Method for manufacturing all-solid-state battery, and apparatus for manufacturing all-solid-state battery

Abstract

This method for manufacturing an all-solid-state battery 1 includes: a block formation step for forming a block B by solidifying a powder material; an electrode laminate formation step for forming an electrode laminate 2 by depositing a powder, which is generated by removing the block B, on a first base material F1; and a superposing step for superposing the electrode laminate 2 and a current collector 3 upon each other.

Description

All-solid-state battery manufacturing method and all-solid-state battery manufacturing device

[0001] The present invention relates to a method for manufacturing an all-solid-state battery and an apparatus for manufacturing an all-solid-state battery.

[0002] 2. Description of the Related Art Conventionally, a method for forming a film of functional powder (powder film) using an electrostatic screen printing device has been known (see Patent Document 1 below).

[0003] JP 2012-140016 A

[0004] In an electrostatic screen printing device such as that described in Patent Document 1, if the powder has low fluidity, the powder may block before being supplied to the screen or the screen may become clogged, which may result in an unstable supply of powder to the substrate or unevenness in the powder film thickness (poor film thickness accuracy).

[0005] If the amount of powder supplied to the substrate becomes unstable, it may be impossible to obtain a powder layer with the desired thickness. Furthermore, if the powder film has an uneven thickness, it may have adverse effects on battery performance, such as reduced charge / discharge efficiency and reduced lifespan.

[0006] The present invention provides a method and an apparatus for manufacturing an all-solid-state battery that can stabilize the amount of powder supplied to a substrate in an electrode laminate formation step and form a powder layer with a uniform thickness.

[0007] The present invention [1] includes a method for manufacturing an all-solid-state battery, which includes a block formation step of solidifying a powder material to form a block, an electrode laminate formation step of depositing powder generated by removing and processing the block on a substrate to form an electrode laminate, and a lamination step of laminating the electrode laminate and a current collector.

[0008] According to this method, in the electrode stack forming step, a block of powder material is removed and processed, and the resulting powder is deposited on a substrate.

[0009] Therefore, the influence of powder properties such as flowability can be reduced, and the amount of powder supplied onto the substrate can be controlled according to the amount of block to be cut.

[0010] As a result, the amount of powder supplied onto the substrate can be stabilized, and a powder layer with a uniform thickness can be formed.

[0011] The present invention [2] includes the method for producing an all-solid-state battery according to the above [1], wherein the powder material is pressure-molded in the block forming step.

[0012] According to this method, the density of the blocks can be made uniform, the amount of powder supplied onto the substrate can be stabilized, and the film thickness of the powder layer can be made uniform.

[0013] The present invention [3] includes the method for producing an all-solid-state battery according to the above [2], wherein the powder material is pressure-molded by a vibration press in the block forming step.

[0014] According to this method, the density of the blocks can be made more uniform, the amount of powder supplied onto the substrate can be made more stable, and the film thickness of the powder layer can be made more uniform.

[0015] The present invention [4] includes the method for producing an all-solid-state battery according to the above [2] or [3], wherein in the block forming step, the powder material is pressure-molded at 100 MPa or less.

[0016] According to this method, the block can be prevented from becoming excessively hard, and the block can be easily removed in the electrode stack formation step.

[0017] The present invention [5] includes the method for manufacturing an all-solid-state battery according to any one of the above [1] to [4], wherein, in the electrode stack formation step, the powder generated by removing the block is moved onto the base material by electrostatic force.

[0018] According to this method, the powder generated by removing the block can be guided onto the substrate by electrostatic force.

[0019] The present invention [6] includes a manufacturing apparatus used in the manufacturing method of an all-solid-state battery according to any one of the above [1] to [5], the manufacturing apparatus for an all-solid-state battery including a block support member that supports the block, a support table that is disposed apart from the block support member and supports the substrate, and a removal member that removes and processes the block supported by the block support member.

[0020] In this configuration, a block of powder material can be removed and the resulting powder can be deposited on a substrate.

[0021] Therefore, the amount of powder supplied onto the substrate can be controlled according to the amount of block to be removed.

[0022] As a result, the amount of powder supplied onto the substrate can be stabilized.

[0023] The present invention [7] includes the all-solid-state battery manufacturing apparatus according to the above [6], further comprising a pressing member that presses the block supported by the block support member toward the removal processing member.

[0024] With this configuration, the block can be brought into stable contact with the removal processing member.

[0025] The present invention [8] includes the all-solid-state battery manufacturing apparatus according to the above [6] or [7], further comprising a mask member disposed between the block support member and the substrate, the mask member having an opening through which the powder generated by removing the block can pass.

[0026] With this configuration, the powder can be deposited on the substrate in a shape that corresponds to the openings in the mask member.

[0027] The present invention [9] includes the all-solid-state battery manufacturing apparatus according to any one of the above [6] to [8], wherein the block support member is fixed to the support base, and the removal processing member is capable of sliding, rotating, or vibrating relative to the block support member.

[0028] The present invention

[10] includes the all-solid-state battery manufacturing apparatus according to any one of the above [6] to [8], wherein the removal processing member is fixed to the support base, and the block support member is capable of sliding, rotating, or vibrating relative to the removal processing member.

[0029] The present invention

[11] includes the all-solid-state battery manufacturing apparatus according to any one of the above [6] to

[10] , wherein the manufacturing apparatus includes a plurality of the removal processing members having different shapes.

[0030] With this configuration, it is possible to switch between a plurality of removal processing members to optimize the speed at which the block is removed and the uniformity of the thickness of the powder layer.

[0031] The present invention

[12] includes the all-solid-state battery manufacturing apparatus according to any one of the above [6] to

[11] , further comprising a measuring member for measuring the thickness of the block supported by the block support member.

[0032] According to this configuration, the amount of block scraping can be calculated by measuring the thickness of the block supported by the block support member.

