF), and metal materials that can withstand the environment in which the all-solid lithium ion battery is used. The content of the conductive material 12 in the positive electrode mixture layer 20a is not particularly limited.

The positive electrode mixture layer 20a of the positive electrode 20 may contain the binder 13 as an arbitrary component. Examples of the binder 13 that can be contained in the positive electrode mixture layer 20a include Acrylonitrile Butadiene Rubber (ABR), Butadiene Rubber (BR), polytetrafluoroethylene (PVdF), Styrene Butadiene Rubber (SBR), and the like. The content of the binder 13 in the positive electrode mixture layer 20a is not particularly limited.

The positive electrode mixture layer 20a of the positive electrode 20 may contain a solid electrolyte other than the sulfide solid electrolyte 11 within a range not impairing the desired effects. For example, an oxide solid electrolyte may be included. The oxide solid electrolyte in this case is a solid electrolyte that does not constitute a coating layer of the composite active material particles 10. The content of the solid electrolyte other than the sulfide solid electrolyte in the positive electrode mixture layer 20a is not particularly limited.

In the positive electrode 20, the thickness of the positive electrode mixture layer 20a is not particularly limited. The performance may be determined as appropriate according to the target performance.

2.4. Positive electrode current collector

The positive electrode 20 preferably includes a positive electrode current collector 20b in contact with the positive electrode mixture layer 20 a. As the positive electrode current collector 20b, a known metal that can be used as a current collector of an all-solid lithium ion battery can be used. Examples of such a metal include a metal material containing one or two or more elements selected from Cu, Ni, Al, V, Au, Pt, Mg, Fe, Ti, Co, Cr, Zn, Ge, and In. The form of the positive electrode current collector 20b is not particularly limited. Various forms such as foil form and net form can be adopted.

The shape of the entire positive electrode 20 is not particularly limited, and is preferably a sheet shape as shown in fig. 2. In this case, the thickness of the entire positive electrode 20 is not particularly limited. The performance may be determined as appropriate according to the target performance.

As described above, the positive electrode 20 includes the composite active material particles 10 and the sulfide solid electrolyte 11 in the positive electrode mixture layer 20 a. Here, in the positive electrode 20, as described above, since the moisture content of the composite active material particles 10 is extremely small, the sulfide solid electrolyte 11 can be suppressed from being deteriorated by moisture contained in the composite active material particles 10, and the sulfide solid electrolyte 11 can maintain high conductivity. This makes it possible to obtain a positive electrode having low resistance.

3. All-solid-state lithium ion battery

Fig. 3 schematically shows the structure of the all-solid lithium ion battery 100. As shown in fig. 3, the all-solid lithium ion battery 100 includes a positive electrode 20, a solid electrolyte layer 30, and a negative electrode 40.

3.1. Positive electrode

The positive electrode 20 is configured as described above.

3.2. Solid electrolyte layer

The solid electrolyte layer 30 contains a solid electrolyte 31. As the solid electrolyte 31 included in the solid electrolyte layer 30, a known solid electrolyte that can be used in all-solid lithium ion batteries can be suitably used. Examples of such a solid electrolyte include solid electrolytes that can be contained in the positive electrode 20 and the negative electrode 40 described later. The content of the solid electrolyte 31 in the solid electrolyte layer 30 is, for example, 60% by mass or more, preferably 70% by mass or more, and particularly preferably 80% by mass or more.

Although not shown in fig. 3, the solid electrolyte layer 30 may contain a binder that binds the solid electrolytes 31 to each other from the viewpoint of exhibiting plasticity or the like. Examples of such a binder include binders that can be contained in the positive electrode 20 and the negative electrode 40 described later. Among them, in order to easily achieve high output, the binder contained in the solid electrolyte layer 30 is preferably 5 mass% or less from the viewpoint of preventing the solid electrolyte 31 from being excessively aggregated and forming the solid electrolyte layer 30 having the solid electrolyte 31 uniformly dispersed, and the like.

The shape of the solid electrolyte layer 30 is not particularly limited, and is preferably a sheet shape as shown in fig. 3. In this case, the thickness of the solid electrolyte layer 60 is not particularly limited. The performance may be determined as appropriate according to the target performance.

3.3. Negative electrode

The negative electrode 40 includes a negative electrode mixture layer 40a containing a negative electrode active material 41. The negative electrode mixture layer 40a may contain a solid electrolyte 42, a binder 43, and a conductive material (not shown) as optional components. Further, the negative electrode 40 may include a negative electrode current collector 40b in contact with the negative electrode mixture layer 40 a.

