JP6761992B2 - Electrodes and their manufacturing methods and all-solid-state lithium-ion batteries - Google Patents

Description

The present invention relates to an electrode, a method for producing the same, and an all-solid-state lithium ion battery. More specifically, the present invention relates to an electrode used in an all-solid-state lithium-ion battery having a structure in which a solid electrolyte is arranged between a pair of electrodes, a method for producing the same, and an all-solid-state lithium-ion battery.

In a lithium ion battery (hereinafter, also simply referred to as "Li ion battery"), when charging, lithium dissolves as ions from the positive electrode, moves to the negative electrode, and is stored in the negative electrode. Further, it is a secondary battery having a reaction form in which lithium ions are returned from the negative electrode to the positive electrode when discharged.
In the field of Li-ion batteries, research is underway to replace electrolytes containing flammable organic solvents with solid electrolytes for reasons such as simplification of safety devices and excellent manufacturing costs and productivity. Has been done. At the same time, the development of electrodes corresponding to the use of this solid electrolyte is underway.

Such an electrode generally has a thin layer called an active material layer laminated on the current collector. If it is a positive electrode, the active material layer contains, for example, a composite oxide capable of occluding and releasing lithium ions as a main component. Further, the active material layer is blended with a solid electrolyte, a conductive auxiliary agent and the like as necessary auxiliary components. These components affect the occlusion, release, and electron transfer of lithium ions in the active material layer, and greatly affect the charge / discharge characteristics of the battery. Therefore, there is a demand for an electrode in which the distribution state and contact state of each component in the active material layer are more highly controlled, and a method for forming such an electrode.

Japanese Patent Publication No. 2014-534592 Japanese Patent Publication No. 2014-535141

Various methods for forming the active material layer in the above electrodes have been proposed, and among them, the above-mentioned main components and sub-components are adjusted to a dispersion liquid such as a paste or a slurry via a solvent, and the dispersion is performed. A method of forming an active material layer using a liquid is known. For example, in the method of slurrying and applying the dispersion liquid, a binder must be added in order to attach the dispersoid to the carrier, and as a result, the above-mentioned main component and sub-components that can be mixed in the dispersion liquid are mixed. The ratio is reduced, which causes a deterioration in electrical characteristics.
Further, in this method, since each component is uniformly distributed over the entire obtained layer, a desired component cannot be arbitrarily and locally arranged, and such an active material layer can be obtained. There is a problem that it cannot be done.
Patent Document 1 and Patent Document 2 disclose a method of depositing these materials on the surface of a conductive substrate by electrophoresis using a suspension containing an anode material, a solid electrolyte material, a cathode material, and the like. Has been done. However, the local arrangement of each component in the electrode has not been studied.

The present invention has been made in view of the above problems, and uses an electrode formed by controlling the distribution of each component such as an active material and a solid electrolyte, a method for producing the electrode, and the electrode. It is an object of the present invention to provide an all-solid-state lithium-ion battery.

The present invention is as follows.
The electrode according to claim 1 is the electrode used in an all-solid-state lithium ion battery having a structure in which a solid electrolyte is arranged between a pair of electrodes.
The gist is to include an active material layer containing an active material as a main component and a solid electrolyte layer containing a solid electrolyte as a main component.
The electrode according to claim 2 is the electrode according to claim 1, which has a laminated structure in which the solid electrolyte layer is interposed between the layers of the active material layer and the two layers of the solid electrolyte layer. The gist is to have at least one of the laminated structures in which the active material layer is interposed between the layers.
The gist of the electrode according to claim 3 is that the solid electrolyte layer is formed thinner than the active material layer in the electrode according to claim 1 or 2.
The electrode according to claim 4 is the electrode according to any one of claims 1 to 3, wherein both the active material layer and the solid electrolyte layer contain a conductive auxiliary agent.
The electrode according to claim 5 is the electrode according to any one of claims 1 to 4, wherein the solid electrolyte is a sulfide solid electrolyte.
The gist of the electrode according to claim 6 is that the electrode according to any one of claims 1 to 5 is a positive electrode.

The method for producing an electrode according to claim 7 includes a deposition step of depositing the particles on a conductive surface of a base material by electrophoresis in a liquid containing particles.
The gist is to use a signal having an asymmetric waveform on the positive electrode side and the negative electrode side as the signal of the applied voltage in the electrophoresis of the deposition step.
The method for manufacturing an electrode according to claim 8 is the method for manufacturing an electrode according to claim 1.
A first deposition step of depositing the active material on the conductive surface of the base material to form the active material layer by electrophoresis in the active material-containing liquid containing the active material is provided.
The gist is to use a signal having an asymmetric waveform on the positive electrode side and the negative electrode side as the signal of the voltage to be applied in the electrophoresis in the first deposition step.
The method for manufacturing an electrode according to claim 9 is the method for manufacturing an electrode according to claim 1.
By electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or its precursor, the solid electrolyte and / or its precursor is deposited on the conductive surface of the base material, and the solid electrolyte layer or its precursor is deposited. With a second deposition step to form the body layer
The gist is to use a signal having an asymmetric waveform on the positive electrode side and the negative electrode side as the signal of the voltage to be applied in the electrophoresis of the second deposition step.
The electrode manufacturing method according to claim 10 is the electrode manufacturing method according to any one of 7 to 9, wherein the signal is a signal in which the absolute value of the peak differs between the positive electrode side and the negative electrode side. Is the gist.
The method for manufacturing an electrode according to claim 11 is the method for manufacturing an electrode according to any one of 7 to 9, wherein the signal is a signal having different application times on the positive electrode side and the negative electrode side. And.
The electrode manufacturing method according to claim 12 is the electrode manufacturing method according to claim 5.
A first deposition step of depositing the active material on the conductive surface of the base material to form the active material layer by electrophoresis in the active material-containing liquid containing the active material is provided.
The gist is that the active material-containing liquid contains a diether compound and / or a carbonyl compound.
The method for manufacturing an electrode according to claim 13 is the method for manufacturing an electrode according to claim 12, as a pre-step or post-step of the first deposition step.
By electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or its precursor, the solid electrolyte and / or its precursor is deposited on the conductive surface of the base material, and the solid electrolyte layer or its precursor is deposited. With a second deposition step to form the body layer
The gist is that the solid electrolyte is a sulfide solid electrolyte.
The method for manufacturing an electrode according to claim 14 is the method for manufacturing an electrode according to claim 12 or 13, wherein the positive electrode side and the negative electrode side are used as signals of the voltage to be applied in the electrophoresis in the first deposition step. The gist is to use a signal having an asymmetric waveform.

It is a gist that the all-solid-state lithium ion battery according to claim 15 includes the electrode according to any one of claims 1 to 6.

The electrode of the present invention includes an active material layer containing an active material as a main component and a solid electrolyte layer containing a solid electrolyte as a main component. That is, it is an electrode formed by controlling the distribution of each component of the active material and the solid electrolyte in a layered manner. With this configuration, any layer structure can be introduced into the active material layer. Therefore, it is possible to realize a structure in which the ion movement path from the active material layer to the solid electrolyte layer is designed in advance.
Among the methods for producing an electrode of the present invention, the first method comprises a deposition step of depositing particles on a conductive surface of a base material by electrophoresis in a liquid containing particles, and in the electrophoresis of the deposition step, This is a method of using a signal having an asymmetric waveform on the positive electrode side and the negative electrode side as the signal of the applied voltage. This makes it possible to more highly control the movement of particles in the liquid during electrophoresis.
In the second method of producing the electrode of the present invention, the active material is deposited on the conductive surface of the base material by electrophoresis in an active material-containing liquid containing the active material to form an active material layer. This is a method in which a first deposition step is provided, and in the electrophoresis of the first deposition step, a signal having an asymmetric waveform on the positive electrode side and the negative electrode side is used as a signal of the voltage to be applied. This makes it possible to more highly control the movement of the active material in the active material-containing liquid during electrophoresis.
Among the methods for producing an electrode of the present invention, the third method is to apply the solid electrolyte and / or to the conductive surface of the base material by electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or its precursor. It is provided with a second deposition step of depositing the precursor to form the solid electrolyte layer or the precursor layer thereof, and is asymmetric between the positive electrode side and the negative electrode side as a signal of the voltage to be applied in the electrophoresis of the second deposition step. This is a method using a signal having a waveform. As a result, the movement of the solid electrolyte and / or its precursor in the solid electrolyte-containing liquid during electrophoresis can be controlled to a higher degree.
In the fourth method of producing the electrode of the present invention, the active material is deposited on the conductive surface of the base material by electrophoresis in an active material-containing liquid containing the active material to form an active material layer. The active material-containing liquid is a method containing a diether compound and / or a carbonyl compound. As a result, when the active material layer is formed on the surface of the solid electrolyte layer, erosion of the solid electrolyte layer can be prevented, and the active material layer and the solid electrolyte layer can be more reliably laminated.
The all-solid-state lithium-ion battery of the present invention includes the electrodes of the present invention. The all-solid-state lithium-ion battery can be charged and discharged by using the electrode having this new configuration.

It is explanatory drawing explaining this all-solid-state lithium ion battery and an electrode. It is explanatory drawing explaining an example of the signal which has the asymmetric waveform on the positive electrode side and the negative electrode side. It is explanatory drawing explaining another example of the signal which has the asymmetric waveform on the positive electrode side and the negative electrode side. It is explanatory drawing explaining another example of the signal which has the asymmetric waveform on the positive electrode side and the negative electrode side. It is explanatory drawing explaining another example of the signal which has the asymmetric waveform on the positive electrode side and the negative electrode side. It is explanatory drawing explaining another example of the signal which has the asymmetric waveform on the positive electrode side and the negative electrode side. It is explanatory drawing explaining an example of the deposition form of a particle. It is explanatory drawing explaining another example of the deposition form of a particle. It is explanatory drawing explaining the morphology which deposited different kinds of particles alternately. It is a graph which shows the correlation between the coverage and frequency which concerns on Example 1. FIG. It is an enlarged image which shows the cross section of the electrode which concerns on Example 3. FIG. It is explanatory drawing explaining the all-solid-state lithium ion battery which concerns on Example 4. FIG. It is explanatory drawing explaining the jig which concerns on Example 4. FIG.