[0033] Furthermore, the amount of powder deposited and the thickness of the powder layer can be calculated from the amount of block removed.

[0034] The present invention

[13] includes the all-solid-state battery manufacturing apparatus according to any one of the above [6] to

[12] , wherein the support table is slidable or rotatable while supporting the substrate.

[0035] According to this configuration, the support table slides or rotates while supporting the substrate, thereby making it possible to deposit powder on the substrate over a large area.

[0036] According to the method for manufacturing an all-solid-state battery and the apparatus for manufacturing an all-solid-state battery of the present invention, the amount of powder supplied onto the substrate in the electrode laminate formation step can be stabilized, and a powder layer with a uniform film thickness can be formed.

[0037] FIG. 1A is a plan view of an all-solid-state battery according to one embodiment of the present invention. FIG. 1B is an A-A cross-sectional view of the all-solid-state battery shown in FIG. 1A. FIG. 2A is a cross-sectional view showing the layer structure of the electrode laminate shown in FIG. 1B. FIG. 2B is an enlarged view of the all-solid-state battery shown in FIG. 1B. FIG. 3A is a plan view of the positive electrode current collector shown in FIG. 2B. FIG. 3B is a B-B cross-sectional view of the positive electrode current collector shown in FIG. 3A. FIG. 4 is a C-C cross-sectional view of the all-solid-state battery shown in FIG. 1A. FIGS. 5A and 5B are process diagrams illustrating a method for manufacturing an all-solid-state battery. FIG. 5A shows a step of forming a positive electrode layer on a first substrate in the electrode laminate formation step. FIG. 5B shows a step of forming a solid electrolyte layer on the positive electrode layer in the electrode laminate formation step. FIGS. 6A to 6C are process diagrams illustrating a method for manufacturing an all-solid-state battery, following FIG. 5B. FIG. 6A shows an electrode laminate obtained in the electrode laminate formation step. FIG. 6B shows a pressing step. FIG. 6C shows a peeling step. Fig. 7 is a perspective view of a manufacturing apparatus that can be used in the electrode stack formation step. Fig. 8 is an explanatory diagram for explaining the structure of the manufacturing apparatus shown in Fig. 7. Fig. 9 shows an example of a removal member having a blade, which is a modified version of the removal member shown in Fig. 7. Figs. 10A and 10B show modified versions of the removal member shown in Fig. 7. Fig. 10A shows an example of a removal member having a blade. Fig. 10B is a DD cross-sectional view of the removal member shown in Fig. 10A. Fig. 11 shows a modified version of the removal member shown in Fig. 7, which is a removal member having a punched metal.

[0038] 1. All-Solid-State Battery An example of an all-solid-state battery 1 will be described. Note that the shape of the all-solid-state battery 1 is not limited to this, as long as it is an all-solid-state battery manufactured according to the present invention [1].

[0039] As shown in FIGS. 1A and 1B , the all-solid-state battery 1 includes a plurality of electrode laminates 2 , a plurality of current collectors 3 , a positive electrode lead 4 , a negative electrode lead 5 , and an exterior material 6 .

[0040] (1) Electrode Stack In this embodiment, the electrode stack 2 has a sheet shape. When viewed in the thickness direction of the electrode stack 2, the electrode stack 2 has a substantially rectangular shape. The shape of the electrode stack 2 is not limited. The electrode stack 2 may have a plate shape or a film shape. Furthermore, the electrode stack 2 may have a substantially circular shape when viewed in the thickness direction of the electrode stack 2.

[0041] The electrode stack 2 has a thickness of, for example, 100 μm or more, preferably 200 μm or more, and for example, 1000 μm or less, preferably 800 μm or less.

[0042] 2A , the electrode stack 2 has a positive electrode layer 21, a negative electrode layer 22, and a solid electrolyte layer 23. The electrode stack 2 is made up of the positive electrode layer 21, the negative electrode layer 22, and the solid electrolyte layer 23. The electrode stack 2 has the solid electrolyte layer 23 between the positive electrode layer 21 and the negative electrode layer 22.

[0043] (1-1) Positive Electrode Layer The positive electrode layer 21 is disposed away from the negative electrode layer 22 in the thickness direction of the electrode laminate 2. The positive electrode layer 21 is disposed on the opposite side of the solid electrolyte layer 23 from the negative electrode layer 22 in the thickness direction of the electrode laminate 2. The positive electrode layer 21 is in contact with the solid electrolyte layer 23 but is not in contact with the negative electrode layer 22.

[0044] The positive electrode layer 21 is made of a powder containing a positive electrode active material. The positive electrode layer 21 may contain a resin such as a binder. In this embodiment, the positive electrode layer 21 is made of a mixture (positive electrode composite) of a powder of the positive electrode active material and a powder of a solid electrolyte. The positive electrode layer 21 may contain a conductive additive. The positive electrode layer 21 does not have to contain a solid electrolyte. The positive electrode layer 21 may be made of only the positive electrode active material.

[0045] The positive electrode active material may be, for example, a lithium-containing oxide. Examples of the lithium-containing oxide include lithium-nickel composite oxide (LiNi Ｘ M １－Ｘ O ２ ), lithium cobalt oxide (LiCoO ２ ), lithium nickel oxide (LiNiO ２ ), lithium nickel cobalt aluminum composite oxide (LiNi０．８ Co ０．１５ Al ０．０５ O ２ , NCA-based layered oxide), lithium manganese oxide (spinel-type lithium manganese oxide (LiMn ２ O ４ )), Li-excess composite oxide (Li ２ MnO ３ -LiMO ２ ) are listed.

[0046] The positive electrode active material is not limited to a lithium-containing oxide as long as it is capable of inserting and extracting lithium ions. Examples of the positive electrode active material include olivine-based compounds (LiMPO ４ ) and sulfur-containing compounds (Li ２ S) can be mentioned.

