JP2017107826A - Electrode and method of manufacturing the same, and all-solid-state lithium ion battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an electrode formed by controlling the distribution of each component, such as an active material and a solid electrolyte; a method of manufacturing the electrode; and an all-solid-state lithium ion battery using the electrode.SOLUTION: The present electrode is an electrode 2 used for an all-solid-state lithium ion battery 1 that has a structure where a solid electrolyte body 3 is arranged between a pair of electrodes 2 (2a and 2b). The electrode includes an active material layer 21 containing an active material as a main constituent and a solid electrolyte layer 22 containing a solid electrolyte as a main constituent. The present method includes a step of depositing particles on a conductive surface of a base material by electrophoresis in a liquid that contains the particles. In the electrophoresis during the step, a signal having a wave form asymmetric on a positive electrode side and on a negative electrode side is used as a signal of a voltage to be applied.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrode, a manufacturing method thereof, and an all solid-state lithium ion battery. 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 body is disposed between a pair of electrodes, a method for manufacturing the electrode, and an all solid-state lithium ion battery.

In a lithium ion battery (hereinafter, also simply referred to as “Li ion battery”), at the time of charging, lithium dissolves as ions from the positive electrode, moves to the negative electrode, and is stored in the negative electrode. In addition, the secondary battery has a reaction mode in which lithium ions return from the negative electrode to the positive electrode during discharge.
In this Li-ion battery field, in addition to simplifying safety devices, research is underway to replace electrolytes containing flammable organic solvents with solid electrolytes for reasons such as superior manufacturing costs and productivity. It has been. At the same time, the development of electrodes corresponding to the use of this solid electrolyte is in progress.

  Such an electrode generally has a thin layer called an active material layer laminated on a current collector. In the active material layer, for example, a composite oxide capable of inserting and extracting lithium ions is blended as a main component in the case of a positive electrode. Further, the active material layer is blended with a solid electrolyte, a conductive aid, and the like as auxiliary components as necessary. These components affect the occlusion and release of lithium ions and the movement of electrons in the active material layer, and greatly affect the charge / discharge characteristics of the battery. Therefore, 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 are required.

Special table 2014-34592 gazette Special table 2014-535141 gazette

Various methods for forming the active material layer in the above electrode have been proposed. Among them, the above-mentioned main component and subcomponent are adjusted to a dispersion such as paste or slurry through a solvent, and this 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, in order to adhere the dispersoid to the carrier, a binder must be blended, and as a result, the blending of the above-mentioned main components and subcomponents that can be blended into the dispersion. The ratio is lowered, which causes a decrease in electrical characteristics.
In addition, this method has a structure in which each component is uniformly distributed throughout the resulting layer, and therefore it is not possible to arrange a desired component arbitrarily and locally, and to obtain such an active material layer. There is a problem that can not be.
Patent Document 1 and Patent Document 2 disclose a method of using a suspension containing an anode material, a solid electrolyte material, a cathode material, and the like and depositing these materials on the surface of a conductive substrate by electrophoresis. Has been. 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 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 use of the electrode. An object of the present invention is 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 for an all-solid-state lithium ion battery having a structure in which a solid electrolyte body is disposed between a pair of electrodes,
The gist is to include an active material layer mainly composed of an active material and a solid electrolyte layer mainly composed of a solid electrolyte.
The electrode according to claim 2 is the electrode according to claim 1, wherein the solid electrolyte layer is interposed between the two active material layers, and the two layers of the solid electrolyte layer The gist of the invention is to have at least one laminated structure in which the active material layer is interposed between layers.
The gist of the electrode according to claim 3 is that in the electrode according to claim 1 or 2, the solid electrolyte layer is formed thinner than the active material layer.
A gist of an 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 additive.
A gist of an 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 the positive electrode in the electrode according to any one of claims 1 to 5.

The method for producing an electrode according to claim 7 includes a deposition step of depositing the particles on a conductive surface of a substrate by electrophoresis in a liquid containing the particles.
In the electrophoresis of the deposition step, a signal having an asymmetric waveform between the positive electrode side and the negative electrode side is used as a voltage signal to be applied.
An electrode manufacturing method according to claim 8 is the electrode manufacturing method according to claim 1,
A first deposition step of depositing the active material on a conductive surface of a base material by electrophoresis in an active material-containing liquid containing the active material to form the active material layer;
In the electrophoresis of the first deposition step, a signal having an asymmetric waveform between the positive electrode side and the negative electrode side is used as a voltage signal to be applied.
The electrode manufacturing method according to claim 9 is the electrode manufacturing method according to claim 1,
The solid electrolyte and / or precursor thereof is deposited on a conductive surface of a substrate by electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or precursor thereof, and the solid electrolyte layer or precursor thereof is deposited. Comprising a second deposition step for forming a body layer;
In the electrophoresis of the second deposition step, a signal having an asymmetric waveform between the positive electrode side and the negative electrode side is used as a voltage signal to be applied.
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 having different peak absolute values on the positive electrode side and the negative electrode side. Is the gist.
The electrode manufacturing method according to claim 11 is the electrode manufacturing method 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 method for producing an electrode according to claim 12 is the method for producing an electrode according to claim 5,
A first deposition step of depositing the active material on a conductive surface of a base material by electrophoresis in an active material-containing liquid containing the active material to form the active material layer;
The gist of the active material-containing liquid includes a diether compound and / or a carbonyl compound.
The method for producing an electrode according to claim 13 is the method for producing an electrode according to claim 12, wherein the pre-process or post-process of the first deposition step is as follows.
The solid electrolyte and / or precursor thereof is deposited on a conductive surface of a substrate by electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or precursor thereof, and the solid electrolyte layer or precursor thereof is deposited. Comprising a second deposition step for forming a body layer;
The gist is that the solid electrolyte is a sulfide solid electrolyte.
The electrode manufacturing method according to claim 14 is the electrode manufacturing method according to claim 12 or 13, wherein, in the electrophoresis of the first deposition step, as a voltage signal to be applied, a positive electrode side and a negative electrode side And using a signal having an asymmetric waveform.

  The gist of the all-solid-state lithium ion battery according to claim 15 is that it comprises the electrode according to any one of claims 1 to 6.

The electrode of the present invention includes an active material layer mainly composed of an active material and a solid electrolyte layer mainly composed of a solid electrolyte. That is, the electrode is formed by controlling the distribution of each component of the active material and the solid electrolyte in layers. With this configuration, an arbitrary layer structure can be introduced into the active material layer. For this reason, the structure which designed beforehand the movement path | route of the ion from an active material layer to a solid electrolyte layer is realizable.
Among the electrode manufacturing methods of the present invention, a first method includes a deposition step of depositing particles on a conductive surface of a substrate by electrophoresis in a liquid containing particles, and in the electrophoresis of the deposition step, In this method, a signal having an asymmetric waveform between the positive electrode side and the negative electrode side is used as the voltage signal to be applied. Thereby, the movement of the particles in the liquid can be controlled to a higher degree during electrophoresis.
Of the electrode manufacturing methods of the present invention, the second method is to deposit an active material on a conductive surface of a substrate by electrophoresis in an active material-containing liquid containing an active material, thereby forming an active material layer. In the electrophoresis of the first deposition step, a signal having an asymmetric waveform between the positive electrode side and the negative electrode side is used as the voltage signal to be applied. Thereby, the movement of the active material in the active material-containing liquid can be controlled to a higher degree during electrophoresis.
Among the methods for producing an electrode of the present invention, the third method is a method in which the solid electrolyte and / or the conductive surface of the substrate is subjected to electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or its precursor. A second deposition step of depositing the precursor and forming the solid electrolyte layer or the precursor layer, and in the electrophoresis of the second deposition step, the voltage signal to be applied is asymmetric between the positive electrode side and the negative electrode side This is a method using a signal having a waveform. Thereby, the movement of the solid electrolyte and / or its precursor in the solid electrolyte-containing liquid can be controlled to a higher degree during electrophoresis.
Of the electrode manufacturing methods of the present invention, the fourth method is to deposit an active material on a conductive surface of a substrate by electrophoresis in an active material-containing liquid containing an active material, thereby forming an active material layer. The active material-containing liquid is a method including a diether compound and / or a carbonyl compound. Thus, 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 stacked.
The all solid-state lithium ion battery of the present invention includes the electrode of the present invention. The all-solid-state lithium ion battery can be charged and discharged using the electrode having this novel configuration.

