Sintered electrode, battery component, and manufacturing method of sintered electrode and battery component; solid electrolyte precursor solution, solid electrolyte precursor and solid electrolyte.

Abstract

This invention provides a sintered electrode, a battery component, and a method for manufacturing the sintered electrode and battery component, which improve safety and enable the battery to operate at low temperatures. The sintered electrode (3) of this invention is characterized by comprising: a carbon electrode material including graphite or hard carbon; and an alkaline ion-conducting solid electrolyte.

Description

Technical Field

[0001] The present invention relates to sintered body electrodes and battery components using sintered body electrodes, as well as methods for manufacturing sintered body electrodes and battery components, alkali ion conductive solid electrolyte precursor solutions, alkali ion conductive solid electrolyte precursors, and alkali ion conductive solid electrolytes. Background Technology

[0002] Lithium-ion rechargeable batteries have established themselves as an indispensable high-capacity, lightweight power source for mobile devices, electric vehicles, and other applications. However, current lithium-ion rechargeable batteries primarily use flammable organic electrolytes, posing a fire hazard. As a solution, the development of all-solid-state lithium-ion batteries using solid electrolytes to replace organic electrolytes is underway. However, due to soaring global raw material costs for lithium, all-solid-state sodium-ion batteries have been researched as an alternative in recent years.

[0003] A sodium battery is disclosed in Patent Document 1 below. This sodium battery has a positive electrode, a negative electrode, and a sulfide solid electrolyte. The positive electrode uses a metal sulfide or sodium metal oxide. The negative electrode uses sodium metal or a sodium alloy.

[0004] Existing technical documents

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2017-208324 Summary of the Invention

[0007] The technical problem that the invention aims to solve

[0008] However, in sodium batteries as described in Patent Document 1, the sodium metal used in the negative electrode is prone to reacting with moisture, making it difficult to adequately improve safety.

[0009] In addition, existing all-solid-state sodium batteries operate at relatively high temperatures, such as above 60°C, in most cases, and also have the problem of not being able to work fully at low temperatures.

[0010] The present invention aims to provide a sintered electrode that improves safety and enables the battery to operate at low temperatures, a battery component, a method for manufacturing the sintered electrode and battery component, a solid electrolyte precursor solution, a solid electrolyte precursor, and a solid electrolyte.

[0011] Technical solutions for solving technical problems

[0012] The sintered electrode of the present invention is characterized in that it comprises: a carbon electrode material including graphite or hard carbon; and an alkaline ion-conducting solid electrolyte.

[0013] Alkali ion-conducting solid electrolytes preferably have sodium ion conductivity.

[0014] Alkali-ion-conducting solid electrolytes preferably include oxides.

[0015] The sintered electrode of the present invention preferably comprises a mixed phase of carbon electrode material and alkali ion conductive solid electrolyte, the mixed phase comprising particles with an average particle size of less than 10 μm.

[0016] The preferred carbon electrode material is a particulate carbon electrode material, which is covered by a coating layer including an alkaline ion-conducting solid electrolyte.

[0017] The preferred carbon electrode material is a particulate carbon electrode material, which is covered by a coating layer comprising: a carbon electrode material different from the particulate carbon electrode material; and an alkaline ion-conducting solid electrolyte.

[0018] The preferred alkali-ion conductive solid electrolyte is a sodium superionic conductor (NASlCON) type crystal, and contains at least one compound selected from the first compound and the second compound, wherein the first compound is of the general formula Na. 1+x Zr2P 3-x Si x O 12 The compound shown in (0≤x≤3) is a compound in which a portion of the Zr of the first compound is replaced with at least one element selected from Ca, Mg, Ba, Sr, Al, Nb, Ta, ln, Ga and Group IIIB elements.

[0019] Alkali-ion conductive solid electrolytes preferably have at least one of β-alumina crystals and β''-alumina crystals.

[0020] Alkali-ion conductive solid electrolytes preferably have the general formula Li7La3Zr2O 12 、Li7La3Zr 2-x M x O 12 (M is at least one selected from Nb, Ga, and Ta, 0 < x < 2) or Li 7-3x Al x La3Zr2O 12 The crystalline phase shown is (0 < x < 2.3).

[0021] The sintered electrode of the present invention preferably contains 0% to 20% by weight of at least one carbon-based conductive agent selected from carbon black, acetylene black, Ketjen black, carbon nanotubes and vapor-grown carbon fiber conductive agent (VGCF).

[0022] The sintered body electrode of the present invention is preferably a negative electrode.

[0023] Preferably, the sintered electrode of the present invention, after being heat-treated in an inert atmosphere at 500°C, is capable of adsorbing and releasing alkali ions at 30°C.

[0024] Preferably, the sintered electrode of the present invention can be reversibly charged and discharged with a charge-discharge efficiency of more than 90% when charged and discharged at a cutoff voltage of 9V to 0.001V.

[0025] The battery component of the present invention is characterized in that it has a solid electrolyte layer and the above-described sintered electrode stacked on the solid electrolyte layer.

[0026] The thickness of the solid electrolyte layer is preferably 5 nm to 1 mm.

[0027] The battery of the present invention is characterized in that it has the above-described battery components.

[0028] The method for manufacturing a sintered electrode according to the present invention is characterized by comprising: a mixing step, wherein an alkali ion-conducting solid electrolyte precursor is mixed with a carbon electrode material precursor to obtain a mixture of the alkali ion-conducting solid electrolyte precursor and the carbon electrode material precursor, wherein the carbon electrode material precursor is a precursor of a carbon electrode material including graphite or hard carbon; a step of forming an electrode forming material layer comprising the mixture after the mixing step; and a step of firing the electrode forming material layer.

[0029] The preferred electrode forming material layer is composed of a paste or pressed powder containing an alkaline ion-conducting solid electrolyte precursor and a carbon electrode material precursor. In the process of firing the electrode forming material layer, both the alkaline ion-conducting solid electrolyte and the carbon electrode material are obtained simultaneously.

[0030] Preferably, in the process of forming the electrode forming material layer, after the first firing process of obtaining carbon electrode material by firing the mixture, an electrode forming material layer is formed, which is composed of a paste or pressed powder containing an alkaline ion-conducting electrolyte precursor and carbon electrode material. In the process of firing the electrode forming material layer, an alkaline ion-conducting solid electrolyte is obtained from the alkaline ion-conducting solid electrolyte precursor.

[0031] Preferably, a third firing step is also included, after the mixing step, to simultaneously obtain an alkaline ion-conducting solid electrolyte and a carbon electrode material by firing the mixture. In the step of forming an electrode forming material layer, an electrode forming material layer is formed, which is composed of a paste or pressed powder containing an alkaline ion-conducting solid electrolyte and a carbon electrode material.

[0032] The method for manufacturing a sintered electrode according to other aspects of the present invention is characterized by comprising: a mixing step, wherein an alkali ion-conducting solid electrolyte precursor is mixed with a particulate carbon electrode material comprising graphite or hard carbon to obtain a mixture of the alkali ion-conducting solid electrolyte precursor and the particulate carbon electrode material; after the mixing step, a step of forming an electrode forming material layer comprising a paste or pressed powder containing the alkali ion-conducting solid electrolyte precursor and the particulate carbon electrode material; and a step of firing the electrode forming material layer to obtain an alkali ion-conducting solid electrolyte from the alkali ion-conducting solid electrolyte precursor, thereby obtaining a particulate carbon electrode material covered by a coating layer comprising the alkali ion-conducting solid electrolyte.

[0033] Another aspect of the present invention describes a method for manufacturing a sintered electrode, comprising: a mixing step, wherein an alkali ion-conducting solid electrolyte precursor, a carbon electrode material precursor, and a particulate carbon electrode material comprising graphite or hard carbon are mixed to obtain a mixture of the alkali ion-conducting solid electrolyte precursor, the carbon electrode material precursor, and the particulate carbon electrode material, wherein the carbon electrode material precursor is a precursor of a carbon electrode material comprising graphite or hard carbon; a step after the mixing step, forming an electrode forming material layer comprising a paste or pressed powder containing the mixture; and a step of firing the electrode forming material layer to obtain an alkali ion-conducting solid electrolyte and a carbon electrode material from the alkali ion-conducting solid electrolyte precursor and the carbon electrode material precursor, thereby obtaining a particulate carbon electrode material covered by a coating layer comprising the alkali ion-conducting solid electrolyte and the carbon electrode material.

[0034] The method for manufacturing a battery component according to the present invention is characterized in that it is a method for manufacturing a battery component comprising a laminate of a sintered electrode and a solid electrolyte layer. The manufacturing method includes: a mixing step, wherein an alkali ion-conducting solid electrolyte precursor and a carbon electrode material precursor are mixed to obtain a mixture of the alkali ion-conducting solid electrolyte precursor and the carbon electrode material precursor, wherein the carbon electrode material precursor is a precursor of a carbon electrode material comprising graphite or hard carbon; a step after the mixing step, forming an electrode forming material layer comprising the mixture; a step of obtaining a sintered electrode by firing the electrode forming material layer; and a step of obtaining a laminate of the sintered electrode and the solid electrolyte layer.

[0035] The preferred electrode forming material layer is composed of a paste or pressed powder containing an alkaline ion-conducting solid electrolyte precursor and a carbon electrode material precursor. By firing the electrode forming material layer, both an alkaline ion-conducting solid electrolyte and a carbon electrode material are obtained simultaneously.

[0036] Preferably, in the process of forming the electrode forming material layer, after the first firing process of obtaining carbon electrode material by firing the mixture, the process of forming an electrode forming material layer composed of a paste or pressed powder containing an alkaline ion-conducting solid electrolyte precursor and carbon electrode material to obtain a sintered electrode is a second firing process, in which an alkaline ion-conducting solid electrolyte is obtained by firing the electrode forming material layer.

[0037] Preferably, a third firing step is also included, which involves firing the mixture after the mixing step to simultaneously obtain an alkaline ion-conducting solid electrolyte and a carbon electrode material. In the step of forming an electrode forming material layer, an electrode forming material layer consisting of a paste or pressed powder containing an alkaline ion-conducting solid electrolyte and a carbon electrode material is formed. The step of obtaining a sintered electrode is a fourth firing step, which involves firing the electrode forming material layer.

[0038] The method for manufacturing a battery component according to another aspect of the present invention is characterized in that it is a method for manufacturing a battery component comprising a laminate of a sintered electrode and a solid electrolyte layer, the method comprising: a mixing step, wherein an alkali ion-conducting solid electrolyte precursor and a particulate carbon electrode material comprising graphite or hard carbon are mixed to obtain a mixture of the alkali ion-conducting solid electrolyte precursor and the particulate carbon electrode material; after the mixing step, a step for forming an electrode forming material layer comprising a paste or pressed powder comprising the alkali ion-conducting solid electrolyte precursor and the particulate carbon electrode material is formed; a step for firing the electrode forming material layer to obtain an alkali ion-conducting solid electrolyte from the alkali ion-conducting solid electrolyte precursor and to obtain the aforementioned particulate carbon electrode material covered by a coating layer comprising the alkali ion-conducting solid electrolyte, thereby obtaining a sintered electrode; and a step for obtaining a laminate of the sintered electrode and the solid electrolyte layer.

[0039] Preferably, the process further includes a lamination process in which a solid electrolyte layer and an electrode forming material layer are stacked together, and after the lamination process, a process for obtaining a sintered electrode is performed.

[0040] Preferably, the process further includes a lamination process in which a solid electrolyte forming material layer composed of a paste or pressed powder containing a solid electrolyte precursor is laminated with an electrode forming material layer. After the lamination process, the electrode forming material layer and the solid electrolyte forming material layer are sintered to obtain a sintered electrode and a solid electrolyte layer.

[0041] The alkaline ion-conducting solid electrolyte precursor solution of the present invention is characterized in that it contains alkali metal elements, transition metal elements and carbonate ions.

[0042] The preferred location is where the carbonate ion is coordinated with a transition metal element.

[0043] The transition metal element is preferably selected from at least one element from Group IIIB and Group IVB.

[0044] The alkaline ion-conducting solid electrolyte precursor solution involved in this invention preferably has a pH value of 7 or higher.

[0045] The preferred balance ion for carbonate ions is NR4. + (In the formula, each R is independently selected from at least one substituent selected from H, CH3, C2H5 and CH2CH2OH).

[0046] The alkaline ion-conducting solid electrolyte precursor solution involved in this invention is preferably a precursor solution of a solid electrolyte containing sodium superionic conductor-type crystals.

[0047] The alkali ion-conducting solid electrolyte precursor solution involved in this invention is preferably a precursor solution of a sodium ion-conducting solid electrolyte.

[0048] The alkaline ion-conducting solid electrolyte precursor of the present invention is characterized in that it comprises a gel or dried product containing the above-mentioned alkaline ion-conducting solid electrolyte precursor solution.

