Surface-modified carbon materials and their manufacturing methods, electrodes and their manufacturing apparatus and methods

Abstract

The object of the present invention is to provide a surface-modified carbon material with excellent self-dispersibility in aprotic polar solvents and the like, which are widely used in electrochemical components. The surface-modified carbon material of the present invention is a surface-modified carbon material with substituents added to a carbon material, represented by the following general formula (1), [Chemical Formula 1] where M is any one of metal ions, organic amines and ammonium, R represents any one of the following general formulas (2) and (3), * represents a binding site, [Chemical Formula 2] where A1, A2, A3, A4 and A5 are each independently CR' or N, A6, A7 and A8 are each independently CR' or N, A9 is CR'R', NR', O or S, R' is each independently any one of hydrogen atom, alkyl and alkoxy, * represents a binding site.

Description

Technical Field

[0001] This invention relates to surface-modified carbon materials, methods for manufacturing surface-modified carbon materials, electrodes, liquid compositions, storage containers, apparatus for manufacturing electrodes, methods for manufacturing electrodes, and electrochemical elements. Background Technology

[0002] By applying a carbon material to the surface of a substrate, the functions of the carbon material can be imparted to the substrate. One method for applying a carbon material to a substrate is to disperse the carbon material in a dispersion medium to obtain a liquid composition, and then coat the liquid composition using a method such as inkjet printing. Typically, dispersants are added to disperse the carbon material in the dispersion medium; however, due to various problems caused by these dispersants, there is a widespread demand in the market for techniques that disperse carbon materials without using dispersants.

[0003] To date, as a technique for dispersing carbon materials in aqueous media, development is underway in fields such as inkjet inks that use carbon particles as pigments. For example, so-called self-dispersible carbon materials have been proposed, which introduce functional groups at the edges of carbon planes through free radical reactions and exhibit dispersibility in aqueous media (see, for example, Patent Documents 1 to 3).

[0004] [Patent Documents]

[0005] [Patent Document 1] International Patent No. 96 / 18688

[0006] [Patent Document 2] Japanese Patent Application Publication No. 2016-27092

[0007] [Patent Document 3] Japanese Patent Application Publication No. 2016-27093 Summary of the Invention

[0008] The object of the present invention is to provide a surface-modified carbon material that has excellent self-dispersibility in aprotic polar solvents and the like, which are widely used in electrochemical components.

[0009] As a means of solving the above problems, the surface-modified carbon material of the present invention is a surface-modified carbon material with substituents added to a carbon material, represented by the following general formula (1).

[0010] [Chemical Formula 1]

[0011]

[0012] (In the formula, M is any one of metal ions, organic amines and ammonium, R represents any one of the following general formulas (2) and (3), and * represents the binding site.)

[0013] [Chemical Formula 2]

[0014]

[0015] (In the formula, A1, A2, A3, A4 and A5 are each independently CR' or N, A6, A7 and A8 are each independently CR' or N, A9 is CR'R', NR', O or S, R' is each independently any one of hydrogen atom, alkyl and alkoxy, and * indicates the bonding site.)

[0016] The effects of this invention are as follows:

[0017] According to the present invention, a surface-modified carbon material with excellent self-dispersibility in aprotic polar solvents and the like, which are widely used in electrochemical elements, can be provided. Attached Figure Description

[0018] Figure 1 This is a diagram representing the general formula (1) in the surface-modified carbon material of the present invention.

[0019] Figure 2 This is a schematic diagram illustrating an example of the electrode of the present invention.

[0020] Figure 3 This is a schematic diagram illustrating an example of a liquid discharge device in an electrode manufacturing apparatus according to this embodiment.

[0021] Figure 4 It means Figure 3 A schematic diagram of a modified liquid discharge device.

[0022] Figure 5 This is a schematic diagram showing another example of a liquid discharge device in an electrode manufacturing apparatus as described in this embodiment.

[0023] Figure 6 It means Figure 5 A schematic diagram of a modified liquid discharge device.

[0024] Figure 7 This is a structural diagram illustrating an example of a printing component using a drum-shaped intermediate transfer body in an electrode manufacturing apparatus as described in this embodiment.

[0025] Figure 8 This is a structural diagram illustrating an example of a printing component using an annular strip-shaped intermediate transfer body in an electrode manufacturing apparatus as described in this embodiment.

[0026] Figure 9 This is an explanatory diagram illustrating an example of a manufacturing process in the method for manufacturing an electrode according to this embodiment.

[0027] Figure 10 This is a structural diagram showing an example of a nozzle with a nozzle plate having a parallelogram shape.

[0028] Figure 11 It indicates the arrangement of multiple Figure 10 A diagram illustrating the status of the nozzle.

[0029] Figure 12 This is a schematic diagram showing an example of an electrochemical element having a negative electrode, a positive electrode, and a membrane.

[0030] The symbols in the diagram have the following meanings:

[0031] 1 Current collector

[0032] 2 Electrode composite material layer

[0033] 10 electrodes

[0034] 15 Positive electrode

[0035] 25 Negative electrode

[0036] 100 Electrochemical Components

[0037] 300' Liquid discharge device (electrode manufacturing device)

[0038] 306 Liquid Discharge Head

[0039] 307 cans (storage containers)

[0040] Specific Implementation Form

[0041] (Surface-modified carbon materials)

[0042] The surface-modified carbon material of the present invention is a surface-modified carbon material with substituents added to a carbon material, represented by the following general formula (1).

[0043] [Chemical Formula 3]

[0044]

[0045] (In the formula, M is any one of metal ions, organic amines and ammonium, R represents any one of the following general formulas (2) and (3), and * represents the binding site.)

[0046] [Chemical Formula 4]

[0047]

[0048] (In the formula, A1, A2, A3, A4 and A5 are each independently CR' or N, A6, A7 and A8 are each independently CR' or N, A9 is CR'R', NR', O or S, R' is each independently any one of hydrogen atom, alkyl and alkoxy, and * indicates the bonding site.)

[0049] The surface-modified carbon material of the present invention was invented to solve the following problems of the prior art.

[0050] That is, the technology requires imparting the functions of carbon materials to the substrate by applying carbon materials to the substrate surface. However, if a dispersant is used to disperse the carbon materials, the surface of the carbon materials will be coated due to the binding principle of the dispersant, which may reduce the conductivity of the carbon materials.

[0051] Furthermore, existing technologies for dispersing carbon materials such as carbon conductive particles without using dispersants are almost all related to dispersion in aqueous media, which has the following problem: there has been no significant progress in the development of particle or liquid compositions using non-aqueous media (especially aprotic polar solvents such as N-methyl-2-pyrrolidone (NMP)) that are widely used in the formation of electrochemical elements, especially secondary batteries, as dispersion media.

[0052] The inventors conducted in-depth research as described below and found that by adding substituents represented by the above general formula (1) to carbon materials, surface-modified carbon materials with excellent self-dispersibility in aprotic polar solvents and the like, which are widely used in electrochemical elements, can be provided, thus completing the present invention.

[0053] To ensure dispersibility in aqueous media, the so-called double-layer repulsion is mostly used for dispersion. Specifically, ionic substituents are often used as dispersing groups. Compared to water, the double-layer repulsion of non-aqueous media, which have lower polarity, is weaker, and dispersion is more difficult than in aqueous media. This can be considered a reason for the limited progress in development.

[0054] As an example of imparting the functions of carbon materials to a substrate by applying carbon materials to the substrate surface, sometimes a liquid composition in which carbon materials are dispersed in a dispersion medium is used to form components of electrochemical elements, such as lithium-ion secondary batteries.

[0055] Because electrochemical devices, represented by lithium-ion secondary batteries, exhibit high energy density, their application in everything from electrical equipment to automobiles is anticipated. In particular, there is a strong desire to further improve the safety of secondary batteries. Generally, electrochemical devices consist of a (positive electrode) current collector, an electrode composite layer (positive electrode layer), a separator made of paper, non-woven fabric, or porous membrane, an electrode composite layer (negative electrode layer), and a (negative electrode) current collector as their basic components.

[0056] Electrode composite layers are typically obtained by coating a current collector foil with a dispersion of active material particles and carbon-based particles or carbon fibers, or a liquid composition obtained by dispersing active material particles in a dispersion medium. Ionic and electronic conductivity are essential for electrode composite layers. To ensure high electronic conductivity, carbon black secondary aggregates with small primary particle size, large specific surface area, and numerous porous aggregates are required. Generally, to stably disperse such particles with large specific surface area and aggregate structure, a large amount of dispersant corresponding to the specific surface area is needed. However, some dispersants do not inherently contribute to battery performance and may even hinder it, depending on the situation.

[0057] In recent years, attempts have been made to improve the battery characteristics of lithium-ion batteries by using carbon-metal composite current collector foils obtained by coating a conductive layer formed of carbon particles onto a current collector foil (see Japanese Patent Application Publication No. 2007-226969, Japanese Patent Application Publication No. 2010-135338, etc.). In these attempts, the battery is typically manufactured by coating a liquid composition containing carbon particles onto a metal current collector foil. When forming the conductive layer s in a thin layer, especially when forming the conductive layer in a non-contact manner using inkjet printing or the like, it is generally necessary to reduce the viscosity of the liquid. In this case, in order to stably disperse the carbon particles, a large amount of dispersant is required, similar to the electrode composite layer. However, since the dispersant does not inherently contribute to conductivity and in some cases can hinder conductivity, it is necessary to control the amount of dispersant used, and it is preferable not to use a dispersant at all.

[0058] In addition, in recent years, lithium batteries with a mixed layer of silver particles and carbon particles coated on the current collector foil have been reported for the purpose of suppressing lithium dendrites (see Japanese Patent Application Publication No. 2019-96610, etc.). In this case, in order to stably disperse the carbon particles as described above, it is predicted that a large amount of dispersant is needed, but these cases also require controlling the amount of dispersant used, and it is more preferable not to use a dispersant.

[0059] Most dispersants used in carbon materials employ aromatic compounds as adsorption groups (e.g., see Chemistry Letters 36(6), pp. 692-697, 2007). The surface of carbon materials is composed of π-planes. Due to the limited number of functional groups, the so-called anchoring portion of the adsorbent dispersant is small; therefore, carbon π-planes are often used as anchoring portions. This utilizes the phenomenon of strong π-π stacking interaction between the adsorption groups of the dispersant and the carbon π-plane.

[0060] However, because the dispersant in this design is located on the π-electron cloud of the carbon particles, foreign molecules such as the dispersant are trapped between the overlaps of the π-electron clouds, which are the main electronic conduction structures between carbon particles. Therefore, the presence of the dispersant can sometimes be a major cause of deterioration in electronic conduction.

[0061] The inventors conducted in-depth research on the above-mentioned content and as a result, completed this invention.

[0062] <Carbon Materials>

[0063] There are no particular restrictions on the carbon materials mentioned above, and appropriate selections can be made according to the purpose. For example, amorphous carbon materials such as carbon black can be cited; carbon fibers such as graphite, graphene, carbon nanotubes, and VGCF; and single materials or composite materials containing so-called graphene structures such as nanodiamonds.

[0064] Carbon black, due to its network structure with a large unit weight caused by the aggregation of tiny particles, is therefore preferred and widely used as the main conductive material for electrochemical components such as lithium-ion batteries.

[0065] There are no particular limitations on the carbon black used, and it can be appropriately selected according to the purpose. Examples include channel black, roller black, disc black, furnace black, thermal cracking black, and acetylene black. Among these, furnace black or acetylene black is more preferred from the viewpoint of having high secondary battery properties. Among furnace blacks, Ketjen black, which has a particularly large specific surface area, is more preferred from the viewpoint of having a particularly large specific surface area.

[0066] <Substituents represented by general formula (1)>

[0067] The above-mentioned substituents are substituents represented by the following general formula (1). Figure 1 This also represents the above general formula (1) in the surface-modified carbon material of the present invention.

[0068] [Chemical Formula 5]

[0069]

[0070] (In the formula, M is any one of metal ions, organic amines and ammonium, R represents any one of the following general formulas (2) and (3), and * represents the binding site.)

[0071] [Chemical Formula 6]

[0072]

[0073] (In the formula, A1, A2, A3, A4 and A5 are each independently CR' or N, A6, A7 and A8 are each independently CR' or N, A9 is CR'R', NR', O or S, R' is each independently any one of hydrogen atom, alkyl and alkoxy, and * indicates the bonding site.)

