Organic positive electrode, battery, manufacturing method, program, and manufacturing system

Abstract

To provide a new organic positive electrode including neither conductive material nor binding agent, and a manufacturing method therefor.SOLUTION: There is provided an organic positive electrode that has reversible oxidation-reduction capability, is comprised of a plurality of pellet type organic materials using lithium ions as charge carriers in oxidation-reduction reaction, and includes no conductive agent. There is provided an organic positive electrode that has reversible oxidation-reduction capability, is comprised of a plurality of pellet type organic materials using lithium ions as charge carriers in oxidation-reduction reaction, and includes a conductive agent having a volume ratio of less than 2%. There is provided an organic positive electrode manufacturing method comprising: a preparation step of preparing a plurality of pellet type organic materials that have reversible oxidation-reduction capability and use lithium ions as charge carriers in oxidation-reduction reaction; and a compression step of compressing the plurality of pellet type organic materials without including any conductive agent in the plurality of pellet type organic materials.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an organic positive electrode, a battery, a manufacturing method, a program, and a manufacturing system. [Background technology]

[0002] Patent Document 1 describes an organic positive electrode produced using an organic material. Patent Documents 2 and 3 describe an electrode active material using an organic compound, and a secondary battery that repeatedly charges and discharges by utilizing the battery electrode reaction of the electrode active material. [Prior art document] [Patent documents] [Patent Document 1] JP 2018-085243 A [Patent Document 2] JP 2011-228050 A [Patent Document 3] JP 2012-079479 A Summary of the Invention

[0003] According to a first aspect of the present invention, an organic positive electrode is provided. The organic positive electrode may be composed of a plurality of pellet-shaped organic materials having reversible redox ability and utilizing lithium ions as charge carriers in the redox reaction. The organic positive electrode may not include a conductive agent.

[0004] The organic positive electrode may not include a binder. The organic material may be an organic material having a carbonyl, an imine, a structure in which a carbonyl has been reduced, or a structure in which an imine has been reduced as an oxidation-reduction site at a specific position in the molecule. The organic material may include 25% or more of the oxidation-reduction site by weight. The organic material may include 50% or more of the oxidation-reduction site by weight. The organic material may include at least one of naphthazarin, quinone, indigo, and pentacene tetron. The organic material may be naphthazarin. The organic material may be a naphthazarin dimer. The organic material may be a naphthazarin monomer. The plurality of pellet-shaped organic materials may include two or more of naphthazarin, quinone, indigo, and pentacene tetron.

[0005] According to a second aspect of the present invention, an organic positive electrode is provided. The organic positive electrode may be composed of a plurality of pellet-shaped organic materials having reversible redox ability and utilizing lithium ions as charge carriers in the redox reaction. The organic positive electrode may have a volume ratio of a conductive agent of less than 2%.

[0006] The organic material may be an organic material having a carbonyl, an imine, a structure in which a carbonyl has been reduced, or a structure in which an imine has been reduced as a redox site at a specific position in the molecule. The organic material may contain 25% or more of the redox site by weight. The organic material may contain at least one of naphthazarin, quinone, indigo, and pentacene tetrone.

[0007] According to a third aspect of the present invention, there is provided a battery, which may include the organic positive electrode, a solid electrolyte, and a negative electrode.

[0008] According to a fourth aspect of the present invention, there is provided a manufacturing method. The manufacturing method may include a preparation step of preparing a plurality of pellet-shaped organic materials having reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in the oxidation-reduction reaction. The manufacturing method may include a compression step of compressing the plurality of pellet-shaped organic materials without including a conductive agent in the plurality of pellet-shaped organic materials. The manufacturing method may include a removal step of removing an organic positive electrode produced by the compression step.

[0009] The compressing step may compress the plurality of pellet-shaped organic materials without including the conductive agent and the binder in the plurality of pellet-shaped organic materials. The preparing step may prepare a plurality of pellet-shaped solid electrolyte materials and the plurality of pellet-shaped organic materials, the compressing step may compress the plurality of pellet-shaped solid electrolyte materials and the plurality of pellet-shaped organic materials without including the conductive agent in the plurality of pellet-shaped organic materials, and the extracting step may extract the organic positive electrode and the solid electrolyte. The manufacturing method may include a producing step of producing a battery by contacting a negative electrode with the solid electrolyte.

[0010] According to a fifth aspect of the present invention, there is provided a manufacturing method. The manufacturing method may include a preparation step of preparing a plurality of pellet-shaped organic materials having reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in the oxidation-reduction reaction. The manufacturing method may include an inclusion step of causing the plurality of pellet-shaped organic materials to contain a conductive agent at a volume ratio of less than 2%. The manufacturing method may include a compression step of compressing the plurality of pellet-shaped organic materials containing less than 2% of the conductive agent. The manufacturing method may include a removal step of removing the organic positive electrode produced by the compression step.

[0011] According to a sixth aspect of the present invention, there is provided a program for causing a computer to execute the above manufacturing method.

[0012] According to a seventh aspect of the present invention, there is provided a system for producing an organic positive electrode. The production system may include a preparation unit for preparing a plurality of pellet-shaped organic materials having a reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in an oxidation-reduction reaction. The production system may include a compression unit for compressing the plurality of pellet-shaped organic materials without including a conductive agent in the plurality of pellet-shaped organic materials.

[0013] According to an eighth aspect of the present invention, there is provided a system for producing an organic positive electrode. The production system may include a preparation unit for preparing a plurality of pellet-shaped organic materials having reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in an oxidation-reduction reaction. The production system may include a containing unit for causing the plurality of pellet-shaped organic materials to contain a conductive agent at a volume ratio of less than 2%. The production system may include a compression unit for compressing the plurality of pellet-shaped organic materials containing less than 2% of the conductive agent.