[0049] The alkali ion-conducting solid electrolyte of the present invention is characterized in that it comprises a sintered product containing the above-mentioned alkali ion-conducting solid electrolyte precursor.

[0050] The effects of the invention

[0051] According to the present invention, a sintered electrode that improves safety and enables the battery to operate at low temperatures, a battery component, a method for manufacturing the sintered electrode and the battery component, a solid electrolyte precursor solution, a solid electrolyte precursor, and a solid electrolyte can be provided. Attached Figure Description

[0052] Figure 1 This is a schematic cross-sectional view showing a battery component according to the first embodiment of the present invention.

[0053] Figure 2 This is a SEM image of a sintered body electrode representing one embodiment of the present invention.

[0054] Figure 3 (a) and Figure 3 (b) is a schematic cross-sectional view illustrating the manufacturing method of a battery component according to the first embodiment of the present invention.

[0055] Figure 4 This is a graph showing the results of the charge-discharge test of the comparative example.

[0056] Figure 5 This is a graph showing the results of the charge-discharge test of Embodiment 1 of the present invention.

[0057] Figure 6 This is a graph showing the charge-discharge test results of the test battery prepared in Example 1 of the present invention when charged and discharged at a cutoff voltage of 9V to 0.001V.

[0058] Figure 7 This is a graph showing the XRD (X-ray diffraction) patterns of the alkaline ion-conducting solid electrolyte precursors prepared in Example 2 and the Reference Example of the present invention after drying and calcination.

[0059] Figure 8 (a) and Figure 8 (b) is a schematic cross-sectional view illustrating the manufacturing method of a battery component according to the second embodiment of the present invention.

[0060] Figure 9 (a) and Figure 9 (b) is a schematic cross-sectional view illustrating the manufacturing method of a battery component according to the third embodiment of the present invention.

[0061] Figure 10 (a) and Figure 10 (b) is a schematic cross-sectional view illustrating the manufacturing method of a battery component according to the fourth embodiment of the present invention.

[0062] Figure 11 (a)~ Figure 11 (c) is a schematic cross-sectional view illustrating the manufacturing method of a battery component according to a modified example 1 of the fourth embodiment of the present invention.

[0063] Figure 12 (a)~ Figure 12 (c) is a schematic cross-sectional view illustrating the manufacturing method of a battery component according to a modified example 2 of the fourth embodiment of the present invention.

[0064] Figure 13 (a) and Figure 13 (b) is a schematic cross-sectional view illustrating the manufacturing method of a battery component according to the fifth embodiment of the present invention.

[0065] Figure 14 (a) and Figure 14 (b) is a schematic cross-sectional view illustrating the manufacturing method of a battery component according to the sixth embodiment of the present invention.

[0066] Figure 15 (a) and Figure 15 (b) is a schematic cross-sectional view illustrating the manufacturing method of the sintered body electrode according to the seventh embodiment of the present invention.

[0067] Figure 16 (a) and Figure 16(b) is a schematic cross-sectional view illustrating the manufacturing method of the sintered body electrode according to the eighth embodiment of the present invention.

[0068] Figure 17 (a) and Figure 17 (b) is a schematic cross-sectional view illustrating the manufacturing method of the sintered body electrode according to the ninth embodiment of the present invention.

[0069] Figure 18 This is a schematic cross-sectional view showing a battery component according to the second embodiment of the present invention.

[0070] Figure 19 (a) and Figure 19 (b) is a schematic cross-sectional view illustrating the manufacturing method of a battery component according to the tenth embodiment of the present invention.

[0071] Figure 20 (a) and Figure 20 (b) is a schematic cross-sectional view illustrating the manufacturing method of a battery component according to the eleventh embodiment of the present invention.

[0072] Figure 21 (a) and Figure 21 (b) is a schematic cross-sectional view illustrating the manufacturing method of the sintered body electrode according to the twelfth embodiment of the present invention.

[0073] Figure 22 This is a schematic cross-sectional view showing a battery component according to the third embodiment of the present invention.

[0074] Figure 23 (a) and Figure 23 (b) is a schematic cross-sectional view illustrating the manufacturing method of a battery component according to the thirteenth embodiment of the present invention.

[0075] Figure 24 This is a graph showing the results of the charge-discharge test of Embodiment 3 of the present invention. Detailed Implementation

[0076] The preferred embodiments are described below. However, these embodiments are merely illustrative, and the present invention is not limited to them. Furthermore, components having substantially the same function are sometimes referred to by the same symbols in the drawings.

[0077] [Battery Components]

[0078] (First embodiment)

[0079] Figure 1 This is a schematic cross-sectional view showing a battery component according to the first embodiment of the present invention. Additionally, Figure 1 This is a schematic cross-sectional view of the component when viewed from the side. The following... Figure 1The same applies to the schematic cross-sectional views of other sections.

[0080] The battery component 1 includes a solid electrolyte layer 2, a sintered electrode 3 according to one embodiment of the present invention, and a current collector 4. The solid electrolyte layer 2 has alkaline ion conductivity. More specifically, in this embodiment, the solid electrolyte layer 2 has sodium ion conductivity. However, the solid electrolyte layer 2 may also have lithium ion conductivity. In addition, in order to improve energy density, it is preferable that the solid electrolyte layer 2 is as thin as possible. Specifically, the thickness is preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 100 μm or less. The lower limit is not particularly limited, but in practice, in order to ensure mechanical strength and separator function, it is preferably 5 nm or more.

[0081] The solid electrolyte layer 2 has a first main surface 2a and a second main surface 2b. The first main surface 2a and the second main surface 2b are opposite to each other. A sintered body electrode 3 is stacked on the first main surface 2a of the solid electrolyte layer 2. A current collector 4 is stacked on the sintered body electrode 3. The current collector 4 is made of a suitable metal thin film. In addition, the battery component 1 does not necessarily have a current collector 4. Furthermore, in the embodiments described later, the illustration of the current collector 4 is sometimes omitted.

[0082] In this embodiment, the sintered body electrode 3 is the negative electrode. A positive electrode is stacked on the second main surface 2b of the solid electrolyte layer 2, thereby obtaining an all-solid-state battery.

[0083] The sintered electrode 3 comprises a carbon electrode material and an alkaline ion-conducting solid electrolyte. The carbon electrode material includes graphite or hard carbon. In this embodiment, the alkaline ion-conducting solid electrolyte has sodium ion conductivity. However, the alkaline ion-conducting solid electrolyte may also have lithium ion conductivity.

[0084] The sintered electrode 3 comprises a mixed phase 5 of carbon electrode material and an alkaline ion-conducting solid electrolyte. The mixed phase 5 is granular. The granular mixed phase 5 is bonded together with each other through sintering.

[0085] Figure 2 This is a SEM image illustrating a sintered body electrode according to one embodiment of the present invention. Figure 2 In this mixture, the particles are bonded together. These particles form a mixed phase 5. It is evident that the boundary between the carbon electrode material and the alkali ion-conducting solid electrolyte is indistinguishable within the mixed phase 5. Thus, the carbon electrode material and the alkali ion-conducting solid electrolyte are uniformly mixed within the mixed phase 5. The average particle size of each particle constituting the mixed phase 5 is preferably 10 μm or less, more preferably 3 μm or less, even more preferably 500 nm or less, and particularly preferably 300 nm or less. This improves the density of the sintered electrode 3.

[0086] return Figure 1The sintered electrode 3 preferably contains a conductive additive 6. By including the conductive additive 6, a conductive path is formed, which reduces the internal resistance of the sintered electrode 3. If too much conductive additive 6 is added, the shrinkage during the drying or sintering of the paste will increase, making electrode formation difficult. Therefore, the addition amount is preferably 0% to 20% by weight, more preferably 0.1% to 10% by weight. However, the sintered electrode 3 does not necessarily need to contain the conductive additive 6. In addition, the sintered electrode 3 does not contain a binder (organic binder).

[0087] The battery component 1 includes the sintered body electrode 3 of the present invention, which comprises a carbon electrode material including graphite or hard carbon and an alkaline ion-conducting solid electrolyte. Unlike electrodes made of sodium metal, the sintered body electrode 3 exhibits low reactivity to moisture. Furthermore, since it can be used in all-solid-state batteries and does not require an organic electrolyte, the risk of fire is reduced. Therefore, safety is improved. Moreover, by using the battery component 1, the battery can be operated at low temperatures. Hereinafter, the effects will be described in detail with reference to the manufacturing method of the first embodiment of the present invention and examples of using the method. In this specification, the embodiments of the present invention are described using different consecutive numbers for the battery component and the manufacturing method. Specifically, the manufacturing methods of the battery components of the first to third embodiments of the present invention, the battery components of the first to thirteenth embodiments of the present invention, and the manufacturing methods of the sintered body electrode will be described below.

[0088] [Manufacturing Method]

[0089] (First embodiment)

[0090] Figure 3 (a) and Figure 3 (b) is a schematic cross-sectional view illustrating the manufacturing method of the battery component according to the first embodiment. First, prepare... Figure 3 The electrode shown in (a) consists of a paste 13A and a solid electrolyte layer 2. The paste 13A is the electrode forming material layer in this invention. In this specification, the electrode forming material layer refers to the material layer used to obtain (form) a sintered electrode by firing. The electrode forming material layer can be composed of a paste, as in this embodiment, or it can be composed of pressed powder.

[0091] When obtaining paste 13A, an alkali-ion-conducting solid electrolyte precursor is prepared. Furthermore, in this stage, an alkali-ion-conducting solid electrolyte precursor solution is preferably prepared. Specific examples of the alkali-ion-conducting solid electrolyte precursor and its solution will be described later. Additionally, a carbon electrode material precursor (including a precursor of a graphite or hard carbon carbon electrode material) is prepared. Appropriate sugars, biomass, or polymers can be used in the carbon electrode material precursor.

[0092] Next, the alkali ion-conducting solid electrolyte precursor solution and the carbon electrode material precursor are mixed and then dried. This yields a mixture of the alkali ion-conducting solid electrolyte precursor and the carbon electrode material precursor. Then, the powder obtained by pulverizing the above mixture is mixed with conductive additive 6 and a binder in an organic solvent. The organic solvent can be, for example, N-methylpyrrolidone. This yields paste 13A.

[0093] On the other hand, the solid electrolyte layer 2 can be obtained by mixing raw material powders, shaping the mixed raw material powders, and then firing them. For example, the solid electrolyte layer 2 can be obtained by slurrying the raw material powders to make a green sheet and then firing the green sheet. Alternatively, the solid electrolyte layer 2 can also be obtained by the sol-gel method.

[0094] Next, as Figure 3 As shown in (a), a paste 13A is applied to the first main surface 2a of the solid electrolyte layer 2. A lamination process is then performed to stack the solid electrolyte layer 2 and the paste 13A, which serves as an electrode forming material layer. Next, the laminate of the solid electrolyte layer 2 and the paste 13A is fired in a N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). Alternatively, the firing can be performed in an inert atmosphere. For example, the firing can be performed in an Ar, Ne, or He atmosphere, or it can be performed in a vacuum. The firing process in other embodiments is the same.

[0095] Thus, by simultaneously obtaining an alkali-ion conductive solid electrolyte and a carbon electrode material, a mixed phase 5 of the alkali-ion conductive solid electrolyte and carbon electrode material is obtained. Thus, as... Figure 3 As shown in (b), a sintered electrode 3 is obtained, and a laminate of the sintered electrode 3 and the solid electrolyte layer 2 is obtained. If the firing temperature is too low, the reaction becomes incomplete, making it difficult to obtain the target sintered electrode 3. As a result, the internal resistance of the sintered electrode 3 increases, and there is a tendency for the charge-discharge efficiency to decrease. On the other hand, if the firing temperature is too high, the alkaline component evaporates from the alkaline ion-conducting solid electrolyte precursor, making it difficult to obtain an alkaline ion-conducting solid electrolyte with the desired composition. As a result, the internal resistance of the sintered electrode 3 increases, and there is a tendency for the charge-discharge efficiency to decrease.

[0096] Next, a current collector 4 is formed on the sintered electrode 3. The method for forming the current collector 4 is not particularly limited; examples include physical vapor deposition (PVD) or sputtering, and chemical vapor deposition (CVD) such as thermal CVD, MOCVD, and plasma CVD. However, it is not mandatory to form the current collector 4.

[0097] Through the above process, battery component 1 can be obtained. Furthermore, the binder decomposes during the above firing process. Therefore, the sintered electrode 3 in battery component 1 does not contain binder. Specific examples of the materials constituting each part of battery component 1 will be described here.

[0098] Carbon electrode material precursor:

[0099] Examples of sugars used in carbon electrode material precursors include sucrose, cellulose, D-glucose, and sucrose. Examples of biomass used in carbon electrode material precursors include corn stalks, sorghum stalks, pine cones, mangosteen, argan shells, rice husks, dandelion, cereal straw cores, hemp fiber, cotton, kelp, and coconut endocarp. Examples of polymers used in carbon electrode material precursors include PAN (polyacrylonitrile), asphalt, PVC (polyvinyl chloride) nanofibers, polyaniline, sodium polyacrylate, tires (tire polymers), and phosphorus-doped PAN.