[0047] In the above chemical formula, M represents a transition metal.

[0048] As the positive electrode active material, a lithium-containing oxide containing at least one selected from the group consisting of Co, Ni, and Mn is preferable, from the viewpoint of easily obtaining a high capacity.

[0049] In addition, the surface of the positive electrode active material may be covered with a coating material from the viewpoint of improving rate characteristics.

[0050] As the coating material, for example, Li ４ Ti ５ O １２ , LiTaO ３ , Li ４ NbO ３ , LiAlO ２ , Li ２ ZrO ３ , Li ２ WO ４ , Li ２ TiO ３ , Li ２ B ４ O ７ , Li ３ P.O. ４ , Li ２ MoO ４ , LiBO ２ , alumina (Al ２ O ３ ), and carbon (C).

[0051] The positive electrode active materials can be used alone or in combination of two or more kinds.

[0052] The solid electrolyte exhibits lithium ion conductivity. Examples of the solid electrolyte include organic solid electrolytes and inorganic solid electrolytes.

[0053] Inorganic solid electrolytes include, for example, sulfides, oxides, nitrides, and hydrides.

[0054] Examples of sulfides include Li ２ Examples of the sulfide include those containing S and other sulfides containing at least one element selected from the group consisting of Group 13 elements, Group 14 elements, and Group 15 elements of the periodic table.

[0055] Examples of Group 13 elements, Group 14 elements, and Group 15 elements of the periodic table include P, Si, Ge, As, Sb, and Al, preferably P, Si, and Ge, and more preferably P.

[0056] Specifically, the sulfide may be, for example, Li ２ S-SiS ２ , Li ２ S-P ２ S ５ , Li ２ S-GeS ２ , Li ２ S-B ２ S ３ , Li ２ S-Ga ２ S ３ , Li ２ S-Al ２ S ３ , Li ２ S-GeS ２ -P ２ S ５ , Li ２ S-Al ２ S ３ -P ２ S ５ , Li ２ S-P ２ S ３ , Li ２ S-P ２ S ３ -P２ S ５ , LiX-Li ２ S-P ２ S ５ , LiX-Li ２ S-SiS ２ , and LiX-Li ２ S-B ２ S ３ (X: I, Br or Cl).

[0057] The solid electrolyte is preferably an inorganic solid electrolyte, more preferably a sulfide. The solid electrolyte may be used alone or in combination of two or more. The ratio of the positive electrode active material to the solid electrolyte is not limited.

[0058] The positive electrode layer 21 has a thickness of, for example, 50 μm or more, or preferably 100 μm or more. The positive electrode layer 21 has a thickness of, for example, 500 μm or less, or preferably 300 μm or less.

[0059] (1-2) Negative Electrode Layer The negative electrode layer 22 is disposed away from the positive electrode layer 21 in the thickness direction of the electrode laminate 2. The negative electrode layer 22 is disposed on the opposite side of the solid electrolyte layer 23 from the positive electrode layer 21 in the thickness direction of the electrode laminate 2. The negative electrode layer 22 is in contact with the solid electrolyte layer 23 but is not in contact with the positive electrode layer 21.

[0060] The negative electrode layer 22 is made of a powder containing a negative electrode active material. The negative electrode layer 22 may contain a resin such as a binder. In this embodiment, the negative electrode layer 22 is made of a mixture (negative electrode composite) of a powder of the negative electrode active material and a powder of a solid electrolyte. The negative electrode layer 22 may contain a conductive additive. The negative electrode layer 22 does not have to contain a solid electrolyte. The negative electrode layer 22 may be made of only the negative electrode active material.

[0061] The negative electrode active material is not limited as long as it is a material capable of inserting and extracting lithium ions, and examples of the negative electrode active material include carbon materials, metals and alloys thereof, semimetals, and compounds of metals or semimetals.

[0062] Examples of carbon materials include graphite (natural graphite, artificial graphite), hard carbon, and amorphous carbon. Examples of metals and their alloys include lithium and its alloys. Examples of metalloids include silicon. Examples of metal or metalloid compounds include oxides, sulfides, nitrides, hydrates, and silicides (lithium silicides) of metals or metalloids. Examples of metal or metalloid oxides include titanium oxide and silicon oxide.

[0063] The negative electrode active material can be used alone or in combination of two or more thereof. For example, silicon oxide and a carbon material can be used in combination as the negative electrode active material.

[0064] Examples of the solid electrolyte contained in the anode layer 22 include the solid electrolytes described above. Preferably, the solid electrolyte contained in the anode layer 22 is the same as the solid electrolyte contained in the cathode layer 21. The ratio of the anode active material to the solid electrolyte is not limited.

[0065] The thickness of the negative electrode layer 22 is approximately the same as the thickness of the positive electrode layer 21. The thickness of the negative electrode layer 22 is, for example, 50 μm or more, or preferably 100 μm or more. The thickness of the negative electrode layer 22 is, for example, 500 μm or less, or preferably 300 μm or less.

[0066] (1-3) Solid Electrolyte Layer The solid electrolyte layer 23 is disposed between the positive electrode layer 21 and the negative electrode layer 22 in the thickness direction of the electrode stack 2. The solid electrolyte layer 23 is made of a powder of a solid electrolyte. The solid electrolyte layer 23 may contain a resin such as a binder.

[0067] The solid electrolyte may be, for example, the solid electrolyte described above. Preferably, the solid electrolyte is the same as the solid electrolyte contained in the positive electrode layer 21.

[0068] The solid electrolyte layer 23 is thinner than the positive electrode layer 21 and the negative electrode layer 22. The thickness of the solid electrolyte layer 23 is, for example, 10 μm or more, or preferably 30 μm or more. The thickness of the solid electrolyte layer 23 is, for example, 300 μm or less, or preferably 100 μm or less.