[0074] The metal ions, organic amines and ammonium in M ​​of the above general formula (1) can also act as counter ion frees relative to the nitrogen atom N of the above general formula (1) through ionic bonds, covalent bonds or bonds formed by a mixture of them.

[0075] The aforementioned metal ions refer to positively charged atoms or molecules. From the viewpoint of dispersion stability, monovalent alkali metal ions are preferred. When using the aforementioned surface-modified carbon material as the carbon material for lithium-ion batteries, lithium ions are preferred as the carrier for ion conduction.

[0076] There are no particular restrictions on the organic amines mentioned above, and they can be appropriately selected according to the purpose. Examples include trimethylamine, N,N-dimethylethylamine, triethylamine, 1-methylpyrrolidine, N-butyldimethylamine, 1-ethylpiperidine, 4-hydroxy-1-methylpiperidine, N,N-dimethylformamide dimethylacetal, N,N-diisopropylethylamine, 4-(2-hydroxyethyl)morpholine, 3-dipropylaminoethanol, 2-[2-(dimethylamino)ethoxy]ethanol, N-ethyldiethanolamine, 2-(dimethylamino)ethanol, pyridine derivatives, etc.

[0077] In the above general formula (2), A1, A2, A3, A4 and A5 are each independently CR' or N. In the above general formula (2), the number of N can be any one of 0 to 5, preferably any one of 1 to 3, and more preferably 1 or 2.

[0078] As the substituent R represented by the above general formula (2), the following substituent R can be preferably cited as an example.

[0079] [Chemical Formula 7]

[0080]

[0081] In the above general formula (3), A6, A7 and A8 are each independently CR' or N, and A9 is CR'R', NR', O or S. In the above general formula (3), the number of heteroatoms N, O and S can be any one of 0 to 4, preferably any one of 1 to 3, and more preferably 2 or 3.

[0082] As the substituent R represented by the above general formula (3), the following substituent R can be preferably cited as an example.

[0083] [Chemical Formula 8]

[0084]

[0085] There are no particular restrictions on the alkyl and alkoxy groups in R' of the above general formulas (2) to (3), and they can be appropriately selected according to the purpose, but alkyl groups with 1 to 12 carbon atoms and alkoxy groups with 1 to 12 carbon atoms are preferred.

[0086] Examples of alkyl groups mentioned above include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, and dodecyl.

[0087] Examples of alkoxy groups mentioned above include methoxy, ethoxy, propoxy, butoxy, hexoxy, octyl, decyl, and dodecyloxy.

[0088] In this invention, "surface modification" and "addition of substituents to carbon materials" refer to the covalent bonding of substituents to the graphene structure within the carbon material as a substrate, and the structure obtained by covalently bonding substituents.

[0089] The surface-modified carbon material of the present invention, which has the above-mentioned substituents added to a carbon material, can be suitably manufactured by the manufacturing method of the surface-modified carbon material of the present invention described later.

[0090] [Dipole moment of surface-modified carbon materials]

[0091] There are no particular limitations on the dipole moment of the aforementioned surface-modified carbon material, which can be appropriately selected according to the purpose. Preferably, it is 4.0 debye or more, and more preferably 5.0 debye or more.

[0092] In the surface-modified carbon materials of this invention, the functional groups can function by being substituted (covalently bonded) to the graphene edges of the carbon material. However, due to the existence of numerous carbon material structures (graphene structures), it is generally necessary to define a model compound that homogenizes the structure of the carbon material and generalize it before performing calculations.

[0093] In this invention, the dipole moment is calculated using a model compound with a target functional group assigned to the 9-position of the anthracene ring. The calculation uses a non-empirical molecular orbital method.

[0094] Here, the dipole moment of the surface-modified carbon material is calculated using a model compound via a non-empirical molecular orbital method. The carbon material of the surface-modified carbon material is converted to anthracene, the substituent is assigned to the 9-position of the anthracene, and the M in the substituent is converted to H, thus obtaining the model compound.

[0095] By setting up model compounds in this way, the structure for quantum science computing is optimized. Then, by performing quantum computing based on the structure of the model compounds, the dipole moment can be calculated.

[0096] Specifically, the dipole moment was calculated using the quantum computing chemistry program Gaussian16 (Gaussian, USA).

[0097] The unit of dipole moment, [debye], is represented by [C·m] in the SI unit system, and can be converted using the formula: 1 [debye] = 3.336 × e -30 [C·m] conversion.

[0098] [Dispersion]

[0099] The dispersibility of the aforementioned surface-modified carbon materials can be evaluated by comparing them with a liquid composition containing the same type of carbon material, using the median particle size in the liquid composition containing the surface-modified carbon material as an indicator.

[0100] That is, in liquid compositions containing poorly dispersible (non-substituent) carbon materials, the carbon materials aggregate in the liquid composition, resulting in a larger median particle size. On the other hand, in liquid compositions containing well-dispersible surface-modified carbon materials, the median particle size decreases.

[0101] Furthermore, since the aforementioned surface-modified carbon materials are self-dispersible without the use of additional dispersants, they sometimes exhibit "self-dispersibility" or high "self-dispersibility".

[0102] The dispersibility of the aforementioned surface-modified carbon materials can be evaluated using the following methods.

[0103] A mixture of surface-modified carbon material with a solid content of 10% by mass was ultrasonically dispersed for 3 minutes in at least one organic solvent, either an aprotic polar solvent or an alcohol solvent, using an ultrasonic homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain a liquid composition. The obtained liquid composition was diluted 1,000 times with the organic solvent used for dispersion, and the particle size distribution was measured using a dynamic light scattering instrument (NanoSAQLA, manufactured by Otsuka Electronics Co., Ltd.) to obtain the median particle size (D). 50 ).

[0104] As at least one of the above-mentioned "aprotic polar solvents and alcohol solvents", it can be appropriately selected from the organic solvents described in the following description of the liquid compositions of the present invention.

[0105] The term "liquid composition" or "dispersion" containing at least one organic solvent selected from the above-mentioned surface-modified carbon materials, aprotic polar solvents, and alcohol solvents refers to the state in which particles of surface-modified carbon materials with a wavelength of approximately 5 nm to 5000 nm are suspended or even suspended in a liquid.

[0106] There are no particular limitations on the method for identifying the structure in a surface-modified carbon material with the above-mentioned substituents added to the carbon material. A known identification method can be appropriately selected according to the purpose. For example, methods using electron spectrometry (X-ray absorption end near-spectrum: XANES), identification by the movement of protons or carbon obtained by solid-state NMR, and identification by the movement of free radicals obtained by ESR can be cited.

[0107] As an electronic spectrophotometric method, specifically, the structure of surface-modified carbon materials is identified by measuring the spectrum of the structure of specific substituents in a sample coated on a glass substrate using an X-ray spectrometer (XPS) (LJPS-9030, manufactured by Nippon Spectroscopy Co., Ltd.).

[0108] As a method for identification by proton or carbon movement through solid-state NMR, specifically, a nuclear magnetic resonance apparatus (JNM-ECA700, manufactured by NEC Corporation) can be used in the powder state to perform measurements at room temperature (25°C). By identifying the proton peak or carbon peak, the structure of the substituent can be identified, thereby identifying the structure of the surface-modified carbon material.

[0109] (Manufacturing method of surface-modified carbon materials)

[0110] The method for manufacturing surface-modified carbon materials of the present invention includes a step of reacting a free radical compound represented by the following general formula (4) with the surface of a carbon material, and bonding a functional group represented by the following general formula (1) with the surface of the carbon material, and may include other steps as needed.

[0111] As a method for bonding (covalently bonding) the substituent represented by the above general formula (1) to the surface of the above carbon material, it can be carried out by known methods, which are also within the scope of the present invention. However, it is preferable to use a method for covalently bonding the radical compound represented by the above general formula (4) obtained by radicalizing the substituent represented by the above general formula (1) to the graphene edge of the above carbon material.

[0112] There are no particular restrictions on the method of radicalizing the substituents and covalently bonding them to the edge of graphene in carbon materials. A known method can be appropriately selected according to the purpose. For example, the method described in International Patent No. 96 / 18688, Japanese Patent Application Publication No. 2016-27092, Japanese Patent Application Publication No. 2016-27093, etc. can be applied to the radical compound represented by the above general formula (4).

[0113] <Free radical compounds represented by general formula (4)>

[0114] The above-mentioned free radical compounds are free radical compounds represented by the following general formula (4).

[0115] [Chemical Formula 9]

[0116]

[0117] (In the formula, M is any one of metal ions, organic amines and ammonium, R represents any one of the following general formulas (2) and (3), and · represents a free radical.)

[0118] [Chemical Formula 10]

[0119]

[0120] (In the formula, M is any one of metal ions, organic amines and ammonium, R represents any one of the following general formulas (2) and (3), and * represents the binding site.)

[0121] [Chemical Formula 11]

[0122]

[0123] (In the formula, A1, A2, A3, A4 and A5 are each independently CR' or N, A6, A7 and A8 are each independently CR' or N, A9 is CR'R', NR', O or S, R' is each independently any one of hydrogen atom, alkyl and alkoxy, and * indicates the bonding site.)

[0124] The metal ions, organic amines and ammonium in M ​​of the above general formula (4) may be appropriately selected from those described in the above general formula (1).

[0125] Similarly, for the above general formulas (2) and (3), the matters described in the above general formula (1) may be appropriately selected.

[0126] There are no particular restrictions on the method for obtaining free radical compounds (organic free radicals). A known method may be appropriately selected according to the purpose. For example, the method described in International Patent No. 96 / 18688, Japanese Patent Application Publication No. 2016-27092, Japanese Patent Application Publication No. 2016-27093, etc., may be appropriately selected. This method is applicable to the free radical compound represented by the above general formula (4).

[0127] From the viewpoint of obtaining surface-modified carbon with high surface modification rate and minimal loss of the original properties of carbon materials, it is preferable to use a method of obtaining a diazonium salt by diazotizing the amino group of the aniline compound with an aniline compound as a starting material.

[0128] Specifically, the free radical compound represented by the above general formula (4) is preferably generated from the diazonium salt represented by the following general formula (5).

[0129] <Diazonium salts represented by general formula (5)>

[0130] The above-mentioned diazonium salt is the diazonium salt represented by the following general formula (5).

[0131] [Chemical Formula 12]

[0132]

[0133] (In the formula, M is any one of metal ions, organic amines and ammonium, and R represents any one of the following general formulas (2) and (3).)

[0134] [Chemical Formula 13]

[0135]

[0136] (In the formula, A1, A2, A3, A4 and A5 are each independently CR' or N, A6, A7 and A8 are each independently CR' or N, A9 is CR'R', NR', O or S, R' is each independently any one of hydrogen atom, alkyl and alkoxy, and * indicates the bonding site.)

[0137] The metal ions, organic amines and ammonium in M ​​of the above general formula (5) may be appropriately selected from those described in the above general formula (1).

[0138] Similarly, for the above general formulas (2) and (3), the matters described in the above general formula (1) may be appropriately selected.

[0139] There are no particular restrictions on the aniline corresponding to the diazonium salt represented by the above general formula (5). It can be appropriately selected according to the purpose. Examples include: sulfapyridine, sulfadiazine, sulfamethoxazole, sulfathiazole, sulfisoxazole, sulfadiazine, sulfadiazine, sulfamethoxypyrimidine, sulfamethoxypyridazine, sulfadiazine, 4-amino-2,5-dimethoxy-N-phenylbenzenesulfonamide, sulfadiazine, sulfadoxine, sulfadiazine, etc.

[0140] (Liquid composition)

[0141] The liquid composition of the present invention contains at least one organic solvent selected from the surface-modified carbon material of the present invention, aprotic polar solvent, and alcohol solvent, preferably further containing an active substance, and further containing other components as needed.

[0142] In the liquid composition, the surface-modified carbon material is self-dispersible without the use of additional dispersants and can be uniformly dispersed in the liquid composition. Preferably, the liquid composition contains surface-modified carbon material particles with a median particle size of approximately 5 nm to 5000 nm, which are in a state of suspension or even floating in the liquid. This can be evaluated using the aforementioned method for determining the median particle size of the surface-modified carbon material.

[0143] <Organic Solvents>

[0144] There are no particular restrictions as long as the organic solvents mentioned above are at least one of aprotic polar solvents and alcohol solvents, and they can be selected appropriately according to the purpose.