The negative electrode mixture layer 40a of the negative electrode 40 contains a negative electrode active material 41. The active material particles 1 can be prepared fromIn the examples, two kinds of substances having different potentials (charge/discharge potentials) for storing and releasing lithium ions are selected from the above substances, and a substance exhibiting a high potential is used as the active material particles 1 and a substance exhibiting a low potential is used as the negative electrode active material 41. The shape of the negative electrode active material 41 is not particularly limited, and for example, a particle shape or a film shape can be used. Average particle diameter (D) of negative electrode active material 41₅₀) For example, it is preferably 1nm to 100 μm, more preferably 10nm to 30 μm. The content of the negative electrode active material 41 in the negative electrode mixture layer 40a is not particularly limited, and is preferably, for example, 40% to 99% by mass%.

The negative electrode mixture layer 40a of the negative electrode 40 may contain a known solid electrolyte 42 as an arbitrary component. Examples of the solid electrolyte 42 include the sulfide solid electrolyte and the oxide solid electrolyte described above. The solid electrolyte 42 may be amorphous or crystalline. The content of the solid electrolyte 42 in the negative electrode mixture layer 40a is not particularly limited.

The negative electrode mixture layer 40a of the negative electrode 40 may contain the binder 43 and the conductive material as optional components. The binder 43 and the conductive material can be appropriately selected from binders and conductive materials exemplified as binders and conductive materials applicable to the positive electrode mixture layer 20 a. The content of the binder 43 and the conductive material in the negative electrode mixture layer 40a is not particularly limited.

In the negative electrode 40, the thickness of the negative electrode mixture layer 40a is not particularly limited. The performance may be determined as appropriate according to the target performance.

The negative electrode 40 preferably includes a negative electrode current collector 40b in contact with the negative electrode mixture layer 40 a. As the negative electrode current collector 40b, a known metal that can be used as a current collector of an all-solid lithium ion battery can be used. Examples of such a metal include a metal material containing one or two or more elements selected from Cu, Ni, Al, V, Au, Pt, Mg, Fe, Ti, Co, Cr, Zn, Ge, and In. The form of the negative electrode current collector 40b is not particularly limited. Various forms such as foil form and net form can be adopted.

The overall shape of the negative electrode 40 is not particularly limited, and is preferably a sheet shape as shown in fig. 3. In this case, the thickness of the entire negative electrode 40 is not particularly limited. The performance may be determined as appropriate according to the target performance.

As described above, the all-solid lithium ion battery 100 includes the composite active material particles 10 and the sulfide solid electrolyte 11 in the positive electrode mixture layer 20a of the positive electrode 20. Here, in the all-solid lithium ion battery 100, since the moisture content of the composite active material particles 10 is extremely small as described above, it is possible to suppress deterioration of the sulfide solid electrolyte 11 in the positive electrode mixture layer 20a and the like due to moisture contained in the composite active material particles 10, and the sulfide solid electrolyte 11 maintains high conductivity. This makes it possible to obtain the all-solid lithium ion battery 100 having a low resistance.

4. Method for producing composite active material particles

Fig. 4 shows a flow of a method S10 for producing composite active material particles. As shown in fig. 4, S10 includes: a 1 st step S1 of coating at least a part of the surface of active material particles with a lithium ion conductive oxide to obtain a composite active material precursor; and a 2 nd step S2 of vacuum-drying the precursor at a temperature of 120 to 300 ℃ for 1 hour or more.

4.1. Step 1S 1

In the step 1, at least a part of the surface of the active material particle is coated with a lithium ion conductive oxide to obtain a composite active material particle. For example, the composite active material particles can be obtained by a method of immersing the active material particles in a solution containing an element constituting the lithium ion conductive oxide, spraying a solution containing an element constituting the lithium ion conductive oxide in a state where the active material particles are fluidized, or the like, coating the surfaces of the active material particles with the solution, and thereafter, drying to remove the solvent and appropriately performing heat treatment. As the solution, a peroxide complex aqueous solution or an alkoxide solution can be used. In the case of using the aqueous peroxide complex solution, the step 1 can be performed according to the procedures disclosed in, for example, Japanese patent laid-open Nos. 2012-74240 and 2016-170973. In the case of using an alkoxide solution, the step 1 can be performed, for example, according to the procedures disclosed in international publication No. 2007/004590, japanese patent application laid-open No. 2015-201252, and the like.