It is explanatory drawing explaining this all solid-state type lithium ion battery and an electrode. It is explanatory drawing explaining an example of the signal which has an asymmetrical waveform by the positive electrode side and the negative electrode side. It is explanatory drawing explaining the other example of the signal which has an asymmetrical waveform by the positive electrode side and the negative electrode side. It is explanatory drawing explaining the other example of the signal which has an asymmetrical waveform by the positive electrode side and the negative electrode side. It is explanatory drawing explaining the other example of the signal which has an asymmetrical waveform by the positive electrode side and the negative electrode side. It is explanatory drawing explaining the other example of the signal which has an asymmetrical waveform by the positive electrode side and the negative electrode side. It is explanatory drawing explaining an example of the deposition form of particle | grains. It is explanatory drawing explaining the other example of the deposition form of particle | grains. It is explanatory drawing explaining the form on which the different types of particles were alternately deposited. 3 is a graph showing a correlation between a coverage and a frequency according to Example 1. It is an image which expands and shows the cross section of the electrode which concerns on Example 3. FIG. 6 is an explanatory view illustrating an all solid state lithium ion battery according to Example 4. FIG. It is explanatory drawing explaining the jig | tool 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 disposed between a pair of electrodes (2a, 2b). 2).
The electrode (2) includes 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 in contact with each other on their main surfaces. The high conductivity of Li ion can be obtained by contacting each other on the wide surfaces.
Moreover, although the electrode provided with the active material layer 21 and the solid electrolyte layer 22 may be obtained in any way, it can be obtained 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 substrate 25 having a conductive surface (conductive surface).
In that case, either the active material layer 21 or the solid electrolyte layer 22 may be in contact with the conductive surface 251, but it is preferable that the active material layer 21 is in contact with the conductive surface 251. That is, the active material layer 21 and the solid electrolyte layer 22 are stacked in this order on the conductive surface 251 of the base material 25 (see FIG. 1).

Although the specific laminated form in the electrode 2 is not particularly limited, any 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 include two or more layers of at least one of the active material layer 21 and the solid electrolyte layer 22.
That is, the present electrode 2 has (1) a laminated structure in which a solid electrolyte layer 22 is interposed between two active material layers 21, and (2) an active material layer 21 is interposed between two solid electrolyte layers 22. It is preferable to have at least one of the stacked structures. These laminated structures may be provided with either one or both laminated structures. The case where both of the laminated structures are provided includes a case where a laminated structure in which two or more active material layers 21 and two or more solid electrolyte layers 22 are alternately laminated is provided. Thus, by having a sandwich-like laminated structure, it is possible to obtain a more excellent Li ion conductivity than when no sandwich-like laminated structure is provided.
The number of stacked active material layers 21 and solid electrolyte layers 22 is not particularly limited, but may be, for example, 1 layer or more and 50 layers or less. The number of stacked layers is preferably 2 or more and 25 or less, more preferably 2 or more and 10 or less.

Furthermore, the active material layer 21 and the solid electrolyte layer 22 may be stacked with the same thickness, but may be stacked with different thicknesses. In this case, it is preferable to form the solid electrolyte layer 22 thinner than the active material layer 21. Thus, when the solid electrolyte layer 22 is thinned with respect to the active material layer 21, the distance between the stacked active material layers is larger than 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 thickness of the active material layer 21 _{(D 21)} and the thickness of the solid electrolyte layer 22 the ratio of the thickness of the _{(D 22) (D 22 /} D 21) is not limited, for example, 0.05 to 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.
Further, the specific thickness of each layer is not limited. For example, the thickness D ₂₁ of the active material layer 21 can be set to 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, a thickness _{D 22} of the solid electrolyte layer 22 may be a 0.25μm or 5μm 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 solid thickness of the electrolyte layer 22 _{(D 22)} shall be measured in the enlarged image of the electrode section 10000 times by electron microscopy. Specifically, an average value of actual dimensions measured at five different points of each layer is defined as thickness D ₂₁ or thickness D ₂₂ .

The active material layer 21 is a layer mainly composed of an active material. The phrase “mainly comprising an active material” means that the active material is contained in an amount of 50 mass% or more when the entire active material layer 21 is 100 mass%. This proportion is preferably 50% by mass or more and 100% by mass or less, 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 active material that can be contained in the active material layer include a solid electrolyte and a conductive additive. By containing these components, a Li ion conduction path (by a solid electrolyte) and an electron conduction path (by a conductive aid) can be formed in the electrode.
These other components may use only 1 type and may use 2 or more types together. When other components are contained, when the entire active material layer 21 is 100% by mass, the content of other components is 50% by mass or less. This content ratio can be 2 mass% or more and 40 mass% or less, and also can be 5 mass% or more and 30 mass% or less.
The solid electrolyte and the conductive aid will be described later.

The active material is a material capable of insertion and desorption of lithium ions, or an alloying / dealloying reaction. Among the active materials, as the positive electrode active material (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 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, “M” is one metal element selected from at least Co, Ni, and Mn among Co, Ni, Mn, and Al.

Among the above, as the lithium composite oxide of type _{2 LiMO, LiCoO 2, LiNiO 2,} LiMnO 2, Li 2 MnO 3, Li (Ni x Co 1-x) O 2 { where is 0 <x <1 . For example, Li (Ni _0.8 Co _0.2 ) O ₂ etc.}, Li (Ni _x Mn _1-x ) O ₂ {where 0 <x <1. For example, Li (Ni _0.5 Mn _0.5 ) O ₂ etc.}, Li (Ni _x Mn _y Co _1-xy ) O ₂ {where 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 {provided that x> 0, y> 0, x + y < 1. For _{example, Li (Ni 0.8 Co 0.15 Al} 0.05) such as _{O 2},} and the like. These may use only 1 type and may use 2 or more types together.
Further, among the above, the lithium composite oxide of _LiM 2 _{O 4 type, LiCo 2 O 4, LiNi 2} O 4, LiMn 2 O 4, Li (Co x Ni 2-x) O 4 { where 0 < x <a _{2}, Li (Co x Mn} 2-x) O 4 { wherein 0 <x <a _{2}, Li (Al x Mn} 2-x) O 4 { where 0 <x <2 _{there}, Li (Mn x Ni 2} -x) O 4 { proviso that 0 <x <2. For _{example, Li (Mn 1.5 Ni 0.5)} O 4 , etc.} and the like. These may use only 1 type and may use 2 or more types together.
Among the above, preferably lithium double oxide of type ₂ LiMO, _furthermore, is _{Li (Ni x Mn y Co 1} -x-y) O 2 { where, x> 0, y> 0 , x + y <1 } (Hereinafter also simply referred to as “NMC”).