[0100] Alkali ion-conducting solid electrolyte in sintered electrode 3:

[0101] Alkali-ion conductive solid electrolytes preferably include oxides. Alkali-ion conductive solid electrolytes containing oxides are atmospherically stable, thus improving battery safety. Furthermore, under normal circumstances, alkali-ion conductive solid electrolytes containing oxides are hard materials with high Young's modulus, and are difficult to soften and flow through heat treatment, making them difficult to densify through cold pressing or sintering. However, the manufacturing method of this embodiment can produce a dense sintered body.

[0102] Examples of alkali-ion conductive solid electrolytes include Beta-alumina crystals and sodium superion conductor crystals, which exhibit excellent sodium ion conductivity. Beta-alumina exists in two crystal forms: β-alumina (theoretical formula: Na₂O·11Al₂O₃) and β”-alumina (theoretical formula: Na₂O·5.3Al₂O₃). Since β”-alumina is metastable, it is typically used with the addition of Li₂O or MgO as a stabilizer. Because β”-alumina has a higher sodium ion conductivity than β-alumina, it is preferable to use β”-alumina alone or a mixture of β”-alumina and β-alumina, and more preferably to stabilize β”-alumina (Na₂O·11Al₂O₃) with Li₂O. 1.7 Li 0.3 Al 10.7 O 17 ) or MgO stabilized β”-alumina ((Al 10.32 Mg 0.68 O 16 (Na) 1.68 O)).

[0103] As a sodium superionic conductor-type crystal, examples include the general formula Na 1+x X2P 3-x Si x O 12 (X is at least one transition metal element selected from Group IVB, 0 ≤ x ≤ 3) The compound shown is particularly preferred. A compound comprising at least one of the following first and second compounds is preferred. The first compound is of the general formula Na. 1+x Zr2P 3-x Si x O 12 The compound shown is (0≤x≤3). The second compound is a compound formed by replacing a portion of the Zr in the first compound with at least one element selected from Ca, Mg, Ba, Sr, Al, Nb, Ta, ln, Ga, and Group IIIB elements. Additionally, at least one element selected from Sc, Y, and La can be listed as a Group IIIB element.

[0104] Examples of the first and second compounds include Na3Zr2Si2PO4. 12 Na3Zr 1.6 Ti 0.4 Si2PO 12 Na3Zr 1.88 Y 0.12 Si2PO 12 Etc. Other examples of sodium superionic conductor-type crystals include Na... 3.2 Zr 1.3 Si 2.2 P 0.7 O 10.5 Na3Hf2Si2PO 12 Na 3.4 Zr 0.9 Hf 1.4 Al 0.6 Si 1.2 P 1.8 O 12 Na3Zr 1.7 Nb 0.24 Si2PO 12 Na 3.6 Ti 0.2 Y 0.7 Si 2.8 O9, Na 3.12 Zr 1.88 Y 0.12 Si2PO 12 Na 3.6 Zr 0.13 Yb 1.67 Si 0.11 P 2.9 O 12Na 3.12 Zr 1.88 Y 0.12 Si2PO 12 wait.

[0105] In addition to the above, Na₅XSi₄O₄ can also be cited as a solid electrolyte with alkaline ion conductivity. 12 The crystal phase is shown. X is selected from Group IIIB transition metal elements, specifically from at least one rare earth element. In addition to Dy, Gd, Y, and Sm, other rare earth elements include Sc, La, Ce, Pr, Nd, Pm, Eu, Tb, Ho, Er, Tm, Yb, and Lu. Pr, Nd, Sm, Gd, Dy, or Y are preferred, and Y, Sm, Dy, or Gd are more preferred. Furthermore, some Si may be replaced with P.

[0106] As a solid electrolyte with alkali ion conductivity, it can also be of the general formula Li7La3Zr2O 12 、Li7La3Zr 2-x M x O 12 (M is at least one selected from Nb, Ga, and Ta, 0 < x < 2) or Li 7-3x Al x La3Zr2O 12 The crystalline phase shown is (0 < x < 2.3).

[0107] Alkali-ion conductive solid electrolyte precursors and their solutions:

[0108] When the alkali ion-conducting solid electrolyte is Beta alumina, the alkali ion-conducting solid electrolyte precursor can be obtained, for example, by mixing aluminum nitrate, sodium nitrate, and lithium nitrate. In this case, the ratio of the above materials is adjusted to achieve the desired composition ratio of the alkali ion-conducting solid electrolyte.

[0109] The alkali ion-conducting solid electrolyte is sodium superionic conductor type crystal or Na5XSi4O. 12 In the case of crystallization, a precursor solution for an alkali-ion conductive solid electrolyte can be a solution containing alkali metal elements and transition metal elements constituting the alkali-ion conductive solid electrolyte, along with carbonate ions. Furthermore, in this solution, the alkali metal elements are contained in the form of alkali ions, and the transition metal elements are contained in the form of transition metal ions. The alkali-ion conductive solid electrolyte precursor is, for example, composed of a gel or dried product of an alkali-ion conductive solid electrolyte precursor solution. Moreover, the aforementioned alkali-ion conductive solid electrolyte is composed of a calcined product of the alkali-ion conductive solid electrolyte precursor.

[0110] The alkali metal element in the precursor or solution of the alkali ion-conducting solid electrolyte is, for example, at least one selected from Li, Na, and K. The transition metal element is, for example, at least one selected from Group IIIB and Group IVB elements. The transition metal element is preferably Ti, Zr, Hf, Sc, Y, La, Sm, Dy, or Gd, more preferably Zr, Hf, Sc, Y, La, Sm, Dy, or Gd, further preferably Zr, Hf, Sc, Y, La, or Sm, and particularly preferably Zr, Hf, Y, La, or Sm. In addition to these transition metal elements, at least one selected from Ca, Mg, Ba, Sr, Al, Nb, Ta, In, and Ga may also be included. In the alkali ion-conducting solid electrolyte precursor solution, carbonate ions may also be present in the form of carbonates (carbonates of transition metals) or in the form of a mixture of carbonate ions and carbonates. In the above cases, the alkali ion-conducting solid electrolyte precursor solution is suitable, for example, as a precursor solution for a sodium ion-conducting solid electrolyte.

[0111] Alternatively, a solution containing nitrate ions instead of carbonate ions can be used in the alkali-conducting solid electrolyte precursor solution. However, for the following reasons, a solution containing carbonate ions is preferred as the alkali-conducting solid electrolyte precursor solution.

[0112] When a solution containing nitrate ions is used as a precursor solution for an alkali-conductive solid electrolyte, uneven precipitation of components occurs during solution mixing and drying, leading to a tendency to form a heterogeneous phase after firing. This heterogeneous phase contributes to reduced ionic conductivity. Furthermore, the significant weight loss due to the decomposition of nitrate ions during firing makes it difficult to form a uniform thin film layer. Additionally, the treatment of NO generated during firing... x The manufacturing costs of equipment handling corrosive gases may increase. Furthermore, since solutions containing nitrate ions are strongly acidic, the manufacturing equipment must possess a high level of chemical durability, which could also increase manufacturing costs.

[0113] On the other hand, when using a solution containing carbonate ions as a precursor solution for an alkali-ion-conducting solid electrolyte, transition metal elements in transition metal oxides such as ZrO2 and Y2O3, which are typically only soluble in acidic regions, dissolve by accepting carbonate ions to form coordination compounds, thus enabling the preparation of neutral to weakly alkaline (pH 7 or higher, 7.5 or higher, 8 or higher, 8.5 or higher, and especially 9 or higher) metal salt solutions. In this case, not only can the alkali metal component constituting the alkali-ion-conducting solid electrolyte dissolve in the solution as a carbonate or hydroxide, but the Si component constituting the alkali-ion-conducting solid electrolyte can also be added as water glass (sodium silicate: Na2O·nSiO2). Therefore, alkali-ion-conducting solid electrolyte precursor solutions can be readily prepared.

[0114] Furthermore, in the precursor solution of an alkaline ion-conductive solid electrolyte, the carbonate ion is preferably bidentate coordinated with the transition metal element. In this case, the transition metal element tends to exist stably in the solution.

[0115] Furthermore, as a counterion for carbonate ions, it is preferable to contain NR4. + (In the formula, each R is an independent substituent selected from H, CH3, C2H5 and CH2CH2OH). In this way, transition metal elements can be stably present in solution.

[0116] Alkali-ion-conducting solid electrolyte precursor solutions can be obtained, for example, by mixing water glass (sodium silicate), tripolyphosphoric acid, and an aqueous solution of zirconium carbonate.

[0117] Conductive additive 6:

[0118] As the conductive additive 6, conductive carbon can be used, for example. Examples of conductive carbon include acetylene black, carbon black, Ketjen black, carbon nanotubes, and fumed carbon fiber conductive additive (VGCF). The conductive additive 6 is preferably a carbon-based conductive additive composed of the above-mentioned materials.

[0119] Adhesive:

[0120] Adhesives are materials used to integrate raw materials (powdered raw materials) together. Examples of adhesives include cellulose derivatives such as carboxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and hydroxymethyl cellulose, as well as water-soluble polymers such as polyvinyl alcohol; thermosetting resins such as polyimide, phenolic resin, epoxy resin, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, and polyurethane; polycarbonate resins such as polypropylene carbonate; and resins such as polyvinylidene fluoride, polyacrylic acid, sodium polyacrylate, polyacrylonitrile, polyethylene oxide, and butyraldehyde.

[0121] Solid electrolyte layer 2:

[0122] The same solid electrolyte as the alkali ion-conducting solid electrolyte in the sintered body electrode 3 can be used.

[0123] Collector 4:

[0124] The material used for current collector 4 is not particularly limited, and can be aluminum, nickel, titanium, silver, copper, stainless steel, tungsten, or alloys thereof. These metals can be used alone or in combination. Furthermore, an alloy refers to an alloy containing at least one of the aforementioned metals.

[0125] The effects of the present invention will be illustrated in detail below through comparative embodiments and comparative examples.

[0126] [Example 1]

[0127] <Preparation of Alkali Ion Conductive Solid Electrolyte Precursors>

[0128] To obtain Na3Zr2Si2PO 12 Sodium superionic conductor-type crystals are obtained by using water glass (sodium silicate: Na2O·nSiO2), zirconium ammonium carbonate aqueous solution ((NH4)2Zr(OH)2(CO3)2), and sodium tripolyphosphate (Na5P3O) 10 A total of 25g was weighed. These were added to 150g of pure water and stirred at 50°C for 24 hours using a hot stirrer. This yielded a alkali-ion-conducting solid electrolyte precursor solution (pH = 9.7). The solution was then allowed to stand overnight in a constant temperature bath at approximately 5°C to allow it to gel. Through the above process, the alkali-ion-conducting solid electrolyte precursor was prepared. <Preparation of a mixture of alkali-ion-conducting solid electrolyte precursor and carbon electrode material precursor>

[0129] Sucrose, a hard carbon source serving as a precursor for carbon electrode materials, was mixed with an alkaline ion-conducting solid electrolyte precursor at a weight ratio of 4:1 in a stirrer for 1 hour to obtain a mixture. The mixture was then dried in a constant-temperature bath at 60°C for 12 hours, followed by vacuum drying at 100°C for 6 hours, and finally pulverized using an agate mortar to form a powder.

[0130] <Preparation of Electrode Paste>

[0131] A mixture of powders containing an alkali ion-conducting solid electrolyte precursor and a carbon electrode material precursor was weighed with a conductive additive (acetylene black) at a weight ratio of 19:1. PPC (polypropylene carbonate) binder was added to this mixture at a weight ratio of 15 wt%, and the mixture was then mixed in N-methylpyrrolidone solvent using a rotary mixer to obtain an electrode paste.

[0132] <Making of Battery Components>

[0133] Additionally, a Na3Zr2Si2PO4 substrate with a thickness of 500 μm was prepared. 12 A solid electrolyte layer is formed. An electrode paste with a thickness of 70 μm is applied to the first main surface of the solid electrolyte layer and dried in a dryer at 50 °C to form an electrode forming material layer. After drying, it is calcined at 1000 °C for 2 hours under a nitrogen atmosphere (N2: 99.9999%) to form Na3Zr2Si2PO4. 12 A mixed phase of an alkali-ion conductive solid electrolyte and a carbon electrode material composed of hard carbon is precipitated to obtain a sintered body electrode. Next, a current collector is formed on the sintered body electrode by sputtering. The current collector is made of an aluminum thin film. Through the above process, a battery component is obtained. Furthermore, the sintered body electrode in this embodiment is a negative electrode.

[0134] <Preparation of the Experimental Battery>

[0135] Inside the glove box, an experimental battery was fabricated by attaching metallic sodium as a counter electrode to the second main surface of the solid electrolyte layer.