[0069] (2) Current Collectors As shown in FIG. 2B , in the case of parallel connection, the multiple current collectors 3 are stacked alternately with the multiple electrode stacks 2. The multiple current collectors 3 include a positive electrode current collector 3A and a negative electrode current collector 3B. The positive electrode current collector 3A contacts the positive electrode layer 21 of the electrode stack 2. The negative electrode current collector 3B contacts the negative electrode layer 22 of the electrode stack 2.

[0070] Specifically, in this embodiment, the positive electrode current collector 3A, the first electrode laminate 2A, the negative electrode current collector 3B, the second electrode laminate 2B, and the positive electrode current collector 3A are stacked in this order from one side to the other in the stacking direction of the electrode laminate 2 and the current collector 3. In the stacking direction, one negative electrode current collector 3B is disposed between the negative electrode layer 22 of the first electrode laminate 2A and the negative electrode layer 22 of the second electrode laminate 2B. In other words, in the stacking direction, one current collector 3 is disposed between two electrode laminates 2. In the case of series connection, multiple electrode laminates 2 are stacked such that the stacking order of the positive electrode layer 21, the solid electrolyte layer 23, and the negative electrode layer 22 is the same, and current collectors 3 are disposed only in the uppermost and lowermost layers.

[0071] As shown in FIGS. 3A and 3B, the current collector 3 has a conductor 31, an insulating member 32, and an adhesive layer 33.

[0072] (2-1) Conductor The conductor 31 is made of, for example, a metal. The conductor 31 has a laminated portion 311 and a tab 312.

[0073] The laminate portion 311 extends in a first direction and a second direction. The first direction is perpendicular to the stacking direction. The second direction is perpendicular to both the first direction and the stacking direction. The laminate portion 311 has a sheet shape. The laminate portion 311 has one side S1 and another side S2 in the thickness direction. In other words, the conductor 31 has one side S1 and another side S2 in the thickness direction. The laminate portion 311 contacts the electrode laminate 2. When the current collector 3 is a positive electrode current collector 3A, the laminate portion 311 contacts the positive electrode layer 21 of the electrode laminate 2. When the current collector 3 is a negative electrode current collector 3B, the laminate portion 311 contacts the negative electrode layer 22 of the electrode laminate 2.

[0074] The tab 312 is disposed on an edge of the laminate portion 311. In the present embodiment, the tab 312 is disposed on one edge of the laminate portion 311 in the second direction. The tab 312 protrudes from the edge of the laminate portion 311. The tab 312 may be a separate member from the laminate portion 311 and may be joined to the laminate portion 311. The tab 312 has a belt shape. The tab 312 does not contact the electrode laminate 2. When the current collector 3 is a positive electrode current collector 3A, the conductor 31 has a positive electrode tab 312A as the tab 312. When the current collector 3 is a negative electrode current collector 3B, the conductor 31 has a negative electrode tab 312B as the tab 312. When the electrode laminate 2, the positive electrode current collector 3A, and the negative electrode current collector 3B are stacked, the negative electrode tab 312B is disposed away from the positive electrode tab 312A. When the electrode laminate 2, the positive electrode current collector 3A, and the negative electrode current collector 3B are stacked, the negative electrode tab 312B does not overlap the positive electrode tab 312A in the stacking direction.

[0075] The thickness of the conductor 31 is, for example, 1 μm or more, or preferably 5 μm or more, and for example, 100 μm or less, or preferably 50 μm or less.

[0076] Examples of materials for the conductor 31 include copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), indium (In), lithium (Li), tin (Sn), and alloys thereof.

[0077] (2-2) Insulating Member As shown in Fig. 3B, the insulating member 32 is laminated on one surface S1 of the conductor 31. As shown in Fig. 3A, the insulating member 32 is disposed on the laminated portion 311 of the conductor 31. The insulating member 32 is laminated on the peripheral edge of the laminated portion 311 of the conductor 31. The insulating member 32 has a substantially rectangular frame shape when viewed from the lamination direction. The insulating member 32 is not disposed on the tab 312 of the conductor 31.

[0078] When the electrode laminate 2, the positive electrode current collector 3A, and the negative electrode current collector 3B are stacked, the insulating member 32 is disposed around the electrode laminate 2. As shown in Fig. 1B , when the electrode laminate 2, the positive electrode current collector 3A, and the negative electrode current collector 3B are stacked, the insulating member 32 is disposed between the positive electrode current collector 3A and the negative electrode current collector 3B in the stacking direction. When the electrode laminate 2, the positive electrode current collector 3A, and the negative electrode current collector 3B are stacked, the insulating member 32 insulates the positive electrode current collector 3A from the negative electrode current collector 3B.

[0079] In the stacking direction, the thickness of the insulating member 32 is thinner than the thickness of the electrode stack 2. When the current collector 3 does not have the adhesive layer 33, the thickness of the insulating member 32 may be the same as the thickness of the electrode stack 2. The thickness of the insulating member 32 is, for example, 50 μm or more, preferably 75 μm or more, and for example, 500 μm or less, preferably 400 μm or less.

[0080] Examples of materials for the insulating member 32 include polyethylene terephthalate and polyimide.

[0081] (2-3) Adhesive Layer As shown in Fig. 3B, an adhesive layer 33 is laminated on the other surface S2 of the conductor 31 at the peripheral edge of the conductor 31. The current collector 3 does not need to have the adhesive layer 33. As shown in Fig. 1B, in a state in which one electrode laminate 2 is laminated between two current collectors 3, the adhesive layer 33 of the current collector 3 arranged on the other side of the electrode laminate 2 in the stacking direction is adhered to the insulating member 32 of the current collector 3 arranged on one side of the electrode laminate 2 in the stacking direction.

[0082] The sum of the thickness of the adhesive layer 33 and the thickness of the insulating member 32 is equal to or less than the thickness of the electrode stack 2. The thickness of the adhesive layer 33 is, for example, 30 μm or more, preferably 50 μm or more, and for example, 300 μm or less, preferably 200 μm or less.