Among the active materials, active materials for negative electrodes (hereinafter also simply referred to as “negative electrode active materials”) include carbon materials (carbon materials as negative electrode active materials), various oxides, magnesium compounds, tin compounds, and antimony compounds. Metal lithium or the like can be used.
Among these, examples of the carbon-based material include graphite, graphene, carbon black, carbon nanotube, lithium carbon compound (Li _x C ₆ ), and the like. Examples of the oxide include SiO, SnO, SnO ₂ , TiO ₂ , Nb ₂ O ₅ , WO ₂ , MoO ₂ , and Li ₄ Ti ₅ O ₁₂ . Examples of the magnesium compound include Mg ₂ Si, Mg ₂ Ge, and Mg ₂ Sn. Examples of the tin compound include 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. These may use only 1 type and may use 2 or more types together.

  The active material contained in the active material layer 21 can be 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 include at least two types of granular active materials having different particle sizes, that is, a larger particle active material and a smaller particle active material. Thereby, the filling property and smoothness of the active material layer 21 can be made compatible. More specifically, a granular active material (large-diameter active material) having a granular shape having a particle size of more than 0.5 μm and not more than 10 μm, and a granular active material having a spherical shape having a particle size of 1 nm to 500 nm ( Small-diameter active material).

The solid electrolyte layer 22 is a layer mainly composed of a solid electrolyte. The phrase “consisting of a solid electrolyte as a main component” means that the solid electrolyte is contained by 50 mass% or more when the entire solid electrolyte layer 22 is 100 mass%. This proportion is preferably 50% by mass or more and 100% by mass or less, 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 an active material and a conductive aid. These other components may use only 1 type and may use 2 or more types together. When other components are contained, the content ratio of the other components is 50% by mass or less, assuming that the entire solid electrolyte layer 22 is 100% by mass. This content ratio can be 2 mass% or more and 40 mass% or less, and also can be 5 mass% or more and 30 mass% or less.
The active material is as described above. The conductive auxiliary will be described later.

A solid electrolyte is a substance that can serve as 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 , 70 Li ₂ S · 30P ₂ S ₅ , 50Li ₂ S · 50 GeS ₂ , Li _3.25 P _0.95 S ₄ , Li _3.25 Ge _0.25 P _0.75 S ₄ , Li ₃ PS ₄ And sulfide solid electrolytes such as Li ₄ P ₃ S ₁₁ and Li ₇ P ₃ S ₁₁ . These may use only 1 type and may use 2 or more types together.
Furthermore, 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. These may use only 1 type and may use 2 or more types together.

Of these, sulfide solid electrolytes are preferred. Furthermore, a sulfide glass solid electrolyte or an amorphous sulfide solid electrolyte of a sulfide glass ceramic solid electrolyte is more preferable. As an amorphous 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 · 50 GeS 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 the like.
Among these, an amorphous sulfide solid electrolyte containing each element of Li, P and S and containing a PS ₄ bond is preferable. Examples of such sulfide solid electrolytes include Li ₃ PS ₄ , Li ₄ P ₃ S ₁₁ , Li ₇ P ₃ S ₁₁ , 70Li ₂ S · 30P ₂ S ₅ , Li _3.25 P _0.95 S _{4 and the} like. Can be mentioned. These may use only 1 type and may use 2 or more types together.

  Further, 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 types of granular solid electrolytes having different particle sizes, that is, a larger granular solid electrolyte and a smaller granular solid electrolyte can be included at the same time. Thereby, the filling property and smoothness of the solid electrolyte layer 22 can be made compatible. More specifically, a granular solid electrolyte (large-diameter solid electrolyte) having a granular shape having a particle size of more than 0.5 μm and not more than 10 μm, and a granular solid electrolyte having a spherical shape having a particle size of 1 nm to 500 nm ( A small-diameter solid electrolyte).

  A conductive aid is a substance that can be an electron conduction path. Specifically, a powdery material having conductivity is preferable. Although the material which comprises such a conductive support agent is not specifically limited, A carbonaceous material (carbonaceous material as a conductive support agent), a metal, a metal compound, etc. are mentioned, Among these, a carbonaceous material is preferable. Examples of the carbon-based material include graphite, graphene, carbon black, and carbon nanotube.

When the electrode of the present invention is a positive electrode and a conductive additive is included, it may be included in only one of the active material layer 21 and the solid electrolyte layer 22, but in both of these layers It is preferably included.
When the conductive material is contained in the active material layer 21 and the entire active material layer 21 is 100% by mass, the content of the conductive auxiliary is preferably 0.1% by mass or more and 35% by mass or less, 1 mass% or more and 25 mass% or less are more preferable.
Similarly, when the conductive aid is included in the solid electrolyte layer 22 and the total amount of the solid electrolyte layer 22 is 100% by mass, the content of the conductive assistant is 0.1% by mass or more and 35% by mass. The following is preferable, and 1 mass% or more and 25 mass% or less are 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 as described above are laminated, target components (active material, solid electrolyte, etc. ) (Hereinafter simply referred to as “target particles”) can be deposited substantially in a substantially single layer (a very thin layer as a whole even if it is partially a multilayer) (specifically, the particles It is preferable that the film can be deposited with a thickness of 1 or more and 3 or less, and it is more preferable that the film can be deposited with a thickness of 1 or more and 2 or less. 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 being deposited thinly, and excellent electrode characteristics can be obtained. That is, the number of stacked layers can be increased within the same thickness, and thereby 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 a very short time, and a thick deposition layer is formed. That is, instead of a deposition layer in which target particles are laminated in a substantially single layer, a deposition layer in which a plurality of target particles are stacked is formed. On the other hand, by reducing the current density of the DC voltage to be applied, the deposition rate can be suppressed and the film thickness can be controlled more easily, but the surface roughness of the obtained deposited layer becomes large. That is, in electrophoresis using DC voltage, the thickness of the deposited layer and the surface roughness are in a trade-off relationship, and it is a substantially single layer in which the film thickness and the surface roughness are compatible, and the surface roughness is small. It turned out to be difficult to obtain a deposited layer.

Therefore, the present inventors tried to use an alternating voltage in electrophoresis. As a result, it was found that the surface roughness of the obtained deposited layer can be suppressed while reducing the deposition rate. However, it has been found that the deposition rate is excessively reduced when AC voltage is used. And it turned out that there is a problem that even if the deposition time is extended, a film thickness of a certain degree or more cannot be formed.
Therefore, the present inventors tried to use a DC voltage and an AC voltage together. As a result, it was found that a deposition layer having a desired film thickness can be obtained while suppressing the surface roughness while controlling the deposition rate within a practical range.
As described above, the combined use of the DC voltage and the AC voltage biases the AC signal having a symmetrical waveform on the positive electrode side and the negative electrode side, and as a result, an asymmetric waveform on the positive electrode side and the negative electrode side. A signal having a signal (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 an applied voltage having an asymmetric signal, as described above, it is possible to obtain a deposited layer having a desired film thickness while suppressing the surface roughness while controlling the deposition rate within a practical range. I understood 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 of manufacturing a first electrode that uses an asymmetric signal as an applied voltage signal in electrophoresis of a deposition process for depositing particles.
(2) A method of manufacturing a second electrode using an asymmetric signal as an applied voltage signal in electrophoresis in a first deposition step for forming an active material layer.
(3) A method for producing a third electrode using an asymmetric signal as an applied voltage signal in electrophoresis in the second deposition step for forming a solid electrolyte layer.