[0014] The above summary of the invention does not list all of the necessary features of the present invention. Also, subcombinations of these features may also be inventions. [Brief description of the drawings]

[0015] [Figure 1] 2 illustrates an example of a functional configuration of the manufacturing system 100. [Diagram 2] FIG. 1 is an explanatory diagram for explaining a method for producing an organic positive electrode 300. [Diagram 3] An example of an organic cathode 300 is shown diagrammatically. [Figure 4] An example of the flow of processing by the positive electrode generation unit 110 is shown in schematic form. [Diagram 5] An example of the flow of processing by the positive electrode generation unit 110 is shown in schematic form. [Figure 6] FIG. 13 is an explanatory diagram for explaining a manufacturing method of the battery 500. [Figure 7] An example of a battery 500 is shown diagrammatically. [Figure 8] An example of a hardware configuration of a computer 1200 that functions as the manufacturing system 100 is shown in schematic form. [Figure 9] The comparison results are shown below. [Figure 10] The test results are shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The present invention will be described below through embodiments of the invention, but the following embodiments do not limit the scope of the invention according to the claims. Furthermore, not all of the combinations of features described in the embodiments are necessarily essential to the solution of the invention.

[0017] 1 is a schematic diagram showing an example of a functional configuration of a manufacturing system 100. The manufacturing system 100 according to the present embodiment may produce an organic positive electrode made of an organic material. The manufacturing system 100 may also produce a battery using the organic positive electrode.

[0018] The manufacturing system 100 may include a positive electrode production unit 110, an electrolyte preparation unit 120, an negative electrode preparation unit 130, and a battery production unit 140. It is not essential that the manufacturing system 100 includes all of these units.

[0019] The positive electrode generation unit 110 includes a preparation unit 112, a compression unit 114, and a containing unit 116. It is not essential that the positive electrode generation unit 110 includes all of these units.

[0020] The preparation unit 112 prepares an organic material. The preparation unit 112 may prepare a plurality of pellet-shaped organic materials. The preparation unit 112 may prepare one type of organic material. The preparation unit 112 may prepare a plurality of types of organic materials.

[0021] The organic material prepared by the preparation unit 112 may be an organic material that has a reversible redox ability and uses lithium ions as charge carriers in the redox reaction. The organic material may be an organic material that has a carbonyl (>C=O) as a redox site at a specific position in the molecule. The organic material may be an organic material that has an imine (-N=) as a redox site at a specific position in the molecule. The organic material may be an organic material that has a structure in which a carbonyl has been reduced as shown in the following formula at a specific position in the molecule.

[0022] [ka]

[0023] The organic material may be an organic material having, as an oxidation-reduction site, a structure in which an imine has been reduced, as shown in the following formula, at a specific position in the molecule.

[0024] [ka]

[0025] The organic material may be an organic material containing 25% or more by weight of the above-mentioned redox moieties.The organic material may be an organic material containing 50% or more by weight of the above-mentioned redox moieties.

[0026] The preparation unit 112 prepares, for example, naphthazarin in pellet form. The preparation unit 112 may prepare naphthazarin dimer in pellet form. The preparation unit 112 may prepare naphthazarin monomer in pellet form.

[0027] The preparation unit 112 may prepare, for example, quinone in pellet form. The preparation unit 112 may prepare 1,4-benzoquinone in pellet form. The preparation unit 112 may prepare anthraquinone in pellet form. The preparation unit 112 may prepare dimethoxybenzoquinone in pellet form. The preparation unit 112 may prepare a pentacene derivative in pellet form, for example. The preparation unit 112 may prepare indigo in pellet form. The preparation unit 112 may prepare indigo carmine in pellet form.

[0028] The organic material used in this embodiment may be an active material of the type in which Li+ enters and leaves, and in this respect, it is different from the molecular group described in JP 2011-228050, which is an active material of the type in which anions enter and leave. The organic material used in this embodiment differs from the molecular group described in JP 2011-228050 in the mechanism of oxidation-reduction during use. As for the structure, the molecular group described in JP 2011-228050 differs from the organic material used in this embodiment in that the proportion of functional groups that accept Li+ is very small. In addition, the organic material used in this embodiment may be an active material of the type that uses the redox of a carbonyl group, and is different from the molecular group described in JP 2012-079479, which is an active material of the type that uses the reduction of imine nitrogen.

[0029] The compression unit 114 generates an organic positive electrode by compressing the organic material prepared by the preparation unit 112. The compression unit 114 may compress one type of organic material. The preparation unit 112 may compress a mixture of multiple types of organic materials.

[0030] The compression unit 114 may compress the plurality of pellet-shaped organic materials without including a conductive agent in the plurality of pellet-shaped organic materials. The compression unit 114 may compress the plurality of pellet-shaped organic materials without including a conductive agent and a binder in the plurality of pellet-shaped organic materials.

[0031] Conventionally, when producing an organic positive electrode, it was considered essential to mix a large amount of conductive agent and use a large amount of binder to bind it in order to compensate for the low conductivity. In contrast, the present inventor focused on the problem that the porosity in the positive electrode increases by containing a conductive agent and a binder, resulting in a structure containing a large amount of electrolyte, and the energy density cannot be increased. And, the present inventor succeeded in manufacturing an organic positive electrode with reduced porosity by compressing a specific organic material without including a conductive agent and a binder through experiments. By using such an organic positive electrode, it is possible to eliminate or reduce the conductive agent and electrolyte that are not involved in the energy capacity, and the organic positive electrode can occupy the part occupied by the material that is not involved in the energy capacity, which can contribute to high capacity.