Hereinafter, the present invention will be described in detail with reference to the drawings.
[1] Electrode The electrode (2) of the present invention is an electrode (1) used for an all-solid-state lithium ion battery (1) having a structure in which a solid electrolyte body (3) is arranged between a pair of electrodes (2a, 2b). 2).
The electrode (2) is characterized by including an active material layer (21) containing an active material as a main component and a solid electrolyte layer (22) containing a solid electrolyte as a main component (see FIG. 1).

The active material layer 21 and the solid electrolyte layer 22 are usually laminated so as to be in contact with each other on their main surfaces. High conductivity of Li ions can be obtained by contacting each other with wide surfaces.
Further, although the electrode including the active material layer 21 and the solid electrolyte layer 22 may be obtained in any way, it can be obtained by using electrophoresis as described later. In this case, the active material layer 21 and the solid electrolyte layer 22 are laminated on the conductive surface 251 of the base material 25 having a conductive surface (conductive surface).
Further, in that case, which of the active material layer 21 and the solid electrolyte layer 22 may be in contact with the conductive surface 251 is preferably brought into contact with the conductive surface 251. That is, the electrode has a structure in which the active material layer 21 and the solid electrolyte layer 22 are laminated in this order on the conductive surface 251 of the base material 25 (see FIG. 1).

The specific laminated form in the electrode 2 is not particularly limited, but one of the active material layer 21 and the solid electrolyte layer 22 may be sandwiched between the other layers. preferable. Therefore, it is preferable to provide two or more layers of at least one of the active material layer 21 and the solid electrolyte layer 22.
That is, the electrode 2 has (1) a laminated structure in which the solid electrolyte layer 22 is interposed between the two layers of the active material layer 21, and (2) the active material layer 21 is interposed between the layers of the two solid electrolyte layers 22. It is preferable to have at least one of the laminated structures obtained. These laminated structures may include only one of them, but may include both laminated structures. The case where both laminated structures are provided means that the active material layer 21 having two or more layers and the solid electrolyte layer 22 having two or more layers are alternately laminated to have a laminated structure. As described above, by having the sandwich-like laminated structure, more excellent Li ion conductivity can be obtained as compared with the case where the sandwich-shaped laminated structure is not provided.
The number of layers of the active material layer 21 and the solid electrolyte layer 22 is not particularly limited, but may be, for example, one layer or more and 50 layers or less, respectively. The number of layers is preferably 2 or more and 25 or less, and more preferably 2 or more and 10 or less.

Further, the active material layer 21 and the solid electrolyte layer 22 may be laminated with the same thickness, but can be laminated with different thicknesses. In this case, it is preferable to form the solid electrolyte layer 22 thinner than the active material layer 21. In this way, when the solid electrolyte layer 22 is thinned with respect to the active material layer 21, the distance between the laminated active material layers is larger than that when the solid electrolyte layer 22 is thickened with respect to the active material layer 21. By reducing the size, the electron conductivity (conductivity) in the vertical direction can be improved. The ratio of the thickness of the active material layer 21 (D ₂₁ ) to the thickness of the solid electrolyte layer 22 (D ₂₂ ) (D ₂₂ / D ₂₁ ) is not limited, but is, for example, 0.05 or more and 0.4. It can be as follows. This ratio (D ₂₂ / D ₂₁ ) is further preferably 0.05 or more and 0.3 or less, and more preferably 0.05 or more and 0.2 or less.
The specific thickness of each layer is not limited, but for example, the thickness D ₂₁ of the active material layer 21 can be 0.05 μm or more and 15 μm or less. The thickness (D ₂₁ ) is further preferably 1 μm or more and 8 μm or less, and more preferably 4 μm or more and 6 μm or less. Similarly, for example, the thickness D ₂₂ of the solid electrolyte layer 22 can be 0.25 μm or more and 5 μm or less. The thickness (D ₂₂ ) is further preferably 0.25 μm or more and 1.5 μm or less, and more preferably 0.25 μm or more and 0.5 μm or less.
The thickness of the active material layer 21 (D ₂₁ ) and the thickness of the solid electrolyte layer 22 (D ₂₂ ) shall be measured in an image in which the cross section of the electrode is magnified 10,000 times by an electron microscope. Specifically, the average value of the actual dimensions measured at five different points of each layer is defined as the thickness D ₂₁ or the thickness D ₂₂ .

The active material layer 21 is a layer containing an active material as a main component. The fact that the active material is the main component means that the active material is contained in an amount of 50% by mass or more when the entire active material layer 21 is 100% by mass. This ratio is preferably 50% by mass or more and 100% by mass or less, and can be 60% by mass or more and 98% by mass or less, and further 70% by mass or more and 95% by mass or less.
Examples of other components other than the active material that can be contained in the active material layer include solid electrolytes and conductive aids. By containing these components, a conduction path for Li ions (due to a solid electrolyte) and an electron conduction path (due to a conductive aid) can be formed in the electrode.
Only one of these other components may be used, or two or more thereof may be used in combination. When other components are contained, assuming that the entire active material layer 21 is 100% by mass, the content ratio of the other components is 50% by mass or less. This content ratio can be 2% by mass or more and 40% by mass or less, and further can be 5% by mass or more and 30% by mass or less.
The solid electrolyte and the conductive auxiliary agent will be described later.

The active material is a substance capable of inserting and removing lithium ions, or alloying and dealloying. Among the active materials, as the active material for the positive electrode (hereinafter, also simply referred to as “positive electrode active material”), a composite oxide containing lithium capable of inserting and removing lithium ions can be used.
Specific examples thereof include lithium composite oxides such as LiMO ₂ , Li ₂ MO ₃ and LiM ₂ O ₄ , and lithium composite oxides in which these are mixed. However, the above-mentioned "M" is one kind of metal element selected from at least Co, Ni and Mn among Co, Ni, Mn and Al.

Among the above, the LiMO ₂ type lithium double oxides include LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , Li ₂ MnO ₃ , and Li (Ni _x Co _1-x ) O ₂ {however, 0 <x <1. .. For example, Li (Ni _0.8 Co _0.2 ) O ₂ etc.}, Li (Ni _x Mn _1-x ) O ₂ {However, 0 <x <1. For example, Li (Ni _0.5 Mn _0.5 ) O ₂ etc.}, Li (Ni _x Mn _y Co _1-x-y ) O ₂ {However, x> 0, y> 0, x + y <1. For example, Li (Ni _1/3 Mn _1/3 Co _1/3 ) O ₂ etc.}, Li (Ni _x Co _y Al _1-xy ) O ₂ {However, x> 0, y> 0, x + y < It is 1. For example, Li (Ni _0.8 Co _0.15 Al _0.05 ) O ₂ etc.} and the like can be mentioned. Only one of these may be used, or two or more thereof may be used in combination.
Among the above, as LiM ₂ O ₄ type lithium double oxides, LiCo ₂ O ₄ , LiNi ₂ O ₄ , LiMn ₂ O ₄ , Li (Co _x Ni _2-x ) O ₄ {However, 0 < x <2}, Li (Co _x Mn _2-x ) O ₄ {However, 0 <x <2}, Li (Al _x Mn _2-x ) O ₄ {However, 0 <x <2 Yes}, Li (Mn _x Ni _2-x ) O ₄ {However, 0 <x <2. For example, Li (Mn _1.5 Ni _0.5 ) O ₄ etc.} and the like can be mentioned. Only one of these may be used, or two or more thereof may be used in combination.
Among the above, LiMO type ₂ lithium double oxide is preferable, and Li (Ni _x Mn _y Co _1-x-y ) O ₂ {however, x> 0, y> 0, x + y <1. } (Hereinafter, also simply referred to as "NMC") is preferable.

Among the active materials, the active material for the negative electrode (hereinafter, also simply referred to as “negative electrode active material”) includes carbon-based materials (carbon-based materials as the negative electrode active material), various oxides, magnesium compounds, tin compounds, and antimony compounds. , Metallic lithium and the like can be used.
Among these, examples of carbon-based materials include graphite, graphene, carbon black, carbon nanotubes, and lithium carbon compounds (Li _x C ₆ ). Examples of the oxide include SiO, SnO, SnO ₂ , TiO ₂ , Nb ₂ O ₅ , WO ₂ , MoO ₂ , Li ₄ Ti ₅ O _{12 and the} like. Examples of the magnesium compound include Mg ₂ Si, Mg ₂ Ge, Mg ₂ Sn and the like. The tin _{compounds, SbSn, SnS 2, CoSn 2} , Ni 3 Sn 2, Cu 6 Sn 5, Ag 3 Sn, LaSn 3, La 3 Co 2 Sn 7, V 2 Sn 3 FeSn 2 , and the like. Examples of the antimony compound include SbSn, Ag ₃ Sb, CeSb ₃ , CoSb ₃ , InSb, Ni ₂ MnSb and the like. Only one of these may be used, or two or more thereof may be used in combination.