[0145] Examples of aprotic polar solvents include styrene, toluene, xylene, methyl ethyl ketone, ethyl acetate, acetone, N,N-dimethylformamide (DMF), N,N-dimethyl sulfoxide (DMSO), 2-pyrrolidone, N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), cyclohexanone, dimethylacetamide (DMAA), hexamethylphosphoric triamine (HMPA), acetonitrile, and dimethyl sulfone.

[0146] Examples of alcohol solvents include methanol, ethanol, n-propanol, isopropanol (IPA), n-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol, and diacetone alcohol.

[0147] They can be used individually or in combination with two or more.

[0148] From the perspective of high solubility for widely used in the manufacture of electrochemical components and fluorinated polymers, nonprotic polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethyl sulfoxide (DMSO), 2-pyrrolidone, N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAA), hexamethylphosphoric triamine (HMPA), acetonitrile, and dimethyl sulfone are preferred.

[0149] <Active Substances>

[0150] There are no particular limitations on the active material used, and a known active material may be appropriately selected according to the use and purpose of the liquid composition. Specifically, an active material may be appropriately selected from those containing the positive electrode active material and the negative electrode active material in the electrode described later.

[0151] [Method for manufacturing liquid composition]

[0152] The above liquid composition can be manufactured by dispersing and mixing the above-mentioned surface-modified carbon material, the above-mentioned organic solvent, and other components such as resin as needed using a dispersion device.

[0153] Examples of dispersing devices include mixers, ball mills, bead mills, ring mills, high-pressure dispersers, rotary high-speed shearing devices, and ultrasonic dispersers.

[0154] (Storage container)

[0155] The storage container of the present invention comprises the liquid composition and container of the present invention described above, wherein the liquid composition is stored in the container.

[0156] For example, examples include glass bottles, plastic containers, plastic bottles, stainless steel bottles, 18-liter metal cans, and barrels.

[0157] (electrode)

[0158] The electrode of the present invention comprises a current collector and an electrode composite material layer containing the surface-modified carbon material of the present invention disposed on the current collector, and may also have other components such as a functional layer as needed.

[0159] The electrode described above can be either a positive electrode or a negative electrode.

[0160] Here, Figure 2 This is a schematic diagram illustrating an example of the electrode of the present invention.

[0161] Figure 2 The electrode 10 has an electrode composite material layer 2 on the current collector 1.

[0162] <Positive electrode>

[0163] A positive electrode is a flat or sheet-like electrode portion having a positive current collector and a composite material layer made of positive electrode material disposed on the positive current collector.

[0164] The positive electrode material contains positive electrode active material, preferably containing binder, conductive additive and thickener, and may also contain other components as needed.

[0165] -Positive electrode active material-

[0166] As a positive electrode active material, there are no particular restrictions as long as it can insert or release alkali metal ions. It can be appropriately selected according to the purpose. For example, transition metal compounds containing alkali metals can be used.

[0167] Examples of alkali metal transition metal compounds include lithium-containing transition metal compounds containing a composite oxide of lithium and one or more elements selected from the group consisting of cobalt, manganese, nickel, chromium, iron and vanadium; and polyanionic compounds with XO4 tetrahedra (X = P, S, As, Mo, W, Si, etc.) in their crystal structure.

[0168] Examples of lithium-containing transition metal compounds include lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide.

[0169] From the perspective of cycle characteristics, lithium iron phosphate, lithium vanadium phosphate and other lithium-containing transition metal phosphate compounds are preferred, and from the perspective of lithium diffusion coefficient and output characteristics, lithium vanadium phosphate is preferred.

[0170] Furthermore, from the viewpoint of electronic conductivity, polyanionic compounds are preferably composited by coating the surface with conductive additives such as carbon materials.

[0171] -Adhesives and Thickeners-

[0172] Adhesives are used to bond positive electrode active materials together or to positive electrode current collectors to maintain the electrode structure.

[0173] There are no particular restrictions on the materials used as adhesives; they can be selected appropriately according to the purpose. Examples include fluorinated adhesives, acrylic latexes, carboxymethyl cellulose (CMC), ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), isoprene rubber, acrylic latexes, carboxymethyl cellulose (CMC), methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyacrylic acid, polyvinyl alcohol, alginate, oxidized starch, phosphate starch, casein, etc. One of these materials can be used alone, or two or more can be used in combination.

[0174] There are no particular limitations on the fluorinated adhesives mentioned above; they can be selected appropriately according to the purpose. For example, polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE) can be cited.

[0175] In addition, the adhesive is any material that is stable to the solvent used in the manufacture of the electrode and the applied potential, without any particular restrictions, and can be selected appropriately according to the purpose.

[0176] -Conductive additive-

[0177] In addition, in this invention, besides surface-modified carbon materials, the following conductive additives may also be added.

[0178] The aforementioned conductive additives refer to conductive materials dispersed in the electrodes to reduce electrode resistance, which play a role in assisting the conductivity between electrode materials and have the function of forming a conductive network.

[0179] Furthermore, even if the surface-modified carbon material has functions other than those described above as conductive aids, it is still treated as a conductive aid as long as it has at least the functions described above. That is, if the surface-modified carbon material has functions such as inserting or releasing alkali metal ions, reducing the resistance of the electrode when dispersed in the electrode, and assisting in the conductivity between electrode materials, the surface-modified carbon material serves as both an active material and a conductive aid.

[0180] The aforementioned conductive additives are preferably made of metallic materials, or carbonaceous materials used in conjunction with the positive electrode active material. They can be used alone or in combination of two or more.

[0181] There are no particular restrictions on the metal materials used in the aforementioned conductive additives; they can be selected appropriately according to the purpose. For example, copper and aluminum can be cited.

[0182] There are no particular restrictions on the carbonaceous materials used in the aforementioned conductive additives; they can be selected appropriately according to the purpose. Examples include conductive carbon blacks such as acetylene black and Ketjen black, which are manufactured by furnace process, acetylene process, gasification process, etc.; artificial graphite, natural graphite, graphene, carbon nanofibers, carbon nanotubes, etc. Among these, acetylene black and Ketjen black are preferred.

[0183] These conductive additives can also be used in combination with active substances to improve conductivity.

[0184] -Positive current collector-

[0185] There are no particular restrictions on the size of the positive current collector, as long as it can be used in energy storage devices, and it can be selected appropriately according to the purpose.

[0186] As for the material of the aforementioned positive current collector, there are no particular restrictions as long as it is made of a conductive material and is stable under the applied potential. It can be appropriately selected according to the purpose. For example, nickel, aluminum, titanium, tantalum, etc. are examples. Among them, stainless steel and aluminum are preferred.

[0187] As for the type (shape, presence or absence of processing) of the aforementioned positive current collector, there are no particular restrictions as long as it has the durability to be used in the manufacturing process of the positive electrode described later. It can be appropriately selected according to the purpose. For example, ordinary metal foil, perforated metal foil, edged metal foil, through metal foil, raised metal foil, and porous metal foil can be mentioned. Among them, ordinary metal foil, perforated metal foil, edged metal foil, through metal foil, and raised metal foil are preferred.

[0188] Alternatively, a coated metal foil pre-coated with the carbonaceous material used in the conductive additive described above can be used as the positive current collector. In this case, the carbonaceous material used as the coating can be the same carbonaceous material used as the conductive additive already described in the conductive additive section. Among these, acetylene black, Ketjen black, artificial graphite, and natural graphite are preferred.

[0189] <Negative electrode>

[0190] The negative electrode is a flat or sheet-like electrode portion having a negative electrode current collector and a negative electrode composite material layer made of negative electrode material disposed on the negative electrode current collector.

[0191] The negative electrode material contains negative electrode active substances, preferably binders, conductive additives and tackifiers, and may contain other components as needed.

[0192] -Negative electrode active material-

[0193] As a negative electrode active material, there are no particular restrictions as long as it can insert or release alkali metal ions, and carbon materials containing graphite with a graphitic crystal structure can be used.

[0194] Examples of carbon materials include natural graphite, artificial graphite, hard carbon (difficult to graphitize), and soft carbon (easy to graphitize).

[0195] Examples of anode active materials other than carbon materials include lithium titanate and titanium oxide.

[0196] Furthermore, from the viewpoint of energy density of electrochemical elements, high-capacity materials such as silicon, tin, silicon alloys, tin alloys, silicon oxide, silicon nitride, and tin oxide are preferred as negative electrode active materials.

[0197] -Conductive additive-

[0198] In addition to the surface-modified carbon materials mentioned above, the following conductive additives can also be added.

[0199] As a conductive additive used in the negative electrode, the same conductive additive as that described in the positive electrode can be used.

[0200] -Adhesives and Thickeners-

[0201] The same adhesives and tackifiers used as those for the positive electrode can be used as the adhesives and tackifiers used for the negative electrode.

[0202] There are no particular limitations on the adhesives and tackifiers mentioned above, and they can be appropriately selected according to the purpose, but fluorinated adhesives, styrene-butadiene rubber (SBR), and carboxymethyl cellulose (CMC) are preferred.

[0203] -Negative current collector-

[0204] There are no particular restrictions on its use as a negative current collector; it can be selected appropriately depending on the purpose.

[0205] As for the material of the aforementioned negative electrode current collector, there are no particular restrictions as long as it is made of a conductive material and is stable to the applied potential. It can be appropriately selected according to the purpose. Examples include stainless steel, nickel, aluminum, and copper. Among them, copper is preferred.

[0206] In addition to being flat, the shape of the negative current collector can also be selected appropriately according to the purpose.

[0207] There are no particular restrictions on the size of the negative current collector, as long as the size of the negative current collector is suitable for use in energy storage devices, and the size of the negative current collector can be appropriately selected according to the purpose.

[0208] -Other ingredients-

[0209] In addition, the following other components may be added to the electrode composite material layer used in this invention.

[0210] Other ingredients are not particularly restricted and can be selected appropriately according to the purpose. Examples include dispersants, surfactants, pH adjusters, rust inhibitors, preservatives, mildew inhibitors, antioxidants, anti-reduction agents, evaporation promoters, chelating agents, and metal nanoparticles.

[0211] The electrode layer in this invention can also be formed by coating an electrode composite material layer onto the current collector described below.

[0212] <Other Components>

[0213] Functional Layer

[0214] To improve the heat resistance of electrochemical elements, the electrodes described above may have insulating particles on the electrode composite material layer. The functional layer may also be a composite electrode composite material layer formed by combining the electrode composite material layer with the electrode composite material layer.

[0215] As the aforementioned insulating particles, inorganic oxides are preferred. Among inorganic oxides, from the viewpoint of heat resistance, alumina and silicon dioxide are preferred, with alumina being particularly preferred.

[0216] In addition, to impart smoothness to the electrode composite layer, conductive particles can be coated onto the electrode composite layer. As conductive particles, carbon black, carbon nanofibers, carbon nanotubes, graphene, graphite powder, etc. are preferred. From the viewpoint that it can be imparted with reduced dispersant dosage or without the use of dispersant, the surface-modified carbon material of the present invention is more preferred.

[0217] (Electrode manufacturing apparatus and electrode manufacturing method)

[0218] The electrode manufacturing apparatus of the present invention includes the storage container of the present invention described above, and an application device for applying the liquid composition of the present invention stored in the storage container to an object to be applied, and may also include other devices as needed.

[0219] The method for manufacturing the electrode of the present invention includes an imparting step of imparting the liquid composition of the present invention described above, and may include other steps as needed.

[0220] <Applying device, applying process>

[0221] The aforementioned applicator is an apparatus for applicating the liquid composition stored in the aforementioned storage container onto the object to be applicated.

[0222] The discharge process is the process of applying the liquid composition to the object to which it is applied, and can be appropriately carried out by the application device.

[0223] By applying the above method, a liquid composition can be applied to the current collector to form a liquid composition layer.

[0224] There are no particular restrictions on the objects to be assigned, and they can be appropriately selected according to the purpose. For example, current collectors (electrode substrates) and active material layers can be mentioned.

[0225] There are no particular limitations on the above-mentioned coating devices and coating processes, and they can be appropriately selected according to the purpose. For example, dip coating, spray coating, spin coating, bar coating, slit die coating, doctor blade coating, offset printing, gravure printing, aniline printing, movable type printing, screen printing, inkjet printing, and electrophotographic printing using liquid development methods can be cited.