(1) First Electrode Manufacturing Method The first electrode manufacturing method (hereinafter also simply referred to as “first manufacturing method”) is performed on a conductive surface of a substrate by electrophoresis in a liquid containing particles. A deposition step of depositing the particles, and in the electrophoresis of the deposition step, a signal having an asymmetric waveform between the positive electrode side and the negative electrode side is used as a voltage signal to be applied.

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

The material of the substrate is not particularly limited, and a wide variety of conductive materials that can form a conductive surface can be used. Examples of the conductive material include gold, platinum, indium, copper, zinc, nickel, tin, aluminum, stainless steel, alloys of these metals, and conductive compounds (ITO) containing these metals. These may use only 1 type and may use 2 or more types together. When using 2 or more types together, it can be laminated 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 used as appropriate. These may use only 1 type and may use 2 or more types together.
That is, for example, as the substrate, a plate-like body made of the above-described conductive material can be used as it is. Moreover, the composite_body | complex which coat | covered the foil-like body which consists of the above-mentioned electrically conductive material on the surface of the plate-shaped body which consists of nonelectroconductive materials (resin etc.) can be utilized as a base material as a whole.
This base material can be used as a current collector as it is in an all-solid-state lithium ion battery.

The “particle-containing liquid” is usually a dispersion liquid in which particles are dispersed. The state of the dispersion is not particularly limited, and may be any of suspension (suspension), emulsion, colloidal liquid and the like.
The particles that are the dispersoid in the dispersion are particles that can be deposited on the conductive surface of the substrate by electrophoresis. The material constituting such particles is not particularly limited, and various components blended in the electrode can be used after being granulated so as to be electrophoresed. Specifically, the above-mentioned active materials (particles made of an active material), solid electrolytes (particles made of a solid electrolyte), conductive assistants (particles made of a conductive assistant), and the like can be mentioned. These may use only 1 type and may use 2 or more types together.

The particle shape of the particles is not particularly limited, and includes substantially spherical shapes, granule shapes (shapes in which smaller particles are gathered together), lump shapes, flake shapes (scale shapes), needle shapes, indefinite shapes, wire shapes, tube shapes, and the like. It is done. These may use only 1 type and may use 2 or more types together.
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 diameter exceeding 7 μm using an applied voltage having an asymmetric signal, but it is difficult to obtain the effect of using an asymmetric signal with such a large particle diameter. That is, for example, a single layer film can be formed relatively easily even when only a DC voltage is used.
On the other hand, in the case of particles having a particle size of 7 μm or less (particularly 4 μm or less), as the particle size decreases, electrophoresis using only a DC voltage or normal AC voltage (that is, between the positive electrode side and the negative electrode side). In electrophoresis using a voltage having a symmetrical waveform signal, it is difficult to form a single layer film. On the other hand, by using an asymmetric signal, it is possible to obtain an increase in the deposition rate of particles and a good dispersibility of the particle arrangement (the particles do not pile up).
For this reason, the particles of the particle-containing liquid preferably include particles having a particle size of 7 μm or less, more preferably have a particle size of 4 μm or less, and particularly preferably have a particle size of 1 μm or less. Since the effect of using an asymmetric signal is obtained as the particle size is smaller, 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. However, the dispersion medium includes at least one of a diether compound, a carbonyl compound, an alcohol compound, and a saturated fatty acid ester compound. It is preferable to use a dispersion medium. These dispersion media may use only 1 type and may use 2 or more types together.
Among these, examples of the diether compound include 1,2-dimethoxyethane (DME), 1,2-diethoxyethane, 1-ethoxy-2-methoxyethane, and the like. These may use only 1 type and may use 2 or more types together. Of these, 1,2-dimethoxyethane is particularly preferred.
Examples of the carbonyl compound include methyl ethyl ketone (MEK), acetone, diethyl ketone, 2-pentanone and the like. These may use only 1 type and may use 2 or more types together. Furthermore, examples of the alcohol compound include isopropyl alcohol (IPA), methanol, ethanol, butanol and the like. These may use only 1 type and may use 2 or more types together. Examples of saturated fatty acid ester compounds include methyl propionate, ethyl propionate, propyl propionate, and butyl propionate. These may use only 1 type and may use 2 or more types together.

  The concentration of the particles contained in the particle-containing liquid is not particularly limited, but when the total of the particles (dispersoid) 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. % Or less. This proportion is preferably 0.5% by mass to 25% by mass, more preferably 1% by mass to 20% by mass, and particularly preferably 1.5% by mass to 15% by mass.

  The voltage applied in this electrophoresis has a signal having an asymmetric waveform between the positive electrode side and the negative electrode side (see FIGS. 2 to 6). Having an asymmetric waveform between the positive electrode side and the negative electrode side means that the signal waveform on the positive electrode side at 0V and the signal waveform on the negative electrode side at 0V are not symmetrical. . Specifically, examples of the asymmetric signal include (1) a signal having different peak absolute values on the positive electrode side and the negative electrode side, and (2) a signal having different application times on the positive electrode side and the negative electrode side. Needless to say, a signal whose absolute value of the peak is different between the positive electrode side and the negative electrode side and whose application time is different 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, an asymmetric signal may be designed as appropriate, or may be formed by superimposing a DC voltage and an AC voltage. When the DC voltage and the AC voltage are superimposed, a signal of one type of frequency may be used as the signal of the AC voltage, or two types of signals having different frequencies may be used in combination.
Examples of the asymmetric signal include signal forms shown in FIGS. These asymmetric signals may be used alone or in combination of two or more.

Among the above, the asymmetric signal in FIG. 2 has a difference between the positive peak absolute value (V ₊ ) and the negative peak absolute value (V ₋ ), and the positive electrode application time (T ₊ ) and the negative electrode application time (T _−). ) Is an asymmetric signal formed by a triangular wave. Such an asymmetric signal can be formed, for example, by applying a bias to the positive electrode side with respect to a triangular wave symmetrical signal (AC signal). That is, it can be formed by superimposing an AC voltage and a DC voltage.
In the asymmetric signal of FIG. 3, the positive peak absolute value (V ₊ ) and the negative peak absolute value (V ₋ ) are different, and the positive electrode application time (T ₊ ) and the negative electrode application time (T ₋ ) are different. It is an asymmetric signal formed by a rectangular wave. This rectangular 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 peak absolute value (V ₊ ) and the negative peak absolute value (V ₋ ) are different, and the positive electrode application time (T ₊ ) and the negative electrode application time (T ₋ ) are different. It is an asymmetric signal formed by a triangular wave.
In the asymmetric signal of FIG. 5, the positive peak absolute value (V ₊ ) and the negative peak absolute value (V ₋ ) are different, and the positive electrode application time (T ₊ ) and the negative electrode application time (T ₋ ) are different. An asymmetric signal represented by a parabola.
In the asymmetric signal of FIG. 6, the positive peak absolute value (V ₊ ) and the negative peak absolute value (V ₋ ) are different, and the positive electrode application time (T ₊ ) and the negative electrode application time (T ₋ ) are different. It is an asymmetric signal formed by a rectangular 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 instantaneously switches to a reverse electric field via the peak top.
In the electrode manufacturing method of the present invention, not only these forms of asymmetric signals but also various asymmetric signals can be used.