Further, the active material contained in the active material layer 21 can be made granular. That is, a granular active material (hereinafter, also simply referred to as “granular active material”) can be used. The particle size of the granular active material is not particularly limited, but it is preferable to simultaneously contain at least two kinds of granular active materials having different particle sizes, that is, a larger diameter granular active material and a smaller diameter granular active material. As a result, both the filling property and the smoothness of the active material layer 21 can be achieved at the same time. More specifically, a granular active material (large diameter active material) having a particle size of more than 0.5 μm and 10 μm or less and a spherical granular active material having a particle size of 1 nm or more and 500 nm or less (a large diameter active material). Small diameter active material) and preferably.

The solid electrolyte layer 22 is a layer containing a solid electrolyte as a main component. The fact that the solid electrolyte is the main component means that the solid electrolyte layer 22 contains 50% by mass or more when the entire solid electrolyte layer 22 is 100% by mass. This ratio is preferably 50% by mass or more and 100% by mass or less, and can be 60% by mass or more and 98% by mass or less, and further 70% by mass or more and 95% by mass or less.
Examples of components other than the solid electrolyte that can be contained in the solid electrolyte layer include active materials and conductive auxiliaries. Only one of these other components may be used, or two or more thereof may be used in combination. When other components are contained, assuming that the entire solid electrolyte layer 22 is 100% by mass, the content ratio of the other components is 50% by mass or less. This content ratio can be 2% by mass or more and 40% by mass or less, and further can be 5% by mass or more and 30% by mass or less.
The active material is as described above. The conductive auxiliary agent will be described later.

A solid electrolyte is a substance that can be a conduction path for Li ions. Specifically, Li _1.07 Al _0.69 Ti _1.46 (PO ₄ ) ₃ , Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ , Li _3.25 Ge _0.25 P _{0.75 S 4, Li 10 GeP 2} S 12, Li 6 PS 5 Cl, 30Li 2 S · 26B 2 S 3 · 44LiI, 63Li 2 S · 36SiS 2 · 1Li 3 PO 4, 57Li 2 S · 38SiS 2 · 5Li ₄ SiO ₄ , 70Li ₂ S / 30P ₂ S ₅ , 50Li ₂ S / 50GeS ₂ , Li _3.25 P _0.95 S ₄ , Li _3.25 Ge _0.25 P _0.75 S ₄ , Li ₃ PS ₄ , Li ₄ P ₃ S ₁₁ , Li ₇ P ₃ S _{11, and} other sulfide solid electrolytes. Only one of these may be used, or two or more thereof may be used in combination.
In addition, La _0.5 Li _0.5 TiO ₃ , La _0.51 Li _0.34 TiO _2.94 , Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ , Li ₇ La ₃ Zr ₂ O ₁₂ , Li ₅ La ₃ Nb ₂ O ₁₂ , 50Li ₄ SiO ₄・ 50Li ₃ BO ₃ , Li _2.9 PO _3.3 N _0.46 , Li _3.6 Si _0.6 P _0.4 O ₄ etc. Non-sulfide solid electrolytes can be mentioned. Only one of these may be used, or two or more thereof may be used in combination.

Of these, sulfide solid electrolytes are preferred. Further, a sulfide glass solid electrolyte or a non-crystalline sulfide solid electrolyte of a sulfide glass ceramic solid electrolyte is more preferable. The non-crystalline sulfide solid _{electrolyte, 30Li 2 S · 26B 2 S} 3 · 44LiI, 63Li 2 S · 36SiS 2 · 1Li 3 PO 4, 57Li 2 S · 38SiS 2 · 5Li 4 SiO 4, 70Li 2 S · 30P ₂ S ₅ , 50Li ₂ S / 50GeS ₂ , Li _3.25 P _0.95 S ₄ , Li _3.25 Ge _0.25 P _0.75 S ₄ , Li ₃ PS ₄ , Li ₄ P ₃ S ₁₁ , Examples thereof include Li ₇ P ₃ S ₁₁ .
Among these, further, Li, include the elements of P and S, noncrystalline sulfide solid electrolyte containing PS ₄ bond. Examples of such sulfide solid electrolytes include Li ₃ PS ₄ , Li ₄ P ₃ S ₁₁ , Li ₇ P ₃ S ₁₁ , 70 Li ₂ S / 30 P ₂ S ₅ , Li _3.25 P _0.95 S _{4 and the} like. Can be mentioned. Only one of these may be used, or two or more thereof may be used in combination.

The form of the solid electrolyte contained in the solid electrolyte layer 22 is not particularly limited, but may be granular. That is, a granular solid electrolyte (hereinafter, also simply referred to as “granular solid electrolyte”) can be used. The particle size of the granular solid electrolyte is not particularly limited, but at least two kinds of granular solid electrolytes having different particle sizes, that is, a larger diameter granular solid electrolyte and a smaller diameter granular solid electrolyte, can be simultaneously contained. As a result, both the filling property and the smoothness of the solid electrolyte layer 22 can be achieved at the same time. More specifically, a granular solid electrolyte (large-diameter solid electrolyte) having a particle size of more than 0.5 μm and 10 μm or less and a spherical solid electrolyte having a particle size of 1 nm or more and 500 nm or less (a spherical solid electrolyte). Small diameter solid electrolyte) and preferably.

A conductive auxiliary agent is a substance that can be an electron conduction path. Specifically, a powdery substance having conductivity is preferable. The material constituting such a conductive auxiliary agent is not particularly limited, and examples thereof include carbon-based materials (carbon-based materials as conductive auxiliary agents), metals, metal compounds, and the like, and among them, carbon-based materials are preferable. Examples of the carbon-based material include graphite, graphene, carbon black, carbon nanotubes and the like.

When the electrode of the present invention is a positive electrode and contains a conductive auxiliary agent, it may be contained in only one of the active material layer 21 and the solid electrolyte layer 22, but in both layers. It is preferably contained.
When the active material layer 21 contains a conductive auxiliary agent, and the total amount of the active material layer 21 is 100% by mass, the content ratio of the conductive auxiliary agent is preferably 0.1% by mass or more and 35% by mass or less. More preferably, it is 1% by mass or more and 25% by mass or less.
Similarly, when the solid electrolyte layer 22 contains a conductive auxiliary agent and the total content of the solid electrolyte layer 22 is 100% by mass, the content ratio of the conductive auxiliary agent is 0.1% by mass or more and 35% by mass. The following is preferable, and 1% by mass or more and 25% by mass or less is more preferable.

[2] Electrode manufacturing method In an electrode of an all-solid-state lithium-ion battery, particularly an electrode having a laminated structure in which an active material layer and a solid electrolyte layer are laminated as described above, a target component (active material, solid electrolyte, etc.) ) (Hereinafter, simply referred to as “target particles”) can be deposited in substantially a single layer (a very thin layer as a whole even if it is partially multi-layered) (specifically, particles). It is preferable that the particles can be deposited with a thickness of 1 or more and 3 or less, and more preferably 1 or more and 2 or less of the particles can be deposited). This is because it is considered that the active material layer in the electrode and the solid electrolyte layer can be brought into close contact with each other by depositing thinly, and excellent electrode characteristics can be obtained. That is, the number of layers can be increased within the same thickness, whereby the contact area between the active material and the solid electrolyte can be increased.
However, when electrophoresis is performed using a DC voltage, target particles are deposited in an extremely short time, and a thick sedimentary layer is formed. That is, instead of a deposited layer in which the target particles are laminated in a substantially single layer, a deposited layer in which a plurality of target particles are stacked is formed. On the other hand, by lowering the current density of the applied DC voltage, it is possible to suppress the deposition rate and make the film thickness control easier, but the surface roughness of the obtained deposited layer becomes large. That is, in electrophoresis using a DC voltage, there is a trade-off relationship between the thickness of the obtained deposited layer and the surface roughness, and the film is a substantially single layer having both the film thickness and the surface roughness and the surface roughness is small. It turned out to be difficult to obtain a sedimentary layer.

Therefore, the present inventors tried to use an AC voltage in electrophoresis. As a result, it was found that the surface roughness of the obtained sedimentary layer can be suppressed while reducing the deposition rate. However, it has been found that the use of AC voltage reduces the deposition rate excessively. Then, it was found that there is a problem that a film thickness higher than a certain level cannot be formed even if the precipitation time is extended.
Therefore, the present inventors have attempted to use both a DC voltage and an AC voltage in combination. As a result, it was found that the deposition rate can be controlled within a practical range, the surface roughness can be suppressed, and a deposition layer having a desired film thickness can be obtained.
In this way, the combined use of the DC voltage and the AC voltage causes a bias to be applied to the AC signal having a symmetric waveform on the positive side and the negative side, and as a result, the asymmetric waveform on the positive side and the negative side. A signal having (hereinafter, also simply referred to as “asymmetric waveform”) (hereinafter, also simply referred to as “asymmetric signal”) is formed (see FIGS. 2 to 6). In this way, by using the applied voltage having an asymmetric signal, it is possible to suppress the surface roughness and obtain a deposited layer having a desired film thickness while controlling the deposition rate within a practical range as described above. I found that I could do it.

That is, the electrode manufacturing method of the present invention includes the following three electrode manufacturing methods.
(1) A method for manufacturing a first electrode, which uses an asymmetric signal as an applied voltage signal in electrophoresis in a deposition process for depositing particles.
(2) A method for manufacturing a second electrode using an asymmetric signal as an applied voltage signal in electrophoresis in the first deposition step of forming an active material layer.
(3) A method for manufacturing a third electrode, which uses an asymmetric signal as an applied voltage signal in electrophoresis in a second deposition step for forming a solid electrolyte layer.

(1) Method for manufacturing the first electrode In this method for manufacturing the first electrode (hereinafter, also simply referred to as “first manufacturing method”), the conductive surface of the base material is subjected to electrophoresis in a liquid containing particles. It is characterized by comprising a deposition step of depositing the particles, and using a signal having an asymmetric waveform on the positive electrode side and the negative electrode side as a signal of the voltage to be applied in the electrophoresis of the deposition step.