[0226] From the viewpoint of being able to precisely control the position of the ejected droplets, an inkjet-type application device and application process are preferred. It should be noted that the electrode composite material layer can be manufactured by the methods described below, but the electrode composite material layer manufacturing method of the present invention is not limited to these methods.

[0227] <Other components, other processes>

[0228] Other components in the electrode manufacturing apparatus are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected according to the purpose; for example, heating devices can be mentioned.

[0229] Other steps in the above-described electrode manufacturing method are not particularly limited as long as they do not impair the effect of the present invention, and can be appropriately selected according to the purpose; for example, a heating step can be cited.

[0230] -Heating devices, heating processes-

[0231] The heating device is a device for heating the liquid composition discharged from the discharge device.

[0232] The heating process is a process of heating the liquid composition discharged in the discharge process.

[0233] The liquid composition layer can be dried by the heating.

[0234] Figure 3 This is a schematic diagram illustrating an example of an electrode manufacturing apparatus (liquid discharge device) for implementing the electrode manufacturing method of this embodiment.

[0235] The electrode manufacturing apparatus is an apparatus that manufactures electrodes using a liquid composition containing the aforementioned surface-modified carbon material. The electrode manufacturing apparatus includes: a discharge unit 110, which performs an application process of applying the liquid composition to a printing substrate 4 having an object to be applied, thereby forming a liquid composition layer; and a heating unit 130, which performs a heating process of heating the liquid composition layer to obtain an electrode composite material layer. The electrode manufacturing apparatus includes a transport unit 5 for transporting the printing substrate 4, the transport unit 5 transporting the printing substrate 4 at a predetermined speed in sequence with the discharge unit 110 and the heating unit 130.

[0236] There are no particular limitations on the manufacturing method of the printing substrate 4 having the aforementioned active material layer and other objects imparted to it, and a known method may be appropriately selected.

[0237] The discharge section 110 includes: an arbitrary printing device 1a corresponding to inkjet printing, which is a device for applying a liquid composition to a printing substrate 4; a storage container 1b for storing the liquid composition; and a supply pipe 1c for supplying the liquid composition stored in the storage container 1b to the printing device 1a.

[0238] The storage container 1b stores the liquid composition 7, and the discharge section 110 discharges the liquid composition 7 from the printing apparatus 1a, applying the liquid composition 7 onto the printing substrate 4 to form a thin film-like liquid composition layer. Alternatively, the storage container 1b can be an integrated structure with the electrode manufacturing apparatus, or it can be a structure detachable from the electrode manufacturing apparatus. It can also be a container for adding to either an integrated storage container with the electrode manufacturing apparatus or a storage container detachable from the electrode manufacturing apparatus.

[0239] The storage container 1b and the supply tube 1c can be any container capable of stably storing and supplying the liquid composition 7.

[0240] like Figure 3 As shown, the heating unit 130 includes a heating device 3a, which is used to heat the solvent remaining in the liquid composition layer, thereby drying and removing it. This allows the formation of an electrode composite material layer. The heating unit 130 can also perform the solvent removal process under reduced pressure.

[0241] There are no particular limitations on the heating device 3a; it can be selected appropriately according to the purpose. For example, substrate heating, IR heater, hot air heater, etc., can be used, or they can be combined.

[0242] In addition, the heating temperature and time can be appropriately selected based on the boiling point of the solvent contained in the liquid composition 7 and the film thickness formed.

[0243] Figure 4 This is a schematic diagram illustrating another example of an electrode manufacturing apparatus (liquid discharge device) used to implement the electrode manufacturing method of this embodiment.

[0244] The liquid discharge device 300' can circulate the liquid composition in the liquid discharge head 306, tank 307, and pipe 308 by controlling the pump 310 and valves 311 and 312.

[0245] In addition, the liquid discharge device 300' is provided with an external tank 313. When the liquid composition in the tank 307 decreases, the liquid composition can also be supplied from the external tank 313 to the tank 307 by controlling the pump 310 and valves 311, 312, and 314.

[0246] Using the manufacturing apparatus for the aforementioned electrodes, a liquid composition can be dispensed to a target portion of an object.

[0247] The aforementioned electrodes can preferably be used as part of the structure of an electrochemical element.

[0248] Figure 5 This illustrates another example of a method for manufacturing an electrode according to this embodiment.

[0249] The method for manufacturing electrode 210 includes a step of sequentially discharging liquid composition 12A onto electrode substrate 211 using liquid discharge device 300'.

[0250] First, prepare an elongated electrode substrate 211. Then, wind the electrode substrate 211 onto a cylindrical core to form one side of the electrode composite material layer 212. Figure 5 The electrode substrate 211 is positioned on the upper side of the feed roller 304 and the take-up roller 305. Here, the feed roller 304 and the take-up roller 305 rotate counterclockwise, and the electrode substrate 211... Figure 5 The liquid is conveyed from right to left. Then, it exits from the liquid discharge head 306, located above the electrode substrate 211 between the feed roller 304 and the take-up roller 305, and... Figure 3 Similarly, droplets of liquid composition 12A are discharged onto the electrode substrate 211, which is delivered sequentially.

[0251] Multiple liquid discharge heads 306 may be provided in a direction substantially parallel or substantially perpendicular to the conveying direction of the electrode substrate 211. Next, the electrode substrate 211, having discharged droplets of liquid composition 12A, is conveyed to the heating mechanism 309 via the delivery roller 304 and the take-up roller 305. As a result, an electrode composite material layer 212 is formed, yielding an electrode 210. Subsequently, the electrode 210 is cut to the desired size using a punching process or the like.

[0252] The heating mechanism 309 can be set on either the upper or lower side of the electrode substrate 211, or multiple heating mechanisms can be set.

[0253] There are no particular limitations on the heating mechanism 309, as long as it does not come into direct contact with the liquid composition 12A. Examples include resistance heaters, infrared heaters, and warm air blowers. Multiple heating mechanisms 309 may also be provided. Additionally, a curing device utilizing ultraviolet light for polymerization may also be provided.

[0254] Furthermore, it is preferable to heat the liquid composition 12A discharged onto the electrode substrate 211. During heating, heating can be performed using a stage or a heating mechanism other than the stage. The heating mechanism can be located on either the upper or lower side of the electrode substrate 211, or multiple heating mechanisms can be provided.

[0255] There are no particular limitations on the heating temperature. The liquid composition 12A is dried by heating to form an electrode composite material layer. However, when the liquid composition 12A contains a binder precursor, the preferred temperature for polymerizing the binder precursor is preferably in the range of 70°C to 150°C from the viewpoint of energy utilization. In addition, ultraviolet light may be irradiated when heating the liquid composition 12A discharged onto the electrode substrate 211.

[0256] In addition, such as Figure 6 As shown, tank 307A can supply a liquid composition from tank 313A connected to tank 307A, and liquid discharge head 306 can have multiple liquid discharge heads 306A, 306B.

[0257] As a method for manufacturing the above-mentioned electrochemical element, in addition to using the electrode composite material layer of the present invention, a known method may be appropriately selected.

[0258] - Manufacturing method of the positive electrode-

[0259] Examples of methods for manufacturing the positive electrode include: adding binders, thickeners, conductive additives, and solvents to the positive electrode active material as needed to form a slurry-like positive electrode material, coating it onto the positive electrode current collector, and then drying it.

[0260] There are no particular restrictions on the solvents used, and they can be selected appropriately according to the purpose. Examples include aqueous solvents such as water and alcohols, and organic solvents such as N-methyl-2-pyrrolidone (NMP), toluene, and anisole.

[0261] Alternatively, the positive electrode active material can be rolled to form a sheet electrode, or compressed to form a granular electrode.

[0262] - Manufacturing method of negative electrode-

[0263] As a method for manufacturing the negative electrode, for example, a slurry-like negative electrode material can be prepared by adding binders, thickeners, conductive additives, solvents, etc., to the negative electrode active material as needed, coating it onto the negative electrode current collector, and then drying it.

[0264] Alternatively, methods such as directly rolling a slurry-like negative electrode material to form a sheet electrode, forming a granular electrode through compression molding, or forming a thin film of the negative electrode active material on the negative electrode current collector through evaporation, sputtering, electroplating, etc., can also be used.

[0265] The solvent used in the manufacturing method of the negative electrode can be the same solvent used in the manufacturing method of the positive electrode.

[0266] Variations of the printing department

[0267] In the above Figure 3 In the electrode manufacturing apparatus (liquid discharge apparatus) shown, the liquid composition discharged from the printing device 1a is directly applied to the printing substrate 4 as the application device, but it can also be applied to the substrate via a transfer process (transfer method). Figures 7-8 Examples illustrating the transfer printing method.

[0268] Figures 7-8 This is an explanatory diagram showing a modified example of the printing section. Figure 7 This indicates the printing section that uses a drum-shaped intermediate transfer body. Figure 8 This indicates the printing section using a ring-shaped intermediate transfer body.

[0269] Figure 7 The printing unit 400' shown is an inkjet printer that transfers a liquid composition containing surface-modified carbon material onto a substrate through an intermediate transfer body 4001, thereby forming a layer containing surface-modified carbon on the surface of the substrate.

[0270] The printing unit 400' includes an inkjet unit 420, a transfer drum 4000, a pretreatment unit 4002, an absorption unit 4003, a heating unit 4004, and a cleaning unit 4005.

[0271] The inkjet unit 420 includes a head module 422 that holds a plurality of heads 101. The heads 101 discharge a liquid composition onto an intermediate transfer body 4001 supported by a transfer drum 4000, thereby forming a liquid composition layer containing a surface-modified carbon material on the intermediate transfer body 4001. Each head 101 is an in-line printhead, with nozzles arranged within the width of the recording area covering the largest usable substrate size.

[0272] The head 101 has a nozzle surface forming a nozzle on its underside, and the nozzle surface faces the surface of the intermediate transfer body 4001 through a tiny gap. In this embodiment, since the intermediate transfer body 4001 is a structure that circulates on a circular track, the plurality of heads 101 are arranged radially.

[0273] The transfer drum 4000 faces the impression cylinder 621, forming a transfer clamping section. The pretreatment unit 4002 applies a reaction liquid to the intermediate transfer body 4001 to increase the viscosity of the liquid composition before the liquid composition is ejected using the head 101. The absorption unit 4003 absorbs the liquid components from the liquid composition layer on the intermediate transfer body 4001 before transfer.

[0274] A heating unit 4004 may also be included if needed. The heating unit 4004 heats the liquid composition layer on the intermediate transfer body 4001 before transfer. By heating the liquid composition layer, the resin in the liquid composition layer melts, improving the transferability to the substrate. The cleaning unit 4005 cleans the surface of the intermediate transfer body 4001 after transfer and removes residual liquid composition and foreign matter such as dust from the intermediate transfer body 4001.

[0275] The outer peripheral surface of the impression cylinder 621 is pressed against the intermediate transfer body 4001. When the substrate passes through the transfer clamping portion of the impression cylinder 621 and the intermediate transfer body 4001, the liquid composition layer on the intermediate transfer body 4001 is transferred onto the substrate. Alternatively, the impression cylinder 621 may also be configured to have at least one clamping mechanism on its outer peripheral surface for holding the front end of the substrate.

[0276] Figure 8 The printing section 400 shown is an inkjet printer that transfers a liquid composition containing surface-modified carbon material onto a substrate via an intermediate transfer belt 4006, thereby forming a layer containing surface-modified carbon material on the surface of the substrate.

[0277] The printing section 400 ejects droplets of a liquid composition containing a surface-modified carbon material from a plurality of heads 101 disposed in the inkjet section 420, forming a liquid composition layer containing the surface-modified carbon material on the outer peripheral surface of the intermediate transfer belt 4006. The liquid composition layer formed on the intermediate transfer belt 4006 is dried by the drying unit 4007, and the liquid composition layer forms a film on the intermediate transfer belt 4006.

[0278] In the transfer clamping section opposite to the transfer roller 622, the liquid composition layer formed on the intermediate transfer belt 4006 is transferred to the substrate. After transfer, the surface of the intermediate transfer belt 4006 is cleaned by the cleaning roller 4008.