Hereinafter, as a preferred embodiment, a preferred embodiment will be described in which a precursor is obtained by drying an aqueous solution of a peroxide complex containing an element constituting a lithium ion conductive oxide on the surface of active material particles in the step 1 (drying step), and the composite active material particles are obtained by firing the precursor (firing step).

In the drying step, an aqueous solution of a peroxide complex containing an element constituting the lithium ion conductive oxide is dried on the surfaces of the active material particles to obtain a precursor. That is, the drying is performed in a state where the peroxide complex aqueous solution is in contact with the surface of the active material particles. Examples of the method of bringing the peroxide complex aqueous solution into contact with the surface of the active material particles include immersion and spraying as described above. Spraying is particularly preferred. In the case of using lithium niobate as the lithium ion conductive oxide, the aqueous solution of a peroxo complex contains a peroxo complex of lithium and niobium. Specifically, a transparent solution is prepared by using hydrogen peroxide water, niobic acid, and ammonia water, and then a lithium salt is added to the prepared transparent solution to obtain a peroxide complex aqueous solution. In this case, the water content of the niobic acid is not particularly limited, since the peroxy complex of niobium is generated even if the water content of the niobic acid changes. The mixing ratio of the niobic acid and the aqueous ammonia is not particularly limited as long as the peroxy complex of niobium can be synthesized. Examples of the lithium salt include LiOH and LiNO₃、Li₂SO₄And the like. The lithium salt may also be a hydrate.

In the drying step, after the complex solution is brought into contact with the surfaces of the active material particles, volatile components such as a solvent and water of hydration contained in the complex solution brought into contact with the surfaces of the active material particles are removed by drying. Such a process can be performed, for example, by using an inverted flow coating apparatus, a spray dryer, or the like. Examples of the reverse flow coating apparatus include マルチプレックス manufactured by パウレック corporation and フローコーター manufactured by フロイント corporation. When focusing attention on one active material particle in the case of using the reverse flow coating apparatus, the complex solution is dried immediately after the complex solution is supplied (sprayed) to the surface of the active material particle, and thereafter the supply of the complex solution to the active material and the drying of the complex solution supplied to the active material are repeated until the thickness of the layer of the precursor of lithium niobate adhering to the surface of the active material particle becomes a target thickness. When the inverted flow coating device is used, when focusing on a plurality of active material particles present in the device, the active material particles to which the complex solution is supplied (sprayed) and the active material particles whose surface complex solution is dried are present in a mixed state. Therefore, when the reverse flow coating apparatus is used, the complex solution can be supplied (sprayed) to the active material particle surface and the complex solution attached to the active material particle surface can be dried in parallel with this. The drying temperature in the spray drying step is not particularly limited. The atmosphere (carrier gas) in the spray drying step is not particularly limited.

In the firing step, the precursor obtained in the drying step is fired at a predetermined temperature. In this way, composite active material particles in which at least a part of the surface of the active material particles is coated with a lithium ion conductive oxide are obtained. The firing step may be performed in an atmospheric atmosphere, for example. The firing temperature in the firing step can be the same as in the conventional case.

4.2. Step 2S 2

According to the findings of the present inventors, when the peroxide complex aqueous solution is used in the 1 st step, the moisture content of the composite active material particles cannot be sufficiently reduced even if the drying step and the firing step are performed as described above. Further, according to the findings of the present inventors, in the case where an alkoxide solution is used in the step 1, since a hydrolysis reaction for producing a lithium ion conductive oxide is required, a large amount of water is produced and remains in the composite active material particles, and even if the drying step and the firing step as described above are performed, the amount of water in the composite active material particles cannot be sufficiently reduced. In this way, the composite active material particles obtained in step 1 contain a certain amount of water or more inside. Therefore, in manufacturing method S10, the 2 nd step is performed in addition to the 1 st step, so that moisture is appropriately removed from the composite active material particles.

That is, in the manufacturing method S10, the following features are provided: in the 2 nd step, the composite active material particles obtained in the 1 st step are vacuum-dried at a temperature of 120 ℃ to 300 ℃ for 1 hour or more.

The drying temperature in the step 2 is required to be 120 ℃ or higher. Preferably 200 ℃ or higher. If the temperature is too low, moisture cannot be effectively removed from the composite active material particles.

The drying temperature in the 2 nd step is required to be 300 ℃ or lower. Preferably 250 ℃ or lower. According to the findings of the present inventors, if the temperature is too high, crystallization of the lithium ion conductive oxide proceeds, and water may be generated from the inside of the structure as appropriate, and the water content may increase conversely. Further, if crystallization of the lithium ion conductive oxide progresses, the resistance of the composite active material particles themselves may increase.