[0083] The adhesive layer 33 is preferably insulating. Examples of materials for the adhesive layer 33 include resins such as acrylic, polyimide, and silicone, and nonwoven fabrics impregnated with these resins.

[0084] (3) Positive Electrode Lead and Negative Electrode Lead As shown in Fig. 1A, a portion of the positive electrode lead 4 is exposed from the exterior packaging material 6. As shown in Fig. 4, the positive electrode lead 4 is joined to a positive electrode tab 312A within the exterior packaging material 6. This electrically connects the positive electrode lead 4 to the positive electrode current collector 3A. The positive electrode lead 4 is not connected to the negative electrode current collector 3B.

[0085] As shown in Fig. 1A, a portion of the negative electrode lead 5 is exposed from the exterior packaging material 6. The negative electrode lead 5 is joined to a negative electrode tab 312B (see Fig. 3A) inside the exterior packaging material 6. This allows the negative electrode lead 5 to be electrically connected to the negative electrode current collector 3B (see Fig. 1B). The negative electrode lead 5 is not connected to the positive electrode current collector 3A.

[0086] The positive electrode lead 4 and the negative electrode lead 5 each have, for example, a substantially rectangular flat plate shape. Examples of materials for the positive electrode lead 4 and the negative electrode lead 5 include pure metals and alloys. Examples of pure metals include copper, nickel, aluminum, gold, and platinum. Examples of alloys include alloys of the above pure metals, stainless steel, and titanium. The positive electrode lead 4 and the negative electrode lead 5 may be plated. For example, the positive electrode lead 4 and the negative electrode lead 5 may be copper plates having a nickel-plated layer and a gold-plated layer.

[0087] 1A and 1B, an exterior material 6 covers the laminate of the electrode stack 2 and the current collector 3. An example of the exterior material 6 is a metal laminate film in which resin films are laminated on both sides of a metal foil.

[0088] 2. Method for Manufacturing All-Solid-State Battery Next, a method for manufacturing the above-described all-solid-state battery 1 will be described.

[0089] The manufacturing method of the all-solid-state battery 1 includes a block forming step, an electrode stack forming step (see FIGS. 5A to 6A ), a pressing step (see FIG. 6B ), a cutting step, a peeling step (see FIG. 6C ), and a stacking step.

[0090] (1) Block Forming Step In the block forming step, powder materials such as a solid electrolyte powder, a positive electrode composite, and a negative electrode composite are solidified to form a block.

[0091] In the block-forming process, the powder material is solidified, preferably by a dry process. Specifically, the powder material is pressure-molded in the block-forming process. Other methods include pouring a solvent containing the powder material into a mold and drying it to remove the solvent, or baking (sintering) the powder material packed into a mold to solidify it.

[0092] Examples of the pressure molding method include uniaxial molding, biaxial molding, and cold isostatic pressing (CIP). Preferably, the pressure molding method is biaxial molding.

[0093] Examples of the pressurizing method include a mechanical press, a hydraulic press, and a vibration press. A preferred pressurizing method is a vibration press.

[0094] In the block forming step, the powder material is preferably pressure-molded using a biaxial vibration press, which can prevent the density of the resulting block from becoming non-uniform.

[0095] The pressure in the pressure molding is, for example, 100 MPa or less, preferably 50 MPa or less, more preferably 20 MPa or less. The pressure in the pressure molding is, for example, 1 MPa or more, preferably 5 MPa or more. The pressure in the pressure molding may be in the range of 1 MPa to 100 MPa, 5 MPa to 50 MPa, or 5 MPa to 20 MPa.

[0096] When the pressure in the pressure molding is equal to or less than the upper limit, the block can be prevented from becoming excessively hard, and the block of powder material can be easily removed in the electrode stack forming step.When the pressure in the pressure molding is equal to or greater than the lower limit, the block can be prevented from easily collapsing, and the handleability of the block can be ensured.

[0097] (2) Electrode Stack Forming Step As shown in FIGS. 5A to 6A , in the electrode stack forming step, the powder generated by removing the block obtained in the block forming step is deposited, preferably dry, on a first substrate F1 to form an electrode stack 2.

[0098] 5A , a block of positive electrode composite is removed to produce powder P1, which is then deposited on a first substrate F1 to form a positive electrode layer 21 on the first substrate F1. Examples of the removal process include cutting, grinding, and polishing. The removal process is not limited to grinding and cutting, and may be any process that produces powder by removing a block.

[0099] In the electrode stack forming step, the powder P1 generated by removing the block may be moved onto the first substrate F1 by electrostatic force.

[0100] Next, as shown in FIG. 5B, powder P2 generated by removing the solid electrolyte block is deposited on the positive electrode layer 21 to form a solid electrolyte layer 23 on the positive electrode layer 21.

[0101] Next, the block of negative electrode composite material is removed and processed to produce powder, which is then deposited on the solid electrolyte layer 23 to form the negative electrode layer 22 (see FIG. 6A) on the solid electrolyte layer 23.

[0102] As a result, as shown in FIG. 6A, the electrode stack 2 is formed on the first substrate F1.

[0103] The material of the first substrate F1 is not limited. Examples of the material of the first substrate F1 include metal foil. Examples of the metal foil include aluminum foil.

[0104] Furthermore, the order in which the positive electrode layer 21, the negative electrode layer 22, and the solid electrolyte layer 23 are formed is not limited as long as the electrode stack 2 can be formed. The negative electrode layer 22 may be formed on the first substrate F1, the solid electrolyte layer 23 may be formed on the negative electrode layer 22, and the positive electrode layer 21 may be formed on the solid electrolyte layer 23.