Further, the asymmetric signal has an absolute value of the positive peak (amplitude from 0 V to the peak end) as V ₊ and an absolute value of the negative peak (0 V to the peak end) as V ₋ (FIG. 2 to FIG. 6), and the ratio (V ₊ / V ₋ ) is preferably 0.02 ≦ V ₊ / V ₋ ≦ 50. In this range, the effect obtained by using signals having different peak absolute 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, and more preferably 1.01 ≦ V ₊ / V ₋ ≦ 30, particularly 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 strengthening the action of migrating to the negative electrode side in particular, 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 preferable, and 0.2 ≦ V ₊ / V ₋ ≦ 0.5 is particularly preferable.

Also, the application time on the positive electrode side (the time indicating the amplitude to the positive electrode side with respect to 0V) is T _+, and the application time on the negative electrode side (the time indicating the amplitude to the negative electrode side with respect to 0V) is When 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 with 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, more preferably 1.01 ≦ T ₊ / T ₋ ≦ 30, particularly 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.
Conversely, when strengthening the action of migrating to the negative electrode side in particular, 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 preferable, and 0.2 ≦ T ₊ / T ₋ ≦ 0.5 is particularly preferable.

Further, the ratio {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} also satisfies 0.02 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} ≦ 50. preferable.
This ratio {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} is 1 <{(V ₊ × T ₊ ) / (V ₋ × T _{− −} ), particularly when the action of migrating to the positive electrode side is strengthened. )} ≦ 50, more preferably 1.01 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} ≦ 30, and 1.3 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} ≦ 10 is particularly preferable, and 1.5 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} ≦ 5 is particularly preferable.
On the contrary, when strengthening the action of migrating to the negative electrode side in particular, 0.02 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} <1 is more preferable, and 0.03 ≦ {(V ₊ × T ₊ ) / (V ₋ × T ₋ )} ≦ 0.99 is more preferable, 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 large, and the obtained particle deposition layer (for example, the active material layer or the 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, when 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 is increased.
When a particle deposition layer having a large surface roughness is observed, lamination of particles is observed. A monolayer in which particles are deposited as a single layer in a desired region of a conductive surface is an ideal particle deposition layer, but a particle deposition layer with a large surface roughness is a particle deposition at a certain part of the conductive surface. The surface roughness tends to increase as a result of an increase in the variation in the deposition thickness such that particles are deposited in two or more layers at other locations.

  That is, for example, when six particles 52 are deposited on the conductive surface of the substrate 51, as illustrated in FIG. 8, when the particles 52 are stacked, the particles 52 are deposited to form a film. A portion where the thickness is increased or a portion where the particles 52 are not deposited is generated, and the surface roughness of the obtained deposited layer is increased. 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 particles deposited is the same as in FIG. Compared to the deposited layer, a deposited layer having a smaller surface roughness can be obtained in FIG. If these operations can be repeated, different types of particles (particles 521 and particles 522) can be regularly deposited to increase the contact area with each other, as shown in FIG.

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

That is, when electrophoresis is performed using an alternating voltage, particles are migrated while an electric field that migrates toward the substrate is acting, and approach the conductive surface of the substrate. It is considered that whether or not the particles reach the conductive surface depends on whether or not the electric field changes when the electric field is reversed. That is, it is considered that particles having a large mass are difficult to follow a change in electric field, remain in the vicinity of the electrophoretic surface that has been migrated, and eventually accumulate. On the other hand, particles with a small mass can easily follow changes in the electric field, and sometimes return from the vicinity of the conductive surface to the solution side, so particles with a small mass are less likely to deposit than particles with a large mass. It is thought that.
Therefore, it is considered that deposition can be achieved even for particles having a small mass by breaking the symmetry of the waveform of the applied voltage and applying an applied voltage in which the action of the electric field migrating to the substrate side is increased.
When the time for strengthening the action of the electric field migrating to the substrate side (for example, the application time on the positive electrode side) becomes longer, the amount of deposition becomes excessively large (deposited beyond being substantially a single layer film). Since there is a possibility, the time for strengthening the action of the electric field migrating to the substrate side is preferably suppressed to a short time as described above. That is, it is preferable to make the migration action toward the substrate strong (the absolute value of the peak is large) and short (the application time is short). In addition, the electric field in the reverse direction is weak (small absolute value of the peak) and has a waveform that acts for a long time (long application time), so that the deposited particles can be dispersed appropriately.

For the reasons described above, particles can be deposited only once by electrophoresis, but can be divided into a plurality of times as necessary. In particular, in the case of using a plurality of types of particles having different particle sizes (that is, having different masses), by using an asymmetric signal suitable for each particle, a substantially single layer with better controllability is obtained. A small particle deposition layer can be obtained.
Specifically, 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 solution and each deposited using an asymmetric signal suitable for 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. The gap formed between the particles can be deposited so as to be filled with small-diameter particles.
In this way, after particles having different particle size groups are dispersed in different particle-containing liquids, electrophoresis is performed using a particle-containing liquid having a large particle diameter, and then electrophoresis is gradually performed using a particle-containing liquid having a small particle diameter. Thus, a dense particle deposition layer having excellent surface smoothness can be formed.

Furthermore, as illustrated in Example 1 described later, a more monolayered deposit can be obtained by controlling the frequency of the applied voltage according to the particle size. That is, it is possible to positively select a frequency at which a single layer can be easily formed. Specifically, according to the particle size to be deposited and the particle size distribution, an appropriate frequency is searched in advance, and voltage application is performed using the frequency (electrophoresis), thereby suppressing the deposition of the second layer or more. Thus, the deposition region of only the first layer (single layer) can be selectively increased.
The frequency of the applied voltage can be, for example, 5 Hz to 13 Hz, preferably 6 Hz to 13 Hz, more preferably 7 Hz to 12 Hz, and particularly preferably 7 Hz to 11 Hz. Although it can be used for particles having any particle size of this frequency, it is particularly suitable for particles having an average particle size of 0.5 μm to 7 μm (particularly 0.7 μm to 6 μm).

(2) Second Electrode Manufacturing Method The second electrode manufacturing method (hereinafter, also simply referred to as “second manufacturing method”) is performed by electrophoresis in an active material-containing liquid containing an active material. A first deposition step of depositing an active material on the conductive surface and forming an active material layer, and using an asymmetric signal as an applied voltage signal in electrophoresis in the first deposition step.
That is, the second manufacturing method means a case where the particles in the first manufacturing 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 “substrate”, the substrate in the first production method can be applied as it is.
The “active material-containing liquid” can be directly applied to the particle-containing liquid in the first production method 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 a diether compound as a dispersion medium, the influence on the solid electrolyte layer 22 can be suppressed when an active material is used as particles. Examples of the diether compound include 1,2-dimethoxyethane, 1,2-diethoxyethane, 1-ethoxy-2-methoxyethane, and the like. These may use only 1 type and may use 2 or more types together. Of these, 1,2-dimethoxyethane is particularly preferred.
As the “asymmetric signal”, the asymmetric signal in the first manufacturing method can be applied as it is.

(3) Third Electrode Manufacturing Method The third electrode manufacturing method (hereinafter also simply referred to as “third manufacturing method”) is performed in a solid electrolyte-containing liquid containing a solid electrolyte and / or a precursor thereof. In the electrophoresis of the second deposition step, the second deposition step of depositing the solid electrolyte and / or its precursor on the conductive surface of the substrate by electrophoresis to form the solid electrolyte layer or its precursor layer is provided. The asymmetric signal is used as the voltage signal to be applied.
That is, in the third production method, the particles in the 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 the second deposition step. Means.