[0136] [Comparative Example]

[0137] Except that the negative electrode is a mixture of hard carbon and PEO (polyethylene oxide) polymer solid electrolyte (a substance formed by mixing PEO and NaPF6 in a weight ratio of 9:1), the test cell was made in the same manner as in Example 1.

[0138] <Charge and Discharge Test>

[0139] The test battery underwent charge-discharge tests in a constant temperature bath at 30°C. Specifically, charging was performed with a cutoff voltage of 0.001V (sodium ion insertion), and discharging was performed with a cutoff voltage of 2.5V (sodium ion removal), and the charging and discharging capacities were measured. In Example 1, the actual capacity was taken as the weight of the fabricated negative electrode, i.e., the sintered electrode described above, multiplied by 300 mAh / g, and the current value was set to achieve a 0.1C rate for charging and discharging. The charging and discharging capacities were also measured at 60°C in the same manner as described above.

[0140] Figure 4 This is a graph showing the results of the charge-discharge test of the comparative example. Figure 5 This is a graph showing the results of the charge-discharge test in Example 1.

[0141] like Figure 4As shown, in the comparative example, the charging and discharging capacities at 60°C were both approximately 250 mAh / g to 280 mAh / g. However, at 30°C, both the charging and discharging capacities were below 10 mAh / g, indicating insufficient operation. This difference arises because the ionic conductivity in the polymer-based electrode changes significantly with temperature.

[0142] In contrast, such as Figure 5 As shown, in Example 1, the charging and discharging capacities both exceed 350 mAh / g not only at 60°C but also at 30°C. Thus, the battery using the battery component of the present invention operates adequately even at low temperatures of 30°C. Furthermore, since no organic electrolyte is required, the risk of fire is low, improving safety.

[0143] Next, regarding the alkali ion-conducting solid electrolyte precursor solution, the effects of the present invention will be shown in detail through comparative examples and reference examples.

[0144] [Example 2]

[0145] A alkali-ion-conducting solid electrolyte precursor solution was obtained in the same manner as in Example 1. The solution was then allowed to gel overnight in a constant-temperature bath at approximately 5°C to obtain the alkali-ion-conducting solid electrolyte precursor.

[0146] The obtained alkali-ion conductive solid electrolyte precursor was dried in a constant temperature bath at 60℃ for 12 hours, and then vacuum dried at 100℃ for 6 hours. The dried alkali-ion conductive solid electrolyte precursor was analyzed by XRD. Figure 7 As shown in the XRD pattern, it is amorphous and its components are uniformly dispersed.

[0147] The dried alkali ion-conducting solid electrolyte precursor was calcined at 1000℃ for 3 hours to obtain the alkali ion-conducting solid electrolyte. XRD analysis of the obtained alkali ion-conducting solid electrolyte showed that... Figure 7 As shown, the desired sodium superionic conductor-type crystals (Na3Zr2Si2PO4) were confirmed to have precipitated. 12 ()( Figure 7 In the figure of "After firing in Example 2", the dot "●" represents Na3Zr2Si2PO4. 12 (Peak positions of crystallization). Additionally, the ionic conductivity of the alkali-conducting solid electrolyte was measured, and the result was 1.5 × 10⁻⁶. -4 S.

[0148] In addition, after forming a gold electrode as an ion-blocking electrode on the surface of an alkaline ion-conducting solid electrolyte, the electrochemical impedance spectroscopy was used to measure the ion content in the range of 1 to 10. 7Ionic conductivity was measured within a frequency range of Hz, and resistance was determined using a Cole plot. Ionic conductivity was then calculated from the obtained resistance value. The measurement using AC impedance spectroscopy was performed at 20℃.

[0149] [Reference Example]

[0150] Except that an aqueous solution of zirconium nitrate (ZrO(NO3)2) was used instead of an aqueous solution of zirconium ammonium carbonate, the alkali ion-conducting solid electrolyte precursor was obtained in the same manner as in Example 2.

[0151] The obtained alkali ion-conducting solid electrolyte precursor was dried in the same manner as in Example 2. The dried alkali ion-conducting solid electrolyte precursor was analyzed by XRD (X-ray diffraction). Figure 7 As shown, sodium nitrate precipitates out and becomes uneven. Figure 7 In the figure of the "Reference Example After Drying", the point "○" indicates the peak position of sodium nitrate crystals.

[0152] The dried alkali ion-conducting solid electrolyte precursor was calcined at 1000℃ for 3 hours to obtain the alkali ion-conducting solid electrolyte. XRD analysis of the obtained alkali ion-conducting solid electrolyte showed that... Figure 7 As shown, sodium superionic conductor-type crystals (Na3Zr2Si2PO4) were confirmed to have precipitated. 12 Furthermore, a heterogeneous phase precipitated. The ionic conductivity of the alkali-ion-conducting solid electrolyte, measured in the same manner as in Example 2, was as low as 6.0 × 10⁻⁶. -7 S. This is due to the low ionic conductivity of the precipitated heterophase.

[0153] In the manufacturing method of the battery component 1 according to the first embodiment described above, a heating step of approximately 1000°C is included. Therefore, even if the sintered electrode 3 is reheated, it is difficult to decompose. For example, after heat treatment of the sintered electrode 3 in an inert atmosphere at 500°C, it is possible to retain and release alkali ions at 30°C. Thus, heat resistance can be effectively improved. On the other hand, for a general electrode containing a binder as a solid electrolyte, if heat treatment is performed in an inert atmosphere at 500°C, the binder decomposes and loses its function as a solid electrolyte, and therefore cannot retain and release alkali ions at 30°C. Furthermore, it is known that even when a voltage of approximately 8V to 9V is applied, the sintered electrode 3 of the present invention is difficult to decompose. For example, Figure 6 This is a graph showing the charge-discharge test results of the test battery prepared in Example 1 above, when charged and discharged at a cutoff voltage of 9V to 0.001V. (See figure) Figure 6As shown, even when a high voltage of 9V is applied, no plateau region caused by decomposition appears, and reversible charge-discharge can be performed with a charge-discharge efficiency of over 90%. This also improves voltage withstand capability. Furthermore, the carbon electrode material precursor used in the fabrication of the sintered electrode 3 can be readily obtained from sugars such as sucrose or biomass. Therefore, productivity can also be effectively improved.

[0154] In the example shown above, water is used as the solvent when mixing the alkali ion-conducting solid electrolyte precursor and the carbon electrode material precursor. In particular, because sugars such as sucrose have high solubility in water, the uniformity of the mixture can be effectively improved when mixing the alkali ion-conducting solid electrolyte precursor and the carbon electrode material precursor. For the battery component of this embodiment, the precursors of both are uniformly mixed before obtaining the alkali ion-conducting solid electrolyte and the carbon electrode material, thus effectively increasing the contact area and enabling high output and high-speed charge / discharge.

[0155] The following are other examples of manufacturing methods for battery components.

[0156] [Manufacturing Method]

[0157] Hereinafter, the manufacturing methods of battery components or sintered electrode according to the second to ninth embodiments of the present invention will be described.

[0158] (Second embodiment)

[0159] Figure 8 (a) and Figure 8 (b) is a schematic cross-sectional view illustrating the manufacturing method of the battery component according to the second embodiment. First, prepare... Figure 8 The electrode shown in (a) has a paste 13B and a solid electrolyte layer 2. The paste 13B is a material layer for forming the electrode according to the present invention.

[0160] When obtaining paste 13B, a powder of a mixture of an alkali ion-conducting solid electrolyte precursor and a carbon electrode material precursor is obtained, similar to the manufacturing method of the first embodiment. Next, the powder of the mixture is calcined under a N2 atmosphere at a temperature of 200°C to 800°C. Furthermore, considering the calcination temperature of the second calcination step described later, the upper limit can also be set to 500°C or lower. Thus, a carbon electrode material is obtained from the carbon electrode material precursor. This step is the first calcination step. Through the first calcination step, a powder of a mixture of an alkali ion-conducting solid electrolyte precursor and a carbon electrode material is obtained. If the calcination temperature is too low, it is difficult for the carbon electrode material precursor to transform into the carbon electrode material. On the other hand, if the calcination temperature is too high, the alkali ion-conducting solid electrolyte precursor tends to transform into an alkali ion-conducting solid electrolyte.

[0161] Next, the powder of the above mixture is pulverized, and then mixed with conductive additive 6 and binder in an organic solvent to obtain paste 13B. Then, as... Figure 8 As shown in (a), a paste 13B is applied to the first main surface 2a of the solid electrolyte layer 2. A lamination process is then performed, stacking the solid electrolyte layer 2 and the paste 13B as an electrode forming material layer. Next, the laminate of the solid electrolyte layer 2 and the paste 13B is fired in a N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). Thus, an alkali-ion conductive solid electrolyte is obtained from the alkali-ion conductive solid electrolyte precursor, thereby obtaining a mixed phase 5 of the alkali-ion conductive solid electrolyte and the carbon electrode material. This process is the second firing process. In the second firing process, firing is performed at a higher temperature than in the first firing process. Through the second firing process, as... Figure 8 As shown in (b), a sintered electrode 3 is obtained. Thus, a laminate of the sintered electrode 3 and the solid electrolyte layer 2 is obtained. If the firing temperature is too low, the reaction becomes incomplete, making it difficult to obtain the desired sintered electrode 3. As a result, the internal resistance of the sintered electrode 3 tends to increase, and the charge / discharge efficiency tends to decrease. On the other hand, if the firing temperature is too high, the alkaline component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition. As a result, the internal resistance of the sintered electrode 3 tends to increase, and the charge / discharge efficiency tends to decrease. Next, a current collector 4 is formed on the sintered electrode 3. Through the above process, a battery component 1 can be obtained.

[0162] exist Figure 3 (a) and Figure 3 In the first embodiment shown in (b), both reactions occur during the firing process: a reaction from an alkali-ion conductive solid electrolyte precursor to an alkali-ion conductive solid electrolyte, and a reaction from a carbon electrode material precursor to a carbon electrode material. Therefore, the firing process involves a high number of decomposition components, resulting in a large difference between the thickness of the paste 13A and the thickness of the sintered electrode 3. Specifically, the thickness of the sintered electrode 3 is more easily reduced than the thickness of the paste 13A.

[0163] In contrast, in this embodiment, a first firing step is performed before the step of forming the electrode forming material layer, i.e., the step of forming the paste 13B. Therefore, the reaction to obtain the carbon electrode material from the carbon electrode material precursor takes place before the formation of the paste 13B. Consequently, there are fewer decomposition components in the second firing step after the formation of the paste 13B. Therefore, the difference between the thickness of the paste 13B and the thickness of the sintered electrode 3 is small. Therefore, the thickness of the sintered electrode 3 is easily adjusted. Furthermore, even when the thickness of the paste 13B is increased, the sintered electrode 3 obtained after firing is less prone to defects such as cracks. As a result, since the thickness of the sintered electrode 3 can be easily increased, the capacity can be easily increased. In particular, in the first embodiment, the firing step for obtaining the sintered electrode 3 is performed only once, thus simplifying the process.

[0164] (Third Implementation)

[0165] Figure 9 (a) and Figure 9 (b) is a schematic cross-sectional view illustrating the manufacturing method of the battery component according to the third embodiment. First, prepare... Figure 9 The electrode shown in (a) has a paste 13C and a solid electrolyte layer 2. The paste 13C is the electrode forming material layer of the present invention.

[0166] When obtaining paste 13C, the process is the same as in the manufacturing method of the first embodiment, to obtain a powder of a mixture of an alkali ion-conducting solid electrolyte precursor and a carbon electrode material precursor. Next, the powder of the mixture is calcined under a N2 atmosphere at a temperature exceeding 500°C and below 1150°C (preferably exceeding 800°C and below 1100°C). This simultaneously yields both an alkali ion-conducting solid electrolyte and a carbon electrode material. This step is the third calcination step. Through the third calcination step, a powder of a mixture of an alkali ion-conducting solid electrolyte and a carbon electrode material is obtained. If the calcination temperature is too low, it is difficult to obtain a powder of the mixture of an alkali ion-conducting solid electrolyte and a carbon electrode material. On the other hand, if the calcination temperature is too high, the alkali component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition.

[0167] Next, the powder of the above mixture is pulverized, and then mixed with conductive additive 6 and binder in an organic solvent to obtain paste 13C. Then, as... Figure 9As shown in (a), a paste 13C is applied to the first main surface 2a of the solid electrolyte layer 2. Thus, a lamination process is performed, stacking the solid electrolyte layer 2 and the paste 13C as an electrode forming material layer. Next, the laminate of the solid electrolyte layer 2 and the paste 13C is fired in a N2 atmosphere at a temperature of 600°C or higher and 1300°C or lower (preferably 900°C or higher and 1250°C or lower). This process is the fourth firing process. In the fourth firing process, firing is performed at a higher temperature than in the third firing process. Through the fourth firing process, as... Figure 9 As shown in (b), a sintered electrode 3 is obtained. If the firing temperature is too low, the sinterability of the sintered electrode 3 and the bonding between the sintered electrode 3 and the solid electrolyte layer 2 may become insufficient. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. On the other hand, if the firing temperature is too high, the alkaline component may evaporate from the alkaline ion-conducting solid electrolyte precursor, making it difficult to obtain an alkaline ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. Next, a current collector 4 is formed on the sintered electrode 3. Through the above process, a battery component 1 can be obtained.