The drying time in the 2 nd step needs to be 1 hour or more. Preferably 5 hours or more. If the drying time is too short, it is difficult to properly remove moisture from the composite active material particles. The upper limit of the drying time is not particularly limited, and is preferably 10 hours or less, for example.

In the 2 nd step, the composite active material particles need to be vacuum-dried. The vacuum drying is to extract water from the composite active material particles by reducing the pressure to 100kPa or less. Preferably 50kPa or less, more preferably 5kPa or less. The 2 nd step can be performed using, for example, a non-exposure type vacuum drying apparatus. Specifically, the drying can be carried out by various methods such as using an open vacuum dryer in a glove box, or heating in a furnace while evacuating in a closed system.

As described above, according to the production method S10, composite active material particles having a greatly reduced water content can be obtained through the 1 st step S1 and the 2 nd step S2. When the composite active material particles are applied to an all-solid lithium ion battery, the sulfide solid electrolyte can be inhibited from deteriorating due to moisture contained in the composite active material particles, and the sulfide solid electrolyte maintains high conductivity. That is, an all-solid lithium ion battery having a low battery resistance can be obtained.

5. Method for manufacturing positive electrode

Fig. 5 shows a method S20 for manufacturing the positive electrode. As shown in fig. 5, S20 includes: a step S11 of mixing the composite active material particles produced by production method S10 with a sulfide solid electrolyte to obtain a positive electrode mixture; and a step S12 of molding the positive electrode mixture.

In step S11, the composite active material particles produced by production method S10 are mixed with a sulfide solid electrolyte to obtain a positive electrode mixture. The composite active material particles and the sulfide solid electrolyte may be mixed in a dry manner, or may be mixed in a wet manner using an organic solvent (preferably, a nonpolar solvent). As described above, the positive electrode mixture may optionally contain a conductive material, a binder, and the like in addition to the composite active material particles and the sulfide solid electrolyte.

In step S12, the positive electrode mixture obtained in step S11 is molded. The positive electrode mixture may be formed in a dry form or a wet form. The positive electrode mixture may be formed separately or may be formed together with the positive electrode current collector. As described later, the positive electrode mixture may be integrally formed on the surface of the solid electrolyte layer.

More specific example of the production method S20 includes a method in which the positive electrode is produced through the following steps: the composite active material particles, the sulfide solid electrolyte, and any conductive auxiliary agent and binder are put into a solvent, and then dispersed by using an ultrasonic homogenizer or the like to prepare a slurry-like positive electrode composition, which is applied to the surface of a positive electrode current collector, followed by drying and optionally pressing. Alternatively, a positive electrode may be produced by charging a powdery positive electrode mixture into a mold or the like and press-molding the mixture in a dry manner.

6. Method for manufacturing all-solid-state lithium ion battery

Fig. 6 shows a flow of a manufacturing method S100 of the all-solid lithium ion battery. As shown in fig. 6, S100 includes step S50 of laminating the positive electrode, the solid electrolyte layer, and the negative electrode manufactured by manufacturing method S20. Thereafter, the all-solid lithium ion battery is manufactured through a step S60 in which connection of the terminals, storage in the battery case, restraint of the battery, and the like are obvious for constituting the all-solid lithium ion battery.

In step S50, a plurality of positive electrodes, solid electrolyte layers, and negative electrodes may be stacked. In step S50, the positive electrode mixture, the solid electrolyte, and the negative electrode mixture may be deposited in powder form and may be integrally formed at one time.

7. Supplement

According to the problem and means to be solved by the present application, when the composite active material is stored after the composite active material particles are produced by production method S10, the composite active material particles need to be stored so as not to be exposed to a high humidity atmosphere. After the composite active material particles are produced by the production method S10, it is necessary to produce the positive electrode and the all-solid-state lithium ion battery so that the composite active material particles are not exposed to a high humidity atmosphere. That is, it is desirable to store the composite active material particles, manufacture the positive electrode, and manufacture the all-solid lithium ion battery in a state in which moisture in the system is removed as much as possible. For example, it is considered effective to reduce the pressure in the system and replace the system with a gas containing substantially no moisture such as an inert gas in the storage step and the respective production steps.

Examples

Hereinafter, the effects of the composite active material particles of the present disclosure will be further described while showing examples.