[0279] The intermediate transfer belt 4006 is mounted on a drive roller 4009a, an opposing roller 4009b, multiple (four in this example) shape-maintaining rollers 4009c, 4009d, 4009e, 4009f, and multiple (four in this example) support rollers 4009g, and moves in the direction of the arrow in the figure. The support rollers 4009g, which are positioned opposite to the head 101, maintain the intermediate transfer belt 4006 in a stretched state when droplets of a liquid composition containing surface-modified carbon material are ejected from the head 101.

[0280] exist Figure 7 The intermediate transfer body 4001 shown and Figure 8 The liquid composition layer formed on the intermediate transfer belt 4006 shown is not limited to a single layer, but can also be a structure in which different liquid compositions are used in each of the multiple heads 101, forming two or more liquid composition layers in one cycle.

[0281] In this case, by, for example Figure 9 The manufacturing steps (1) to (3) in the electrode manufacturing method of this embodiment shown can form a first layer W20 (X20) and a second layer X30 on the object W10.

[0282] In the case of intermediate transfer printing, the liquid composition layer is reversed at the final stage of transferring the liquid composition layer to the object W10. Therefore, in process (1), the liquid composition is applied to the intermediate transfer body 4001 (intermediate transfer belt 4006) using the head 101 that sprays out the liquid composition for the second layer, and the second layer X30 is formed on the intermediate transfer body 4001 (intermediate transfer belt 4006).

[0283] Next, in step (2), the intermediate transfer body 4001 (intermediate transfer belt 4006) is given a first layer liquid composition and a second layer liquid composition. Then, the first layer W20 (X20) and the second layer X30 are further formed on the second layer X30 on the intermediate transfer body 4001 (intermediate transfer belt 4006).

[0284] The first layer W20 (X20) and the second layer X30 in process (2) can be produced in one process by a head capable of spraying out the liquid composition for the first layer and the liquid composition for the second layer. Alternatively, they can be produced in two processes by using a head that sprays out the liquid composition for the first layer and a head that sprays out the liquid composition for the second layer.

[0285] The liquid composition layer prepared on the intermediate transfer body 4001 (intermediate transfer belt 4006) is transferred from the intermediate transfer body 4001 (intermediate transfer belt 4006) to the object to be applied W10 in step (3). When using the intermediate transfer method, the first layer W20 (X20) and the second layer X30 are prepared on the object to be applied W10 by the steps described above.

[0286] Variations of Liquid Discharge Heads

[0287] In the electrode manufacturing apparatus described above, as the structure of the head 101, the nozzle surface (the surface on which the nozzle is formed) of the nozzle plate is rectangular, but the nozzle plate can also be a shape other than a rectangle, such as a trapezoid, rhombus, or parallelogram. Figure 10 and Figure 11 This section describes an example of a nozzle with a nozzle plate having a parallelogram shape.

[0288] Figure 10 This is an explanatory diagram showing a modified example of a liquid discharge head. Figure 11 It indicates the arrangement of multiple Figure 10 A diagram illustrating the liquid discharge from the head.

[0289] The nozzle 1R has a shape (ridge) that is inclined at an angle θ relative to the short side of the nozzle plate, and the liquid ejection part 101R of the nozzle 1R and the nozzle plate 10R are also formed along this ridge. That is, the liquid ejection part 101R has a nozzle plate 10R with a parallelogram shape, and a plurality of nozzles 11R are regularly arranged in a two-dimensional shape on the nozzle plate 10R.

[0290] The nozzles 11R are arranged in such a way that, for example, N nozzles 11R form a nozzle column 11N, and multiple columns of the nozzle column 11N are arranged in the direction of the long side of the nozzle plate that is parallel to the aforementioned ridge line and orthogonal to the short side direction of the nozzle plate.

[0291] like Figure 11 As shown, the above-described nozzle 1R can arrange multiple nozzles 1Ra and 1Rb in a row along the long side of the nozzle plate, thereby obtaining a linear nozzle that can match the recording width of the substrate used to obtain the desired length.

[0292] (Electrochemical element)

[0293] The electrochemical element of the present invention includes the electrode of the present invention as described above, and may also include other components as needed.

[0294] The aforementioned electrodes can be either positive or negative.

[0295] Electrochemical components typically include a positive electrode, a negative electrode, an electrolyte, and a membrane disposed between the positive and negative electrodes to retain the electrolyte.

[0296] Figure 12 An example of the electrochemical element of the present invention is shown.

[0297] The electrochemical element 100 has an electrolyte layer 81 formed in the electrochemical element unit 40, which is composed of an aqueous electrolyte solution or a non-aqueous electrolyte, and is sealed by a sealing container 82. In the electrochemical element 100, leads 41 and 42 are led out to the outside of the sealing container 82.

[0298] In the electrochemical element unit 40, the positive electrode 15 and the negative electrode 25 are stacked with a separator 30 in between. Here, the negative electrode 25 is stacked on both sides of the positive electrode 15. In addition, a lead 41 is connected to the positive electrode current collector 11, and a lead 42 is connected to the negative electrode current collector 21.

[0299] The negative electrode 25 forms a negative electrode composite material layer 22 on both sides of the negative electrode current collector 21. A first insulating layer 24 is formed on the negative electrode composite material layer 22 as needed. In addition, a second insulating layer 26 is used to cover the negative electrode composite material layer 22 and the first insulating layer 24 as needed.

[0300] The negative electrode composite material layer 22 can be formed by coating a liquid composition for forming a positive electrode composite material layer.

[0301] The liquid composition for forming the negative electrode composite layer contains active substances and a dispersion medium, and may also contain conductive additives, dispersants, etc., as needed.

[0302] Examples of coating methods for liquid compositions used in forming negative electrode composite layers include comma coating, mold coating, curtain coating, spraying, and liquid ejection.

[0303] The positive electrode 15 has a positive electrode composite material layer 12 formed on both sides of the positive electrode current collector 11.

[0304] The positive electrode composite material layer 12 can be formed by coating a liquid composition for forming a positive electrode composite material layer.

[0305] The liquid composition for forming the positive electrode composite layer contains active substances and a dispersion medium, and may also contain conductive additives, dispersants, etc., as needed.

[0306] Examples of coating methods for liquid compositions used in forming positive electrode composite layers include comma coating, molding, curtain coating, spraying, and liquid ejection.

[0307] <Current Collector>

[0308] In this specification, the current collector refers to a material with high conductivity. Typically, aluminum is used for the positive electrode and copper for the negative electrode, but in this specification, the current collector includes, but is not limited to, the aforementioned materials. Additionally, materials with a so-called carbon coating on a metal substrate are also preferred.

[0309] Furthermore, there are no particular restrictions on the number of stacked layers of the positive electrode 15 and the negative electrode 25 in the electrochemical element unit 40.

[0310] In addition, the number of positive electrodes 15 and negative electrodes 25 in the electrochemical element unit 40 can be the same or different.

[0311] The electrochemical element 100 may also have other components as needed.

[0312] There are no particular limitations on the shape of the electrochemical element 100. Examples include laminated type, cylindrical type with sheet electrode and separator in a spiral shape, cylindrical type with an inside-out structure combining particulate electrode and separator, and coin type formed by stacking particulate electrode and separator.

[0313] Examples of electrochemical elements 100 include aqueous energy storage elements and non-aqueous energy storage elements.

[0314] <Septum>

[0315] To prevent short circuits between the positive electrode 15 and the negative electrode 25, a diaphragm 30 is provided between the positive electrode 15 and the negative electrode 25 as needed.

[0316] Examples of membranes 30 include kraft paper, vinylon blended paper, synthetic pulp blended paper, cellophane, polyethylene grafted film, polyolefin nonwoven fabrics such as melt-flow polypropylene nonwoven fabric, polyamide nonwoven fabric, glass fiber nonwoven fabric, and microporous membranes.

[0317] The size of the diaphragm 30 is not particularly limited as long as it can be used in electrochemical elements.

[0318] The diaphragm 30 can be a single-layer structure or a multilayer structure.

[0319] In addition, when using a solid electrolyte as a non-aqueous electrolyte, the diaphragm 30 can be omitted.

[0320] <Electrolyte aqueous solution>

[0321] Examples of electrolyte salts that constitute aqueous electrolyte solutions include sodium hydroxide, potassium hydroxide, sodium chloride, potassium chloride, ammonium chloride, zinc chloride, zinc acetate, zinc bromide, zinc iodide, zinc tartrate, and zinc perchlorate.

[0322] <Non-aqueous electrolytes>

[0323] As a non-aqueous electrolyte, a solid electrolyte or a non-aqueous electrolyte solution can be used.

[0324] Here, non-aqueous electrolyte is an electrolyte in which electrolyte salts are dissolved in a non-aqueous solvent.

[0325] -Non-aqueous solvent-

[0326] There are no particular restrictions on the use of non-aqueous solvents; for example, aprotic organic solvents are preferred.

[0327] As a non-protic organic solvent, carbonate organic solvents such as chain carbonates and cyclic carbonates can be used. Among them, chain carbonates are preferred from the viewpoint of high solubility of electrolyte salts.

[0328] In addition, aprotic organic solvents are preferably low in viscosity.

[0329] Examples of chain carbonates include dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC).

[0330] The content of the chain carbonate in the non-aqueous solvent is preferably 50% by mass or more. If the content of the chain carbonate in the non-aqueous solvent is 50% by mass or more, even if the non-aqueous solvent other than the chain carbonate is a cyclic substance with a high dielectric constant (e.g., cyclic carbonate, cyclic ester), the content of the cyclic substance will be reduced. Therefore, even when producing a non-aqueous electrolyte with a high concentration of 2M or more, the viscosity of the non-aqueous electrolyte becomes lower, and the penetration or ion diffusion of the non-aqueous electrolyte into the electrode becomes better.

[0331] Examples of cyclic carbonates include propylene carbonate (PC), ethylene carbonate (EC), butyl carbonate (BC), and vinylene carbonate (VC).

[0332] In addition, as a non-aqueous solvent other than carbonate organic solvents, ester organic solvents such as cyclic esters and chain esters, and ether organic solvents such as cyclic ethers and chain ethers can be used.

[0333] Examples of cyclic esters include γ-butyrolactone (γBL), 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, and γ-valerolactone.

[0334] Examples of chain esters include alkyl propionates, dialkyl malonates, alkyl acetates (e.g., methyl acetate (MA) and ethyl acetate), and alkyl formates (e.g., methyl formate (MF) and ethyl formate).

[0335] Examples of cyclic ethers include tetrahydrofuran, alkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, 1,4-dioxolane, etc.

[0336] Examples of chain ethers include 1,2-dimethoxyethane (DME), diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, etc.

[0337] -Electrolyte salt-

[0338] As an electrolyte salt, there are no particular restrictions as long as it has high ionic conductivity and can dissolve in non-aqueous solvents.

[0339] Electrolyte salts preferably contain halogen atoms.

[0340] Examples of cations that constitute electrolyte salts include lithium ions.

[0341] Examples of anions that constitute electrolyte salts include BF4. - PF6 - AsF6 - CF3SO3 - (CF3SO2)2N - and (C2F5SO2)2N - .

[0342] There are no particular limitations on the lithium salts used; appropriate selection can be made based on the intended purpose. Examples include lithium hexafluorophosphate (LiPF6), lithium fluoroborate (LiBF4), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethylsulfonyl)imide (LiN(CF3SO2)2), and lithium bis(pentafluoroethylsulfonyl)imide (LiN(C2F5SO2)2). From the perspective of ionic conductivity, LiPF6 is preferred, while from the perspective of stability, LiBF4 is preferred.

[0343] Furthermore, one type of electrolyte salt can be used alone, or two or more types can be used together.

[0344] There are no particular restrictions on the concentration of electrolyte salts in non-aqueous electrolytes, and they can be selected appropriately according to the purpose. However, when the non-aqueous energy storage element is of the swing type, it is preferred to be above 1 mol / L and below 2 mol / L. When the non-aqueous energy storage element is of the storage type, it is preferred to be above 2 mol / L and below 4 mol / L.

[0345] Applications of surface-modified carbon materials

[0346] There are no particular limitations on the uses of the aforementioned surface-modified carbon materials, and they can be appropriately selected according to the purpose. For example, the aforementioned uses such as forming electrodes and three-dimensional modeling (3D printing) are preferred.

