WO2018143123A1 - Matière carbonée, matériau d'électrode mettant en œuvre celle-ci, et batterie - Google Patents

Matière carbonée, matériau d'électrode mettant en œuvre celle-ci, et batterie Download PDF

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WO2018143123A1
WO2018143123A1 PCT/JP2018/002710 JP2018002710W WO2018143123A1 WO 2018143123 A1 WO2018143123 A1 WO 2018143123A1 JP 2018002710 W JP2018002710 W JP 2018002710W WO 2018143123 A1 WO2018143123 A1 WO 2018143123A1
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carbonaceous
electrode
carbonaceous material
nonwoven fabric
fiber nonwoven
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PCT/JP2018/002710
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English (en)
Japanese (ja)
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俊克 円城寺
貴弘 松村
小林　真申
良平 岩原
真佐子 龍田
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東洋紡株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4242—Carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a carbonaceous material used for an electrode material of a redox battery.
  • electrodes have been developed with emphasis on battery performance.
  • a carbon material is often used for this type because of its conductivity and chemical resistance.
  • an electrode of a redox flow battery which has been actively developed for power storage, uses a carbon fiber aggregate having chemical resistance, conductivity, and liquid permeability.
  • the redox flow battery has been increased in energy density from a type using an aqueous hydrochloric acid solution of iron for the positive electrode and an aqueous solution of chromium hydrochloric acid for the negative electrode to a type using a sulfuric acid aqueous solution of vanadium having a high electromotive force for both electrodes.
  • a type using manganese for the positive electrode and chromium, vanadium, and titanium for the negative electrode has been developed as described in Patent Document 1, and a much higher energy has been developed. Densification is progressing.
  • the main configuration of the redox flow battery is composed of external tanks 6 and 7 for storing an electrolytic solution and an electrolytic cell EC as shown in FIG.
  • an electrolytic solution containing an active material is sent from the external tanks 6 and 7 to the electrolytic cell EC by the pumps 8 and 9, and electrochemical energy conversion, that is, charging, is performed on the electrode incorporated in the electrolytic cell EC. Discharge occurs.
  • the electrolytic cell EC has a liquid flow type structure as shown in FIG.
  • the liquid flow type electrolytic cell is referred to as a single cell, and is used as a minimum unit alone or in a multi-layered manner. Since the electrochemical reaction in the liquid flow type electrolytic cell is a heterogeneous phase reaction that occurs on the electrode surface, it generally involves a two-dimensional electrolytic reaction field. If the electrolytic reaction field is two-dimensional, there is a problem that the reaction amount per unit volume of the electrolytic cell is small.
  • FIG. 2 is an exploded perspective view of a liquid flow type electrolytic cell having a three-dimensional electrode.
  • an ion exchange membrane 3 is disposed between two opposing current collector plates 1 and 1, and an electrolyte solution is provided along the inner surface of the current collector plates 1 and 1 by spacers 2 on both sides of the ion exchange membrane 3.
  • Liquid passages 4a and 4b are formed.
  • An electrode material 5 such as a carbon fiber aggregate is disposed in at least one of the liquid passages 4a and 4b, and thus a three-dimensional electrode is configured.
  • the current collector plate 1 is provided with a liquid inlet 10 and a liquid outlet 11 for the electrolyte.
  • an electrolyte containing V 2+ is supplied to the liquid passage 4a on the negative electrode side during discharge.
  • An electrolytic solution containing V 5+ (actually an ion containing oxygen) is supplied to the liquid passage 4b on the positive electrode side.
  • V 2+ releases electrons in the three-dimensional electrode 5 and is oxidized to V 3+ .
  • V 5+ to V 4+ actually oxygen-containing ions
  • SO in the negative electrode electrolyte 4 2 is insufficient, because SO 4 2- is excessive in the positive electrolyte through the ion-exchange membrane 3 SO 4 2- move charge balance from the positive electrode side to the negative electrode side is maintained.
  • the charge balance can be maintained by moving H + through the ion exchange membrane from the negative electrode side to the positive electrode side.
  • the electrode material used for such a redox flow battery is required to have the following performance.
  • Patent Document 2 discloses that the ⁇ 002> plane spacing obtained by X-ray wide angle analysis is 3.43 to 3.60 mm, the crystallite size in the c-axis direction is 15 to 33 mm, and the crystallite in the a-axis direction.
  • the redox flow battery using the carbonaceous material proposed in Patent Document 2 has a problem that the cell resistance during initial charge / discharge is high and the battery energy efficiency is lowered.
  • this invention is made in view of the said subject, and when it uses as an electrode material for electrolyzers of a redox flow battery, the carbon electrode material which can reduce cell resistance at the time of initial stage charge / discharge, and can improve battery energy efficiency It is a problem to provide. In particular, it can be effectively used for a vanadium redox flow battery.