As the “substrate”, the substrate in the first production method can be applied as it is.
Further, the “solid electrolyte-containing liquid” can be directly applied to the particle-containing liquid in the first production method 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 a particle, particularly as a solid electrolyte. Examples of the saturated fatty acid ester compound include methyl propionate, ethyl propionate, propyl propionate, and butyl propionate. These may use only 1 type and may use 2 or more types together. Of these, ethyl propionate is particularly preferred.
The “solid electrolyte precursor” refers to particles that change into a solid electrolyte by removing the dispersion medium and, if necessary, performing post-treatment such as heating.
As the “asymmetric signal”, the asymmetric signal in the first manufacturing method can be applied as it is.

(4) Fourth Electrode Manufacturing Method The fourth electrode manufacturing method (hereinafter also simply referred to as “fourth manufacturing method”) includes an active material layer containing an active material as a main component and a solid electrolyte as a main component. A solid electrolyte layer, wherein the solid electrolyte is a sulfide solid electrolyte. That is, the active material containing liquid includes a first deposition step of depositing the active material on the conductive surface of the base material by electrophoresis in the active material containing liquid containing the active material to form an active material layer. It contains a diether compound and / or a carbonyl compound.
Further, in the fourth production method, as a pre-process or a post-process of the first deposition process, a solid electrolyte is applied to the conductive surface of the substrate by electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or its precursor. A second deposition step of depositing the electrolyte and / or its precursor to form a solid electrolyte layer or its precursor layer; At this time, the solid electrolyte is a sulfide solid electrolyte.
Also in the fourth production 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 producing electrode The all-solid-state lithium ion battery (1) of the present invention includes 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 disposed between the pair of electrodes (2a, 2b). Among 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.
Furthermore, the solid electrolyte body (3) is a Li ion conductor containing a solid electrolyte. The shape, size, and the like are not particularly limited and can be set appropriately. Moreover, as a solid electrolyte which comprises a solid electrolyte body (3), what was mentioned above as a solid electrolyte which can be utilized for an electrode (2) can be utilized 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.
The all solid-state lithium ion battery (1) of the present invention can be provided with a known configuration as necessary, for example, a separator, in addition to the above.

[1] Example 1 (effect of frequency)
<1> Preparation of Active Material-Containing Liquid (Dispersion) Using the following granular active material, an active material-containing liquid (dispersion) was prepared by the following procedure.
(1) The following active material was put into a 5% by mass aqueous solution of poly (diallyldimethylammonium chloride) (cationic surfactant) and subjected to ultrasonic treatment to be dispersed.
(2) The dispersion liquid of the above (1) was centrifuged, and the upper layer of the obtained separation liquid was removed to recover the lower layer.
(3) Into the liquid (2) (recovered lower layer), isopropyl alcohol is added, centrifuged, and the operation of 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, an active material-containing liquid (dispersion, solid content concentration of 3.0 mass) in which the active material is dispersed using an active material as a dispersoid, isopropyl alcohol as a dispersion medium, and poly (diallyldimethylammonium chloride) as a dispersant. %).
Active material: Powder of Li-containing double oxide represented by Li (Ni _x Mn _y Co _z ) O ₂ , average particle size 5 μm

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

<3> Measurement of coverage rate Using the following laser microscope, the coverage rate of the first layer of the active material layer formed on the conductive surface of the ITO substrate obtained up to the above <2> by the following procedure; The coverage of the upper layer which is the second layer or higher was measured.
Specifically, using an active material having an average particle diameter of 5 μm, a laminate having a single layer (monolayer) region prepared separately was measured for the thickness of the single layer region 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 deposition thickness of 3 to 5 μm was defined as a single layer region (that is, a region covered with the first layer), and the area ratio of this region was calculated as the coverage ratio of the first layer. Furthermore, since the region where the deposition thickness is 6 μm or more is a region where particles are deposited in multiple layers, it is defined as a multilayered region (that is, a region coated with an upper layer deposited on the first layer). The area ratio of the region was calculated as the coverage of the upper layer. The results are shown graphically in FIG.
In the above-described deposition thickness measurement, an image is obtained by taking a 100-magnification image with a laser microscope (manufactured by Olympus Corporation, model “LEXT OLS4100”), and then two mode values seen in the height histogram of this image. The difference between the respective heights of the substrate surface and the deposition height of the deposited particles was used as the film thickness.

<4> Effects of Example 1 From FIG. 10, it can be seen that there are a frequency region where the coverage of the first layer is high and a frequency region where the coverage of the upper layer is high. Therefore, it is possible to select a frequency region in which the coverage of the first layer is greater than the coverage of the upper layer, thereby creating an environment that facilitates the formation of a more ideal single layer (monolayer). I understand that I can do it. In particular, in this case, the result was obtained at a particle size of 5 μm, and thus it was shown that the most ideal deposition can be obtained at 10 Hz in a particle size range exhibiting a particle size of 5 μm or similar behavior.
[2] Example 2 (Influence of applied voltage and its signal waveform)
<1> Preparation of active material-containing liquid (dispersion) [2] In the same manner as in <2> of Example 2, the active material is a dispersoid, isopropyl alcohol is a dispersion medium, and poly (diallyldimethylammonium chloride) is dispersed. As an agent, an active material-containing liquid in which an active material was dispersed (dispersion, solid content concentration of 3.0% by mass) was obtained. However, the average particle diameter of the active material was adjusted to 1 μm as described below.
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 the above <1> was put into an electrophoresis tank, and the positive electrode and the negative electrode were opposed to each other with an interval of 5 mm in this active material-containing liquid. A base material (ITO substrate) having a conductive surface made of ITO (indium tin oxide) was used for each of the positive electrode and the negative electrode.
And the applied voltage shown in following Table 1 was applied between said positive electrode and negative electrode, and electrophoresis was performed over the time (electrophoresis time) shown in following Table 1. Details of the applied voltage at this time are also shown in Table 1. Thereafter, the positive electrode (cathode) that had passed the migration time was pulled up from the migration tank and then naturally dried to obtain an active material layer formed on the conductive surface of the ITO substrate.
As described above, [1] Using the result of Example 1, 10 Hz is selected as the frequency.

<3> Measurement of film thickness and average surface roughness Using the following laser microscope, the average film thickness of the active material layer formed on the conductive surface of the ITO substrate obtained up to the above <2> by the following procedure. Then, the average surface roughness was measured. The results are also shown in Table 1.
For the average film thickness, two mode values (respectively the height of the substrate surface and the height of the substrate surface) are obtained by using an image obtained by photographing at 100 magnifications 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 using the arithmetic average roughness Sa obtained by calculating three-dimensional parameters from the same laser microscope image (100 times) as described above to which an 80 μm λc contour curve filter was applied.