The "deposition step" is a step of depositing particles on the conductive surface of a base material by electrophoresis in a liquid containing particles (hereinafter, simply referred to as "particle-containing liquid").
Here, the above-mentioned "base material" has a conductive surface for depositing particles, and functions as a support for the resulting deposited layer of particles (hereinafter, also simply referred to as "deposited layer"). It is something to do.

The material of the base material is not particularly limited, and a conductive material capable of forming a conductive surface can be widely used. Examples of the conductive material include gold, platinum, indium, copper, zinc, nickel, tin, aluminum, stainless steel, alloys of these metals, and a conductive compound (ITO) containing these metals. Only one of these may be used, or two or more thereof may be used in combination. When two or more types are used in combination, they can be stacked and used.
The form of the conductive material is not particularly limited, and for example, a plate-like body, a foil-like body, a mesh-like body, or the like can be appropriately used. Only one of these may be used, or two or more thereof may be used in combination.
That is, for example, as the base material, the plate-like body made of the above-mentioned conductive material can be used as it is. Further, a composite in which the surface of a plate-like body made of a non-conductive material (resin or the like) is coated with the foil-like body made of the above-mentioned conductive material can be used as a base material as a whole.
This base material can be used as it is as a current collector in an all-solid-state lithium-ion battery.

The above-mentioned "particle-containing liquid" is usually a dispersion liquid containing dispersed particles. The state of the dispersion liquid is not particularly limited, and may be any of suspension (suspension), emulsion, colloidal liquid and the like.
The particles that are the dispersoids in this dispersion are particles that can be deposited on the conductive surface of the base material by electrophoresis. The material constituting such particles is not particularly limited, and various components blended in the electrode can be granulated so as to be electrophoretic and used as appropriate. Specific examples thereof include the above-mentioned active material (particles made of active material), solid electrolyte (particles made of solid electrolyte), conductive auxiliary agent (particles made of conductive auxiliary agent), and the like. Only one of these may be used, or two or more thereof may be used in combination.

The grain shape of the particles is not particularly limited, and includes substantially spherical shape, granule shape (shape in which smaller particles are gathered together), lump shape, flake shape (scale shape), needle shape, indefinite shape, wire shape, tube shape, and the like. Be done. Only one of these may be used, or two or more thereof may be used in combination.
The particle size (maximum length) of the particles is not particularly limited, but is usually 7 μm or less. Electrophoresis may be performed on particles having a particle size of more than 7 μm using an applied voltage having an asymmetric signal, but it is difficult to obtain the effect of using the asymmetric signal for particles having such a large particle size. That is, for example, it is possible to form a single-layer film relatively easily by using only a DC voltage.
On the other hand, for particles having a particle size of 7 μm or less (particularly 4 μm or less), as the particle size becomes smaller, electrophoresis using only DC voltage or normal AC voltage (that is, positive electrode side and negative electrode side) Electrophoresis using a voltage having a signal having a symmetrical waveform makes it difficult to form a monolayer film. On the other hand, by using an asymmetric signal, it becomes possible to increase the deposition rate of particles and obtain good dispersibility of particle arrangement (particles do not stack).
For this reason, the particles of the particle-containing liquid preferably contain particles having a particle size of 7 μm or less, more preferably 4 μm or less, and particularly preferably 1 μm or less. The smaller the particle size, the more effective the use of an asymmetric signal can be obtained. Therefore, the lower limit of the particle size is not particularly limited, but can be, for example, 50 nm.

On the other hand, the dispersion medium constituting the particle-containing liquid is not particularly limited, and various liquids can be used, but at least one of a diether compound, a carbonyl compound, an alcohol compound, and a saturated fatty acid ester compound is contained. It is preferable to use a dispersion medium. Only one type of these dispersion media may be used, or two or more types may be used in combination.
Among these, examples of the diether compound include 1,2-dimethoxyethane (DME), 1,2-diethoxyethane, 1-ethoxy-2-methoxyethane and the like. Only one of these may be used, or two or more thereof may be used in combination. Of these, 1,2-dimethoxyethane is particularly preferable.
Examples of the carbonyl compound include methyl ethyl ketone (MEK), acetone, diethyl ketone, 2-pentanone and the like. Only one of these may be used, or two or more thereof may be used in combination. Further, examples of the alcohol compound include isopropyl alcohol (IPA), methanol, ethanol, butanol and the like. Only one of these may be used, or two or more thereof may be used in combination. Examples of the saturated fatty acid ester compound include methyl propionate, ethyl propionate, propyl propionate, butyl propionate and the like. Only one of these may be used, or two or more thereof may be used in combination.

The concentration of the particles contained in the particle-containing liquid is not particularly limited, but when the total of the particles (dispersant) and the dispersion medium is 100% by mass, the content ratio of the particles is 0.1% by mass or more and 30% by mass. It can be less than or equal to%. This ratio is preferably 0.5% by mass or more and 25% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and particularly preferably 1.5% by mass or more and 15% by mass or less.

Further, the voltage applied in this electrophoresis has a signal having an asymmetric waveform on the positive electrode side and the negative electrode side (see FIGS. 2 to 6). Having an asymmetrical waveform between the positive electrode side and the negative electrode side means that the signal waveform on the positive electrode side with 0V as the boundary and the signal waveform on the negative electrode side with 0V as the boundary are not symmetrical. .. That is, specific examples of the asymmetric signal include (1) a signal in which the absolute value of the peak differs between the positive electrode side and the negative electrode side, and (2) a signal in which the application time differs between the positive electrode side and the negative electrode side. As a matter of course, a signal in which the absolute value of the peak differs between the positive electrode side and the negative electrode side and the application time differs between the positive electrode side and the negative electrode side is also included.

Such an asymmetric signal may be formed in any way. That is, the asymmetric signal may be appropriately designed, or may be formed by superimposing a DC voltage and an AC voltage. When the DC voltage and the AC voltage are superimposed, the signal of one kind of frequency may be used as the signal of the AC voltage, or the signal of two kinds of different frequencies may be used in combination.
As the asymmetric signal, for example, the form of the signal shown in FIGS. 2 to 7 can be mentioned. Only one type of these asymmetric signals may be used, or two or more types may be used in combination.

Of the above, in the asymmetric signal of FIG. 2, the positive electrode side peak absolute value (V ₊ ) and the negative electrode side peak absolute value (V ₋ ) are different, and the positive electrode side application time (T ₊ ) and the negative electrode side application time (T ₋ ) are different. ) Is the same as an asymmetric signal formed by a triangular wave. Such an asymmetric signal can be formed, for example, by biasing a triangular wave symmetric signal (AC signal) toward the positive electrode side. That is, it can be formed by superimposing an AC voltage and a DC voltage.
In the asymmetric signal of FIG. 3, the positive electrode side peak absolute value (V ₊ ) and the negative electrode side peak absolute value (V ₋ ) are different, and the positive electrode side application time (T ₊ ) and the negative electrode side application time (T ₋ ) are different. It is an asymmetric signal formed by a square wave. This square wave has a signal form in which a constant peak absolute value (V ₊ or V ₋ ) is maintained for a certain period of time on both the positive electrode side and the negative electrode side.
In the asymmetric signal of FIG. 4, the positive electrode side peak absolute value (V ₊ ) and the negative electrode side peak absolute value (V ₋ ) are different, and the positive electrode side application time (T ₊ ) and the negative electrode side application time (T ₋ ) are different. It is an asymmetric signal formed by a triangular wave.
In the asymmetric signal of FIG. 5, the positive electrode side peak absolute value (V ₊ ) and the negative electrode side peak absolute value (V ₋ ) are different, and the positive electrode side application time (T ₊ ) and the negative electrode side application time (T ₋ ) are different. It is an asymmetric signal represented by a parabola.
In the asymmetric signal of FIG. 6, the positive electrode side peak absolute value (V ₊ ) and the negative electrode side peak absolute value (V ₋ ) are different, and the positive electrode side application time (T ₊ ) and the negative electrode side application time (T ₋ ) are different. It is an asymmetric signal formed by a square wave. This rectangular wave has a signal form in which the applied voltage increases with time on both the positive electrode side and the negative electrode side, and at the same time, it instantly switches to a reverse electric field after passing through the peak top.
In the electrode manufacturing method of the present invention, not only these asymmetric signal forms but also various asymmetric signals can be used.

For the asymmetric signal, the absolute value of the peak on the positive electrode side (amplitude from 0V to the peak end) is V _+, and the absolute value of the peak on the negative electrode side (amplitude from 0V to the peak end) is V ₋ (Fig. 2 to FIG. 6), the ratio (V ₊ / V ₋ ) is preferably 0.02 ≦ V ₊ / V ₋ ≦ 50. In this range, the effect of using signals having different absolute peak values on the positive electrode side and the negative electrode side can be obtained particularly well.
This ratio (V ₊ / V ₋ ) is more preferably 1 <V ₊ / V ₋ ≦ 50, further preferably 1.01 ≦ V ₊ / V ₋ ≦ 30, especially when the action of migrating to the positive electrode side is strengthened. , 1.3 ≤ V ₊ / V ₋ ≤ 10 is particularly preferable, and 1.5 ≤ V ₊ / V ₋ ≤ 5 is particularly preferable.
On the contrary, when the action of migrating to the negative electrode side is particularly strengthened, 0.02 ≦ V ₊ / V ₋ <1 is more preferable, 0.03 ≦ V ₊ / V ₋ ≦ 0.99 is further preferable, and 0.1. ≦ _V + / _{V -} ≦ 0.7 is particularly preferred, 0.2 ≦ _V + / _{V -} particularly preferably ≦ 0.5.