[0347] In 3D modeling, such as SLS, SMS, FDM, MJF (Multi-Jet Fusion), or Binder Jetting (BJ) methods, surface-modified carbon materials can be used as additives added to the liquid composition for 3D modeling to adjust color tone, enhance strength, and so on. By using the surface-modified carbon material of this embodiment, various problems caused by the presence of dispersants in 3D modeling can be suppressed.

[0348] Therefore, the present invention can also be applied to a liquid composition for three-dimensional modeling containing the surface-modified carbon material of the present invention, a storage container for three-dimensional modeling storing the liquid composition for three-dimensional modeling, a three-dimensional modeling apparatus and a three-dimensional modeling method using the liquid composition for three-dimensional modeling, and a three-dimensional model containing the surface-modified carbon material.

[0349] Applications of electrochemical components

[0350] The applications of electrochemical components are not particularly limited, and examples include: vehicles; smartphones, laptops, pen-based personal computers, mobile personal computers, e-book players, mobile phones, portable fax machines, portable copiers, portable printers, stereo headphones, video conferencing, LCD TVs, portable vacuum cleaners, portable CD players, mini-discs, walkie-talkies, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, electric motors, lighting fixtures, toys, game consoles, clocks, flashlights, cameras, and other electrical equipment. Vehicles and electrical equipment are preferred.

[0351] As for vehicles, examples include ordinary cars, large special cars, small special cars, trucks, dump trucks, large motorized two-wheelers, and ordinary motorized two-wheelers.

Example

[0352] The present invention will now be described in more detail based on embodiments, but the present invention includes, but is not limited to, the following embodiments.

[0353] (Example 1-1)

[0354] <Manufacturing of Surface-Modified Carbon Material 1>

[0355] Under room temperature and stirring conditions, 18 parts by weight of furnace black (LITX300, manufactured by Cabot, with a primary particle size of 20 nm and a BET value of 160 μm) as the carbon material were used. 2 g -1The first dispersion was added to 320 parts by mass of ion-exchanged water and stirred for 1 hour. After stirring, 1.5 parts by mass of sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.), a compound of aniline, and 0.7 parts by mass of lithium nitrite (manufactured by Mitsukawa Chemical Co., Ltd.) were added every 4 hours. The pH was adjusted to 2.5 with hydrogen chloride, and the mixture was stirred repeatedly for a total of 4 times. After the fourth addition, the mixture was stirred for another 4 hours. After stirring, the mixture was centrifuged, and the residue after removing the supernatant was redispersed repeatedly with ion-exchanged water 4 times. The pH of the first dispersion was adjusted to 10 with 7N lithium hydroxide aqueous solution, and the mixture was stirred repeatedly for a total of 4 times. After the fourth addition, the mixture was stirred for another 4 hours. After stirring, the mixture was centrifuged, and the residue after removing the supernatant was redispersed repeatedly with ion-exchanged water 3 times. The obtained second dispersion was centrifuged to remove the supernatant, and the residue was dried using a vacuum dryer to obtain the surface-modified carbon material 1 of Example 1-1, which is a carbon material with a substituent represented by general formula (1) added to it.

[0356] As shown in the following reaction formula (I), in the manufacture of surface-modified carbon material 1, sulfathiazole (compound (a)) as an aniline compound is diazotized by using nitrous acid to obtain compound (b) as a diazonium salt represented by general formula (5). By free radicalizing compound (b), compound (c) as a free radical compound represented by general formula (4) is obtained. By covalently bonding compound (c) to the edge of the graphene structure of furnace black as a carbon material, surface-modified carbon material 1 with a substituent (d) represented by general formula (1) added to the carbon material is obtained. Wherein, · represents a free radical, and * represents the bonding site with the carbon material.

[0357] [Chemical Formula 14]

[0358]

[0359] (Examples 1-2)

[0360] Except that sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) was replaced with sulfadiazine (manufactured by Tokyo Chemical Co., Ltd.), the target substituent was obtained by the same method as in Example 1-1 and added to the carbon material to obtain surface-modified carbon material 2 of Example 1-2.

[0361] (Examples 1-3)

[0362] Except that sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) was replaced with sulfamethoxazole (manufactured by Tokyo Chemical Co., Ltd.), the target substituent was obtained by the same method as in Example 1-1 and added to the carbon material to obtain the surface-modified carbon material 3 of Example 1-3.

[0363] (Examples 1-4)

[0364] Except that sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) was replaced with sulfadiazine (manufactured by Tokyo Chemical Co., Ltd.), the target substituent was obtained by the same method as in Example 1-1 and added to the carbon material to obtain the surface-modified carbon material 4 of Example 1-4.

[0365] (Examples 1-5)

[0366] Except that sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) was replaced with sulfapyridine (manufactured by Tokyo Chemical Co., Ltd.), the target substituent was obtained by the same method as in Example 1-1 and added to the carbon material to obtain the surface-modified carbon material 5 of Example 1-5.

[0367] (Examples 1-6)

[0368] Except that sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) was replaced with sulfadimethazine (manufactured by Tokyo Chemical Co., Ltd.), the target substituent was obtained by the same method as in Examples 1-1 and added to the carbon material to obtain the surface-modified carbon material 6 of Examples 1-6.

[0369] (Examples 1-7)

[0370] Except for replacing sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) with sulfamethoxypyrimidine (manufactured by Tokyo Chemical Co., Ltd.), the target substituent was obtained by the same method as in Examples 1-1 and added to the carbon material to obtain the surface-modified carbon material 7 of Examples 1-7.

[0371] (Examples 1-8)

[0372] Except that sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) was replaced with sulfadimethoxypyrimidine (manufactured by Tokyo Chemical Co., Ltd.), the target substituent was obtained by the same method as in Examples 1-1 and added to the carbon material to obtain the surface-modified carbon material 8 of Examples 1-8.

[0373] (Examples 1-9)

[0374] Except that sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) was replaced with sulfadoxine (manufactured by Tokyo Chemical Co., Ltd.), the target substituent was obtained by the same method as in Examples 1-1 and added to the carbon material to obtain the surface-modified carbon material 9 of Examples 1-9.

[0375] (Examples 1-10)

[0376] Except that sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) was replaced with 4-amino-N-(5-methoxypyrimidin-4-yl)benzenesulfonamide (manufactured by Tokyo Chemical Co., Ltd.), the target substituent was obtained by the same method as in Examples 1-1 and added to the carbon material to obtain the surface-modified carbon material 10 of Examples 1-10.

[0377] (Examples 1-11)

[0378] Except that sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) was replaced with sulfamethoxazine (manufactured by Tokyo Chemical Co., Ltd.), the target substituent was obtained by the same method as in Example 1-1 and added to the carbon material to obtain the surface-modified carbon material 11 of Example 1-11.

[0379] (Examples 1-12)

[0380] Except that sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) was replaced with sulfaisoxazole (manufactured by Tokyo Chemical Co., Ltd.), the target substituent was obtained by the same method as in Example 1-1 and added to the carbon material to obtain the surface-modified carbon material 12 of Example 1-12.

[0381] (Examples 1-13)

[0382] Except for replacing the lithium hydroxide aqueous solution with a sodium hydroxide aqueous solution (10N) and adjusting the pH of the first dispersion to 10, the target substituent was obtained by the same method as in Examples 1-1 and added to the carbon material to obtain the surface-modified carbon material 13 of Examples 1-13.

[0383] (Examples 1-14)

[0384] Except for replacing the lithium hydroxide aqueous solution with a potassium hydroxide aqueous solution and adjusting the pH of the first dispersion to 10, the target substituent was obtained by the same method as in Examples 1-1 and added to the carbon material to obtain the surface-modified carbon material 14 of Examples 1-14.

[0385] (Examples 1-15)

[0386] Except for replacing the lithium hydroxide aqueous solution with ammonia and adjusting the pH of the first dispersion to 10, the target substituent was obtained by the same method as in Examples 1-1 and added to the carbon material to obtain the surface-modified carbon material 15 of Examples 1-15.

[0387] (Examples 1-16)

[0388] Except for replacing the lithium hydroxide aqueous solution with diethylaminoethanol (manufactured by Tokyo Chemical Co., Ltd.) and adjusting the pH of the first dispersion to 10, the target substituent was obtained by the same method as in Examples 1-1 and added to the carbon material to obtain the surface-modified carbon material 16 of Examples 1-16.

[0389] (Examples 1-17)

[0390] In addition to using furnace black (LITX300, manufactured by Cabot, with a primary particle size of 20 nm and a BET value of 160 nm) as a carbon material, 2 g -1 Replace with furnace black (LITXHP, manufactured by Cabot, primary particle size 20nm, BET value 100m). 2 g -1 In addition to the above, the target substituents were obtained by the same method as in Example 1-1 and added to the carbon material to obtain the surface-modified carbon material 17 of Example 1-17.

[0391] (Examples 1-18)

[0392] In addition to using furnace black (LITX300, manufactured by Cabot, with a primary particle size of 20 nm and a BET value of 160 nm) as a carbon material, 2 g -1 Replace with acetylene black (DenkaBlackLi100, manufactured by Denka Corporation, primary particle size 35nm, BET value 69m). 2 g -1 In addition to the above, the target substituents are obtained by the same method as in Example 1-1 and added to the carbon material to obtain the surface-modified carbon material 18 of Example 1-18.

[0393] (Examples 1-19)

[0394] In addition to using furnace black (LITX300, manufactured by Cabot, with a primary particle size of 20 nm and a BET value of 160 nm) as a carbon material, 2 g -1 Replace with acetylene black (Ketjen 600J, manufactured by Ketjen, primary particle size 35nm, BET value 1280m). 2 g -1 In addition to the above, the target substituents were obtained by the same method as in Example 1-1 and added to the carbon material to obtain the surface-modified carbon material 19 of Example 1-19.

[0395] (Comparative Example 1-1)

[0396] Except for replacing sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) with sulfanilamide (manufactured by Tokyo Chemical Co., Ltd.), the surface-modified carbon material a of Comparative Example 1-1, which does not satisfy general formula (1), was obtained by the same method as in Example 1-1.

[0397] (Comparative Examples 1-2)

[0398] Except for replacing sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) with sulfamethoxazole (manufactured by Tokyo Chemical Co., Ltd.), surface-modified carbon materials b of Comparative Examples 1-2 were obtained by adding substituents that do not satisfy general formula (1) to carbon materials using the same method as in Examples 1-1.

[0399] (Comparative Examples 1-3)

[0400] Except for replacing sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) with 4-aminofumaric acid (manufactured by Tokyo Chemical Co., Ltd.), surface-modified carbon materials c of Comparative Examples 1-3 were obtained by adding substituents that do not satisfy general formula (1) to carbon materials using the same method as in Examples 1-1.

[0401] (Comparative Examples 1-4)

[0402] Except for replacing sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) with sulfanilamide (manufactured by Tokyo Chemical Co., Ltd.), surface-modified carbon materials d of Comparative Examples 1-4 were obtained by adding substituents that do not satisfy general formula (1) to carbon materials using the same method as in Examples 1-17.

[0403] (Comparative Examples 1-5)

[0404] Except for replacing sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) with sulfanilamide (manufactured by Tokyo Chemical Co., Ltd.), surface-modified carbon materials e of Comparative Examples 1-5 were obtained by adding substituents that do not satisfy general formula (1) to carbon materials using the same method as in Examples 1-18.

[0405] (Comparative Examples 1-6)

[0406] Except for replacing sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.) with sulfanilamide (manufactured by Tokyo Chemical Co., Ltd.), surface-modified carbon materials f of Comparative Examples 1-6 were obtained by adding substituents that do not satisfy general formula (1) to carbon materials using the same method as in Examples 1-19.

[0407] The ingredients used in Examples 1-1 to 1-19 and Comparative Examples 1-1 to 1-6 are shown in Table 1.

[0408] [Table 1]

[0409]

[0410] (Example 2-1)

[0411] <Preparation of Liquid Composition 1>

[0412] The surface-modified carbon material 1 of Example 1-1 was 10% by mass. It was mixed with N-methyl-2-pyrrolidone as an organic solvent and subjected to ultrasonic irradiation for 3 minutes using an ultrasonic homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain the liquid composition 1 of Example 2-1 as the target.

[0413] <Evaluation of Dispersibility: Determination of Median Particle Size>

[0414] The obtained liquid composition 1 was diluted 100 times with the organic solvent used, and the median particle size was determined using a dynamic light scattering apparatus (nanoSAQLA, manufactured by Otsuka Electronics Co., Ltd.). The results are shown in Table 2.