<4> Effects of Example 2 As shown in Experimental Example 1, 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 laminate having a single layer (monolayer) region (see FIG. 7) separately prepared using an active material having an average particle diameter of 1 μm, the deposition thickness of the single layer region was measured by the laser microscope described above. However, it was found that the deposition thickness was in the range of 0.4 to 0.6 μm, and the average deposition thickness was about 0.5 μm. Therefore, from this empirical value, the region having a deposition thickness of 0.4 to 0.6 μm is substantially a single layer region.
Based on the above, since the film thickness of Experimental Example 1 is 6 μm, which is about 12 times the target value, it can be seen that particles were deposited in multiple layers in a very short time.
In contrast, in Experimental Examples 2 to 5, attempts were made to control the film thickness by reducing the current density of the DC voltage or shortening the migration time. As a result, in Experimental Examples 3 to 5, the average film thickness is 0.422 to 0.577 μm, which indicates that the target value has been reached. However, the average surface roughness was 0.163 μm in Experimental Example 1, but was 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 This is because there are areas where active materials are deposited in a single layer, but there are areas where no active material is deposited or areas where active materials are stacked in multiple layers, resulting in severe irregularities. This is considered to be a result (see FIG. 8). That is, it can be seen that when a film thickness is controlled using a DC voltage, it is difficult to obtain a smooth active material layer although a film thickness close to the target value can be obtained by controlling the current density.

  Therefore, in Experimental Examples 6 to 8, electrophoresis is performed using an alternating voltage (a symmetric signal). As a result, it can be seen that the film thickness can be controlled by controlling the maximum voltage value. And it turns out that a comparatively favorable value with an average surface roughness of 0.117-0.173 micrometers is obtained. However, for example, in Experimental Examples 3 to 5, the target film thickness was obtained by electrophoresis for 5 to 50 seconds, whereas in Experimental Examples 6 to 8, if electrophoresis was not performed for 900 seconds, the target value was obtained. It can be seen that the film thickness cannot be obtained.

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

[3] Example 3 (Lamination of active material layer and solid electrolyte layer)
<1> Preparation of Solid Electrolyte-Containing Liquid (Dispersion) The following lithium sulfide powder and the following diphosphorus pentasulfide powder were weighed so as to have a molar ratio of 3: 1 and mixed in an agate mortar. 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. Reacted. After 24 hours, the zirconia balls were removed from the resin container to obtain a solid electrolyte-containing liquid which was a dispersion (suspension, solid content concentration 11.7% by mass) in which the solid electrolyte and / or its precursor were dispersed. .
Lithium sulfide (Li ₂ S) powder: manufactured by Mitsuwa Chemical Co., Ltd., purity 99%, average particle size 53 μm
Diphosphorus pentasulfide (P ₂ S ₅ ) powder: Aldrich, purity 99%, average particle size 100 μm

<2> Formation of Solid Electrolyte Layer The solid electrolyte-containing liquid obtained in the above <1> was put into an electrophoresis tank, and a positive electrode and a negative electrode were opposed to each other with a space of 10 mm in this solid electrolyte-containing liquid. . A base material (ITO substrate) having a conductive surface made of ITO (indium tin oxide) was used for each of the positive electrode and the negative electrode. Then, electrophoresis was carried out by applying a DC voltage at a voltage of 100 V for 10 seconds between the positive electrode and the negative electrode.
Then, after lifting the negative electrode which passed the said migration time from the migration tank, natural drying was performed and the solid electrolyte layer formed in the electroconductive surface of an ITO board | substrate was obtained.

<3> Preparation of Active Material-Containing Liquid (Dispersion) Using the following granular active material, an active material-containing liquid (dispersion) 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 be dispersed.
(2) The operation of adding water to the dispersion liquid of the above (1) and centrifuging, removing the upper layer of the obtained separation liquid and recovering the lower layer was repeated three times.
(3) The liquid (collected lower layer) of the above (2) was vacuum-dried to obtain a powder (a powder having polyethyleneimine attached around the active material).
(4) 1,2-Dimethoxyethane is added to the powder obtained in the above (3), and is subjected to ultrasonic treatment to disperse the active material as a dispersoid, and 1,2-dimethoxyethane is used as a dispersion medium. Then, an active material-containing liquid in which the active material was dispersed (dispersion, solid content concentration: 3% by mass) was obtained using polyethyleneimine as a dispersant.
Active material: Powder of Li-containing double oxide 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 the above <3> was put into an electrophoresis tank, and a positive electrode and a negative electrode were opposed to each other with an interval of 10 mm in the active material-containing liquid. . Among these, as the negative electrode, the ITO substrate on which the solid electrolyte layer was formed in the above <2> was used. On the other hand, an ITO substrate having a conductive surface made of ITO (indium tin oxide) was used as the positive electrode. Then, electrophoresis was performed by applying a DC voltage at a voltage of 100 V for 45 seconds between the positive electrode and the negative electrode.
Thereafter, the positive electrode (cathode) that has passed the migration time is lifted from the migration tank and then naturally dried to form a laminate in which a solid electrolyte layer and an active material layer formed on the conductive surface of the ITO substrate are laminated. Got the body.

<5> Lamination of Solid Electrolyte Layer After a new solid electrolyte-containing liquid is obtained by the operation of <1> above, this is put into an electrophoresis tank, and a positive electrode is provided in the solid electrolyte-containing liquid with an interval of 10 mm. And the negative electrode were opposed. Among these, as the negative electrode, the ITO substrate in which the active material layer was laminated on the solid electrolyte layer in the above <4> was used. On the other hand, an ITO substrate having a conductive surface made of ITO (indium tin oxide) was used as the positive electrode. Then, electrophoresis was carried out by applying a DC voltage at a voltage of 100 V for 10 seconds between the positive electrode and the negative electrode.
Thereafter, the positive electrode (cathode) that has passed the migration time is lifted from the migration tank and then naturally dried, so that the solid electrolyte layer, the active material layer, and the solid electrolyte layer formed on the conductive surface of the ITO substrate are The laminated body laminated | stacked in order was obtained.

<6> Effects of Example 3 The positive electrode (laminated body modified ITO) obtained up to the above <5> was linearly divided in the laminating direction to expose the fracture surface. The obtained sample with the fracture surface exposed was attached to a sample stage 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 times. Magnified and observed. The obtained image is shown in FIG.
As a result, in Example 3, the ITO substrate (25), the solid electrolyte layer deposited on the conductive surface thereof with a thickness of about 700 nm, the active material layer deposited with a thickness of about 1 μm, the thickness of about 500 nm. It can be seen from FIG. 11 that an electrode is obtained in which the solid electrolyte layers deposited in (1) are stacked in this order.

[4] Example 4 (All-solid-state lithium ion battery)
<1> Preparation of Active Material-Containing Liquid (Dispersion) Using the following granular active material, an active material-containing liquid (dispersion) was prepared by the following procedure.
(1) The following active material was put into a 10% by mass aqueous solution of poly (diallyldimethylammonium chloride) (cationic surfactant) and subjected to ultrasonic treatment to be dispersed.
(2) Ion exchanged water was added to the dispersion liquid of (1) above and centrifuged, and the upper layer of the obtained separation liquid was removed to recover the lower layer.
(3) Into the liquid (2) (recovered lower layer), isopropyl alcohol is added, centrifuged, and the operation of 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, an active material-containing liquid in which the active material is dispersed using the active material as a dispersoid, isopropyl alcohol as a dispersion medium, and poly (diallyldimethylammonium chloride) as a dispersant (dispersion, solid content concentration: 3% by mass) Got.
Active material: Powder of Li-containing double oxide represented by Li (Ni _x Mn _y Co _z ) O ₂ , average particle size 5 μm

<2> Lamination of active material layer The active material-containing liquid obtained in the above <1> was put into an electrophoresis tank, and a positive electrode and a negative electrode were opposed to each other with an interval of 10 mm in this active material-containing liquid. . Of these, an aluminum substrate (diameter 10 mm) was used for the positive electrode and an aluminum substrate 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, after lifting the negative electrode which passed the said migration time from the migration tank, natural drying was performed and the laminated body on which the active material layer formed in the electroconductive surface of the board | substrates made from aluminum was laminated | stacked was obtained.
Further, as the asymmetric signal, an asymmetric signal obtained by superimposing an AC voltage having a symmetric signal composed of a triangular wave (90 V) and a DC voltage of 10 V was used. This asymmetric signal is shown in FIG. However, V ₊ = 100 V, V ₋ = 100 V, T ₊ = 0.02 seconds, T ₋ = 0.02 seconds, frequency 20 Hz).