Further, the application time on the positive electrode side (time indicating the amplitude toward the positive electrode side with reference to 0V) is defined as T _+, and the application time on the negative electrode side (time indicating the amplitude toward the negative electrode side with reference to 0V) is defined as T _+. Assuming T ₋ (see FIGS. 2 to 6), the ratio (T ₊ / T ₋ ) is preferably 0.02 ≦ T ₊ / T ₋ ≦ 50. In this range, the effect of using signals having different application times on the positive electrode side and the negative electrode side can be obtained particularly well.
This ratio (T ₊ / T ₋ ) is more preferably 1 <T ₊ / T ₋ ≦ 50, further preferably 1.01 ≦ T ₊ / T ₋ ≦ 30, especially when the action of migrating to the positive electrode side is strengthened. , 1.3 ≤ T ₊ / T ₋ ≤ 10 is particularly preferable, and 1.5 ≤ T ₊ / T ₋ ≤ 5 is particularly preferable.
On the contrary, when the action of migrating to the negative electrode side is particularly strengthened, 0.02 ≦ T ₊ / T ₋ <1 is more preferable, 0.03 ≦ T ₊ / T ₋ ≦ 0.99 is further preferable, and 0.1. ≦ _T + / _{T -} ≦ 0.7 is particularly preferred, 0.2 ≦ _T + / _{T -} particularly preferably ≦ 0.5.

Furthermore, the ratio {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} can also be 0.02 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} ≦ 50. preferable.
This ratio {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} is 1 <{(V ₊ × T ₊ ) / (V ₋ × T ₋ ), especially when the action of migrating to the positive electrode side is strengthened. )} ≦ 50 is more preferable, 1.01 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} ≦ 30 is more preferable, 1.3 ≦ {(V ₊ × T ₊ ) / (V) ₋ × T ₋ )} ≦ 10 is particularly preferable, and 1.5 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} ≦ 5 is particularly preferable.
On the contrary, 0.02 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} <1 is more preferable, and 0.03 ≦ {(V ₊ ), especially when the action of migrating to the negative electrode side is strengthened. × T ₊ ) / (V ₋ × T ₋ )} ≦ 0.99 is more preferable, and 0.1 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} ≦ 0.7 is particularly preferable. 0.2 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} ≦ 0.5 is particularly preferable.
The current density at the time of electrophoresis, without limitation, it is preferable to 10 .mu.A / cm ² or less (typically, 0.1 .mu.A / cm ² or higher).

As described above, when only the DC voltage is used, when the current density is high (for example, 100 μA / cm ² ), the deposition rate is high, and the resulting particle deposition layer (for example, active material layer or solid electrolyte layer) There is a problem that the film thickness becomes excessively thick in a short time and the film thickness cannot be controlled. On the other hand, if the current density is small, the deposition rate can be reduced, but there is a problem that the surface roughness of the obtained particle deposition layer becomes large.
Then, when the particle deposition layer having a large surface roughness is observed, the particles are laminated to each other. Where a monolayer in which particles are deposited in a single layer on a desired region of a conductive surface is an ideal particle deposition layer, a particle deposition layer having a large surface roughness is a particle deposition in a certain part of the conductive surface. However, particles are deposited in two or more layers in other places, and as a result of the large variation in the deposition thickness, the surface roughness tends to increase.

That is, for example, when six particles 52 are deposited on the conductive surface of the base material 51, when the particles 52 are laminated with each other as illustrated in FIG. 8, the particles 52 are deposited with each other to form a film. There will be places where the thickness has increased and where the particles 52 will not be deposited at all, and the surface roughness of the obtained deposited layer will increase. On the other hand, as illustrated in FIG. 7, for example, if all the particles 52 can be deposited in one layer, even if the number of deposited particles is the same as in the case of FIG. 8, FIG. In FIG. 7, a sedimentary layer having a smaller surface roughness can be obtained as compared with the sedimentary layer. Then, if these operations can be repeated, as shown in FIG. 9, different types of particles (particles 521 and particles 522) can be regularly deposited to increase the contact area with each other.

In this regard, when an asymmetric signal is used, it is possible to obtain a particle deposition layer having a small surface roughness and a sufficiently small deposition thickness with respect to the particle size of the particles. That is, ideal particle deposition can be obtained as illustrated in FIGS. 7 and 9. It is not clear why the particle distribution can be controlled by using such an asymmetric signal. Furthermore, it is not clear why the effect of using an asymmetric signal appears for particles having a smaller particle size. However, from the background of the experiments so far, it is considered that the mass difference (inertia) of the moving particles has an influence.

That is, when electrophoresis is performed using an AC voltage, the particles are electrophoresed while the electric field traveling toward the substrate is acting, and are close to the conductive surface of the substrate. Then, it is considered that whether or not the particles reach the deposition on the conductive surface depends on whether or not the particles follow the change of the electric field when the electric field is reversed. That is, it is considered that particles having a large mass do not easily follow changes in the electric field, remain in the vicinity of the electrophoresed conductive surface, and eventually lead to deposition. On the other hand, particles with a small mass easily follow changes in the electric field and may revert to the solution side from the vicinity of the conductive surface, so particles with a small mass are less likely to be deposited than particles with a large mass. I think it might be.
Therefore, it is considered that if the symmetry of the waveform of the applied voltage is broken and the applied voltage in which the action of the electric field flowing toward the substrate is strengthened is applied, even particles having a small mass can be deposited.
Then, when the time for strengthening the action of the electric field flowing to the substrate side (for example, the application time on the positive electrode side) becomes long, the amount of deposition becomes excessively large (accumulation beyond being a substantially single-layer film). Since there is a possibility, it is preferable to suppress the time for strengthening the action of the electric field flowing to the substrate side to a short time as described above. That is, it is preferable that the migration action on the substrate side is strong (the absolute value of the peak is large) and short (the application time is short). In addition, it is considered that the deposited particles can be appropriately dispersed by making the electric field in the opposite direction weak (small absolute value of the peak) and acting for a long time (long application time).

For the reasons described above, the particles can be deposited only once by electrophoresis, but can be divided into a plurality of times as needed. In particular, when a plurality of types of particles having different particle sizes (that is, different masses) are used, by using an asymmetric signal suitable for each particle, it is possible to obtain a substantially single layer with better controllability and surface roughness. A small particle deposition layer can be obtained.
Specifically, there is a case where a first particle-containing liquid containing large-diameter particles and a second particle-containing liquid containing small-diameter particles are used. That is, each particle can be contained in a different particle-containing liquid and deposited using an asymmetric signal suitable for each electrophoresis. In particular, electrophoresis is performed in the first particle-containing liquid to deposit large-diameter particles, and then electrophoresis is performed in the second particle-containing liquid to deposit small-diameter particles and large-diameter particles. Small-diameter particles can be deposited so as to fill the gaps formed between the particles.
In this way, particles having different particle size groups are dispersed in different particle-containing liquids, electrophoresis is performed with a particle-containing liquid having a large particle size, and then electrophoresis is performed with a particle-containing liquid having a gradually smaller particle size. This makes it possible to form a dense particle deposition layer with excellent surface smoothness.

Further, as illustrated in Example 1 described later, by controlling the frequency of the applied voltage according to the particle size, a more monolayered deposit can be obtained. That is, it is possible to positively select a frequency that makes it easier to form a single layer. Specifically, an appropriate frequency is searched in advance according to the particle size to be deposited and the particle size distribution thereof, and a voltage is applied (electrophoresis) using that frequency to suppress the deposition of the second layer or higher. , The deposition area of only the first layer (single layer) can be selectively increased.
The frequency of the applied voltage can be, for example, 5 Hz or more and 13 Hz or less, preferably 6 Hz or more and 13 Hz or less, more preferably 7 Hz or more and 12 Hz or less, and particularly preferably 7 Hz or more and 11 Hz or less. It can be used for particles of any particle size at this frequency, but is particularly suitable for particles having an average particle size of 0.5 μm or more and 7 μm or less (particularly 0.7 μm or more and 6 μm or less).

(2) Method for manufacturing the second electrode This method for manufacturing the second electrode (hereinafter, also simply referred to as “second manufacturing method”) is a base material obtained by electrophoresis in an active material-containing liquid containing an active material. A first deposition step of depositing an active material to form an active material layer is provided on the conductive surface of the above, and an asymmetric signal is used as a signal of an applied voltage in the electrophoresis of the first deposition step.
That is, this second production method means a case where the particles in the above-mentioned first production method are active materials, the particle-containing liquid is an active material-containing liquid, and the deposition step is the first deposition step.

As the above-mentioned "base material", the base material in the first production method can be applied as it is.
Further, as the above-mentioned "active material-containing liquid", the particle-containing liquid in the first production method can be applied as it is except for the dispersion medium. The dispersion medium of the active material-containing liquid is not particularly limited, but a diether compound is preferable. By using the diether compound as a dispersion medium, the influence on the solid electrolyte layer 22 can be suppressed when the active material is used as the particles. Examples of the diether compound include 1,2-dimethoxyethane, 1,2-diethoxyethane, 1-ethoxy-2-methoxyethane and the like. Only one of these may be used, or two or more thereof may be used in combination. Of these, 1,2-dimethoxyethane is particularly preferable.
As the above-mentioned "asymmetric signal", the asymmetric signal in the first manufacturing method can be applied as it is.