[0168] In this embodiment, a third firing step is performed before the process of forming the paste 13C. Therefore, both the reaction from the alkali-ion conductive solid electrolyte precursor to the alkali-ion conductive solid electrolyte and the reaction from the carbon electrode material precursor to the carbon electrode material are performed before the formation of the paste 13C. Consequently, there are fewer decomposition components in the fourth firing step after the formation of the paste 13C. Therefore, the difference between the thickness of the paste 13C and the thickness of the sintered electrode 3 is smaller. Therefore, it is easier to adjust the thickness of the sintered electrode 3. Furthermore, since it is easier to increase the thickness of the sintered electrode 3, it is easier to increase the capacity. In particular, in the second embodiment, the battery component 1 can be manufactured at a lower temperature than in the third embodiment.

[0169] (Fourth Implementation)

[0170] Figure 10 (a) and Figure 10 (b) is a schematic cross-sectional view illustrating the manufacturing method of the battery component according to the fourth embodiment. First, prepare... Figure 10 The image (a) shows the pressed powder 23A and the paste 22 containing the solid electrolyte precursor. The pressed powder 23A is the electrode forming material layer of the present invention. The paste 22 is the solid electrolyte forming material layer of the present invention. In this specification, the solid electrolyte forming material layer refers to a material layer used to obtain (form) a solid electrolyte layer by firing. The solid electrolyte forming material layer may, for example, be composed of a paste as in this embodiment, or it may be composed of pressed powder.

[0171] When obtaining the pressed powder 23A, the same operation as in the first embodiment is performed to obtain a powder of a mixture of an alkali ion-conducting solid electrolyte precursor and a carbon electrode material precursor. Next, the powder of the above mixture is mixed with the conductive additive 6, and then press-molded to obtain the pressed powder 23A of the alkali ion-conducting solid electrolyte precursor, the carbon electrode material precursor, and the conductive additive 6. For example, uniaxial pressing can be used during press-molding. Furthermore, it is not necessary to add the conductive additive 6.

[0172] On the other hand, paste 22 can be obtained by adding the mixed raw material powder to an organic solvent. Then, as... Figure 10 As shown in (a), a paste 22 is applied to a suitable substrate 27. The substrate 27 can be a plate made of a suitable metal or ceramic, etc. Next, powder 23A is laminated onto the paste 22. Then, the laminate of paste 22 and powder 23A is fired under a N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). Thus, as Figure 10 As shown in (b), a solid electrolyte layer 2 and a sintered electrode 3 can be obtained simultaneously. Thus, a laminate of the solid electrolyte layer 2 and the sintered electrode 3 is obtained. If the firing temperature is too low, the reaction becomes insufficient, making it difficult to obtain the target sintered electrode 3. Furthermore, it is difficult to obtain the target solid electrolyte layer 2. Moreover, the bonding between the sintered electrode 3 and the solid electrolyte layer 2 may become insufficient. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. On the other hand, if the firing temperature is too high, the alkaline component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. Next, as... Figure 10 As shown in (b), the laminate of the solid electrolyte layer 2 and the sintered electrode 3 is peeled off from the substrate 27, and a current collector 4 is formed on the sintered electrode 3. Alternatively, the laminate of the solid electrolyte layer 2 and the sintered electrode 3 can be peeled off from the substrate 27 after the current collector 4 is formed on the sintered electrode 3. Through the above process, a battery component 1 can be obtained.

[0173] In this embodiment, since both the solid electrolyte layer 2 and the sintered electrode 3 are obtained simultaneously, productivity can be improved. Furthermore, since the paste 22 is used in the fabrication of the solid electrolyte layer 2, the solid electrolyte layer 2 can be easily thinned. Additionally, the following describes a variation of this embodiment.

[0174] (Modification 1 of the fourth embodiment)

[0175] Figure 11 (a)~ Figure 11(c) is a schematic cross-sectional view illustrating the manufacturing method of the battery component in Modification 1 of the fourth embodiment. In this modification, as... Figure 11 As shown in (a), a paste 22 is applied to the pressed powder 23A. Next, similar to the fourth embodiment, the laminate of the paste 22 and the pressed powder 23A is fired under a N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). Thus, as... Figure 11 As shown in (b), both the solid electrolyte layer 2 and the sintered electrode 3 can be obtained simultaneously. If the firing temperature is too low, the reaction becomes insufficient, making it difficult to obtain the target sintered electrode 3. Furthermore, it is difficult to obtain the target solid electrolyte layer 2. Moreover, the bonding between the sintered electrode 3 and the solid electrolyte layer 2 may become insufficient. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. On the other hand, if the firing temperature is too high, the alkaline component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. Next, as... Figure 11 As shown in (c), a current collector 4 is formed on the sintered electrode 3. Through the above process, a battery component 21 can be obtained.

[0176] The battery component 1 manufactured in the fourth embodiment is as follows: Figure 1 As shown, in a top view, the outer peripheral edge of the solid electrolyte layer 2 is located outside the outer peripheral edge of the sintered electrode 3. Furthermore, in this specification, "top view" refers to... Figure 1 The direction viewed from above. On the other hand, as... Figure 11 As shown in (a), in this modified example, paste 22 is applied to the pressed powder 23A. Therefore, in Figure 11 In the battery component 21 shown in (c), when viewed from above, the outer peripheral edge of the solid electrolyte layer 2 and the outer peripheral edge of the sintered electrode 3 are at the same position.

[0177] (Modification 2 of the fourth embodiment)

[0178] Figure 12 (a)~ Figure 12 (c) is a schematic cross-sectional view illustrating the manufacturing method of the battery component in Modification 2 of the fourth embodiment. In this modification, preparation Figure 12 The pressed powder 22A shown in (a) is not... Figure 10The paste 22 shown in (a) is used. The pressed powder 22A is the solid electrolyte forming material layer of the present invention. The pressed powder 22A can be obtained by pressing and molding a mixed raw material powder. Next, a pressed powder 23A, serving as an electrode forming material layer, is stacked on top of the pressed powder 22A, which serves as the solid electrolyte forming material layer. Then, similarly to the fourth embodiment, the stack of pressed powder 22A and pressed powder 23A is fired under a N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). Thus, as... Figure 12 As shown in (b), both the solid electrolyte layer 2 and the sintered electrode 3 can be obtained simultaneously. If the firing temperature is too low, the reaction becomes insufficient, making it difficult to obtain the target sintered electrode 3. Furthermore, it is difficult to obtain the target solid electrolyte layer 2. Moreover, the bonding between the sintered electrode 3 and the solid electrolyte layer 2 may become insufficient. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. On the other hand, if the firing temperature is too high, the alkaline component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. Next, as... Figure 12 As shown in (c), a current collector 4 is formed on the sintered electrode 3. Through the above process, a battery component 21 can be obtained.

[0179] (Fifth Implementation)

[0180] Figure 13 (a) and Figure 13 (b) is a schematic cross-sectional view illustrating the manufacturing method of the battery component according to the fifth embodiment. First, prepare... Figure 13 The pressed powder 23B and paste 22 are shown in (a). The pressed powder 23B is the electrode forming material layer of the present invention.

[0181] When obtaining pressed powder 23B, the same operation as in the first embodiment is performed to obtain a powder of a mixture of an alkali ion-conducting solid electrolyte precursor and a carbon electrode material precursor. Next, the powder of the above mixture is calcined under a N2 atmosphere at a temperature of 200°C to 800°C. Furthermore, considering the calcination temperature of the second calcination step described later, the upper limit can also be set to 500°C or lower. This step is the same as the first calcination step in the second embodiment described above. Specifically, in this step, a powder of a mixture of an alkali ion-conducting solid electrolyte precursor and a carbon electrode material is obtained. If the calcination temperature is too low, the carbon electrode material precursor is difficult to transform into a carbon electrode material. On the other hand, if the calcination temperature is too high, the alkali ion-conducting solid electrolyte precursor tends to transform into an alkali ion-conducting solid electrolyte. Next, the powder of the above mixture is mixed with the conductive additive 6 and then press-molded to obtain pressed powder 23B.

[0182] On the other hand, such as Figure 13 As shown in (a), a paste 22, serving as a material layer for forming a solid electrolyte, is applied onto a suitable substrate 27. Next, powder 23B is laminated onto the paste 22. Then, the laminate of paste 22 and powder 23B is fired under a N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). This process is the same as the second firing process in the second embodiment. Thus, as... Figure 13 As shown in (b), the solid electrolyte layer 2 and the sintered electrode 3 can be obtained simultaneously. Thus, a laminate of the solid electrolyte layer 2 and the sintered electrode 3 is obtained. If the firing temperature is too low, the reaction becomes insufficient, making it difficult to obtain the target sintered electrode 3. Furthermore, it is difficult to obtain the target solid electrolyte layer 2. Moreover, the bonding between the sintered electrode 3 and the solid electrolyte layer 2 may become insufficient. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. On the other hand, if the firing temperature is too high, the alkaline component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. Next, after peeling the laminate of the solid electrolyte layer 2 and the sintered electrode 3 from the substrate 27, a current collector 4 is formed on the sintered electrode 3. Through the above process, a battery component 1 can be obtained. In this embodiment, since the solid electrolyte layer 2 is obtained simultaneously with the sintered electrode 3, productivity can be improved. Furthermore, similar to the second embodiment, the thickness of the sintered body electrode 3 can be easily adjusted. Moreover, since the thickness of the sintered body electrode 3 can be easily increased, the capacity can be easily increased.

[0183] (Sixth Implementation Method)

[0184] Figure 14(a) and Figure 14 (b) is a schematic cross-sectional view illustrating the manufacturing method of the battery component according to the sixth embodiment. First, prepare... Figure 14 The pressed powder 23C and the solid electrolyte paste 22 are shown in (a). The pressed powder 23C is the electrode forming material layer of the present invention.

[0185] When obtaining pressed powder 23C, the same operation as in the first embodiment is performed to obtain a powder of a mixture of an alkali ion-conducting solid electrolyte precursor and a carbon electrode material precursor. Next, the powder of the mixture is calcined under a N2 atmosphere at a temperature exceeding 500°C and below 1150°C (preferably exceeding 800°C and below 1100°C). This simultaneously yields an alkali ion-conducting solid electrolyte and a carbon electrode material. This process is the same as the third calcination process described in the third embodiment. Through the third calcination process, a powder of a mixture of an alkali ion-conducting solid electrolyte and a carbon electrode material is obtained. If the calcination temperature is too low, it is difficult to obtain a powder of the mixture of an alkali ion-conducting solid electrolyte and a carbon electrode material. On the other hand, if the calcination temperature is too high, the alkali component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition. Next, the powder of the mixture is mixed with the conductive additive 6 and then press-molded to obtain pressed powder 23C.

[0186] On the other hand, such as Figure 14 As shown in (a), a paste 22, serving as a material layer for forming a solid electrolyte, is applied onto a suitable substrate 27. Next, powder 23C is laminated onto the paste 22. Then, the laminate of paste 22 and powder 23C is fired under a N2 atmosphere at a temperature of 600°C or higher and 1300°C or lower (preferably above 800°C and below 1250°C). This process is the same as the fourth firing process in the third embodiment. Through the fourth firing process, as... Figure 14 As shown in (b), a solid electrolyte layer 2 and a sintered electrode 3 are obtained simultaneously. Thus, a laminate of the solid electrolyte layer 2 and the sintered electrode 3 is obtained. If the firing temperature is too low, the sinterability of the sintered electrode 3 and the bonding between the sintered electrode 3 and the solid electrolyte layer 2 may become insufficient. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. On the other hand, if the firing temperature is too high, the alkaline component may evaporate from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. Next, after peeling the laminate of the solid electrolyte layer 2 and the sintered electrode 3 from the substrate 27, a current collector 4 is formed on the sintered electrode 3. Through the above process, a battery component 1 can be obtained.

[0187] In this embodiment, since both the solid electrolyte layer 2 and the sintered electrode 3 are obtained simultaneously, productivity can be improved. Furthermore, similar to the third embodiment, the thickness of the sintered electrode 3 is easier to adjust. Moreover, since the thickness of the sintered electrode 3 can be increased more easily, the capacity can be increased more readily.

[0188] Alternatively, the sintered body electrode 3 according to one embodiment of the present invention can also be used alone. The following illustrates an example of a method for manufacturing the sintered body electrode 3.