[0415] (Examples 2-2 to 2-24, and Comparative Examples 2-1 to 2-11)

[0416] In addition to using the combination of surface-modified carbon material and organic solvent shown in Table 1, the liquid compositions of Examples 2-2 to 2-24 and Comparative Examples 2-1 to 2-11, which were the targets, were obtained by the same method as in Example 2-1. Furthermore, the median particle size (unit: nm) of each liquid composition was determined by the same method as in Example 2-1. The results are shown in Tables 2-1 to 2-2.

[0417] (Comparative Examples 2-12 to 2-14)

[0418] As comparative examples 2-12 to 2-14, liquid compositions were obtained by the following methods, but all were gel-like and could not be obtained as liquid compositions, and the particle size distribution could not be determined.

[0419] (Comparative Example 2-12)

[0420] 18 parts by weight of furnace black (LITX300, manufactured by Cabot Corporation, primary particle size 20 nm, BET value 160 μm) was used as the carbon material. 2 g -1 The mixture was added to 160 parts by weight of N-methyl-2-pyrrolidone and subjected to ultrasonic irradiation for 3 minutes using an ultrasonic homogenizer (manufactured by Nippon Seiki Co., Ltd.).

[0421] (Comparative Example 2-13)

[0422] 18 parts by weight of furnace black (LITX300, manufactured by Cabot Corporation, primary particle size 20 nm, BET value 160 μm) was used as the carbon material. 2 g -1 The solution was added to 162 parts by mass of ion-exchanged water and stirred for 1 hour. After stirring, 1.5 parts by mass of sulfathiazole (manufactured by Tokyo Chemical Co., Ltd.), an aniline compound, was added every 4 hours, and the pH was adjusted to 10 with 7N lithium hydroxide aqueous solution. After adjustment, the water was removed using an evaporator, and then vacuum dried at 60°C for 12 hours. After drying, 162 parts by mass of N-methyl-2-pyrrolidone was added, and the mixture was ultrasonically irradiated for 3 minutes using an ultrasonic generator (manufactured by Nippon Seiki Co., Ltd.).

[0423] (Comparative Example 2-14)

[0424] 18 parts by weight of furnace black (LITX300, manufactured by Cabot Corporation, primary particle size 20 nm, BET value 160 μm) was used as the carbon material. 2 g -1 5 parts by weight of dispersion medium (Maria Rim150A, manufactured by Nippon Oil Co., Ltd.) were added to 160 parts by weight of N-methyl-2-pyrrolidone, and then subjected to ultrasonic irradiation for 3 minutes using an ultrasonic homogenizer (Ultrasonic Generator, manufactured by Nippon Seiki Co., Ltd.).

[0425] [Table 2-1]

[0426] Surface-modified carbon materials organic solvents Median particle size [nm] Example 2-1 Surface-modified carbon material 1 N-Methyl-2-pyrrolidone 160 Example 2-2 Surface-modified carbon materials 2 N-Methyl-2-pyrrolidone 158 Example 2-3 Surface-modified carbon materials 3 N-Methyl-2-pyrrolidone 159 Examples 2-4 Surface-modified carbon materials 4 N-Methyl-2-pyrrolidone 159 Examples 2-5 Surface-modified carbon materials 5 N-Methyl-2-pyrrolidone 162 Examples 2-6 Surface-modified carbon materials 6 N-Methyl-2-pyrrolidone 159 Examples 2-7 Surface-modified carbon materials 7 N-Methyl-2-pyrrolidone 161 Examples 2-8 Surface-modified carbon materials 8 N-Methyl-2-pyrrolidone 162 Examples 2-9 Surface-modified carbon materials 9 N-Methyl-2-pyrrolidone 171 Example 2-10 Surface-modified carbon material 10 N-Methyl-2-pyrrolidone 169 Example 2-11 Surface-modified carbon materials 11 N-Methyl-2-pyrrolidone 158 Example 2-12 Surface-modified carbon material 12 N-Methyl-2-pyrrolidone 196 Example 2-13 Surface-modified carbon material 13 N-Methyl-2-pyrrolidone 158 Example 2-14 Surface-modified carbon material 14 N-Methyl-2-pyrrolidone 159 Example 2-15 Surface-modified carbon material 15 N-Methyl-2-pyrrolidone 165 Example 2-16 Surface-modified carbon material 16 N-Methyl-2-pyrrolidone 167 Example 2-17 Surface-modified carbon materials 17 N-Methyl-2-pyrrolidone 171 Example 2-18 Surface-modified carbon material 18 N-Methyl-2-pyrrolidone 351 Example 2-19 Surface-modified carbon materials 19 N-Methyl-2-pyrrolidone 402 Example 2-20 Surface-modified carbon material 1 dimethyl sulfoxide 159 Example 2-21 Surface-modified carbon material 1 dimethylformamide 161 Example 2-22 Surface-modified carbon material 1 ethanol 168 Example 2-23 Surface-modified carbon material 1 Isopropanol 169 Example 2-24 Surface-modified carbon material 1 Acetonitrile 167

[0427] [Table 2-2]

[0428]

[0429] <Calculation of the dipole moment of surface-modified carbon materials>

[0430] Setting up model compounds

[0431] As a model compound for calculating the dipole moment of surface-modified carbon materials, in surface-modified carbon material 1 of Example 1-1, the carbon material was converted to anthracene, and the substituent (b) in the above reaction formula (I) was applied as a substituent at the 9 position of the anthracene, and the model compound 1 was set to convert M in the substituent to H.

[0432] Calculation of Dipole Moment

[0433] Using the established model compound 1, the dipole moment was calculated using the non-empirical molecular orbital method.

[0434] Specifically, the dipole moment was calculated using the quantum computing chemistry program Gaussian16 (manufactured by Gaussian Corporation (USA)). Additionally, the structure of the model compound prepared at this time was optimized.

[0435] For surface-modified carbon materials 2 to 12 in Examples 1-2 to 1-12 and surface-modified carbon materials a to c in Comparative Examples 1-1 to 1-3, the model compound was set and the dipole moment was calculated using the same method as for surface-modified carbon material 1.

[0436] Tables 3-1 to 3-4 show the types of carbon materials, the structure of the model compounds, the Smails linear label of the structure, the calculated dipole moment (Debye), and the median particle size (nm) shown in Tables 2-1 to 2-2.

[0437] [Table 3-1]

[0438]

[0439] [Table 3-2]

[0440]

[0441] [Table 3-3]

[0442]

[0443] [Table 3-4]

[0444]

[0445] The results in Tables 2-1 to 2-2 confirm that when comparing the surface-modified carbon materials 1-16 of Examples 2-1 to 2-16 using the same carbon material with the surface-modified carbon materials a-c of Comparative Examples 2-1 to 2-3, the median particle size of the examples is smaller. Therefore, compared with the surface-modified carbon materials of the prior art, the surface-modified carbon materials of the present invention are more micronized and have better dispersibility. Furthermore, the same trend can be confirmed in the comparison of the surface-modified carbon materials 17-19 of Examples 2-17 to 2-19 with the surface-modified carbon materials d-f of Comparative Examples 2-4 to 2-6.

[0446] Furthermore, in Examples 2-20 to 2-24, when using various aprotic polar solvents and alcohol solvents other than N-methyl-2-pyrrolidone (NMP), it was confirmed that the surface-modified carbon materials of the present invention exhibit superior dispersibility compared to prior art surface-modified carbon materials when using any solvent. Specifically, it was confirmed that NMP, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and acetonitrile, as aprotic polar solvents, exhibited superior dispersibility compared to the evaluated alcohol solvents.

[0447] Furthermore, the results in Tables 3-1 to 3-4 confirm that, compared to surface-modified carbon materials a to c (which are existing technologies), the surface-modified carbon materials 1 to 12 of this invention exhibit excellent dispersibility regardless of the dipole moment. This demonstrates that the dispersibility primarily stems from the structural characteristics of the surface-modified functional groups, rather than the amount of dipole moment.

[0448] Moreover, more significant stable dispersion can be confirmed in surface-modified carbon materials with a dipole moment of 4.0 debye or greater.

[0449] (Examples 3-4)

[0450] The following steps are used to fabricate current collector foils, electrodes, and electrochemical elements containing the surface-modified carbon material of the present invention.

[0451] (Example 3-1)

[0452] <Example of fabrication of carbon material-metal composite current collector foil>

[0453] The liquid composition 1 containing the carbon material 1 from Example 2-1 is coated onto a copper foil (manufactured by Furukawa Electric Industries, Ltd., thickness: 15 μm) using a rod coater to achieve an average thickness of 1 μm, and then dried at 150°C for 2 hours to produce a carbon material-metal composite current collector foil.

[0454] As a result, carbon material can be visually and uniformly coated on the current collector foil without the use of dispersants.

[0455] (Example 3-2)

[0456] <Making of Negative Electrode 1>

[0457] Fabrication of Negative Electrode Composite Layer 1

[0458] A mixture of 93 parts by weight of graphite powder KS6 (manufactured by Timcal) and 5 parts by weight of acetylene black (DENKA BLACK LI, manufactured by Denka Co., Ltd.) was mixed with water, followed by the addition of 1 part by weight of a 2% by weight aqueous solution of carboxymethyl cellulose (manufactured by Daicel Co., Ltd.). Further, 1 part by weight of styrene-butadiene rubber (manufactured by Zeon Co., Ltd.) was added to prepare a slurry for the negative electrode composite layer 1.

[0459] After coating a copper foil (manufactured by Furukawa Electric Industries, Ltd., thickness: 15 μm) serving as the negative electrode current collector with a slurry for the negative electrode composite layer 1, the foil was vacuum dried at 150°C for 12 hours. Next, the foil was stamped using a stamping press (manufactured by Tester Industries, Ltd.) to form a solid content of 1.6 g / cm³ per unit volume on the negative electrode current collector.3 The negative electrode composite material layer 1 is formed. By performing the same operation on the opposite side, a negative electrode 1 with the negative electrode composite material layer 1 formed on both sides of the negative electrode current collector is obtained.

[0460] Fabrication of Composite Negative Electrode Composite Layer 1

[0461] Using a liquid discharge device (EV2500, manufactured by Ricoh Co., Ltd.) and a liquid nozzle (5421FHead, manufactured by Ricoh Co., Ltd.), a liquid composition 20 containing the surface-modified carbon material 1 from Examples 2-20 was coated onto the negative electrode composite material layer 1, such that the solid content per unit area was 0.5 mg / cm². 2 After drying at 120°C for 10 minutes, the composite negative electrode material layer 1 was prepared by vacuum drying at 100°C for 2 hours.

[0462] As described above, a negative electrode 1 is produced by forming a composite negative electrode composite material layer 1, which is a combination of a negative electrode composite material layer 1 and a surface-modified carbon material 1, on both sides of a copper foil that serves as a negative electrode current collector.

[0463] (Example 3-3)

[0464] <The Making of Positive Electrode 1>

[0465] Fabrication of Positive Electrode Composite Layer 1

[0466] A slurry for the positive electrode composite layer 1 is obtained by mixing 93 parts by mass of lithium nickel cobalt magnesium composite oxide (NCA, manufactured by Sigma-Aldrich), 3 parts by mass of acetylene black (DENKABLACK, manufactured by Denka Corporation) as a conductive agent, 4 parts by mass of polyvinylidene fluoride (manufactured by Sigma-Aldrich) as an adhesive resin, and 100 parts by mass of N-methyl-2-pyrrolidone.

[0467] Next, using a die-coating method, a slurry for the positive electrode composite layer 1 was applied to an aluminum foil (manufactured by UACJ Corporation, thickness: 15 μm) serving as the positive electrode current collector at a conveying speed of 0.5 m / min, and then dried to form a solid content of 15.0 mg / cm² per unit area. 2 Positive electrode composite layer 1. By performing the same operation on the opposite side, positive electrode composite layer 1 is formed on both sides of the aluminum foil.

[0468] Fabrication of Composite Positive Electrode Layers

[0469] Using a liquid discharge device (EV2500, manufactured by Ricoh Co., Ltd.) and a liquid nozzle (5421FHead, manufactured by Ricoh Co., Ltd.), a liquid composition 20 containing the surface-modified carbon material 1 from Examples 2-20 was coated onto the obtained cathode composite material layer 1, such that the solid content per unit area was 0.5 mg / cm². 2 After drying at 120°C for 10 minutes, the composite cathode material layer 1 is prepared by vacuum drying at 100°C for 2 hours.