[0105] (2) Pressing Step The pressing step is performed after the electrode stack forming step. As shown in Fig. 6B, in the pressing step, a second substrate F2 is laminated on the electrode stack 2, and the resulting laminate L is pressed. The resulting laminate L is a laminate of the first substrate F1, the electrode stack 2, and the second substrate F2.

[0106] The material of the second substrate F2 may be the same as or different from the material of the first substrate F1.

[0107] The pressure applied to the laminate L is not limited as long as it can form the electrode laminate 2. The pressure applied to the laminate L is, for example, 100 MPa or more, preferably 500 MPa or more, and for example, 5000 MPa or less, preferably 3000 MPa or less. After the pressing step, the laminate L may be charged and discharged to check its performance.

[0108] (3) Cutting Step The cutting step is performed after the pressing step. In the cutting step, the electrode stack 2 is cut into a desired shape. In this embodiment, the electrode stack 2 is cut into a substantially rectangular shape when viewed in the thickness direction of the electrode stack 2. Note that the cutting step does not necessarily have to be performed.

[0109] (4) Peeling Step The peeling step is performed after the cutting step. Note that the peeling step may be performed before the cutting step. In the peeling step, as shown in FIG. 6C , at least one of the first substrate F1 and the second substrate F2 is peeled from the electrode stack 2. In the present embodiment, both the first substrate F1 and the second substrate F2 are peeled from the electrode stack 2. Note that in order to prevent the electrode stack 2 from collapsing, only one of the first substrate F1 and the second substrate F2 may be peeled from the electrode stack 2. Note that the peeling step does not have to be performed. In that case, the first substrate F1 and the second substrate F2 may be used as the current collector 3 in the stacking step.

[0110] (5) Stacking Step In the stacking step, as shown in Fig. 1B, electrode laminates 2 and current collectors 3 (see Fig. 3B) are stacked alternately. The stacking step is completed when a desired number of electrode laminates 2 and current collectors 3 have been stacked.

[0111] After the lamination step, as shown in FIG. 4 , the positive electrode tab 312A is joined to the positive electrode lead 4, the negative electrode tab 312B is joined to the negative electrode lead 5, and the laminate of the electrode laminate 2 and the current collector 3 is vacuum-packed in an exterior material 6.

[0112] This completes the production of the all-solid-state battery 1 described above.

[0113] 3. All-Solid-State Battery Manufacturing Apparatus Next, a manufacturing apparatus 10 used in the electrode stack formation step of the above-described method for manufacturing the all-solid-state battery 1 will be described with reference to FIGS. 7 and 8.

[0114] The manufacturing apparatus 10 includes a block support member 11, a support table 12 (see FIG. 8), a removal processing member 13, a pressing member 14, and a mask member 15 (see FIG. 8).

[0115] (1) Block Support Member As shown in FIG. 8 , the block support member 11 supports a block B. In this embodiment, the block support member 11 has a cylindrical shape capable of accommodating the block B. The block support member 11 extends in the vertical direction. The block support member 11 has an entrance 111 and an exit 112. The entrance 111 is located at the upper end of the block support member 11. The block B is set in the block support member 11 through the entrance 111. The exit 112 is located at the lower end of the block support member 11. The block B in the block support member 11 faces the removal member 13 through the exit 112. The shape of the block support member 11 is not limited as long as it can position the block B relative to the removal member 13. In this embodiment, the block support member 11 is fixed to the support base 12.

[0116] (2) Support Base As shown in Fig. 8, the support base 12 is disposed at a distance from the block support member 11 in the vertical direction. The support base 12 supports the first substrate F1. The support base 12 is made of metal. A predetermined voltage is applied to the support base 12.

[0117] (3) Removal Member As shown in FIG. 8 , the removal member 13 faces the outlet 112 of the block support member 11. The removal member 13 is disposed between the block support member 11 and the support table 12 in the vertical direction. When a block B is set in the block support member 11 and a first substrate F1 is set on the support table 12, the removal member 13 is disposed between the block B and the first substrate F1 in the vertical direction. The removal member 13 can move or vibrate horizontally relative to the block support member 11. The horizontal movement can be sliding (linear movement) or rotation. In other words, the removal member 13 can slide, rotate, or vibrate relative to the block support member 11. The sliding direction of the removal member 13 is defined as the sliding direction. When a block B is set in the block support member 11, the removal member 13 comes into contact with the block B. With the block B in the block support member 11 in contact with the removal member 13, the removal member 13 moves relative to the block support member 11, causing the removal member 13 to remove the block B supported by the block support member 11. A predetermined voltage is applied to the removal member 13 so as to generate an electric field between the removal member 13 and the support base 12. Examples of the removal member 13 include a cutting member, a grinding member, and a polishing member.

[0118] In this embodiment, as shown in FIG. 7, the removal processing member 13 has a frame 131 and a mesh 132 .

[0119] The frame 131 has a generally rectangular flat plate shape and is made of metal. The frame 131 has an opening 130.

[0120] In this embodiment, the mesh 132 is a metal mesh. The mesh 132 covers the opening 130 of the frame 131. When the removal member 13 moves relative to the block support member 11 while the block B in the block support member 11 is in contact with the mesh 132, the mesh 132 removes the block B supported by the block support member 11. As shown in Fig. 8 , powder generated by removing the block B passes through the openings of the mesh 132 and is deposited on the first substrate F1.

[0121] (4) Pressing Member The pressing member 14 is disposed on the opposite side of the block B from the removal member 13. The pressing member 14 presses the block B supported by the block support member 11 toward the removal member 13. In this embodiment, the pressing member 14 is a metal weight. The pressing member 14 is not limited as long as it can press the block B toward the removal member 13. The pressing member 14 does not have to be a weight. The pressing member 14 may be a piston that is pressed against the block B by an air cylinder.