(3) Method for manufacturing the third electrode The method for manufacturing the third electrode (hereinafter, also simply referred to as “third manufacturing method”) is carried out in a solid electrolyte-containing liquid containing a solid electrolyte and / or a precursor thereof. A second deposition step is provided in which a solid electrolyte and / or a precursor thereof is deposited on the conductive surface of the base material by electrophoresis to form a solid electrolyte layer or a precursor layer thereof, and in the electrophoresis of the second deposition step. It is characterized in that an asymmetric signal is used as a signal of the applied voltage.
That is, in this third production method, when the particles in the above-mentioned first production method are a solid electrolyte and / or a precursor thereof, the particle-containing liquid is a solid electrolyte-containing liquid, and the deposition step is a second deposition step. Means.

As the above-mentioned "base material", the base material in the first production method can be applied as it is.
Further, as the above-mentioned "solid electrolyte-containing liquid", the particle-containing liquid in the first production method can be applied as it is except for the dispersion medium. The dispersion medium of the solid electrolyte-containing liquid is not particularly limited, but a saturated fatty acid ester compound is preferable. By using a saturated fatty acid ester compound as a dispersion medium, a sulfide solid electrolyte can be used as particles, particularly as a solid electrolyte. Examples of the saturated fatty acid ester compound include methyl propionate, ethyl propionate, propyl propionate, butyl propionate and the like. Only one of these may be used, or two or more thereof may be used in combination. Of these, ethyl propionate is particularly preferred.
The "precursor of a solid electrolyte" is a particle that changes into a solid electrolyte by removing the dispersion medium and performing post-treatment such as heating as necessary.
As the above-mentioned "asymmetric signal", the asymmetric signal in the first manufacturing method can be applied as it is.

(4) Method for manufacturing the fourth electrode In the method for manufacturing the fourth electrode (hereinafter, also simply referred to as “fourth manufacturing method”), an active material layer containing an active material as a main component and a solid electrolyte as a main component are used. This is a method for producing an electrode, which comprises a solid electrolyte layer and the solid electrolyte is a sulfide solid electrolyte. That is, the active material-containing liquid is provided with a first deposition step of depositing the active material on the conductive surface of the base material to form an active material layer by electrophoresis in the active material-containing liquid containing the active material. It is characterized by containing a diether compound and / or a carbonyl compound.
Further, in the fourth production method, as a pre-step or a post-step of the first deposition step, a solid is formed on the conductive surface of the base material by electrophoresis in a solid electrolyte-containing liquid containing a solid electrolyte and / or a precursor thereof. It comprises a second deposition step of depositing the electrolyte and / or its precursor to form the solid electrolyte layer or its precursor layer. At this time, the solid electrolyte is a sulfide solid electrolyte.
Further, also in the fourth manufacturing method, an asymmetric signal can be used in electrophoresis as described above.
Each of the above descriptions in the fourth manufacturing method has already been described in the first to third manufacturing methods.

[3] Method for Manufacturing Electrode The all-solid-state lithium-ion battery (1) of the present invention is characterized by including the electrode (2) according to the present invention.
That is, the all-solid-state lithium-ion battery (1) has a structure in which the solid electrolyte body (3) is arranged between the pair of electrodes (2a, 2b). Of these, one of the pair of electrodes functions as a positive electrode and the other functions as a negative electrode. Each electrode is as described above.
Further, the solid electrolyte body (3) is a Li ion conductor containing the solid electrolyte. The shape, size, etc. are not particularly limited and may be appropriate. Further, as the solid electrolyte constituting the solid electrolyte body (3), the above-mentioned solid electrolyte that can be used for the electrode (2) can be used as it is. However, it is preferable that the solid electrolyte contained in the electrode (2) and the solid electrolyte contained in the solid electrolyte body (3) are the same.
In addition to the above, the all-solid-state lithium-ion battery (1) of the present invention may be provided with a known configuration, for example, a separator or the like, if necessary.

[1] Example 1 (effect of frequency)
<1> Preparation of active material-containing liquid (dispersion liquid) Using the following granular active material, an active material-containing liquid (dispersion liquid) was prepared by the following procedure.
(1) The following active material was put into a 5% by mass aqueous solution of polychlorinated diallyldimethylammonium (cationic surfactant) and subjected to ultrasonic treatment to disperse it.
(2) The dispersion liquid of (1) above was centrifuged, and the upper layer of the obtained separated liquid was removed to recover the lower layer.
(3) The operation of adding isopropyl alcohol to the liquid (recovered lower layer) of the above (2), performing a centrifugation treatment, removing the upper layer of the obtained separation liquid, and recovering the lower layer is repeated three times. The dispersion medium was replaced with isopropyl alcohol by removing water from the liquid. In this way, the active material is used as a dispersant, isopropyl alcohol is used as a dispersion medium, and polyallyldimethylammonium chloride is used as a dispersant, and the active material-containing liquid (dispersion liquid, solid content concentration: 3.0 mass) in which the active material is dispersed is used. %) Was obtained.
Active material: Li (Ni _x Mn _y Co _z ) O ₂ represented by Li-containing double oxide powder, average particle size 5 μm

<2> Electrophoresis The active material-containing liquid obtained in <1> above was put into an electrophoresis tank, and the positive electrode and the negative electrode were opposed to each other at intervals of 5 mm in the active material-containing liquid. For the positive electrode and the negative electrode, a base material (ITO substrate) having a conductive surface made of ITO (indium tin oxide) was used.
Then, between the positive electrode and the negative electrode, seven types of AC voltage (symmetric signal, V ₊ is 100V, V ₋ is 100V) having frequencies of 1Hz, 3Hz, 5Hz, 7.5Hz, 10Hz, 15Hz and 20Hz. , T ₊ for 0.05 to 5 seconds, T ₋ for 0.05 to 5 seconds), and electrophoresis was performed for 1800 seconds. Then, the positive electrode (cathode) that had passed the above migration time was pulled up from the migration tank and then air-dried to obtain an active material layer formed on the conductive surface of the ITO substrate.

<3> Measurement of coverage The coverage of the first layer of the active material layer formed on the conductive surface of the ITO substrate obtained up to <2> above and the coverage by the following procedure using the laser microscope below. The coverage of the upper layer, which is the second layer or higher, was measured.
Specifically, in a laminated body having a monolayer region prepared separately using an active material having an average particle size of 5 μm, the deposition thickness of the monolayer region was actually measured with the following laser microscope. Was found to fall within the range of 3-5 μm. Therefore, from this empirical value, a region having a deposit thickness of 3 to 5 μm was defined as a monolayer region (that is, a region covered by the first layer), and the area ratio of this region was calculated as the coverage ratio of the first layer. Further, since the region where the deposit thickness is 6 μm or more is a region where particles are deposited in multiple layers, it is defined as a multi-layered region (that is, a region in which an upper layer is deposited and covered on the first layer). The area ratio of the area was calculated as the coverage ratio of the upper layer. This result is shown graphically in FIG.
In addition, in the above-mentioned deposition thickness measurement, after taking an image at 100 magnification with a laser microscope (manufactured by Olympus Corporation, model "LEXT OLS4100"), the two most frequent values seen in the height histogram of this image. The difference between the height of the substrate surface and the distribution of the deposited height of the deposited particles was used as the film thickness.

<4> Effect of Example 1 From FIG. 10 above, it can be seen that there are a frequency region in which the coverage of the first layer is high and a frequency region in which the coverage of the upper layer is high. Therefore, it is possible to select a frequency domain in which the coverage of the first layer is larger than that of the upper layer, thereby constructing an environment in which a more ideal single layer (monolayer) can be easily formed. I know I can do it. In particular, in this case, since the results were obtained at a particle size of 5 μm, it was shown that the most ideal deposition was obtained at 10 Hz in the particle size range showing a particle size of 5 μm or similar behavior.
[2] Example 2 (Effect of applied voltage and its signal waveform)
<1> Preparation of active material-containing liquid (dispersion liquid) In the same manner as in <1> of Example 2 above, the active material is used as a dispersant, isopropyl alcohol is used as a dispersion medium, and polyallyldimethylammonium chloride is dispersed. As an agent, an active material-containing liquid (dispersed liquid, solid content concentration 3.0% by mass) in which the active material was dispersed was obtained. However, as described below, the average particle size of the active material was adjusted to be 1 μm.
Active material: Powder of Li-containing double oxide represented by Li (Ni _x Mn _y Co _z ) O ₂ , average particle size 1 μm

<2> Electrophoresis The active material-containing liquid obtained in <1> above was put into an electrophoresis tank, and the positive electrode and the negative electrode were opposed to each other at intervals of 5 mm in the active material-containing liquid. For the positive electrode and the negative electrode, a base material (ITO substrate) having a conductive surface made of ITO (indium tin oxide) was used.
Then, the applied voltage shown in Table 1 below was applied between the positive electrode and the negative electrode, and the time (electrophoresis time) shown in Table 1 below was applied to perform electrophoresis. The details of the applied voltage at this time are also shown in Table 1. Then, the positive electrode (cathode) that had passed the above migration time was pulled up from the migration tank and then air-dried to obtain an active material layer formed on the conductive surface of the ITO substrate.
As described above, 10 Hz is selected as the frequency by using the result of [1] Example 1.

<3> Measurement of film thickness and average surface roughness Using the laser microscope below, the average film thickness of the active material layer formed on the conductive surface of the ITO substrate obtained up to <2> above is performed by the following procedure. And the average surface roughness was measured. The results are also shown in Table 1.
The average film thickness is the two most frequent values (each with the height of the substrate surface) seen in the height histogram using an image obtained by taking a 100-magnification image with a laser microscope (manufactured by Olympus Corporation, model "LEXT OLS4100"). It was calculated from the difference in the deposition height distribution of the deposited particles.
Further, the average surface roughness was obtained by calculating a three-dimensional parameter from the same laser microscope image (100 times) as above to which an 80 μm λc contour curve filter was applied, and using the obtained arithmetic average roughness Sa.