[0032] In the manufacturing system 100 according to this embodiment, the organic material prepared by the preparation unit 112 may contain a conductive agent and a binder at a smaller ratio than in the past.

[0033] The containing unit 116, for example, contains a conductive agent in the organic material prepared by the preparing unit 112. "Containing" may mean "mixing." The containing unit 116 may mix the organic material prepared by the preparing unit 112 with a conductive agent. In existing organic positive electrodes, a conductive agent is used at a volume ratio of 2% or more. The containing unit 116 may contain a conductive agent in the organic material prepared by the preparing unit 112 so that the volume ratio of the conductive agent is more than 0% and less than 2%.

[0034] The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 1.9%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 1.8%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 1.7%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 1.6%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 1.5%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 1.4%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 1.3%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 1.2%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 1.1%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 1.0%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 0.9%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 0.8%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 0.7%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 0.6%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 0.5%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 0.4%. The containing section 116 may contain a conductive agent in the organic material prepared by the preparing section 112 so that the volume ratio of the conductive agent is less than 0.3%.The containing unit 116 may contain a conductive agent in the organic material prepared by the preparing unit 112 so that the volume ratio of the conductive agent is less than 0.2%. The containing unit 116 may contain a conductive agent in the organic material prepared by the preparing unit 112 so that the volume ratio of the conductive agent is less than 0.1%. By reducing the volume ratio of the conductive agent compared to conventional organic positive electrodes, the porosity can be reduced compared to conventional organic positive electrodes.

[0035] The containing unit 116 may contain a donor in the organic material prepared by the preparing unit 112. Examples of the donor include pyrene, perylene, a TTF (tetrathiafulvalene) derivative, a TTP (tetrathiapentalene) derivative, and tetramethylbenzidine (TMB).

[0036] The preparation unit 112 may contain an acceptor in the organic material prepared by the preparation unit 112. Examples of the acceptor include tetracyanoquinodimethane (TCNQ), chloranil, dichlorodicyanobenzoquinone (DDQ), tetrafluorotetracyanoquinodimethane (F4TCNQ), and fullerene.

[0037] The containing section 116 may contain a binder in the organic material in addition to the conductive agent. The containing section 116 may contain a binder in an amount that matches the amount of the conductive agent in the organic material. The containing section 116 may contain, for example, a binder in the organic material at the same volume ratio as the conductive agent.

[0038] The containing section 116 may contain an existing positive electrode material in the organic material prepared by the preparing section 112. For example, the containing section 116 contains lithium cobalt oxide (LCO) in the organic material. Also, for example, the containing section 116 contains nickel-cobalt-manganese (NCM) in the organic material. The ratio of the organic material to the existing positive electrode material may be arbitrarily set. The containing section 116 may use an organic material as an additive to the existing positive electrode, such as LCO and NCM.

[0039] The electrolyte preparing unit 120 prepares an electrolyte. The electrolyte preparing unit 120 prepares, for example, a solid electrolyte. The electrolyte preparing unit 120 may be an example of a solid electrolyte preparing unit. The electrolyte preparing unit 120 obtains, for example, a solid electrolyte produced externally. The electrolyte preparing unit 120 may also produce the solid electrolyte by compressing a solid electrolyte material.

[0040] The electrolyte preparation unit 120 prepares, for example, a sulfide-based solid electrolyte. Examples of sulfide-based solid electrolytes include glass-based sulfides (e.g., Li2S_P2S5, Li2S-SiS2-P2S-LiI, etc.), argyrodyte-type sulfides (e.g., Li7PS6, Li6PS5CI, Li6PS5Br, Li6PS5I, etc.), thiolithium-based sulfides (e.g., Li4-xGe1XPXS4 (0≦x≦1), etc.), Li73!1Li10GeP2S12 (LGPS), Li.4Si74.44S117CI0.3 (LiSiPSCI) Li9.6P3S12, Li-Sn-Si-PS (LSSPS) systems, etc.

[0041] The electrolyte preparation unit 120 prepares, for example, a liquid electrolyte. The electrolyte preparation unit 120 may prepare an electrolyte solution.

[0042] The negative electrode preparing unit 130 prepares a negative electrode. The negative electrode preparing unit 130 prepares a negative electrode corresponding to the type of battery to be produced. For example, when producing an all-solid-state battery, the negative electrode preparing unit 130 prepares a lithium metal negative electrode.

[0043] The battery generating unit 140 generates a battery using the organic positive electrode generated by the positive electrode generating unit 110, the electrolyte prepared by the electrolyte preparing unit 120, and the negative electrode prepared by the negative electrode preparing unit 130. The battery generating unit 140 generates an all-solid-state battery, for example, by compressing the organic positive electrode and the solid electrolyte, and then contacting and attaching the negative electrode to the solid electrolyte. The battery generating unit 140 also generates various batteries, for example, by arranging and sealing the organic positive electrode, the negative electrode, and the electrolyte in a container.

[0044] The manufacturing system 100 may be configured by one device. Also, the manufacturing system 100 may be configured by multiple devices. For example, the positive electrode production unit 110 is configured by one device, and the solid electrolyte preparation unit 120, the negative electrode preparation unit 130, and the battery production unit 140 are configured by one or more devices.

[0045] 2 is an explanatory diagram for explaining a method for producing an organic positive electrode. Here, the case of producing a button-shaped organic positive electrode will be explained.