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

<4> Formation of Solid Electrolyte Layer The solid electrolyte-containing liquid obtained in the above <3> was put into an electrophoresis tank, and a positive electrode and a negative electrode were opposed to each other with a space of 5 mm in this solid electrolyte-containing liquid. . An aluminum substrate was used for the positive electrode, and an aluminum substrate in which an active material layer was deposited on the conductive surface obtained in <2> was used for the negative electrode. Then, electrophoresis was performed by applying a DC voltage at a voltage of 25 V for 10 seconds between the positive electrode and the negative electrode.
Thereafter, the negative electrode after the above migration time was lifted from the electrophoresis tank, preliminarily 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). ), A laminate in which an active material layer and a solid electrolyte layer were laminated in this order was obtained.

<5> Lamination of solid electrolyte body Lamination obtained by pressing the solid electrolyte body with a thickness of 1000 μm obtained by pressure-molding 80 mg of LPS (75Li ₂ S · 25P ₂ S ₅ ) up to the above <4> It pressed on the surface of the solid electrolyte layer of the body (electrode).

<6> Lamination of indium foil An indium foil having a thickness of 100 μm is pressure-bonded to the surface of the solid electrolyte body of the laminated body (laminated body of electrodes and solid electrolyte body) obtained up to the above <5>. A lithium ion battery was obtained.
That is, as shown in FIG. 12, the all solid-state lithium ion battery 1 of Example 4 includes a base material (current collector) 25 made of an aluminum substrate, and an active material 211 (active material) laminated on its conductive surface. The electrode 2b includes 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. Furthermore, it has the solid electrolyte body 3 laminated | stacked on the surface of the solid electrolyte layer 22 of the electrode 2b. Furthermore, it has the electrode 2a laminated | stacked on the surface of the solid electrolyte body 3. FIG. In this 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> Charging / Discharging Confirmation and Effect of Example 4 The jig containing the all-solid-state lithium ion battery obtained up to the above <6> is sealed in a glass container, and the gas in the glass container is converted to argon gas. The measurement cell was obtained by replacement. The charge / discharge of the obtained measurement cell was observed by a constant current / constant voltage / charge method using an electrochemical measurement apparatus (manufactured by Solartron, model “SI 1287”). Specifically, 3.8 V vs. Constant current charging was performed at a rate of 0.01 C until In-Li, and then constant voltage charging was performed until 100 hours had passed. Immediately thereafter 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. Thereby, it was shown that charging and discharging are possible.

  Note that the jig 70 shown in FIG. 13 was used as the jig. That is, the all solid-state lithium ion battery 1 obtained up to the above <6> was accommodated in the through hole 74a of the cylindrical body 74 made of polyetheretherketone (PEEK). On the other hand, a pair of pressing pins 72 (a positive electrode side and a negative electrode side) assembled with a stainless steel convex block and a stainless steel screw were prepared. And the press pin 72 was inserted in the through-hole 74a so that the upper and lower sides of the all solid-state lithium ion battery 1 might be pinched | interposed. Further, in order to tighten these pressing pins 72, a pair of stainless pressing plates 71 (positive electrode side and negative electrode side) and three stainless steel tightening screws 73 for tightening the pressing plates are prepared. Were clamped with a pressing plate 71, and these pressing plates 71 were tightened with tightening screws 73 (screw restraint pressure: 9 N · m), and the all solid-state lithium ion battery 1 was accommodated in the jig 70. Various energizations are performed from the convex portions of the pressing pins 72 (locations denoted by reference numeral 72 in FIG. 13).

  The electrode of the present invention, the manufacturing method thereof, and the all-solid-state lithium ion battery include power supplies such as household appliances such as personal computers and cameras, portable electronic devices such as mobile phones or communication devices, electric tools such as power tools, and the like. It is suitable as a large battery mounted on an electric vehicle (EV), a hybrid electric vehicle (HEV) or the like, 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 body,
51; substrate, 52, 521, 522; particles.

Claims (15)

The electrode used in an all solid-state lithium ion battery having a structure in which a solid electrolyte body is disposed between a pair of electrodes,
An electrode comprising: an active material layer mainly composed of an active material; and a solid electrolyte layer mainly composed of a solid electrolyte.   At least one of a laminated structure in which the solid electrolyte layer is interposed between two layers of the active material layer and a laminated structure in which the active material layer is interposed between two layers of the solid electrolyte layer The electrode according to claim 1, which has a laminated structure of   The electrode according to claim 1, wherein the solid electrolyte layer is formed thinner than the active material layer.   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 additive.   The electrode according to any one of claims 1 to 4, wherein the solid electrolyte is a sulfide solid electrolyte.   The electrode according to any one of claims 1 to 5, which is a positive electrode. A deposition step of depositing the particles on the conductive surface of the substrate by electrophoresis in a liquid containing the particles;
In the electrophoresis in the deposition step, a signal having an asymmetric waveform on the positive electrode side and the negative electrode side is used as a voltage signal to be applied. It is a manufacturing method of the electrode according to claim 1, Comprising:
A first deposition step of depositing the active material on a conductive surface of a base material by electrophoresis in an active material-containing liquid containing the active material to form the active material layer;
In the electrophoresis in the first deposition step, a signal having an asymmetric waveform on the positive electrode side and the negative electrode side is used as a voltage signal to be applied. It is a manufacturing method of the electrode according to claim 1, Comprising:
The solid electrolyte and / or precursor thereof is deposited on a conductive surface of a substrate by electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or precursor thereof, and the solid electrolyte layer or precursor thereof is deposited. Comprising a second deposition step for forming a body layer;
In the electrophoresis in the second deposition step, a signal having an asymmetric waveform between the positive electrode side and the negative electrode side is used as a voltage signal to be applied.   The method for manufacturing an electrode according to claim 7, wherein the signal is a signal having different peak absolute values on the positive electrode side and the negative electrode side.   10. 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. It is a manufacturing method of the electrode according to claim 5,
A first deposition step of depositing the active material on a conductive surface of a base material by electrophoresis in an active material-containing liquid containing the active material to form the active material layer;
The 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 a post-process of the first deposition process,
The solid electrolyte and / or precursor thereof is deposited on a conductive surface of a substrate by electrophoresis in a solid electrolyte-containing liquid containing the solid electrolyte and / or precursor thereof, and the solid electrolyte layer or precursor thereof is deposited. Comprising a second deposition step for forming a body layer;
The method for producing an electrode according to claim 12, wherein the solid electrolyte is a sulfide solid electrolyte.   The method for manufacturing an electrode according to claim 12 or 13, wherein a signal having an asymmetric waveform on the positive electrode side and the negative electrode side is used as a voltage signal to be applied in the electrophoresis in the first deposition step.   An all-solid-state lithium ion battery comprising the electrode according to claim 1.