<4> Effect of Example 2 As shown in Experimental Example 1, it can be seen that when a DC voltage is applied at a current density of 10 μA / cm ² , an active material layer of 6,000 μm is formed by electrophoresis for 30 seconds. ..
Here, in a laminated body having a monolayer region (see FIG. 7) separately prepared using an active material having an average particle size of 1 μm, the deposition thickness of the monolayer region was actually measured by the above-mentioned laser microscope. However, it was found that the deposit thickness was within the range of 0.4 to 0.6 μm, and the average deposit thickness was about 0.5 μm. Therefore, from this empirical value, the region where the deposition thickness is 0.4 to 0.6 μm is considered to be a substantially monolayer region.
Based on the above, the film thickness of Experimental Example 1 is 6 μm, which is about 12 times the target value, so that it can be seen that the particles were deposited in multiple layers in an extremely short time.
On the other hand, in Experimental Examples 2 to 5, the film thickness was controlled by lowering the current density of the DC voltage and shortening the migration time. As a result, in Experimental Examples 3 to 5, the average film thickness was 0.422 to 0.577 μm, and it can be seen that the target value was reached. However, the average surface roughness was 0.163 μm in Experimental Example 1, but increased to 0.222 to 0.284 μm in Experimental Examples 3 to 5, and the surface roughness increased by 36.2 to 74.2%. You can see that it is doing. It is considered that there is a region where the active material is deposited in a single layer, but there are regions where the active material is not deposited at all and regions where the active material is laminated in multiple layers, and the unevenness becomes severe. This is considered to be the result (see FIG. 8). That is, when trying to control the film thickness using a DC voltage, it is possible to obtain a film thickness close to the target value by controlling the current density, but it is difficult to obtain a smooth active material layer.

Therefore, in Experimental Examples 6 to 8, electrophoresis is performed using an AC voltage (symmetric signal). As a result, it can be seen that the film thickness can be controlled by controlling the maximum voltage value. It can be seen that the average surface roughness is also 0.117 to 0.173 μm, which is a relatively good value. However, for example, in Experimental Examples 3 to 5, the target value film thickness was obtained by electrophoresis for 5 to 50 seconds, whereas in Experimental Examples 6 to 8, the target value was obtained unless electrophoresis was performed for 900 seconds. It can be seen that the film thickness of is not obtained.

On the other hand, in Experimental Example 9, the AC / DC superimposition voltage having the obtained asymmetric signal is applied by superimposing the AC voltage and the DC voltage. As a result, an active material layer having a film thickness of 0.472 μm, which is very close to the ideal value of 0.5 μm, was obtained by electrophoresis for 60 seconds. Further, the average surface roughness of the obtained active material layer was as small as 0.099 μm. From this result, by using an asymmetric signal, it is possible to obtain an extremely flat particle deposition layer having an ideal film thickness in a short time within an easy-to-handle range and having an extremely small surface roughness. You can see that you can.

[3] Example 3 (Lamination of active material layer and solid electrolyte layer)
<1> Preparation of solid electrolyte-containing liquid (dispersion liquid) The following lithium sulfide powder and the following diphosphorus pentasulfide powder were weighed and mixed in an agate mortar so that the molar ratio was 3: 1. The obtained mixture, ethyl propionate, and zirconia balls (diameter 4 mm) are put into a resin container, shaken at a temperature of 24 ° C., an amplitude of about 1 cm, and about 1500 times / minute, and contacted with each other. It was reacted. After 24 hours, the zirconia balls were removed from the resin container to obtain a solid electrolyte-containing liquid (suspension, solid content concentration 11.7% by mass) in which the solid electrolyte and / or its precursor was dispersed. ..
Powder lithium sulfide _(Li 2 S): Co. Mitsuwa Kagaku, purity of 99% and an average particle size of 53μm
Powder diphosphorus pentasulfide _(P 2 _{S 5):} Aldrich Co., 99% purity, mean particle diameter 100μm

<2> Formation of solid electrolyte layer The solid electrolyte-containing liquid obtained in <1> above was put into an electrophoresis tank, and positive and negative electrodes were opposed to each other at intervals of 10 mm in the solid electrolyte-containing liquid. .. For the positive electrode and the negative electrode, a base material (ITO substrate) having a conductive surface made of ITO (indium tin oxide) was used. Then, a DC voltage was applied between the positive electrode and the negative electrode at a voltage of 100 V for 10 seconds to perform electrophoresis.
Then, the negative electrode after the above-mentioned migration time was pulled up from the migration tank and then air-dried to obtain a solid electrolyte layer formed on the conductive surface of the ITO substrate.

<3> Preparation of active material-containing liquid (dispersion liquid) Using the following granular active material, an active material-containing liquid (dispersion liquid) was prepared by the following procedure.
(1) The following active material was put into a 10% by mass aqueous solution of polyethyleneimine and subjected to ultrasonic treatment to disperse it.
(2) Water was added to the dispersion liquid of (1) above to perform centrifugation, and the operation of removing the upper layer of the obtained separation liquid and recovering the lower layer was repeated three times.
(3) The liquid (recovered lower layer) of (2) above was vacuum-dried to obtain a powder (powder in which polyethyleneimine was adhered around the active material).
(4) 1,2-Dimethoxyethane is added to the powder obtained in (3) above and dispersed by ultrasonic treatment to make the active material a dispersoid, and 1,2-dimethoxyethane is used as a dispersion medium. Then, using polyethyleneimine as a dispersant, an active material-containing liquid (dispersed liquid, solid content concentration: 3% by mass) in which the active material was dispersed was obtained.
Active material: Li-containing double oxide powder represented by Li (Ni _x Mn _y Co _z ) O ₂ , average particle size 6.2 μm

<4> Lamination of active material layer The active material-containing liquid obtained in <3> above was put into an electrophoresis tank, and positive and negative electrodes were opposed to each other at intervals of 10 mm in the active material-containing liquid. .. Of these, the ITO substrate on which the solid electrolyte layer was formed in <2> above was used as the negative electrode. On the other hand, as the positive electrode, an ITO substrate having a conductive surface made of ITO (indium tin oxide) was used. Then, a DC voltage was applied between the positive electrode and the negative electrode at a voltage of 100 V for 45 seconds to perform electrophoresis.
Then, after the positive electrode (cathode) that has passed the above migration time is pulled up from the migration tank, it is naturally dried, and the solid electrolyte layer and the active material layer formed on the conductive surface of the ITO substrate are laminated. I got a body.

<5> Lamination of Solid Electrolyte Layers After obtaining a new solid electrolyte-containing liquid by the operation of <1> above, this is put into an electrophoresis tank, and positive electrodes are placed in the solid electrolyte-containing liquid at intervals of 10 mm. And the negative electrodes were opposed to each other. Of these, as the negative electrode, the ITO substrate in which the active material layer was laminated on the solid electrolyte layer in <4> above was used. On the other hand, as the positive electrode, an ITO substrate having a conductive surface made of ITO (indium tin oxide) was used. Then, a DC voltage was applied between the positive electrode and the negative electrode at a voltage of 100 V for 10 seconds to perform electrophoresis.
After that, the positive electrode (cathode) that has passed the above migration time is pulled up from the migration tank, and then air-dried to obtain the solid electrolyte layer, the active material layer, and the solid electrolyte layer formed on the conductive surface of the ITO substrate. A laminated body laminated in order was obtained.

<6> Effect of Example 3 The positive electrode (laminated body modified ITO) obtained up to <5> above was linearly divided in the stacking direction to expose the fracture surface. The obtained sample with the exposed fracture surface was attached to the sample table of a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, model "S-4800") using carbon tape, and the above fracture surface was multiplied by 10,000. It was magnified and observed. Then, the obtained image is shown in FIG.
As a result of the above, in Example 3, the ITO substrate (25), a solid electrolyte layer deposited on the conductive surface thereof at a thickness of about 700 nm, an active material layer deposited at a thickness of about 1 μm, and a thickness of about 500 nm. It can be seen from FIG. 11 that the solid electrolyte layers deposited in (1) are laminated in this order to obtain an electrode.

[4] Example 4 (all-solid-state lithium-ion battery)
<1> Preparation of active material-containing liquid (dispersion liquid) Using the following granular active material, an active material-containing liquid (dispersion liquid) was prepared by the following procedure.
(1) The following active material was put into a 10% by mass aqueous solution of polychlorinated diallyldimethylammonium (cationic surfactant) and subjected to ultrasonic treatment to disperse it.
(2) Ion-exchanged water was added to the dispersion liquid of the above (1) for centrifugation, and the upper layer of the obtained separation liquid was removed to recover the lower layer.
(3) The operation of adding isopropyl alcohol to the liquid (recovered lower layer) of the above (2), performing a centrifugation treatment, removing the upper layer of the obtained separation liquid, and recovering the lower layer is repeated three times. The dispersion medium was replaced with isopropyl alcohol by removing water from the liquid. In this way, the active material is dispersed, the active material is used as a dispersant, isopropyl alcohol is used as a dispersion medium, and polyallyldimethylammonium chloride is used as a dispersant, and the active material is dispersed (dispersion liquid, solid content concentration: 3% by mass). Got
Active material: Li (Ni _x Mn _y Co _z ) O ₂ represented by Li-containing double oxide powder, average particle size 5 μm

<2> Lamination of active material layer The active material-containing liquid obtained in <1> above was put into an electrophoresis tank, and positive and negative electrodes were opposed to each other at intervals of 10 mm in the active material-containing liquid. .. Of these, an aluminum substrate was used for the positive electrode, and an aluminum substrate (diameter 10 mm) was used for the negative electrode. Then, a voltage having an asymmetric signal was applied between the positive electrode and the negative electrode for 45 seconds to perform electrophoresis.
Then, the negative electrode after the above-mentioned migration time was pulled up from the migration tank and then air-dried to obtain a laminate in which the active material layer formed on the conductive surface of the aluminum substrate was laminated.
Further, as the asymmetric signal, an asymmetric signal obtained by superimposing an AC voltage having a symmetric signal composed of a triangular wave (90V) and a DC voltage of 10V was used. This asymmetric signal is shown in FIG. However, V ₊ = 100V, V ₋ = 100V, T ₊ = 0.02 seconds, T ₋ = 0.02 seconds, frequency 20Hz).