[0189] (Seventh Implementation)

[0190] Figure 15 (a) and Figure 15 (b) is a schematic cross-sectional view illustrating the manufacturing method of the sintered body electrode according to the seventh embodiment. First, as... Figure 15 As shown in (a), pressed powder 23A is prepared in the same manner as in the fourth embodiment. Pressed powder 23A is an electrode forming material layer comprising an alkali ion-conducting solid electrolyte precursor, a carbon electrode material precursor, and a conductive additive 6. However, the electrode forming material layer does not necessarily need to contain the conductive additive 6. Next, the pressed powder 23A is calcined under a N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). This simultaneously yields an alkali ion-conducting solid electrolyte and a carbon electrode material, thereby obtaining a mixed phase 5 of the alkali ion-conducting solid electrolyte and the carbon electrode material. Thus, as... Figure 15 As shown in (b), a sintered electrode 3 can be obtained. If the firing temperature is too low, the reaction becomes incomplete, making it difficult to obtain the target sintered electrode 3. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. On the other hand, if the firing temperature is too high, the alkaline component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease.

[0191] (Eighth Implementation Method)

[0192] Figure 16 (a) and Figure 16 (b) is a schematic cross-sectional view illustrating the manufacturing method of the sintered body electrode according to the eighth embodiment. First, as... Figure 16As shown in (a), similar to the fifth embodiment, pressed powder 23B is prepared. Specifically, the powder of a mixture of an alkali ion-conducting solid electrolyte precursor and a carbon electrode material precursor is calcined at a temperature of 200°C to 800°C under a N2 atmosphere. Furthermore, considering the calcination temperature of the second calcination step described later, the upper limit can also be set to 500°C or below. Thus, carbon electrode material is obtained from the carbon electrode material precursor. This step is the same as the first calcination step in the fifth embodiment. Through the first calcination step, a powder of a mixture of an alkali ion-conducting solid electrolyte precursor and a carbon electrode material is obtained. If the calcination temperature is too low, it is difficult for the carbon electrode material precursor to become carbon electrode material. On the other hand, if the calcination temperature is too high, there is a tendency for the alkali ion-conducting solid electrolyte precursor to become an alkali ion-conducting solid electrolyte. Next, the powder of the above mixture is mixed with the conductive additive 6, and then pressed to obtain pressed powder 23B.

[0193] Next, the pressed powder 23B is calcined under a N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). This yields an alkali-ion conductive solid electrolyte precursor, resulting in a mixed phase 5 of the alkali-ion conductive solid electrolyte and the carbon electrode material. This process is the same as the second calcination process in the fifth embodiment. In the second calcination process, calcination is performed at a higher temperature than in the first calcination process. Thus, as... Figure 16 As shown in (b), a sintered electrode 3 is obtained. If the firing temperature is too low, the reaction becomes incomplete, making it difficult to obtain the target sintered electrode 3. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. On the other hand, if the firing temperature is too high, the alkaline component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease.

[0194] (Ninth Implementation)

[0195] Figure 17 (a) and Figure 17 (b) is a schematic cross-sectional view illustrating the manufacturing method of the sintered body electrode according to the ninth embodiment. First, as... Figure 17As shown in (a), pressed powder 23C is prepared in the same manner as in the sixth embodiment. Specifically, under a N2 atmosphere, the powder of a mixture of an alkali ion-conducting solid electrolyte precursor and a carbon electrode material precursor is calcined at a temperature exceeding 500°C and below 1150°C (preferably exceeding 800°C and below 1100°C). This simultaneously yields both an alkali ion-conducting solid electrolyte and a carbon electrode material. This process is the same as the third calcination process in the sixth embodiment. Through the third calcination process, a powder of a mixture of an alkali ion-conducting solid electrolyte and a carbon electrode material is obtained. If the calcination temperature is too low, it is difficult to obtain a powder of the mixture of an alkali ion-conducting solid electrolyte and a carbon electrode material. On the other hand, if the calcination temperature is too high, the alkali component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition. Next, the powder of the above mixture is mixed with the conductive additive 6 and then press-molded to obtain pressed powder 23C.

[0196] Next, the pressed powder 23C is fired in a N2 atmosphere at a temperature of 600°C or higher and 1300°C or lower (preferably 900°C or higher and 1250°C or lower). This process is the fourth firing process, the same as in the sixth embodiment. In the fourth firing process, firing is carried out at a higher temperature than in the third firing process. Thus, as Figure 17 As shown in (b), a sintered electrode 3 is obtained. If the firing temperature is too low, the sinterability of the sintered electrode 3 may become insufficient. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease. On the other hand, if the firing temperature is too high, the alkaline component may evaporate from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain an alkali ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 3 to increase and the charge / discharge efficiency to decrease.

[0197] [Battery Components]

[0198] (Second embodiment)

[0199] Figure 18 This is a schematic cross-sectional view showing the battery component according to the second embodiment. This embodiment differs from the first embodiment in the configuration of the sintered electrode 33 and in the absence of a current collector. Except for the aspects described above, the battery component 31 of this embodiment has the same configuration as the battery component 1 of the first embodiment. Furthermore, the battery component 31 may also have a current collector.

[0200] The sintered electrode 33 includes a particulate carbon electrode material 38 and a coating layer 39. The particulate carbon electrode material 38 has a density (D50) of 1 μm. The particulate carbon electrode material 38 is composed of graphite or hard carbon. Furthermore, the D50 of the particulate carbon electrode material 38 is preferably 50 μm or less, more preferably 10 μm or less. This improves the density of the sintered electrode 33. The lower limit of the D50 of the particulate carbon electrode material 38 is not particularly limited, and for example, it is 10 nm, 0.1 μm, 0.3 μm, 0.5 μm, and 0.6 μm.

[0201] like Figure 18 As shown, the particulate carbon electrode material 38 is covered by a coating layer 39. The coating layer 39 is composed of an alkaline ion-conducting solid electrolyte. In this embodiment, the alkaline ion-conducting solid electrolyte has sodium ion conductivity. However, the alkaline ion-conducting solid electrolyte may also have lithium ion conductivity. The particulate carbon electrode materials 38 are bonded to each other via the coating layer 39. Furthermore, the sintered electrode 33 is bonded to the solid electrolyte layer 2 via the coating layer 39.

[0202] The sintered electrode 33 preferably contains a conductive additive 6. By including the conductive additive 6, a conductive path is formed, which can reduce the internal resistance of the sintered electrode 33. However, the sintered electrode 33 does not necessarily need to contain the conductive additive 6. In addition, the sintered electrode 33 does not contain a binder.

[0203] In the battery component 31 of this embodiment, similar to the battery component 1 of the first embodiment, safety, heat resistance, and voltage resistance can be improved. Furthermore, in the battery component 31 of this embodiment, by appropriately adjusting the amount of granular carbon electrode material 38, the thickness of the sintered electrode 33 can be easily increased (high loading). Moreover, by selecting the granular carbon electrode material 38 used, its performance can be easily adjusted. Additionally, the sintered electrode 33 of one embodiment of the present invention can also be used alone.

[0204] Hereinafter, examples of a method for manufacturing the battery component 31 and a method for manufacturing the sintered electrode 33 according to this embodiment will be shown.

[0205] [Manufacturing Method]

[0206] Hereinafter, the manufacturing methods of battery components or sintered body electrodes according to the tenth to twelfth embodiments of the present invention will be described.

[0207] (Tenth Implementation)

[0208] Figure 19 (a) and Figure 19 (b) is a schematic cross-sectional view illustrating the manufacturing method of the battery component according to the tenth embodiment. First, prepare... Figure 19The paste 43 and solid electrolyte layer 2 are shown in (a). The paste 43 is the electrode forming material layer of the present invention.

[0209] When obtaining paste 43, an alkali ion-conducting solid electrolyte precursor is prepared using the same manufacturing method as in the first embodiment. Additionally, particulate carbon electrode material 38 is prepared. Next, the alkali ion-conducting solid electrolyte precursor and the particulate carbon electrode material 38 are mixed and then dried. This yields a powder of the mixture of the alkali ion-conducting solid electrolyte precursor and the particulate carbon electrode material 38. Next, the powder of the above mixture is added to an organic solvent, and then mixed with the conductive additive 6 and a binder. For example, N-methylpyrrolidone can be used as the organic solvent. This yields paste 43. However, it is not always necessary to add the conductive additive 6.

[0210] Next, as Figure 19 As shown in (a), a paste 43 is applied to the first main surface 2a of the solid electrolyte layer 2. A lamination process is then performed to stack the solid electrolyte layer 2 and the paste 43, which serves as an electrode forming material layer. Next, the laminate of the solid electrolyte layer 2 and the paste 43 is fired under a N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). Thus, as... Figure 19 As shown in (b), an alkali-ion conductive solid electrolyte is obtained from an alkali-ion conductive solid electrolyte precursor, thereby obtaining a coating layer 39 composed of the alkali-ion conductive solid electrolyte. At this time, particulate carbon electrode materials 38 are bonded to each other via the coating layer 39 to obtain a sintered electrode 33. A laminate of the sintered electrode 33 and the solid electrolyte layer 2 is then obtained. Simultaneously, the sintered electrode 33 is bonded to the solid electrolyte layer 2 via the coating layer 39. Through the above process, a battery component 31 is obtained. If the firing temperature is too low, the reaction becomes insufficient, making it difficult to obtain the target sintered electrode 33. As a result, there is a tendency for the internal resistance of the sintered electrode 33 to increase and the charge / discharge efficiency to decrease. Furthermore, the bonding between the sintered electrode 33 and the solid electrolyte layer 2 may become insufficient. On the other hand, if the firing temperature is too high, the alkali component evaporates from the alkali-ion conductive solid electrolyte precursor, making it difficult to obtain a coating layer 39 composed of an alkali-ion conductive solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 33 to increase and the charging and discharging efficiency to decrease.

[0211] (Eleventh Implementation Method)

[0212] Figure 20 (a) and Figure 20 (b) is a schematic cross-sectional view illustrating the manufacturing method of the battery component according to the eleventh embodiment. First, prepare... Figure 20The pressed powder 53 and paste 22 are shown in (a). The pressed powder 53 is the electrode forming material layer of the present invention. The paste 22 is the solid electrolyte forming material layer of the present invention.

[0213] When obtaining the pressed powder 53, the same method as in the tenth embodiment is used to obtain a powder of a mixture of an alkali ion-conducting solid electrolyte precursor and a particulate carbon electrode material 38. Next, the powder of the above mixture is mixed with the conductive additive 6, and then pressed to obtain the pressed powder 53.

[0214] On the other hand, paste 22 can be obtained by adding the mixed raw material powder to an organic solvent. Then, as... Figure 20 As shown in (a), a paste 22 is applied to a suitable substrate 27. Next, a lamination process is performed, where a pressed powder 53, serving as an electrode forming material layer, is laminated onto the paste 22, which is a material layer for forming a solid electrolyte. Then, the laminate of the paste 22 and the pressed powder 53 is fired under a N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). Thus, as... Figure 20 As shown in (b), a solid electrolyte layer 2 and a sintered electrode 33 can be obtained simultaneously. Thus, a laminate of the sintered electrode 33 and the solid electrolyte layer 2 is obtained. If the firing temperature is too low, the reaction becomes insufficient, making it difficult to obtain the target sintered electrode 33. As a result, there is a tendency for the internal resistance of the sintered electrode 33 to increase and the charge / discharge efficiency to decrease. Furthermore, it is difficult to obtain the target solid electrolyte layer 2. Moreover, the bonding between the sintered electrode 33 and the solid electrolyte layer 2 may become insufficient. On the other hand, if the firing temperature is too high, the alkaline component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain the coating layer 39 and the solid electrolyte layer 2 composed of an alkali ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 33 to increase and the charge / discharge efficiency to decrease.

[0215] Alternatively, it can also be with Figure 11 Similarly, in the example shown in (a), paste 22 is applied to the pressed powder 53. Alternatively, it can be prepared with... Figure 12 In the example shown in (a), the same pressed powder 22A is used instead of the paste 22. In this case, firing can be performed after the pressed powder 53, which serves as a material layer for forming electrodes, and the pressed powder 22A, which serves as a material layer for forming solid electrolytes, are stacked.

[0216] (Twelfth Implementation)

[0217] Figure 21 (a) and Figure 21 (b) is a schematic cross-sectional view illustrating the manufacturing method of the sintered body electrode according to the twelfth embodiment. First, as... Figure 21 As shown in (a), the pressed powder 53 is prepared in the same manner as in the eleventh embodiment. The pressed powder 53 is the electrode forming material layer of the present invention. Next, the pressed powder 53 is fired in an N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). Thus, as Figure 21 As shown in (b), a sintered electrode 33 is obtained. If the firing temperature is too low, the reaction becomes incomplete, making it difficult to obtain the target sintered electrode 33. As a result, there is a tendency for the internal resistance of the sintered electrode 33 to increase and the charge / discharge efficiency to decrease. On the other hand, if the firing temperature is too high, the alkaline component evaporates from the alkali ion-conducting solid electrolyte precursor, making it difficult to obtain a coating layer 39 composed of an alkali ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 33 to increase and the charge / discharge efficiency to decrease.