[0046] The compression section 114 may include a compressor 200. The compressor 200 is arranged, for example, under an Ar atmosphere. The compressor 200 includes a compression section 202 in which an object to be compressed is arranged. The compression section 202 is surrounded by a container 210. The container 210 may be, for example, an insulating cylinder.

[0047] The preparation unit 112 may prepare a pallet-shaped organic material 30 in the compression unit 202. The organic material 30 may be an organic material that has a reversible oxidation-reduction ability and uses lithium ions as charge carriers in the oxidation-reduction reaction. The organic material 30 may be an organic material that has, as an oxidation-reduction site, a carbonyl, an imine, a structure in which a carbonyl has been reduced, or a structure in which an imine has been reduced at a specific position in the molecule. The preparation unit 112 puts, for example, 5 to 10 mg of the organic material 30 into the compression unit 202.

[0048] The compressor 200 compresses the organic material 30 placed in the compression section 202. The compressor 200 may compress the organic material 30 with settings according to the material of the organic material 30. The compressor 200 pressurizes the organic material 30 at 500 MPa for 1 to 5 minutes, for example.

[0049] The compressor 200 compresses the organic material 30 to form pellets of the organic material 30, thereby producing a button-shaped organic positive electrode.

[0050] 3 shows a schematic diagram of an example of an organic positive electrode 300 manufactured by the manufacturing system 100. The organic positive electrode 300 is composed of a plurality of organic materials 30 in the form of pellets.

[0051] In the organic positive electrode 300, a plurality of pellet-shaped organic materials 30 are aggregated together. In the organic positive electrode 300, a plurality of pellet-shaped organic materials 30 may be powder-molded.

[0052] The organic positive electrode 300 may not include a conductive agent. The organic positive electrode 300 may include a conductive agent with a volume ratio of more than 0% and less than 2%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.9%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.8%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.7%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.6%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.5%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.4%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.3%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.2%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.1%. The organic positive electrode 300 includes, for example, a conductive agent at a volume ratio of less than 1.0%. The organic positive electrode 300 includes, for example, a conductive agent at a volume ratio of less than 0.9%. The organic positive electrode 300 includes, for example, a conductive agent at a volume ratio of less than 0.8%. The organic positive electrode 300 includes, for example, a conductive agent at a volume ratio of less than 0.7%. The organic positive electrode 300 includes, for example, a conductive agent at a volume ratio of less than 0.6%. The organic positive electrode 300 includes, for example, a conductive agent at a volume ratio of less than 0.5%. The organic positive electrode 300 includes, for example, a conductive agent at a volume ratio of less than 0.4%. The organic positive electrode 300 includes, for example, a conductive agent at a volume ratio of less than 0.3%. The organic positive electrode 300 includes, for example, a conductive agent at a volume ratio of less than 0.2%. The organic positive electrode 300 includes, for example, a conductive agent at a volume ratio of less than 0.1%.

[0053] The organic positive electrode 300 may not include a binder. The organic positive electrode 300 may include a binder with a volume ratio greater than 0% and less than 2%. The organic positive electrode 300 includes, for example, the same volume ratio of the binder as the conductive agent.

[0054] After the organic positive electrode 300 and the solid electrolyte are compressed, a negative electrode may be attached to the solid electrolyte to form an all-solid-state battery. Alternatively, the organic positive electrode 300, an electrolytic solution, and a negative electrode may be placed in a container and sealed to form a battery.

[0055] 4 shows an example of a process flow by the positive electrode production unit 110. Here, the process by which the positive electrode production unit 110 produces the organic positive electrode 300 will be described in brief.

[0056] In step (step may be abbreviated as S) 102, the preparation unit 112 places a plurality of pellet-shaped organic materials 30 in the compression unit 202. The preparation unit 112 may place one type of organic material 30 in the compression unit 202. The preparation unit 112 may also mix a plurality of types of organic materials 30 and place the resulting mixture in the compression unit 202.

[0057] In S104, the compression unit 114 compresses the organic material 30 placed in the compression unit 202. The compression unit 114 compresses the organic material 30 without including the conductive agent and the binder.

[0058] In S106, the compression unit 114 takes out the organic positive electrode produced by compressing the organic material 30. Through this process, the organic positive electrode is produced.

[0059] After S106, the battery production unit 140 may manufacture a battery using the organic positive electrode extracted in S106, the electrolyte prepared by the electrolyte preparation unit 120, and the negative electrode prepared by the negative electrode preparation unit 130.

[0060] 5 shows an example of a process flow by the positive electrode production unit 110. Here, the process flow by which the positive electrode production unit 110 produces the organic positive electrode 300 will be described in brief.

[0061] In S202, the preparation unit 112 places a plurality of pellet-shaped organic materials 30 in the compression unit 202. The preparation unit 112 may place one type of organic material 30 in the compression unit 202. The preparation unit 112 may mix a plurality of types of organic materials 30 and place them in the compression unit 202.

[0062] In S204, the containing unit 116 contains a conductive agent in the organic material 30. The containing unit 116 may contain a conductive agent in the organic material 30 so that the volume ratio of the conductive agent in the organic material 30 is less than 2%. The containing unit 116 may further contain a binder in the organic material 30. The containing unit 116 may contain a binder in the organic material 30 at a volume ratio corresponding to the volume ratio of the conductive agent. The containing unit 116 contains the binder in the organic material 30 so that the volume ratio is the same as that of the conductive agent, for example. The containing unit 116 may contain the conductive agent and the binder in the organic material 30 before the organic material 30 is placed in the compression unit. For example, the containing unit 116 may add a conductive agent and a binder to the organic material 30 prepared by the preparing unit 112, and the preparing unit 112 or the containing unit 116 may place the organic material 30 containing the conductive agent and the binder in the compressing unit 202.