  • the present invention is as follows.
  • the ⁇ 002> plane spacing determined by X-ray wide angle analysis is 3.40-3.60 mm
  • the crystallite size in the c-axis direction is 15-150 mm
  • the crystallite size in the a-axis direction is 25 It has a crystal structure which is ⁇ 75 ⁇
  • the intensity ratio of the spectrum obtained by laser Raman spectroscopy of the excitation wavelength 532 nm, 1360 cm -1 vicinity of the peak intensity and (ID) 1580 cm -1 vicinity of the peak intensity and (IG) ( ID / IG) is 0.2 to 2.0
  • the Ti content obtained by ICP emission analysis is 0.1 to 30% by weight. 2.
  • pores can be formed by adding Ti metal, which is a carbon oxidation catalyst, to the surface of a carbonaceous material used as an electrode material, and performing heat treatment, and reducing the number of heat treatments, thereby reducing the cost of the battery. It was confirmed that energy efficiency could be improved.
  • the carbonaceous material with pores increases in contact area with the electrolyte with an increase in the geometric surface area compared to the nonporous material, and the fibers
  • the electrode reaction activity can be enhanced. Thereby, cell resistance at the time of initial stage charge / discharge can be reduced, and battery energy efficiency can be improved.
  • the present invention when used as an electrode material for an electrolytic cell of a redox flow battery, it is possible to provide a carbonaceous material capable of reducing cell resistance during initial charge / discharge and improving battery energy efficiency. .
  • the carbonaceous material of the present invention is suitably used for flow type and non-flow type Redox batteries, or redox batteries that are combined with lithium, capacitor, and fuel cell systems.
  • FIG. 2 is a diagram showing an example of the structure of an electrolytic cell EC using the carbonaceous material of the present embodiment as an electrode material.
  • the electrode material using the carbonaceous material of this embodiment is called a carbon electrode material.
  • an ion exchange membrane 3 is disposed between two opposing current collector plates 1, 1, and an electrolytic solution along the inner surfaces of the current collector plates 1, 1 by spacers 2 on both sides of the ion exchange membrane 3.
  • Liquid passages 4a and 4b are formed.
  • the carbon electrode material 5 of this embodiment is disposed in at least one of the liquid passages 4a and 4b.
  • the carbon electrode material 5 of the present embodiment is disposed in both the liquid passages 4a and 4b. In this way, the electrolytic cell EC is configured.
  • the current collector plate 1 is provided with a liquid inlet 10 and a liquid outlet 11 for the electrolyte.
  • the carbonaceous material constituting the carbon electrode material 5 is not particularly limited in the structure, but is preferably one that can increase the electrode surface area. Specifically, a spun yarn made of carbonaceous fibers, a filament bundle yarn, a nonwoven fabric, a knitted fabric, a woven fabric, a special knitted fabric (see, for example, Patent Document 3), or a carbonaceous fiber aggregate made of a hybrid structure thereof, porous carbon Body, carbon-carbon composite, particulate carbon material, and the like.
  • a carbonaceous fiber aggregate is preferable, and in particular, a non-woven fabric, a knitted fabric, a woven fabric, a special woven or knitted fabric composed of carbonaceous fibers, which is a sheet-shaped material composed of carbonaceous fibers, or a carbonaceous fiber assembly composed of a hybrid structure thereof.
  • the body is more preferable in terms of handling, processability, manufacturability and the like.
  • the thickness of the spacer 2 sandwiched between the current collector plate 1 and the ion exchange membrane 3 in FIG. 2 is 0.3.
  • 10 preferably ⁇ 1000g / m 2, 10 ⁇ 1000g / m 2 when configuration organization of knitting, 10 ⁇ 800g / m 2 in the case of textiles, in the case of the nonwoven fabric 10 ⁇ 600g / m 2 is preferred.
  • the groove width and groove depth are preferably at least 0.1 mm.
  • the thickness of the carbonaceous material is preferably at least larger than the thickness of the spacer 2, and in the case of a low density material such as a nonwoven fabric, the thickness of the spacer 2 is preferably 1.5 to 8.0 times. However, if the thickness is too thick, the ion-exchange membrane 3 may be broken due to the compressive stress of the sheet-like material. Therefore, it is preferable to use a sheet-like material having a compressive stress of 8 MPa or less. Depending on the carbonaceous material, it is possible to use multiple layers of carbonaceous material such as two or three layers to adjust the basis weight, thickness, and compressive stress. Combinations of these are also possible.
  • the average fiber diameter is preferably 0.2 to 20 ⁇ m
  • the average fiber length is preferably 30 mm or more
  • a tissue sheet is used in order to reduce the establishment of fiber piercing into the membrane. Long fibers having no cross section from end to end are more preferred.