[0470] As described above, a positive electrode 1 is produced by forming a composite positive electrode composite material layer 1, which is composed of a positive electrode composite material layer 1 and a surface-modified carbon material 1, on both sides of an aluminum foil that serves as a positive electrode current collector.

[0471] (Examples 3-4)

[0472] <The Making of Positive Electrode 2>

[0473] Fabrication of Composite Positive Electrode Layer 2

[0474] Three parts by weight of surface-modified carbon material 1 and 100 parts by weight of N-methyl-2-pyrrolidone were mixed and then irradiated with ultrasound for a total of 15 minutes using an ultrasonic generator (manufactured by Nippon Seiki Co., Ltd.).

[0475] A liquid composition for use in composite cathode composite layer 2 is obtained by mixing 93 parts by mass of lithium nickel cobalt aluminum composite oxide (NCA, manufactured by Sigma-Aldrich), 3 parts by mass of acetylene black (DENKABLACK, manufactured by Denka Corporation) as a conductive agent, and 4 parts by mass of polyvinylidene fluoride (manufactured by Sigma-Aldrich) as an adhesive resin.

[0476] Next, the liquid composition for the composite cathode composite layer 2 was coated onto aluminum foil (manufactured by UACJ Corporation, thickness: 15 μm) at a conveying speed of 0.5 m / min using a die-coating method, and then dried to form a solid content of 15.0 mg / cm² per unit area. 2 Composite positive electrode composite material layer 2. The obtained electrode composite material layer is flipped over, and the same operation is performed to form composite positive electrode composite material layer 2 on both sides of the aluminum foil.

[0477] As described above, a positive electrode 2 is produced by forming a composite positive electrode composite material layer 2 containing surface-modified carbon material 1 on both sides of an aluminum foil that serves as the positive electrode current collector.

[0478] (Example 4-1)

[0479] <Fabrication of Electrochemical Component 1>

[0480] Preparation of Non-Aqueous Electrolytes

[0481] LiPF6 was dissolved in a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate (mass ratio 1:1:1) to obtain a concentration of 1.5 M, thus yielding a non-aqueous electrolyte.

[0482] Fabrication of Electrochemical Component 1

[0483] Use positive electrode 1 as the positive electrode and negative electrode 1 as the negative electrode.

[0484] Three positive electrodes and four negative electrodes are alternately stacked through a thin membrane to obtain an electrode element. At this point, the areas of the negative electrode where no negative electrode composite layer has formed are welded together to form nickel leads. Conversely, the areas of the positive electrode where no positive electrode composite layer has formed are welded together to form aluminum leads (see reference). Figure 12 ).

[0485] After injecting a non-aqueous electrolyte into the electrode element, it is encapsulated with an aluminum laminate to produce an electrochemical element 100, which serves as a non-aqueous energy storage element.

[0486] (Example 4-2)

[0487] <Fabrication of Electrochemical Component 2>

[0488] Except that positive electrode 2 is used as positive electrode and negative electrode 1 is used as negative electrode, electrochemical element 2 is fabricated in the same way as in Example 4-1.

[0489] [Determination of the output of electrochemical components]

[0490] The electrochemical elements 1 to 2 obtained in Examples 4-1 to 4-2 were evaluated by measuring their output using the following steps.

[0491] The leads of the electrochemical element were connected to the charge-discharge test apparatus (TOSCAT-3100, manufactured by Toyo Systems Co., Ltd.). After 5 hours of constant current and constant voltage charging at a maximum voltage of 4.2V and a current rate of 0.2C, a 10-minute rest was taken, and then 2.5 hours of constant current discharging was performed at a current rate of 0.2C to achieve a charging rate of 50% for the non-aqueous energy storage element.

[0492] Next, pulse discharge at a current rate of 1C to 10C is applied for 10 seconds. The power required to reach the 2.5V cutoff voltage is calculated from the correlation line between the voltage and current after discharge, and the output is calculated.

[0493] In addition, if the output of the non-aqueous energy storage element is 10.5W or more, it is considered good. In Examples 4-1 to 4-2, the electrochemical elements 1 to 2 all have an output of 10.5W or more.

[0494] That is, it can be seen that by using the surface-modified carbon material of the present invention, even electrochemical elements manufactured using liquid compositions without dispersants exhibit excellent output characteristics as electrochemical elements.

[0495] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention.

[0496] The forms involved in this embodiment are as follows:

[0497] <1>

[0498] A surface-modified carbon material, characterized in that a substituent represented by the following general formula (1) is added to the carbon material.

[0499] [Chemical Formula 15]

[0500]

[0501] In the formula, M is any one of metal ions, organic amines, and ammonium.

[0502] R represents any one of the following general formulas (2) and (3).

[0503] * indicates the junction.

[0504] [Chemical Formula 16]

[0505]

[0506] In the formula, A1, A2, A3, A4, and A5 are each independently CR' or N.

[0507] A6, A7, and A8 are each independently CR' or N.

[0508] A9 is CR'R', NR', O, or S.

[0509] R' can be any one of hydrogen atom, alkyl group, and alkoxy group.

[0510] * indicates the joint area.

[0511] <2>

[0512] According to <1>, the surface-modified carbon material is characterized in that the carbon material of the surface-modified carbon material is converted into anthracene, and the substituent is assigned to the 9th position of the anthracene, in such a model compound, the dipole moment determined by non-empirical molecular orbital method is 4.0 debye or greater.

[0513] <3>

[0514] The surface-modified carbon material according to <1> or <2> is characterized in that the metal ion is a lithium ion.

[0515] <4>

[0516] The surface-modified carbon material according to any one of <1> to <3> is characterized in that it is used to form an electrode.

[0517] <5>

[0518] A method for manufacturing a surface-modified carbon material, characterized by comprising a step of reacting a free radical compound represented by the following general formula (4) with the surface of the carbon material, and bonding a functional group represented by the following general formula (1) to the surface of the carbon material.

[0519] [Chemical Formula 17]

[0520]

[0521] In the formula, M is any one of metal ions, organic amines, and ammonium.

[0522] R represents any one of the following general formulas (2) and (3).

[0523] • Represents free radicals,

[0524] [Chemical Formula 18]

[0525]

[0526] In the formula, M is any one of metal ions, organic amines, and ammonium.

[0527] R represents any one of the following general formulas (2) and (3).

[0528] * indicates the junction.

[0529] [Chemical Formula 19]

[0530]

[0531] In the formula, A1, A2, A3, A4, and A5 are each independently CR' or N.

[0532] A6, A7, and A8 are each independently CR' or N.

[0533] A9 is CR'R', NR', O, or S.

[0534] R' can be any one of hydrogen atom, alkyl group, and alkoxy group.

[0535] * indicates the joint area.

[0536] <6>

[0537] According to the method for manufacturing surface-modified carbon materials described in <5>, the free radical compound represented by the general formula (4) is generated from a diazonium salt represented by the following general formula (5).

[0538] [Chemical Formula 20]

[0539]

[0540] In the formula, M is any one of metal ions, organic amines, and ammonium.

[0541] R represents either of the general formulas (2) and (3).

[0542] <7>

[0543] An electrode, characterized in that it comprises:

[0544] Current collector; and

[0545] An electrode composite material layer is disposed on the current collector and contains any one of the surface-modified carbon materials described in <1> to <4> above.

[0546] <8>

[0547] A liquid composition, characterized in that it comprises:

[0548] The surface-modified carbon material as described in any one of <1> to <4>, and

[0549] Organic solvents that are at least one of aprotic polar solvents and alcohol solvents.

[0550] <9>

[0551] The liquid composition according to <8> is characterized in that it further comprises an active substance.

[0552] <10>

[0553] A storage container, characterized in that it contains the liquid composition described in <8> or <9>.

[0554] <11>

[0555] An electrode manufacturing apparatus, characterized in that it comprises:

[0556] The storage container described in <10>, and

[0557] An applicator applies the liquid composition contained in the storage container to an object to be applicated.

[0558] <12>

[0559] A method for manufacturing an electrode, characterized by comprising an imparting step of imparting the liquid composition described in <8> or <9>.

[0560] <13>

[0561] The method for manufacturing the electrode according to <12> is characterized in that the liquid composition is applied by inkjet printing.

[0562] <14>

[0563] An electrochemical element, characterized in that it comprises the electrode described in <7>.

[0564] According to any one of the surface-modified carbon materials described in <1> to <4> above, according to any one of the manufacturing methods of the surface-modified carbon materials described in <5> to <6> above, according to any one of the liquid compositions described in <8> to <9> above, and according to the storage container described in <10> above, various existing problems can be solved and the object of the present invention can be achieved.

[0565] According to the electrode described in <7> above, the electrode manufacturing apparatus described in <11> above, and the electrode manufacturing method described in <12> above, the goal is to solve various existing problems and achieve the following objective: that is, the electrode, the electrode manufacturing apparatus, and the electrode manufacturing method described above will provide an electrode, an electrode manufacturing apparatus, and an electrode manufacturing method containing a surface-modified carbon material with excellent dispersibility and uniformity without the use of a dispersant.

Claims

1. A surface-modified carbon material, characterized in that, The following general formula (1) represents the addition of substituents to carbon materials. [Chemical Formula 1] In the formula, M is any one of metal ions, organic amines, and ammonium. R represents any one of the following general formulas (2) and (3). * indicates the junction. [Chemical Formula 2] In the formula, A1, A2, A3, A4, and A5 are each independently CR' or N. A6, A7, and A8 are each independently CR' or N. A9 is CR'R', NR', O, or S. R' can be any one of hydrogen atom, alkyl group, and alkoxy group. * indicates the joint area.

2. The surface-modified carbon material according to claim 1, characterized in that, The carbon material of the surface-modified carbon material is converted into anthracene, and the substituent is assigned to the 9-position of the anthracene. In such a model compound, the dipole moment determined by non-empirical molecular orbital method is greater than 4.0 debye.

3. The surface-modified carbon material according to claim 1, characterized in that, The metal ion is a lithium ion.

4. The surface-modified carbon material according to claim 1, characterized in that, Used to form electrodes.

5. A method for manufacturing a surface-modified carbon material, characterized in that, The method comprises a process of reacting a free radical compound represented by the following general formula (4) with the surface of a carbon material, and bonding a functional group represented by the following general formula (1) to the surface of the carbon material. [Chemical Formula 3] In the formula, M is any one of metal ions, organic amines, and ammonium. R represents any one of the following general formulas (2) and (3). • Represents free radicals, [Chemical Formula 4] In the formula, M is any one of metal ions, organic amines, and ammonium. R represents any one of the following general formulas (2) and (3). * indicates the junction. [Chemical Formula 5] In the formula, A1, A2, A3, A4, and A5 are each independently CR' or N. A6, A7, and A8 are each independently CR' or N. A9 is CR'R', NR', O, or S. R' can be any one of hydrogen atom, alkyl group, and alkoxy group. * indicates the joint area.

6. The method for manufacturing surface-modified carbon material according to claim 5, characterized in that, The free radical compound represented by general formula (4) is generated from the diazonium salt represented by the following general formula (5). [Chemical Formula 6] In the formula, M is any one of metal ions, organic amines, and ammonium. R represents either of the general formulas (2) and (3).

7. An electrode, characterized in that, include: Current collector; and An electrode composite material layer, disposed on the current collector, contains a surface-modified carbon material as described in any one of claims 1 to 4.

8. A liquid composition, characterized in that, include: The surface-modified carbon material according to any one of claims 1 to 4, and Organic solvents that are at least one of aprotic polar solvents and alcohol solvents.

9. The liquid composition according to claim 8, characterized in that, This further includes active substances.

10. A storage container, characterized in that, The liquid composition of claim 8 is included.

11. An apparatus for manufacturing an electrode, characterized in that, include: The storage container as described in claim 10, and An applicator applies the liquid composition contained in the storage container to an object to be applicated.

12. A method for manufacturing an electrode, characterized in that, The process includes a dispensing step, which dispenses the liquid composition of claim 8.

13. The method for manufacturing an electrode according to claim 12, characterized in that, The liquid composition is applied by inkjet printing.

14. An electrochemical element, characterized in that, Includes the electrode as described in claim 7.

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