[0122] (5) Mask Member The mask member 15 is disposed between the block support member 11 and the first substrate F1, if necessary. The mask member 15 is disposed between the removal processing member 13 and the first substrate F1. The mask member 15 has an opening 150. Powder generated by removing the block B can pass through the opening 150. The opening 150 is smaller than the opening 130 in the frame 131 of the removal processing member 13. The shape of the opening 150 is not limited as long as an electrode stack 2 having a desired shape can be obtained. In this embodiment, the opening 150 has a rectangular shape so that a rectangular electrode stack 2 can be obtained.

[0123] 4. Effects (1) According to the manufacturing method for the all-solid-state battery 1 and the manufacturing apparatus 10 for the all-solid-state battery 1, as shown in FIG. 8 , the density of the powder material is made uniform in the block forming step, and in the electrode stack forming step, the block B of the powder material is removed and processed, and the resulting powder is deposited on the first substrate F1.

[0124] Therefore, the influence of powder physical properties such as flowability can be reduced, and the amount of powder supplied onto the first substrate F1 can be controlled according to the amount of block B to be removed.

[0125] As a result, the amount of powder supplied onto the first substrate F1 can be stabilized, and a powder layer (positive electrode layer 21, negative electrode layer 22 or solid electrolyte layer 23) with a uniform thickness can be formed.

[0126] (2) In the block forming step of the manufacturing method of the all-solid-state battery 1, a powder material is pressure-molded.

[0127] This makes it possible to make the density of the blocks B uniform, stabilize the amount of powder supplied onto the first substrate F1, and make the film thickness of the powder layer uniform.

[0128] (3) According to the manufacturing method of the all-solid-state battery 1, in the block forming step, the powder material is pressure-molded by a vibration press.

[0129] This makes it possible to make the density of the blocks B more uniform, to make the amount of powder supplied onto the first substrate F1 more stable, and to make the film thickness of the powder layer more uniform.

[0130] (4) According to the manufacturing method of the all-solid-state battery 1, in the block forming step, the powder material is pressure-molded at 100 MPa or less.

[0131] This prevents the blocks B from becoming excessively hard, and allows the blocks B to be easily removed in the electrode stack formation step.

[0132] (5) According to the manufacturing method of the all-solid-state battery 1 and the manufacturing apparatus 10 of the all-solid-state battery 1, in the electrode stack formation step, the powder generated by removing the block B is moved onto the first substrate F1 by electrostatic force.

[0133] This allows the powder generated by removing the block B to be guided onto the first substrate F1 by electrostatic force.

[0134] (6) According to the manufacturing apparatus 10 for the all-solid-state battery 1, as shown in FIG. 8, the block B supported by the block support member 11 can be pressed toward the removal processing member 13 by the pressing member 14.

[0135] Therefore, the block B can be brought into stable contact with the removal processing member 13 .

[0136] (7) According to the manufacturing apparatus 10 for the all-solid-state battery 1, as shown in FIG. 8, the mask member 15 is disposed between the block support member 11 and the first substrate F1.

[0137] Therefore, the powder can be deposited on the first substrate F1 in a shape that corresponds to the opening 15 of the mask member 15.

[0138] 5. Modifications Modifications will be described below. In the modifications, the same components as those in the above-described embodiment are denoted by the same reference numerals, and the description thereof will be omitted.

[0139] (1) The support table 12 may be capable of moving horizontally together with the mask member 15 while supporting the first substrate F1. The horizontal movement may be sliding (linear movement) or rotation.

[0140] According to this modification, the support table 12 moves horizontally while supporting the first substrate F1, so that powder can be deposited over a large area on the first substrate F1.

[0141] (2) In the above-described embodiment, the block support member 11 is fixed to the support base 12, and the removal member 13 slides, rotates, or vibrates relative to the block support member 11. However, the removal member 13 may be fixed to the support base 12, and the block support member 11 may slide, rotate, or vibrate relative to the removal member 13.

[0142] This modification also provides the same effects as those of the above embodiment.

[0143] (3) The structure of the removal member 13 is not limited as long as it can remove the block B.

[0144] 9 , the removal member 13 may have a frame 161 with a slit 160 and a blade 162. The slit 160 extends in a direction intersecting the sliding direction of the removal member 13. The blade 162 is attached to the edge of the slit 160. The blade 162 extends in a direction intersecting the sliding direction of the removal member 13. In this modification, the powder scraped out of the block B by the blade 162 passes through the slit and is deposited on the first substrate F1.

[0145] 10A and 10B, the removal member 13 may include a base frame 170, a support plate 171, a blade 172, and a spacer 173. That is, the removal member 13 may include the blade 172 instead of the mesh 132. The base frame 170 has a frame shape. The support plate 171 is attached to one half of the base frame 170 in the sliding direction of the removal member 13. The support plate 171 supports a block B (see FIG. 10B). The blade 172 is spaced apart from the support plate 171 in the sliding direction of the removal member 13. The blade 172 is attached to the other half of the base frame 170 in the sliding direction of the removal member 13. The blade 172 extends in a direction intersecting the sliding direction of the removal member 13. The spacer 173 is disposed between the blade 172 and the base frame 170 in the vertical direction. The spacer 173 positions the cutting edge of the blade 172 above the upper surface of the support plate 171. As a result, as shown in FIG. 10B , when the removal member 13 is slid with the block B in contact with the upper surface of the support plate 171, the cutting edge of the blade 172 can scrape the block B. In this modification, the thickness of the spacer 173 can adjust the vertical distance between the cutting edge of the blade 172 and the upper surface of the support plate 171. The amount of scraping can be adjusted by adjusting the vertical distance between the cutting edge of the blade 172 and the upper surface of the support plate 171. Note that the removal member 13 does not need to include the spacer 173 as long as the vertical distance between the cutting edge of the blade 172 and the upper surface of the support plate 171 can be adjusted. For example, the amount of scraping can be adjusted by adjusting the difference in thickness between the support plate 171 and the blade 172, or by adjusting the angle of the blade 172 relative to the support plate 171.