1. Preparation of peroxide complex solution

To 870.4g of hydrogen peroxide water having a concentration of 30% by mass, 987.4g of ion-exchanged water and niobic acid (Nb)₂O₅·3H₂O，Nb₂O₅Content 72%) 44.2 g. Then, 87.9g of 28 mass% aqueous ammonia was added thereto, and the mixture was sufficiently stirred to obtain a transparent solution. To the obtained transparent solution was added lithium hydroxide monohydrate (LiOH. H)₂O)10.1g, an aqueous solution of a peroxo complex containing a lithium and niobium complex was obtained. The obtained peroxyThe molar concentrations of Li and Nb in the aqueous solution of the chemical complex were each 0.12 mol/kg.

2. Spraying and firing active material particles

Using a coating apparatus (MP-01, manufactured by パウレック Co.), positive electrode active material particles (LiNi)_1/3Mn_1/3Co_{1/ 3}O₂) 2840g of 1kg of an aqueous peroxide complex solution was sprayed to attach the aqueous peroxide complex solution to the surface of active material particles. The operating conditions were: nitrogen was used as an intake gas, the intake temperature was 120 ℃ and the intake air volume was 0.4m³The rpm was 400rpm, and the spraying speed was 4.8 g/min. After the completion of the operation, the composite active material particles were fired at 200 ℃ for 5 hours in the air to obtain composite active material particles before water removal.

3. Removal of water

3.1. Example 1

The composite active material particles were vacuum-dried at 200 ℃ for 1 hour and 5kPa or less using ガラスチューブオーブン (available from Kaita chemical Co., Ltd.) as a non-exposure type vacuum drying apparatus, and the composite active material particles were collected in a glove box (dew point-70 ℃ or less) under an Ar atmosphere without exposure to the atmospheric atmosphere.

3.2. Example 2

Moisture was removed in the same manner as in example 1 except that the vacuum drying time was set to 5 hours, and composite active material particles were collected.

3.3. Example 3

Moisture was removed in the same manner as in example 1 except that the vacuum drying time was set to 10 hours, and composite active material particles were collected.

3.4. Example 4

Moisture was removed in the same manner as in example 1 except that the vacuum drying time was set to 20 hours, and composite active material particles were collected.

3.5. Example 5

Moisture was removed in the same manner as in example 1 except that the vacuum drying temperature was 120 ℃ and the vacuum drying time was 5 hours, and composite active material particles were collected.

3.6. Example 6

The procedure was as in example 2. That is, water was removed in the same manner as in example 1 except that the vacuum drying time was set to 5 hours, and composite active material particles were collected.

3.7. Example 7

Moisture was removed in the same manner as in example 1 except that the vacuum drying temperature was 250 ℃ and the vacuum drying time was 5 hours, and composite active material particles were collected.

3.8. Example 8

Moisture was removed in the same manner as in example 1 except that the vacuum drying temperature was 300 ℃ and the vacuum drying time was 5 hours, and composite active material particles were collected.

3.9. Comparative examples 1 and 2

The composite active material particles before water removal were recovered as they were.

4. Manufacture of positive electrode and manufacture of all-solid-state lithium ion battery

4.1. Examples 1 to 4 and comparative example 1

The recovered composite active material particles and sulfide solid electrolyte (Li)₃PS₄) 3% by mass of VGCF (manufactured by Showa Denko K.K.) as a conductive material and 0.7% by mass of a butene rubber (manufactured by JSR) as a binder were put into heptane to prepare a positive electrode mixture slurry. The resulting slurry was dispersed by an ultrasonic homogenizer, coated on an aluminum foil, dried at 100 ℃ for 30 minutes, and then punched out to 1cm²To obtain a positive electrode. The volume ratio of the composite active material particles to the sulfide solid electrolyte was set to 6: 4.

A negative electrode mixture slurry was prepared by charging a negative electrode active material (lamellar carbon), a sulfide solid electrolyte, and 1.2 mass% of butene rubber into heptane. The prepared slurry was dispersed by an ultrasonic homogenizer, coated on a copper foil, dried at 100 ℃ for 30 minutes, and then punched out to 1cm²To obtain a negative electrode. The volume ratio of the negative electrode active material particles to the sulfide solid electrolyte was set to 6: 4.

Solidifying the sulfideA bulk electrolyte of 64.8mg is placed in the cross-sectional area of the inner diameter of 1cm²The cylindrical ceramic of (3) was smoothed and then pressed by 1 ton to form a solid electrolyte layer.