  • the carbonaceous material is pressed and incorporated into the battery as an electrode material, and a high-viscosity electrolyte flows through the thin gap. Therefore, in order for the carbonaceous material not to fall off, the tensile strength of the carbonaceous material is increased. It is preferably 0.49 N / cm 2 or more. Further, in order to improve the contact resistance with the current collector plate, when the carbonaceous material is a nonwoven fabric structure, the density should be 0.01 g / cm 3 or more and the repulsive force against the electrode surface should be 0.98 N / cm 2 or more. Is preferred.
  • the carbonaceous material has a ⁇ 002> plane spacing determined by X-ray wide-angle analysis of 3.40 to 3.60 mm, a crystallite size in the c-axis direction of 15 to 150 mm, and a crystallite in the a-axis direction.
  • the ⁇ 002> plane spacing is 3.45 to 3.52 mm
  • the crystallite size in the c-axis direction is 20 to 50 mm
  • the crystallite size in the a-axis direction is 25 to It has a pseudographite crystal structure that is 70%.
  • the crystallite size in the c-axis direction is smaller than 15 mm, or in the a-axis direction
  • the electrode material conductive resistance component of the battery internal resistance (cell resistance) cannot be ignored.
  • cell resistance increases, that is, voltage efficiency decreases and energy efficiency decreases.
  • the crystallite size in the c-axis direction is larger than 65 mm, or in the a-axis direction
  • a functional group such as an oxygen functional group that improves the affinity with the electrolytic solution, and the energy efficiency is lowered.
  • the carbonaceous material it is preferable to use a carbonaceous material in which the number of bonded oxygen atoms on the surface of the carbonaceous material determined by XPS (X-ray photoelectron spectroscopy) surface analysis is 0.5% or more of the total surface carbon atoms.
  • XPS X-ray photoelectron spectroscopy
  • the carbonaceous material As the carbonaceous material, a carbonaceous material having pores in the range of 0.1 to 2 ⁇ m on the surface is used. Since the carbonaceous material has the pores, the surface described in Patent Document 2 has a larger outer surface area than the nonporous carbonaceous material, and the carbon crystal edge surface is exposed, so that the active material in the electrolytic solution As a result, the surface area of reaction with the ions increases and the reaction activity increases.
  • the carbonaceous material preferably has 5 or more pores having a pore diameter of 0.1 to 2 ⁇ m in 10 ⁇ m 2 of the scanning electron microscope observation image. When the number is less than 5, since there are almost no pores, the surface area becomes small and the reaction activity becomes low.
  • polyacrylonitrile As raw materials for carbonaceous materials, polyacrylonitrile, isotropic pitch, mesophase pitch, cellulose, phenol, polyparaphenylene benzobisoxazole (PBO), etc. that have undergone initial air oxidation at 200 to 300 ° C. under tension can be used. .
  • the carbonaceous material In order to form pores on the surface of the carbonaceous material, it can be obtained by applying a metal having a catalytic gasification reaction to the inside or the surface of the carbonaceous material and performing a heat treatment.
  • the metal species include Na, Mg, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn.
  • at least Ti is added. This is because Ti is relatively inexpensive and easily available, and when used for an electrode of a battery in which Ti is contained in the electrolytic solution, it does not cause a problem as a contamination even if it is not completely removed.
  • Examples of the form of imparting Ti include metal particles, metal chelates, metal alkoxides, metal complexes, metal oxides, metal compounds, etc., but when imparting to a carbonaceous material, it is preferable that it can be imparted in a uniformly dispersed state inside or on the surface. In addition, it is preferable that the carbonaceous material does not easily fall off due to physical vibration or impact. Furthermore, it is preferable that the size of the metal particles and the compound to be applied is smaller because uniform and small pores can be formed and the reaction activity is improved.
  • the Ti to be added is preferably 0.1% by weight to 30% by weight as the content of the carbonaceous material. If it is 0.1% by weight or less, it is insufficient for pore formation, and if it is 30% by weight or more, pore formation becomes excessive, fiber strength is lowered, and handling becomes difficult.
  • the timing of applying Ti may be before the step of carbonizing at 600 to 1250 ° C. in an inert gas (or nitrogen gas) atmosphere, or in the step of graphitizing at 1300 to 2300 ° C. in an inert gas (or nitrogen gas) atmosphere.
  • the reaction is preferably accelerated because of the temperature at which the metal starts to melt before, and the oxidation gasification reaction is promoted by the intervention of oxygen before the dry oxidation treatment step.
  • the method of oxidation treatment is not limited to dry oxidation.
  • a highly reactive decomposition gas such as HCN, NH 3 , CO, etc. at the time of temperature rise causes the surface of the carbonaceous material to have a catalytic ability. It is presumed that the reaction with carbon is promoted and pores are formed. In Patent Document 2, it is difficult to form pores because there is no catalyst that promotes the reaction.