[0063] In S206, the compression unit 114 compresses the organic material 30 placed in the compression unit 202. In S208, the compression unit 114 removes the organic positive electrode produced by compressing the organic material 30. Through this process, the organic positive electrode is produced.

[0064] After S208, the battery production unit 140 may manufacture a battery using the organic positive electrode extracted in S208, the electrolyte prepared by the electrolyte preparation unit 120, and the negative electrode prepared by the negative electrode preparation unit 130.

[0065] 2 to 5, an example has been described in which the positive electrode production unit 110 produces the organic positive electrode 300 by compressing only the organic material 30, but the present invention is not limited to this. The positive electrode production unit 110 may produce the organic positive electrode 300 to which the solid electrolyte is attached by compressing the organic material 30 and the solid electrolyte material together.

[0066] For example, the preparation unit 112 places a plurality of pellet-shaped solid electrolyte material in the compression unit 202. Next, the preparation unit 112 places a plurality of pellet-shaped organic material 30 on the plurality of pellet-shaped solid electrolyte material. The preparation unit 112 may adjust the speed of each operation so that the solid electrolyte material and the organic material 30 are not mixed. It should be noted that even if the solid electrolyte material and the organic material 30 are mixed to some extent, there is no effect on the performance.

[0067] The compression unit 114 compresses the organic material 30 and the solid electrolyte material together. This produces an organic positive electrode 300 with a solid electrolyte attached. The battery production unit 140 may produce a battery by attaching a negative electrode prepared by the negative electrode preparation unit 130 to the solid electrolyte of the organic positive electrode 300 produced in this manner.

[0068] The manufacturing system 100 may produce a battery by compressing the anode, solid electrolyte material, and organic material 30 together with a compressor 200.

[0069] 6 shows an example of a process flow by the manufacturing system 100. Here, a process flow in which the manufacturing system 100 manufactures button batteries will be described.

[0070] First, the preparation unit 112 prepares a plurality of pellet-shaped organic materials 30. The preparation unit 112 may prepare one type of organic material 30. The preparation unit 112 may prepare a plurality of types of organic materials 30. When preparing a plurality of types of organic materials 30, the preparation unit 112, for example, puts the plurality of types of organic materials 30 in a ball mill and mixes them. The mixing may be performed according to any setting, but for example, mixing is performed at 100 to 200 ppm for 10 to 60 minutes. The preparation unit 112 may mix the organic material 30 with less than 1% of a conductive agent. The preparation unit 112 may mix the organic material 30 with less than 1% of a conductive agent and a binder.

[0071] Then, the preparation section 112 places the Li metal 50 on the bottom of the compression section 202. The Li metal 50 may have a thickness of, for example, 20 to 100 μm. Note that instead of the Li metal 50, an In—Li alloy may be used.

[0072] Next, the preparation unit 112 puts in the solid electrolyte material 40. The preparation unit 112 puts in, for example, Li10GeP2S12 (LGPS) as the solid electrolyte material 40. The amount of the material put in can be set arbitrarily, but is, for example, 50 mg. The compressor 200 may lightly compress the solid electrolyte material 40 to flatten the surface.

[0073] Next, the preparation unit 112 pours the prepared organic material 30. The amount of the organic material 30 to be poured can be set arbitrarily, but is, for example, 5 to 10 mg.

[0074] Then, the compressor 200 compresses the organic material 30, the solid electrolyte material 40, and the Li metal 50. The compressor 200 pressurizes the organic material 30, the solid electrolyte material 40, and the Li metal 50 at 500 MPa for 1 to 5 minutes, for example.

[0075] In this way, an all-solid-state battery composed of the Li metal 50 as the negative electrode, the solid electrolyte 400, and the organic positive electrode 300 can be manufactured.

[0076] 7 shows a schematic diagram of an example of a battery 500. The battery 500 is composed of an organic positive electrode 300, a solid electrolyte 400, and Li metal 50.

[0077] The organic positive electrode 300 is composed of a plurality of pellet-shaped organic materials 30. In the organic positive electrode 300, the plurality of pellet-shaped organic materials 30 are aggregated together. In the organic positive electrode 300, the plurality of pellet-shaped organic materials 30 may be powder-molded.

[0078] The organic positive electrode 300 may not include a conductive agent. The organic positive electrode 300 may include a conductive agent with a volume ratio of less than 2%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 2.0%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.9%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.8%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.7%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.6%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.5%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.4%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.3%. The organic positive electrode 300 includes, for example, a conductive agent with a volume ratio of less than 1.2%. The organic positive electrode 300 includes, for example, less than 1.1% by volume of a conductive agent. The organic positive electrode 300 includes, for example, less than 1.0% by volume of a conductive agent. The organic positive electrode 300 includes, for example, less than 0.9% by volume of a conductive agent. The organic positive electrode 300 includes, for example, less than 0.8% by volume of a conductive agent. The organic positive electrode 300 includes, for example, less than 0.7% by volume of a conductive agent. The organic positive electrode 300 includes, for example, less than 0.6% by volume of a conductive agent. The organic positive electrode 300 includes, for example, less than 0.5% by volume of a conductive agent. The organic positive electrode 300 includes, for example, less than 0.4% by volume of a conductive agent. The organic positive electrode 300 includes, for example, less than 0.3% by volume of a conductive agent. The organic positive electrode 300 includes, for example, less than 0.2% by volume of a conductive agent. The organic positive electrode 300 includes, for example, less than 0.1% by volume of a conductive agent.