After a positive electrode was placed on one surface of the solid electrolyte layer and a negative electrode was placed on the other surface of the solid electrolyte layer, and the layers were pressed at 4.3 tons for 1 minute, a stainless steel rod was placed between the two electrodes, and restraint was performed at 1 ton, thereby producing an all-solid-state lithium ion battery.

4.2. Examples 5 to 8 and comparative example 2

Except using Li₃PS₄LiI instead of Li₃PS₄An all-solid lithium ion battery was produced in the same manner as described above except that the volume ratio of the active material particles to the sulfide solid electrolyte in the positive electrode and the negative electrode was set to 4:6 as the sulfide solid electrolyte.

Table 1 below shows the conditions (temperature and time) of vacuum drying, the type of sulfide solid electrolyte, and the volume ratio of active material particles to sulfide solid electrolyte for each of the examples and comparative examples.

TABLE 1

5. Evaluation of all-solid lithium ion Battery

The batteries according to examples and comparative examples were charged to a voltage of 4.55V, then discharged to 2.5V, and thereafter measured for resistance at 3.6V by an ac impedance method. In the evaluation, the resistance of the battery according to comparative example 1 was set to 100, and the resistances of the batteries according to examples 1 to 4 were normalized (to be subjected to sizing) as "resistance ratios". The resistance of the battery according to comparative example 2 was set to 100, and the resistances of the batteries according to examples 5 to 8 were normalized as "resistance ratio". The results are shown in table 2 below.

6. Moisture content measurement

The water content of each of the composite active material particles of examples and comparative examples was measured by karl fischer titration. Specifically, in a trace moisture measuring apparatus (manufactured by biogas industry), moisture released from composite active material particles was measured by flowing the moisture in a heating part set at 200 ℃ through a measuring part using nitrogen gas as a carrier gas. The measurement time was set to 40 minutes. The results are shown in table 2 below.

TABLE 2

As shown in table 2, it can be seen that: the composite active material particles according to examples 1 to 8 in which moisture was removed by vacuum drying were able to significantly reduce the amount of moisture as compared with the composite active material particles according to comparative examples 1 and 2 in which moisture was not removed. In addition, the batteries according to examples 1 to 8 had significantly lower resistance than the batteries according to comparative examples 1 and 2. The effect of vacuum drying is considered as follows. That is, by removing the moisture contained in the composite active material particles to a large extent, the deterioration of the sulfide solid electrolyte in contact with the composite active material particles in the battery due to moisture is suppressed. From this, it is considered that the conductivity of the sulfide solid electrolyte is maintained high, and as a result, the battery resistance is lowered.

7. Case of Using alkoxide solution (comparative example 3)

7.1. Preparation of alkoxide solution

An alkoxide solution was prepared using lithium ethoxide, niobium pentaethoxide, and absolute ethanol. After lithium ethoxide was dissolved and uniformly dispersed in anhydrous ethanol, niobium pentaethoxide was added so that the ratio of lithium to niobium was 1:1, and stirring was continued until uniform mixing was achieved. Here, the amount of lithium ethoxide charged was adjusted so that the solid content ratio of the solution became 6.9 wt%.

7.2. Spraying and firing active substance particles

680g of the alkoxide solution thus prepared was sprayed onto 1kg of the active material particles. The operating conditions were: the air was used as the intake gas, the intake temperature was 80 ℃ and the intake air volume was 0.3m³The rpm was 300rpm, and the spraying speed was 1.5 g/min. Run inAfter completion, the resultant was fired at 350 ℃ for 5 hours in the air to obtain composite active material particles according to comparative example 3.

7.3. Moisture content measurement

The water content of the obtained composite active material particles was measured by Karl Fischer titration method in the same manner as in examples 1 to 8 and comparative examples 1 and 2, and the water content was 1367 ppm.

As can be seen from comparative example 3, even when composite active material particles were produced using an alkoxide solution, the amount of moisture contained in the particles was large. It is considered that moisture remains in the particles due to the decomposition reaction at the time of forming the coating layer. Therefore, it is clear that even when an alkoxide solution is used, the same problem (moisture deterioration of the sulfide solid electrolyte) as that in the case of using a peroxide complex solution occurs. In this regard, it was found that the moisture content in the composite active material particles was reduced by vacuum drying as in examples 1 to 8, and the battery resistance was reduced.

Industrial applicability of the invention

The composite active material particles of the present disclosure can be used, for example, as positive electrode active material particles for all-solid lithium ion batteries. The all-solid-state lithium ion battery can be used as a large-scale power supply for vehicle mounting. In addition, the power supply can also be applied as an emergency power supply and a civil power supply.