[0146] 11 , the removal processing member 13 may have a punched metal 180 instead of the mesh 132. The punched metal 180 has a plurality of through holes 181 and a plurality of blades 182 arranged around each through hole 181. In this modification, the powder scraped out of the block B by the blades 182 passes through the through holes 181 and is deposited on the first substrate F1.

[0147] (4) The manufacturing apparatus 10 may include a plurality of removal members 13 having different shapes. Examples of the plurality of removal members 13 include a removal member 13 having the mesh 132 described above (see FIG. 7 ), a removal member 13 having the blade 162 or blade 172 described above (see FIGS. 9 and 10A ), and a removal member 13 having the punched metal 180 described above (see FIG. 11 ). The removal member 13 may also include a plurality of meshes 132 with different openings or line shapes, or a removal member 13 having a plurality of blades with different blade angles.

[0148] According to this modification, by switching between the multiple removal processing members 13, it is possible to optimize the speed at which the block is removed and the uniformity of the thickness of the powder layer.

[0149] (5) The manufacturing apparatus 10 may further include a measuring member for measuring the thickness of the block B supported by the block support member 11. The measuring member is not limited to a specific type. For example, the measuring member may be a scale provided on the inner surface of the block support member 11, or a sensor for measuring the stroke amount of an air cylinder used in the pressing member 14.

[0150] According to this modification, the amount of the block B that has been removed can be calculated by measuring the thickness of the block B supported by the block support member 11 .

[0151] Furthermore, the amount of deposited powder and the thickness of the powder layer can be calculated from the amount of block B that has been removed.

[0152] (6) The positive electrode layer 21, the negative electrode layer 22, and the solid electrolyte layer 23 may be formed by different methods. For example, the positive electrode layer 21 may be formed by electrostatic screen printing, and then the solid electrolyte layer 23 may be formed by laminating powder produced by removing the solid electrolyte block B on the positive electrode layer 21, and the negative electrode layer 22 may be formed on the solid electrolyte layer 23 by electrostatic screen printing.

[0153] Alternatively, the positive electrode layer 21 may be applied to the first substrate F1 using a coater or the like, and the solid electrolyte block B may be removed and processed to produce a powder, which may then be stacked on the positive electrode layer 21 to form the solid electrolyte layer 23. The negative electrode layer 22 may be applied to the second substrate F2 using a coater or the like, and the resulting product may then be disposed on the solid electrolyte layer 23.

[0154] Alternatively, the positive electrode layer 21 may be formed by laminating powder produced by removing the block B of the positive electrode composite, the solid electrolyte layer 23 may be formed by laminating powder produced by removing the block B of the solid electrolyte on the positive electrode layer 21, and a sheet of silicone or lithium metal may be disposed on the solid electrolyte layer 23 as the negative electrode layer 22.

[0155] (7) In the block forming step, the powder material may be agglomerated to form first granules, and the first granules may be solidified to form a block. Alternatively, in the block forming step, the first granules formed by agglomerating the powder material may be crushed to form second granules smaller than the first granules, and the second granules may be solidified to form a block.

[0156] The above invention is provided as an exemplary embodiment of the present invention, but it is merely an example and should not be interpreted as being limiting. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims.

[0157] The method for manufacturing an all-solid-state battery of the present invention and the apparatus for manufacturing an all-solid-state battery of the present invention can be used to manufacture all-solid-state batteries.

[0158] REFERENCE SIGNS LIST 1 all-solid-state battery 2 electrode laminate 3 current collector 10 manufacturing apparatus 11 block support member 12 support table 13 removal processing member 14 pressing member 15 mask member

Claims

1. A method for manufacturing an all-solid-state battery, comprising: a block forming step of solidifying a powder material to form a block; an electrode laminate forming step of depositing the powder generated by removing the block on a substrate to form an electrode laminate; and a laminating step of laminating the electrode laminate and a current collector.

2. The method for manufacturing an all-solid-state battery according to claim 1, wherein in the block forming step, the powder material is compression molded.

3. The method for manufacturing an all-solid-state battery according to claim 2, wherein in the block forming step, the powder material is compression molded by a vibration press.

4. The method for manufacturing an all-solid-state battery according to claim 2, wherein in the block forming step, the powder material is compression molded at 100 MPa or less.

5. The method for manufacturing an all-solid-state battery according to claim 1, wherein in the electrode laminate forming step, the powder generated by removing the block is moved onto the substrate by electrostatic force.

6. A manufacturing apparatus used for the method for manufacturing an all-solid-state battery according to any one of claims 1 to 5, comprising: a block support member for supporting the block; a support base disposed apart from the block support member for supporting the substrate; and a machining member for removing the block supported by the block support member.

7. The manufacturing apparatus for an all-solid-state battery according to claim 6, further comprising a pressing member for pressing the block supported by the block support member toward the machining member.

8. The manufacturing apparatus for an all-solid-state battery according to claim 6, further comprising a mask member disposed between the block support member and the substrate and having an opening through which the powder generated by removing the block can pass.

9. The manufacturing apparatus for an all-solid-state battery according to claim 6, wherein the block support member is fixed to the support base, and the machining member is slidable, rotatable, or vibratable with respect to the block support member.

10. The manufacturing apparatus for an all-solid-state battery according to claim 6, wherein the machining member is fixed to the support base, and the block support member is slidable, rotatable, or vibratable with respect to the machining member.

11. The manufacturing apparatus for an all-solid-state battery according to claim 6, wherein the manufacturing apparatus comprises a plurality of the machining members having different shapes from each other.

12. The manufacturing apparatus for an all-solid-state battery according to claim 6, further comprising a measuring member for measuring the thickness of the block supported by the block support member.

13. The manufacturing apparatus for an all-solid-state battery according to claim 6, wherein the support table is slidable or rotatable while supporting the base material.

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