[0079] The organic positive electrode 300 may not include a binder. The organic positive electrode 300 may include a binder with a volume ratio greater than 0% and less than 2%. The organic positive electrode 300 includes, for example, the same volume ratio of the binder as the conductive agent.

[0080] The solid electrolyte 400 is composed of a plurality of pellet-shaped solid electrolyte materials. In the solid electrolyte 400, a plurality of pellet-shaped solid electrolyte materials are aggregated. In the solid electrolyte 400, a plurality of pellet-shaped solid electrolyte materials may be powder-molded.

[0081] 8 is a schematic diagram showing an example of a hardware configuration of a computer 1200 functioning as the manufacturing system 100. A program installed on the computer 1200 can cause the computer 1200 to function as one or more "parts" of an apparatus according to the present embodiment, or cause the computer 1200 to execute operations associated with the apparatus according to the present embodiment or one or more "parts" thereof, and / or cause the computer 1200 to execute a process according to the present embodiment or steps of the process. Such a program can be executed by the CPU 1212 to cause the computer 1200 to execute specific operations associated with some or all of the blocks of the flowcharts and block diagrams described herein.

[0082] The computer 1200 according to this embodiment includes a CPU 1212, a RAM 1214, and a graphics controller 1216, which are connected to each other by a host controller 1210. The computer 1200 also includes input / output units such as a communication interface 1222, a storage device 1224, a DVD drive, and an IC card drive, which are connected to the host controller 1210 via an input / output controller 1220. The DVD drive may be a DVD-ROM drive, a DVD-RAM drive, etc. The storage device 1224 may be a hard disk drive, a solid state drive, etc. The computer 1200 also includes a legacy input / output unit such as a ROM 1230 and a keyboard, which are connected to the input / output controller 1220 via an input / output chip 1240.

[0083] The CPU 1212 operates according to a program stored in the ROM 1230 and the RAM 1214, thereby controlling each unit. The graphic controller 1216 acquires image data generated by the CPU 1212 into a frame buffer or the like provided in the RAM 1214 or into itself, and causes the image data to be displayed on the display device 1218.

[0084] The communication interface 1222 communicates with other electronic devices via a network. The storage device 1224 stores programs and data used by the CPU 1212 in the computer 1200. The DVD drive reads programs or data from a DVD-ROM or the like and provides them to the storage device 1224. The IC card drive reads programs and data from an IC card and / or writes programs and data to an IC card.

[0085] The ROM 1230 stores therein a boot program or the like that is executed by the computer 1200 upon activation, and / or a program that depends on the hardware of the computer 1200. The input / output chip 1240 may also connect various input / output units to the input / output controller 1220 via a USB port, a parallel port, a serial port, a keyboard port, a mouse port, and the like.

[0086] The programs are provided by a computer-readable storage medium such as a DVD-ROM or an IC card. The programs are read from the computer-readable storage medium, installed in the storage device 1224, the RAM 1214, or the ROM 1230, which are also examples of computer-readable storage media, and executed by the CPU 1212. Information processing described in these programs is read by the computer 1200, and brings about cooperation between the programs and the various types of hardware resources described above. An apparatus or method may be constructed by implementing operations or processing of information according to the use of the computer 1200.

[0087] For example, when communication is performed between the computer 1200 and an external device, the CPU 1212 may execute a communication program loaded in the RAM 1214 and instruct the communication interface 1222 to perform communication processing based on the processing described in the communication program. Under the control of the CPU 1212, the communication interface 1222 reads transmission data stored in a transmission buffer area provided in the RAM 1214, the storage device 1224, a DVD-ROM, or a recording medium such as an IC card, and transmits the read transmission data to the network, or writes reception data received from the network to a reception buffer area or the like provided on the recording medium.

[0088] Furthermore, the CPU 1212 may cause all or a necessary portion of a file or database stored in an external recording medium such as the storage device 1224, a DVD drive (DVD-ROM), an IC card, etc. to be read into the RAM 1214, and perform various types of processing on the data on the RAM 1214. The CPU 1212 may then write back the processed data to the external recording medium.

[0089] Various types of information, such as various types of programs, data, tables, and databases, may be stored in the recording medium and undergo information processing. The CPU 1212 may perform various types of processing on the data read from the RAM 1214, including various types of operations, information processing, conditional judgment, conditional branching, unconditional branching, information search / replacement, etc., as described throughout this disclosure and specified by the instruction sequence of the program, and write back the results to the RAM 1214. The CPU 1212 may also search for information in a file, database, etc. in the recording medium. For example, when a plurality of entries each having an attribute value of a first attribute associated with an attribute value of a second attribute are stored in the recording medium, the CPU 1212 may search for an entry whose attribute value of the first attribute matches a specified condition from among the plurality of entries, read the attribute value of the second attribute stored in the entry, and thereby obtain the attribute value of the second attribute associated with the first attribute that satisfies a predetermined condition.

[0090] The above-described programs or software modules may be stored in a computer-readable storage medium on the computer 1200 or in the vicinity of the computer 1200. In addition, a recording medium such as a hard disk or a RAM provided in a server system connected to a dedicated communication network or the Internet can be used as a computer-readable storage medium, thereby providing the programs to the computer 1200 via the network.

[0091] The blocks in the flowcharts and block diagrams in the present embodiment may represent stages of a process in which an operation is performed or "parts" of an apparatus responsible for performing the operation. Particular stages and "parts" may be implemented by dedicated circuitry, programmable circuitry provided with computer-readable instructions stored on a computer-readable storage medium, and / or a processor provided with computer-readable instructions stored on a computer-readable storage medium. The dedicated circuitry may include digital and / or analog hardware circuits, and may include integrated circuits (ICs) and / or discrete circuits. The programmable circuitry may include reconfigurable hardware circuits, such as, for example, field programmable gate arrays (FPGAs), programmable logic arrays (PLAs), and the like, including AND, OR, XOR, NAND, NOR, and other logical operations, flip-flops, registers, and memory elements.