<3> Preparation of solid electrolyte-containing liquid (dispersion liquid) In the same manner as in the preparation of the solid electrolyte-containing liquid (dispersion liquid) of Example 3 [3] <1> above, the solid electrolyte and / or its precursor is dispersed. A solid electrolyte-containing liquid (suspension, solid content concentration of 10 mg / mL) was obtained.

<4> Formation of Solid Electrolyte Layer The solid electrolyte-containing liquid obtained in <3> above was put into the electrophoresis tank, and the positive and negative electrodes were opposed to each other at intervals of 5 mm in the solid electrolyte-containing liquid. .. An aluminum substrate was used as the positive electrode, and an aluminum substrate having an active material layer deposited on the conductive surface obtained in <2> above was used as the negative electrode. Then, a DC voltage was applied between the positive electrode and the negative electrode at a voltage of 25 V for 10 seconds to perform electrophoresis.
Then, the negative electrode after the above migration time was pulled up from the migration tank, pre-dried at room temperature for 30 minutes, and then vacuum-dried in a vacuum environment at 170 ° C. for 3 hours to obtain an aluminum substrate (diameter 10 mm). ), The active material layer and the solid electrolyte layer were laminated in this order to obtain a laminate.

<5> of the stack 80mg of the solid electrolyte body _{of LPS (75Li 2 S · 25P 2 S} 5) were obtained by compression molding, a solid electrolyte body having a thickness of 1000 .mu.m, obtained by the <4> laminate It was pressure-bonded to the surface of the solid electrolyte layer of the body (electrode).

<6> Lamination of indium foil An all-solid-state type indium foil having a thickness of 100 μm is pressure-bonded to the surface of the solid electrolyte of the laminate (laminate of electrode and solid electrolyte) obtained up to <5> above. Obtained a lithium-ion battery.
That is, as shown in FIG. 12, the all-solid-state lithium-ion battery 1 of Example 4 has a base material (current collector) 25 made of an aluminum substrate and an active material 211 (active material 211) laminated on the conductive surface thereof. It has an electrode 2b including an active material layer 21 containing particles) and a solid electrolyte layer 22 containing solid electrolyte 221 (solid electrolyte particles) laminated on the surface of the active material layer 21. Further, it has a solid electrolyte body 3 laminated on the surface of the solid electrolyte layer 22 of the electrode 2b. Further, it has an electrode 2a laminated on the surface of the solid electrolyte body 3. Then, in the all-solid-state lithium ion battery 1, the electrode 2b functions as a positive electrode, and the electrode 2a functions as a negative electrode.

<7> Confirmation of charge / discharge and effect of Example 4 The jig containing the all-solid-state lithium-ion battery obtained up to <6> above is enclosed in a glass container, and the gas in the glass container is converted to argon gas. Substitution was performed to obtain a measurement cell. Whether or not the obtained measurement cell could be charged or discharged was observed by a constant current, constant voltage, and charging method using an electrochemical measuring device (manufactured by Solartron, model "SI 1287"). Specifically, 3.8 V vs. Constant current charging was performed up to In-Li at a rate of 0.01 C, and then constant voltage charging was performed until 100 hours had passed. Immediately after that, 1.6 V vs. Discharge was performed at a rate of 0.01 C to the potential of In-Li. As a result, a discharge capacity of about 0.133 mAh / g could be obtained. This indicates that charging and discharging are possible.

As the jig, the jig 70 shown in FIG. 13 was used. That is, the all-solid-state lithium-ion battery 1 obtained up to <6> above was housed in the through hole 74a of the tubular body 74 made of polyetheretherketone (PEEK). On the other hand, a pair (positive electrode side and negative electrode side) of holding pins 72 assembled by a stainless steel convex block and a stainless steel screw was prepared. Then, the holding pin 72 was inserted into the through hole 74a so as to sandwich the upper and lower sides of the all-solid-state lithium ion battery 1. Further, in order to tighten these holding pins 72, a pair of stainless steel holding plates 71 (positive electrode side and negative electrode side) and three stainless steel tightening screws 73 for tightening the holding plates are prepared, and each holding pin 72 is tightened. The upper and lower sides were sandwiched between the holding plates 71, and these holding plates 71 were tightened with the tightening screws 73 (screw restraint pressure: 9 Nm), and the all-solid-state lithium ion battery 1 was housed in the jig 70. Various energization is performed from the convex portion of the holding pin 72 (the portion marked with the reference numeral 72 on FIG. 13).

The electrode of the present invention, its manufacturing method, and an all-solid-state lithium-ion battery can be used as a power source for home appliances such as personal computers and cameras, portable electronic devices such as mobile phones or communication devices, and electric tools such as power tools. , A large battery mounted on an electric vehicle (EV), a hybrid electric vehicle (HEV), etc., and an electrode constituting the large battery.

1: All-solid-state lithium-ion battery,
2, 2a, 2b: Electrodes,
21; active material layer, 211; active material (active material particles),
22; solid electrolyte layer, 221; solid electrolyte (solid electrolyte particles),
25; substrate, 251; conductive surface,
3; solid electrolyte,
51; substrate, 52, 521, 522; particles.

Claims (14)

A total solid type is that electrodes used in lithium ion batteries with solid body electrolyte is arranged structure,
It is composed of a laminate including an active material layer containing an active material as a main component and a solid electrolyte layer containing a solid electrolyte as a main component .
At least one of a laminated structure in which the solid electrolyte layer is interposed between the layers of the active material layer of two layers and a laminated structure in which the active material layer is interposed between the layers of the solid electrolyte layer of two layers. Has a laminated structure of
The solid electrolyte layer is formed thinner than the active material layer.
The thickness of the active material layer is 1 μm to 15 μm.
An electrode characterized in that the thickness of the solid electrolyte layer is 0.25 μm to 5 μm . The electrode according to claim 1, wherein the ratio of the thickness of the solid electrolyte layer to the thickness of the active material layer (solid electrolyte layer / active material layer) is 0.05 to 0.7. The electrode according to claim 1 or 2 , wherein both the active material layer and the solid electrolyte layer contain a conductive auxiliary agent. The electrode according to any one of claims 1 to 3 , wherein the solid electrolyte is a sulfide solid electrolyte. The electrode according to any one of claims 1 to 4 , which is a positive electrode. A method for manufacturing a laminate used for an electrode of an all-solid-state lithium-ion battery.
The laminate has an active material layer containing an active material as a main component and a solid electrolyte layer containing a solid electrolyte as a main component.
An active material layer deposition step of depositing the active material by electrophoresis in an active material-containing liquid containing the active material to form the active material layer.
A solid electrolyte that deposits the solid electrolyte and / or its precursor by electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or its precursor to form the solid electrolyte layer or its precursor layer. With a layer deposition process
A method for producing an electrode, which comprises using a signal having an asymmetric waveform on the positive electrode side and the negative electrode side as a signal of an applied voltage in the electrophoresis of the active material layer deposition step and the solid electrolyte layer deposition step. .. The method for manufacturing an electrode according to claim 1.
A first deposition step of depositing the active material on the conductive surface of the base material to form the active material layer by electrophoresis in the active material-containing liquid containing the active material is provided.
A method for manufacturing an electrode, which comprises using a signal having an asymmetric waveform on the positive electrode side and the negative electrode side as a signal of a voltage to be applied in the electrophoresis in the first deposition step. The method for manufacturing an electrode according to claim 1.
By electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or its precursor, the solid electrolyte and / or its precursor is deposited on the conductive surface of the base material, and the solid electrolyte layer or its precursor is deposited. With a second deposition step to form the body layer
A method for manufacturing an electrode, which comprises using a signal having an asymmetric waveform on the positive electrode side and the negative electrode side as a signal of a voltage to be applied in the electrophoresis in the second deposition step. The method for manufacturing an electrode according to claim 7 or 8 , wherein the signal is a signal in which the absolute value of the peak differs between the positive electrode side and the negative electrode side. The method for manufacturing an electrode according to claim 7 or 8 , wherein the signal is a signal in which the application time differs between the positive electrode side and the negative electrode side. The method for manufacturing an electrode according to claim 4 .
A first deposition step of depositing the active material on the conductive surface of the base material to form the active material layer by electrophoresis in the active material-containing liquid containing the active material is provided.
A method for producing an electrode, wherein the active material-containing liquid contains a diether compound and / or a carbonyl compound. As a pre-process or post-process of the first deposition step,
By electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or its precursor, the solid electrolyte and / or its precursor is deposited on the conductive surface of the base material, and the solid electrolyte layer or its precursor is deposited. With a second deposition step to form the body layer
The method for producing an electrode according to claim 11 , wherein the solid electrolyte is a sulfide solid electrolyte. The method for manufacturing an electrode according to claim 11 or 12 , wherein a signal having an asymmetric waveform on the positive electrode side and the negative electrode side is used as a signal of the voltage to be applied in the electrophoresis in the first deposition step. An all-solid-state lithium-ion battery comprising the electrode according to any one of claims 1 to 5 .