[0218] Alternatively, it can be combined with Figure 19 In the tenth embodiment shown in (a), the same paste 43, which is a material layer for forming electrodes, is applied to a suitable substrate and then fired to obtain a sintered electrode 33.

[0219] [Battery Components]

[0220] (Third Implementation)

[0221] Figure 22 This is a schematic cross-sectional view showing the battery component according to the third embodiment. This embodiment differs from the second embodiment in the configuration of the coating layer 49 on the sintered electrode 73. Apart from the aspects described above, the battery component 41 of this embodiment has the same configuration as the battery component 31 of the second embodiment.

[0222] The coating layer 49 comprises a carbon electrode material and an alkaline ion-conducting solid electrolyte. The carbon electrode material is a substance distinct from the particulate carbon electrode material 38, and is composed of graphite or hard carbon. In this embodiment, the alkaline ion-conducting solid electrolyte has sodium ion conductivity. However, the alkaline ion-conducting solid electrolyte may also have lithium ion conductivity. The coating layer 49 comprises a mixed phase of the carbon electrode material and the alkaline ion-conducting solid electrolyte. The mixed phase is particulate. The particulate mixed phase is bonded together by sintering. The particles of the particulate carbon electrode material 38 are bonded together via the coating layer 49. Furthermore, the sintered electrode 73 is bonded to the solid electrolyte layer 2 via the coating layer 49.

[0223] In the battery component 41 of this embodiment, similar to the battery component 1 of the first embodiment, safety, heat resistance, and voltage resistance can be improved. Furthermore, in the battery component 41 of this embodiment, by appropriately adjusting the amount of particulate carbon electrode material 38, the thickness of the sintered electrode 73 can be easily increased (high loading). Moreover, as shown in Embodiment 3 described later, the battery component 41 of this embodiment has excellent initial charge-discharge efficiency (irreversible capacity).

[0224] [Manufacturing Method]

[0225] Hereinafter, a method for manufacturing a battery component according to the thirteenth embodiment of the present invention will be described.

[0226] (Thirteenth Implementation Method)

[0227] Figure 23 (a) and Figure 23 (b) is a schematic cross-sectional view illustrating the manufacturing method of the battery component according to the thirteenth embodiment. First, a paste 83 and a solid electrolyte layer 2 are prepared. The paste 83 is an electrode forming material of the present invention.

[0228] To obtain paste 83, an alkali ion-conducting solid electrolyte precursor and a carbon electrode material precursor are prepared using the same manufacturing method as in the first embodiment. Additionally, particulate carbon electrode material 38 is prepared. Next, the alkali ion-conducting solid electrolyte precursor, the carbon electrode material precursor, and the particulate carbon electrode material 38 are mixed and then dried. This yields a powder of the mixture of the alkali ion-conducting solid electrolyte precursor, the carbon electrode material precursor, and the particulate carbon electrode material 38. Next, the powder of the above mixture is added to an organic solvent, and then mixed with the conductive additive 6 and a binder. For example, N-methylpyrrolidone can be used as the organic solvent. This yields paste 83. However, it is not always necessary to add the conductive additive 6.

[0229] Next, as Figure 23 As shown in (a), a paste 83 is applied to the first main surface 2a of the solid electrolyte layer 2. A lamination process is then performed, stacking the solid electrolyte layer 2 and the paste 83, which serves as an electrode forming material layer. Next, the laminate of the solid electrolyte layer 2 and the paste 83 is fired under a N2 atmosphere at a temperature exceeding 500°C and below 1300°C (preferably exceeding 800°C and below 1150°C). Thus, the alkali ion-conducting solid electrolyte precursor and the carbon electrode material precursor become a mixed phase of the carbon electrode material and the alkali ion-conducting solid electrolyte, while... Figure 23As shown in (b), a coating layer 49 composed of the aforementioned mixed phase is formed on the surface of the particulate carbon electrode material 38. At this time, the particulate carbon electrode materials 38 are bonded to each other via the coating layer 49 to obtain a sintered electrode 73. A laminate of the sintered electrode 73 and the solid electrolyte layer 2 is then obtained. Simultaneously, the sintered electrode 73 is bonded to the solid electrolyte layer 2 via the coating layer 49. Through the above process, a battery component 41 is obtained. If the firing temperature is too low, the reaction becomes insufficient, making it difficult to obtain the target sintered electrode 73. As a result, there is a tendency for the internal resistance of the sintered electrode 73 to increase and the charge / discharge efficiency to decrease. Furthermore, the bonding between the sintered electrode 73 and the solid electrolyte layer 2 may become insufficient. On the other hand, if the firing temperature is too high, the alkaline component evaporates from the alkaline ion-conducting solid electrolyte precursor, making it difficult to obtain a coating layer 49 containing an alkaline ion-conducting solid electrolyte with the desired composition. As a result, there is a tendency for the internal resistance of the sintered electrode 73 to increase and the charge / discharge efficiency to decrease.

[0230] Alternatively, it can be like Figure 20 As shown in the eleventh embodiment, a paste serving as a solid electrolyte forming material layer is applied to a suitable substrate, and a pressed powder serving as an electrode forming material layer is laminated onto the paste. A battery component is then obtained by firing. Here, the pressed powder can be obtained by mixing a conductive additive into a powder of a mixture of an alkaline ion-conductive solid electrolyte precursor, a carbon electrode material precursor, and a particulate carbon electrode material, followed by pressure molding. Alternatively, it can be obtained as follows... Figure 21 As shown in the twelfth embodiment, a sintered electrode is obtained by firing the pressed powder.

[0231] The following describes an embodiment of the battery component according to the third embodiment.

[0232] [Example 3]

[0233] To obtain Na3Zr2Si2PO 12 To obtain a NASICON-type crystal, 25g of a mixture of sodium silicate, ammonium zirconium carbonate aqueous solution, and sodium tripolyphosphate was weighed. These were added to 150g of pure water and stirred at 50°C for 24 hours using a hot stirrer. This yielded a precursor solution for an alkali-ion-conducting solid electrolyte. The solution was then allowed to stand overnight in a constant temperature bath at approximately 5°C to allow gelation. Through this process, an alkali-ion-conducting solid electrolyte precursor was prepared. <Preparation of a mixture of alkali-ion-conducting solid electrolyte precursor and carbon electrode material precursor>

[0234] Sucrose, a hard carbon source serving as a precursor for carbon electrode materials, was mixed with an alkaline ion-conducting solid electrolyte precursor at a weight ratio of 4:1 in a stirrer for 1 hour to obtain a mixture. The mixture was then dried in a constant-temperature bath at 60°C for 12 hours, followed by vacuum drying at 100°C for 6 hours. Finally, it was pulverized into powder using an agate mortar and pestle.

[0235] <Preparation of Electrode Paste>

[0236] The powder of a mixture of alkali ion-conducting solid electrolyte precursor and carbon electrode material precursor, and hard carbon powder (average particle size D) 50 =1μm) and conductive additive (acetylene black) were weighed at a weight ratio of 57:40:3. PPC (polypropylene carbonate) binder was added to the mixture at a weight ratio of 15wt%, and the mixture was mixed in N-methylpyrrolidone solvent using a rotary stirrer to obtain the electrode paste.

[0237] <Making of Battery Components>

[0238] Additionally, a Na3Zr2Si2PO4 substrate with a thickness of 500 μm was prepared. 12 A solid electrolyte layer was constructed. An electrode paste with a thickness of 70 μm was applied to the first main surface of the solid electrolyte layer and dried in a dryer at 50 °C. After drying, it was calcined at 1000 °C for 2 hours under a nitrogen atmosphere (N2: 99.9999%) to obtain a sintered electrode formed by hard carbon powder being covered by the coating layer. The coating layer was formed by applying Na3Zr2Si2PO4. 12 The sintered electrode is formed by the precipitation of a mixed phase of an alkaline ion-conductive solid electrolyte and a carbon electrode material composed of hard carbon. Next, a current collector is formed on the sintered electrode by sputtering. The current collector is made of an aluminum thin film. Through the above process, a battery component is obtained. Furthermore, the sintered electrode in this embodiment is a negative electrode.

[0239] <Preparation of the Experimental Battery>

[0240] Inside the glove box, an experimental battery was fabricated by attaching metallic sodium as a counter electrode to the second main surface of the solid electrolyte layer.

[0241] <Charge and Discharge Test>

[0242] Charge-discharge tests were conducted on the test battery in a constant temperature bath at 60°C. Specifically, charging was performed with a cutoff voltage of 0.001V (sodium ion insertion), and discharging was performed with a cutoff voltage of 2.5V (sodium ion removal), and the charging and discharging capacities were measured. In Example 3, the actual capacity was taken as the weight of the fabricated negative electrode, i.e., the sintered electrode described above, multiplied by 300 mAh / g, and the current was set to achieve a 0.1C rate for charging and discharging. The results of the charge-discharge tests are shown below. Figure 24 .

[0243] like Figure 24 As shown, the charging capacity is 379 mAh / g, the discharging capacity is 293 mAh / g, and the initial charge / discharge efficiency is 77.3%. In Example 1 of the battery component according to the first embodiment of the present invention, the initial charge / discharge efficiency at 60°C is 68%. Therefore, it can be seen that the initial charge / discharge efficiency of Example 3 of the battery component according to the third embodiment is even better.

[0244] The embodiments using carbon electrode materials made of graphite or hard carbon as active materials have been described above. Carbon electrode materials made of graphite or hard carbon are primarily used as negative electrode active materials; however, the present invention can also be applied when a positive electrode active material is used instead of this carbon electrode material. For example, in... Figure 18 The battery component and the battery according to the second embodiment of the present invention are shown. Figures 19-21 In the manufacturing methods of the battery component according to the tenth to twelfth embodiments of the present invention, a positive electrode active material can be used instead of the particulate carbon electrode material 38. This allows for the production of a sintered electrode containing a positive electrode active material and an alkaline ion-conducting solid electrolyte. Alternatively, a battery component having a solid electrolyte layer and the aforementioned sintered electrode laminated thereon can be obtained. The positive electrode active material is not particularly limited; for example, Na... x M y P2O z (M is a transition metal element selected from Fe, Cr, Mn, Co and Ni, 1.20≤x≤2.10, 0.95≤y≤1.60) crystalline or crystallized glass.

[0245] [Example 4]

[0246] <Preparation of Alkali Ion Conductive Solid Electrolyte Precursors>

[0247] To obtain the composition ratio of Li7La3Zr2O 12To crystallize the lanthanum acetate dihydrate (CH3COOLi·2H2O), lanthanum acetate 1,5-hydrate (La(CH3COO)3·1.5H2O), and zirconium propoxy(IV) solution (Zr(OCH2CH2CH3)4) totaling 25g, these were added to 150g of pure water and stirred at 50°C for 24 hours using a hot stirrer. This yielded a precursor solution of an alkali-ion-conducting solid electrolyte. The solution was then allowed to stand overnight in a constant temperature bath at approximately 5°C to allow gelation. Through this process, an alkali-ion-conducting solid electrolyte precursor was prepared.

[0248] <Preparation of a mixture of alkali-ion-conducting solid electrolyte precursors and carbon electrode material precursors>

[0249] Using sucrose, a hard carbon source and a precursor for carbon electrode materials, as well as the aforementioned alkali ion-conducting solid electrolyte precursor, a powder of a mixture of the alkali ion-conducting solid electrolyte precursor and the carbon electrode material precursor was obtained in the same manner as in Example 1.

[0250] <Preparation of Electrode Paste>

[0251] Using the powder of the mixture of the above-obtained alkali ion-conducting solid electrolyte precursor and carbon electrode material precursor, an electrode paste was obtained in the same manner as in Example 1.

[0252] <Making of Battery Components>

[0253] Additionally, a 500μm thick Li7La3Zr2O film was prepared. 12 A solid electrolyte layer is formed. An electrode paste with a thickness of 70 μm is applied to the first main surface of the solid electrolyte layer and dried in a dryer at 50 °C to form an electrode forming material layer. After drying, it is calcined at 1000 °C for 2 hours under a nitrogen atmosphere (N2: 99.9999%) to form Li7La3Zr2O. 12 A sintered electrode is obtained by precipitating a mixed phase of an alkaline ion-conductive solid electrolyte and a carbon electrode material composed of hard carbon. Next, a current collector is formed on the sintered electrode by sputtering. The current collector is made of a copper thin film. Through the above process, a battery component is obtained. Furthermore, the sintered electrode in this embodiment is a negative electrode.

[0254] <Preparation of the Experimental Battery>

[0255] Inside the glove box, an experimental battery was fabricated by attaching metallic lithium as a counter electrode to the second main surface of the solid electrolyte layer.