[0092] A computer-readable storage medium may include any tangible device capable of storing instructions that are executed by a suitable device, such that a computer-readable storage medium having instructions stored thereon comprises an article of manufacture that includes instructions that can be executed to create means for performing the operations specified in the flowcharts or block diagrams. Examples of computer-readable storage media may include electronic storage media, magnetic storage media, optical storage media, electromagnetic storage media, semiconductor storage media, and the like. More specific examples of computer-readable storage media may include floppy disks, diskettes, hard disks, random access memories (RAMs), read-only memories (ROMs), erasable programmable read-only memories (EPROMs or flash memories), electrically erasable programmable read-only memories (EEPROMs), static random access memories (SRAMs), compact disk read-only memories (CD-ROMs), digital versatile disks (DVDs), Blu-ray disks, memory sticks, integrated circuit cards, and the like.

[0093] The computer readable instructions may include either assembler instructions, instruction set architecture (ISA) instructions, machine instructions, machine-dependent instructions, microcode, firmware instructions, state setting data, or source or object code written in any combination of one or more programming languages, including object-oriented programming languages ​​such as Smalltalk®, JAVA®, C++, etc., and conventional procedural programming languages ​​such as the “C” programming language or similar programming languages.

[0094] Computer readable instructions may be provided to a processor of a general purpose computer, special purpose computer, or other programmable data processing apparatus, or to a programmable circuit, either locally or over a local area network (LAN), a wide area network (WAN), such as the Internet, etc., to cause the processor of the general purpose computer, special purpose computer, or other programmable data processing apparatus, or to a programmable circuit, to execute the computer readable instructions to generate means for performing the operations specified in the flowcharts or block diagrams. Examples of processors include computer processors, processing units, microprocessors, digital signal processors, controllers, microcontrollers, etc. EXAMPLES

[0095] Positive electrode plates having different conductive material volume ratios were prepared for an existing organic material and an organic material according to this embodiment that has reversible oxidation-reduction ability and uses lithium ions as charge carriers in the oxidation-reduction reaction, and the capacity retention rates at the same number of cycles were compared.

[0096] As existing organic materials, NCM111 and an organic material disclosed in a prior art document (JP Patent Publication 2012-079479 A) were used. A positive electrode plate was created so that 0.05 C charge, 0.05 C discharge ⇒ 0.05 mA / cm2, 1 mAh / cm2. Table 1 and FIG. 9 show the comparison results. Note that, although the capacity retention rate is shown here when naphthazarin dimer is used as the organic material according to this embodiment, the other organic materials according to this embodiment also showed similar capacity retention rates.

[0097] [Table 1]

[0098] As shown by the comparison results, in a positive electrode plate using an existing organic material, when the volume ratio of the conductive agent is less than 2%, the capacity retention rate is extremely low. In contrast, in the positive electrode plate according to the present embodiment, even when the volume ratio of the conductive agent is less than 2%, a high capacity retention rate can be achieved compared to a positive electrode plate using an existing organic material. EXAMPLES

[0099] Using a jig for making 5 mmφ disk-shaped pellets, pellets of naphthazarin dilithium salt represented by the following formula were molded onto aluminum foil (20 μm) that had been subjected to a surface roughening treatment.

[0100] [ka]

[0101] The pressure used during molding was 60kN / 5mmφ. After that, the electrode was made by vacuum and heat drying (120℃, 1 hour). A coin-type battery was made using this as the positive electrode material, lithium foil as the negative electrode material, lithium bis(trifluoromethanesulfonyl)imide / sulfolane (2.4mol / kg) as the electrolyte, and a glass filter as the separator. A charge-discharge test was performed on this battery under conditions similar to the constant current intermittent titration method (GITT) in an atmosphere of 30℃, at a current density of 20mA / g, and in the potential range of 1.2-4.2V (vs.Li+ / Li). Figure 10 shows the test results.

[0102] Although the present invention has been described above using the embodiments, the technical scope of the present invention is not limited to the scope described in the above embodiments. It is clear to those skilled in the art that various modifications and improvements can be made to the above embodiments. It is clear from the description of the claims that such modifications and improvements can also be included in the technical scope of the present invention.

[0103] It should be noted that the order of execution of each process, such as operations, procedures, steps, and stages, in the devices, systems, programs, and methods shown in the claims, specifications, and drawings is not specifically stated as "before" or "prior to," and that the process may be performed in any order unless the output of a previous process is used in a later process. Even if the operational flow in the claims, specifications, and drawings is described using "first," "next," etc. for convenience, it does not mean that the process must be performed in this order. [Explanation of symbols]

[0104] 30 organic material, 40 solid electrolyte material, 50 Li metal, 100 manufacturing system, 110 positive electrode production section, 112 preparation section, 114 compression section, 116 containing section, 120 electrolyte preparation section, 130 negative electrode preparation section, 140 battery production section, 200 compressor, 202 compression section, 210 container, 300 organic positive electrode, 400 solid electrolyte, 500 battery, 1200 computer, 1210 host controller, 1212 CPU, 1214 RAM, 1216 graphic controller, 1218 display device, 1220 input / output controller, 1222 communication interface, 1224 storage device, 1230 ROM, 1240 input / output chip

Claims

1. An organic positive electrode comprising a plurality of granular organic materials having reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in an oxidation-reduction reaction, the organic positive electrode being free of conductive agents and binders, the organic material being naphthazarin.

2. An organic positive electrode comprising a plurality of granular organic materials having reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in an oxidation-reduction reaction, the organic positive electrode containing no conductive agent and containing a binder having a volume ratio greater than 0% and less than 2%, the organic material being naphthazarin.

3. The organic positive electrode according to claim 1 or 2, wherein the organic material is a naphthazarin dimer.

4. The organic positive electrode according to claim 1 , wherein the organic material is a naphthazarin monomer.

5. 1. An organic positive electrode comprising a plurality of granular organic materials having reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in an oxidation-reduction reaction, wherein a volume ratio of a conductive agent is less than 2%, and the organic positive electrode contains a binder in the same volume ratio as the conductive agent, and the organic material is naphthazarin.

6. An organic positive electrode comprising a plurality of granular organic materials having reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in an oxidation-reduction reaction, a volume ratio of a conductive agent being less than 2%, and a volume ratio of a binder being greater than 0% and less than 2%, the organic material being naphthazarin.

7. The organic positive electrode according to claim 1 , wherein the plurality of granular organic materials are aggregated together.

8. The organic positive electrode according to claim 1 , wherein the plurality of granular organic materials are powder-formed.

9. The organic positive electrode according to any one of claims 1 to 8, A solid electrolyte; Negative electrode and A battery comprising:

10. preparing a plurality of granular organic materials having reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in an oxidation-reduction reaction; a compressing step of compressing the plurality of granular organic materials without including a conductive agent and a binder in the plurality of granular organic materials; a step of removing the organic positive electrode produced by the compression step; Equipped with The organic material is naphthazarin. A method for producing an organic positive electrode.

11. The preparing step includes preparing a plurality of granular solid electrolyte materials and a plurality of granular organic materials; the compressing step compresses the plurality of granular solid electrolyte materials and the plurality of granular organic materials without including a conductive agent and a binder in the plurality of granular organic materials; The removing step removes the organic positive electrode and the solid electrolyte. The method of claim 10.

12. forming a battery by contacting a negative electrode with the solid electrolyte; The method of claim 11 , comprising:

13. preparing a plurality of granular organic materials having reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in an oxidation-reduction reaction; a compressing step of compressing the plurality of granular organic materials, the plurality of granular organic materials not containing a conductive agent and containing a binder at a volume ratio of more than 0% and less than 2%; a step of removing the organic positive electrode produced by the compression step; Equipped with The organic material is naphthazarin. A method for producing an organic positive electrode.

14. preparing a plurality of granular organic materials having reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in an oxidation-reduction reaction; a step of adding a conductive agent having a volume ratio of less than 2% and a binder having the same volume ratio as the conductive agent to the plurality of granular organic materials; a compressing step of compressing the plurality of granular organic materials containing less than 2% of the conductive agent and the same volume ratio of the binder as the conductive agent; a step of removing the organic positive electrode produced by the compression step; Equipped with The organic material is naphthazarin. A method for producing an organic positive electrode.

15. preparing a plurality of granular organic materials having reversible oxidation-reduction ability and utilizing lithium ions as charge carriers in an oxidation-reduction reaction; an inclusion step of injecting a conductive agent having a volume ratio of less than 2% and a binder having a volume ratio of more than 0% and less than 2% into the plurality of granular organic materials; a compressing step of compressing the plurality of granular organic materials containing the conductive agent at less than 2% and the binder at a ratio of more than 0% and less than 2%; a step of removing the organic positive electrode produced by the compression step; Equipped with The organic material is naphthazarin. A method for producing an organic positive electrode.

16. A program for causing a computer to execute the method for producing an organic positive electrode according to claim 10 .

17. A preparation unit that prepares a plurality of granular organic materials that have a reversible oxidation-reduction ability and utilize lithium ions as charge carriers in an oxidation-reduction reaction; a compression unit that compresses the plurality of granular organic materials without including a conductive agent and a binder in the plurality of granular organic materials; Equipped with The organic material is naphthazarin. A manufacturing system for organic positive electrodes.

18. A preparation unit that prepares a plurality of granular organic materials that have a reversible oxidation-reduction ability and utilize lithium ions as charge carriers in an oxidation-reduction reaction; a compression unit that compresses the plurality of granular organic materials, the plurality of granular organic materials not including a conductive agent and including a binder having a volume ratio of more than 0% and less than 2%; Equipped with The organic material is naphthazarin. A manufacturing system for organic positive electrodes.

19. A preparation unit that prepares a plurality of granular organic materials that have a reversible oxidation-reduction ability and utilize lithium ions as charge carriers in an oxidation-reduction reaction; a containing portion for containing a conductive agent having a volume ratio of less than 2% and a binder having the same volume ratio as the conductive agent in the plurality of granular organic materials; a compression unit that compresses the plurality of granular organic materials containing less than 2% of the conductive agent and a binder having the same volume ratio as the conductive agent; Equipped with The organic material is naphthazarin. A manufacturing system for organic positive electrodes.

20. A preparation unit that prepares a plurality of granular organic materials that have a reversible oxidation-reduction ability and utilize lithium ions as charge carriers in an oxidation-reduction reaction; a containing portion for containing a conductive agent having a volume ratio of less than 2% and a binder having a volume ratio of more than 0% and less than 2% in the plurality of granular organic materials; a compression unit that compresses the plurality of granular organic materials containing the conductive agent at less than 2% and the binder at a ratio of more than 0% and less than 2%; Equipped with The organic material is naphthazarin. A manufacturing system for organic positive electrodes.

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