[0256] <Charge and Discharge Test>

[0257] The test battery underwent charge-discharge tests in a constant temperature bath at 60°C. Specifically, charging (lithium-ion insertion) was performed with a cutoff voltage of 0.001V, and discharging (lithium-ion removal) was performed with a cutoff voltage of 1.5V. The charging and discharging capacities were measured. The actual capacity was calculated as 400 mAh / g × the weight of the fabricated negative electrode (the sintered electrode described above). The current was set to achieve a 0.1C rate for charging and discharging. The results showed a charging capacity of 419 mAh / g, a discharging capacity of 314 mAh / g, and an initial charge-discharge efficiency of 74.9%.

[0258] Explanation of symbols

[0259] 1: Battery component; 2: Solid electrolyte layer; 2a, 2b: First main surface, second main surface; 3: Sintered electrode; 4: Current collector; 5: Mixed phase; 6: Conductive additive; 13A-13C: Paste; 21: Battery component; 22: Paste; 22A: Pressed powder; 23A-23C: Pressed powder; 27: Substrate; 31: Battery component; 33: Sintered electrode; 38: Particulate carbon electrode material; 39: Coating layer; 41: Battery component; 43: Paste; 49: Coating layer; 53: Pressed powder; 73: Sintered electrode; 83: Paste.

Claims

1. A sintered body electrode, characterized in that, Include: Carbon electrode materials, including graphite or hard carbon; and Sodium ion-conducting solid electrolyte, The sintered electrode is a sintered electrode formed by mixing the precursor of the sodium ion conductive solid electrolyte with the precursor of the carbon electrode material including graphite or hard carbon and / or the particulate carbon electrode material including graphite or hard carbon, and then sintering them.

2. The sintered body electrode as described in claim 1, characterized in that: The sodium ion-conducting solid electrolyte includes oxides.

3. The sintered electrode as described in claim 1 or 2, characterized in that: A mixed phase comprising the carbon electrode material and the sodium ion-conductive solid electrolyte. The mixed phase comprises particles with an average particle size of less than 10 μm.

4. The sintered body electrode as described in claim 1 or 2, characterized in that: The carbon electrode material is a granular carbon electrode material. The particulate carbon electrode material is covered by a coating layer comprising the sodium ion-conductive solid electrolyte.

5. The sintered body electrode as described in claim 1 or 2, characterized in that: The carbon electrode material is a granular carbon electrode material. The particulate carbon electrode material is covered by a coating layer comprising: a carbon electrode material different from the particulate carbon electrode material; and the sodium ion-conducting solid electrolyte.

6. The sintered body electrode as described in claim 1 or 2, characterized in that: The sodium ion-conducting solid electrolyte is a sodium superionic conductor crystal and contains at least one compound selected from a first compound and a second compound, wherein the first compound is of the general formula Na. 1+x Zr2P 3-x Si x O 12 The compound shown, wherein 0 ≤ x ≤ 3; the second compound is a compound formed by replacing a portion of the Zr in the first compound with at least one element selected from Ca, Mg, Ba, Sr, Al, Nb, Ta, ln, Ga and Group IIIB elements.

7. The sintered body electrode as described in claim 1 or 2, characterized in that: The sodium ion-conducting solid electrolyte has at least one of β-alumina crystals and β''-alumina crystals.

8. The sintered body electrode as described in claim 1 or 2, characterized in that: It contains 0% to 20% by weight of a carbon-based conductive additive, wherein the carbon-based conductive additive is carbon black.

9. The sintered body electrode as described in claim 1 or 2, characterized in that: It contains 0% to 20% by weight of at least one carbon-based conductive additive selected from acetylene black, Ketjen black, carbon nanotubes and vapor-grown carbon fiber conductive additive (VGCF).

10. The sintered body electrode as described in claim 1 or 2, characterized in that: It is the negative electrode.

11. The sintered body electrode as described in claim 1 or 2, characterized in that: After heat treatment in an inert atmosphere at 500℃, it can absorb and release sodium ions at 30℃.

12. The sintered body electrode as described in claim 1 or 2, characterized in that: When charged and discharged with a cutoff voltage of 9V to 0.001V, it can reversibly charge and discharge with a charge and discharge efficiency of over 90%.

13. A component for a battery, characterized in that, have: Solid electrolyte layer; and The sintered electrode according to any one of claims 1 to 12, which is laminated on the solid electrolyte layer.

14. The battery component as claimed in claim 13, characterized in that: The thickness of the solid electrolyte layer is 5 nm to 1 mm.

15. A battery, characterized in that: It has the battery component as described in claim 13 or 14.

16. A method for manufacturing a sintered electrode, characterized in that, include: The mixing process involves mixing a sodium ion-conducting solid electrolyte precursor and a carbon electrode material precursor to obtain a mixture of the sodium ion-conducting solid electrolyte precursor and the carbon electrode material precursor, wherein the carbon electrode material precursor is a precursor of a carbon electrode material including graphite or hard carbon. Following the mixing process, a process is performed to form an electrode forming material layer comprising the mixture; and The process of firing the material layer for forming the electrode.

17. The method for manufacturing a sintered body electrode as described in claim 16, characterized in that: The electrode forming material layer is composed of a paste or pressed powder containing the sodium ion-conductive solid electrolyte precursor and the carbon electrode material precursor. In the process of firing the material layer for forming the electrode, a sodium ion conductive solid electrolyte and the carbon electrode material are obtained simultaneously.

18. The method for manufacturing a sintered body electrode as described in claim 16, characterized in that: In the process of forming the electrode forming material layer, after the first firing process of obtaining carbon electrode material by firing the mixture, the electrode forming material layer is formed, which is composed of a paste or pressed powder containing the sodium ion conductive solid electrolyte precursor and the carbon electrode material. In the process of firing the material layer for forming the electrode, a sodium ion-conducting solid electrolyte is obtained from the sodium ion-conducting solid electrolyte precursor.

19. The method for manufacturing a sintered body electrode as described in claim 16, characterized in that: It also includes a third firing step, after the mixing step, in which the mixture is fired to simultaneously obtain a sodium ion-conductive solid electrolyte and a carbon electrode material. In the process of forming the electrode forming material layer, the electrode forming material layer is formed by a paste or pressed powder comprising the sodium ion conductive solid electrolyte and the carbon electrode material.

20. A method for manufacturing a sintered electrode, characterized in that, include: The mixing process involves mixing a sodium ion-conducting solid electrolyte precursor with a particulate carbon electrode material comprising graphite or hard carbon to obtain a mixture of the sodium ion-conducting solid electrolyte precursor and the particulate carbon electrode material. Following the mixing process, a process is performed to form an electrode forming material layer consisting of a paste or pressed powder containing the sodium ion-conductive solid electrolyte precursor and the particulate carbon electrode material; and The process involves firing the material layer for forming the electrode to obtain a sodium ion-conducting solid electrolyte from the sodium ion-conducting solid electrolyte precursor, thereby obtaining the particulate carbon electrode material covered by a coating layer including the sodium ion-conducting solid electrolyte.

21. A method for manufacturing a sintered electrode, characterized in that, include: The mixing process involves mixing a sodium ion-conducting solid electrolyte precursor, a carbon electrode material precursor, and a particulate carbon electrode material comprising graphite or hard carbon, thereby obtaining a mixture of the sodium ion-conducting solid electrolyte precursor, the carbon electrode material precursor, and the particulate carbon electrode material, wherein the carbon electrode material precursor is a precursor of a carbon electrode material comprising graphite or hard carbon. Following the mixing process, a process is performed to form an electrode forming material layer consisting of a paste or pressed powder containing the mixture. and The process involves firing the electrode forming material layer to obtain a sodium ion conductive solid electrolyte and a carbon electrode material from the sodium ion conductive solid electrolyte precursor and the carbon electrode material precursor, thereby obtaining the particulate carbon electrode material covered by a coating layer comprising the sodium ion conductive solid electrolyte and the carbon electrode material.

22. A method for manufacturing a battery component, characterized in that: It is a method for manufacturing battery components comprising a laminate containing sintered electrodes and a solid electrolyte layer. The manufacturing method includes: The mixing process involves mixing a sodium ion-conducting solid electrolyte precursor and a carbon electrode material precursor to obtain a mixture of the sodium ion-conducting solid electrolyte precursor and the carbon electrode material precursor, wherein the carbon electrode material precursor is a precursor of a carbon electrode material including graphite or hard carbon. Following the mixing process, a process is performed to form an electrode forming material layer containing the mixture; The process of obtaining a sintered electrode by firing the material layer for forming the electrode; and The process of obtaining the laminate of the sintered electrode and the solid electrolyte layer.

23. The method for manufacturing a battery component as described in claim 22, characterized in that: The electrode forming material layer is composed of a paste or pressed powder containing the sodium ion-conductive solid electrolyte precursor and the carbon electrode material precursor. By firing the material layer for forming the electrode, a sodium ion conductive solid electrolyte and a carbon electrode material are obtained simultaneously.

24. The method for manufacturing a battery component as described in claim 22, characterized in that: In the process of forming the electrode forming material layer, after the first firing process of obtaining carbon electrode material by firing the mixture, the electrode forming material layer is formed, which is composed of a paste or pressed powder containing the sodium ion conductive solid electrolyte precursor and the carbon electrode material. The process of obtaining the sintered electrode is a second firing process, which obtains a sodium ion conductive solid electrolyte by firing the electrode forming material layer.

25. The method for manufacturing a battery component as described in claim 22, characterized in that: It also includes a third firing step, after the mixing step, in which the mixture is fired to simultaneously obtain a sodium ion-conductive solid electrolyte and a carbon electrode material. In the process of forming the electrode forming material layer, the electrode forming material layer is formed of a paste or pressed powder comprising the sodium ion conductive solid electrolyte and the carbon electrode material. The process of obtaining the sintered electrode is a fourth firing process, which involves firing the material layer for forming the electrode.

26. A method for manufacturing a battery component, characterized in that: It is a method for manufacturing battery components comprising a laminate containing sintered electrodes and a solid electrolyte layer. The manufacturing method includes: The mixing process involves mixing a sodium ion-conducting solid electrolyte precursor with a particulate carbon electrode material, including graphite or hard carbon, to obtain a mixture of the sodium ion-conducting solid electrolyte precursor and the particulate carbon electrode material. Following the mixing process, a process is performed to form an electrode forming material layer consisting of a paste or pressed powder containing the sodium ion-conductive solid electrolyte precursor and the particulate carbon electrode material. The process involves sintering the material layer for forming the electrode, obtaining a sodium ion-conducting solid electrolyte from the sodium ion-conducting solid electrolyte precursor, and obtaining the particulate carbon electrode material covered by a coating layer including the sodium ion-conducting solid electrolyte, thereby obtaining a sintered electrode; and The process of obtaining the laminate of the sintered electrode and the solid electrolyte layer.

27. The method for manufacturing a battery component as claimed in any one of claims 22 to 26, characterized in that: It also includes a lamination process of stacking the solid electrolyte layer with the electrode forming material layer. After the lamination process, a process is performed to obtain the sintered electrode.

28. A method for manufacturing a battery component as claimed in any one of claims 22 to 26, characterized in that: It also includes a lamination process of stacking a solid electrolyte forming material layer with the electrode forming material layer, wherein the solid electrolyte forming material layer is composed of a paste or pressed powder containing a solid electrolyte precursor. After the lamination process, the sintered electrode and the solid electrolyte layer are obtained by firing the electrode forming material layer and the solid electrolyte forming material layer.

29. A sodium ion-conducting solid electrolyte precursor solution for manufacturing the sodium ion-conducting solid electrolyte in the sintered body electrode of claim 1, characterized in that: It contains alkali metal elements, transition metal elements, and carbonate ions, wherein the carbonate ions are coordinated with the transition metal elements.

30. The sodium ion-conducting solid electrolyte precursor solution as described in claim 29, characterized in that: The transition metal element is selected from at least one element from Group IIIB and Group IVB.

31. The sodium ion-conducting solid electrolyte precursor solution as described in claim 29 or 30, characterized in that: pH value above 7.

32. The sodium ion-conducting solid electrolyte precursor solution as described in claim 29 or 30, characterized in that: The balancing ion for the carbonate ion includes NR4. + In the formula, each R is independently selected from at least one substituent selected from H, CH3, C2H5 and CH2CH2OH.

33. The sodium ion-conducting solid electrolyte precursor solution as described in claim 29 or 30, characterized in that: It is a precursor solution of a solid electrolyte containing sodium superionic conductor-type crystals.

34. A sodium ion-conductive solid electrolyte precursor, characterized in that: A gel or dried product comprising the sodium ion-conducting solid electrolyte precursor solution according to any one of claims 29 to 33.

35. A sodium ion-conducting solid electrolyte, characterized in that: A sintered product comprising the sodium ion-conductive solid electrolyte precursor of claim 34.

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