  • the ⁇ 002> plane spacing and the crystallite size in the a-axis direction and the c-axis direction are determined in the thermal history of the carbonaceous material treated during firing (carbonization) or heat treatment in an oxidizing atmosphere.
  • the maximum heat treatment temperature, the heating rate, the time, etc. can be controlled.
  • the number of bonded oxygen atoms on the surface depends on the crystallinity (crystal growth degree) of the pseudographite crystal structure, but can be controlled mainly by adjusting the oxygen concentration, temperature, time, etc. of the dry oxidation treatment.
  • d002 face spacing
  • Lc crystallite size in the c-axis direction
  • La crystallite size in the a-axis direction
  • ICP emission analysis method employed in this embodiment
  • the measurement methods for the number of pores per 10 ⁇ m 2 , current efficiency, voltage efficiency (cell resistance R), energy efficiency, and change over time of the charge / discharge cycle using an electron microscope will be described.
  • the following simple method is used without correcting the so-called Lorentz factor, polarization factor, absorption factor, atomic scattering factor and the like. That is, the actual intensity from the baseline of the peak corresponding to ⁇ 002> diffraction is re-plotted to obtain a ⁇ 002> corrected intensity curve. Find the midpoint of the line segment where the line parallel to the angle axis drawn to 2/3 of the peak height of this curve intersects the correction intensity curve, and correct the midpoint angle with the internal standard.
  • the ⁇ 002> plane spacing is obtained from the Bragg equation of the following Equation 1 from the wavelength ⁇ of CuK ⁇ .
  • the wavelength ⁇ 1.5418 ⁇
  • ⁇ represents the ⁇ 002> diffraction angle
  • wavelength ⁇ 1.54184
  • structure coefficient k1 0.9
  • ⁇ represents the ⁇ 002> diffraction angle
  • ⁇ represents the half width of the ⁇ 002> diffraction peak.
  • the actual intensity from the baseline of the peak corresponding to ⁇ 10> diffraction is re-plotted to obtain a ⁇ 10> corrected intensity curve.
  • the size of the crystallite in the a-axis direction is calculated by the following Equation 3. Find La.
  • wavelength ⁇ 1.54184
  • structure coefficient k2 1.84
  • ⁇ represents the ⁇ 10> diffraction angle
  • ⁇ represents the half width of the ⁇ 10> diffraction peak.
  • the apparatus used for the measurement of the X-ray photoelectron spectroscopy abbreviated as ESCA or XPS uses ULVAC-PHI 5801MC.
  • the sample was fixed on the sample holder with a Mo plate, exhausted sufficiently in the preliminary exhaust chamber, and then put into the chamber of the measurement chamber.
  • a monochromatic AlK ⁇ ray is used as the radiation source, the output is 14 kV, 12 mA, and the vacuum in the apparatus is 10 ⁇ 8 torr.
  • a full element scan is performed to examine the composition of the surface elements, a narrow scan is performed on the detected and expected elements, and the abundance ratio is evaluated. The ratio of the number of surface-bound oxygen atoms to the total number of surface carbon atoms is calculated as a percentage (%).
  • the analysis of Ti (titanium) content in a sample is performed as follows.
  • the measuring device is an Ametec ICP emission spectrometer SPECTROBLUE, and the measuring solution is prepared as follows. Weigh accurately 0.5-1.0 g of sample into a quartz Erlenmeyer flask, add 3.0 ml of concentrated sulfuric acid and heat on a hot plate. The temperature is raised to 300 ° C., 30% hydrogen peroxide solution is added, and heating is continued until the solution becomes transparent, and the sample is decomposed. If there is any insoluble matter after decomposition, it is filtered and made up to a volume of 50 ml using ultrapure water, and this is used as a measurement test solution by ICP emission analysis.
  • the amount of titanium in the sample is quantified as follows.
  • the emission intensity of titanium at an emission wavelength of 334.941 nm is measured with an ICP emission spectrometer, and the titanium concentration in the solution is determined from a calibration curve.
  • evaluation of the number of pores per 10 ⁇ m 2 using an electron microscope is performed as follows.
  • the obtained carbonaceous material is observed with a transmission electron microscope, and a 40,000 times micrograph is obtained.
  • the photograph is magnified 4 times, the corners of the photograph are connected with a diagonal line, the intersection of the diagonal lines is set at the center of the photograph, and 10 ⁇ m 2 is trimmed from the center of the photograph based on the scale marker of the electron microscope. Holes included in the range of 0.1 to 2.0 ⁇ m in width, height, or depth included in the cropped photograph are counted. This operation is performed on 10 photos, and the average value of the number of pores of 10 ⁇ m 2 is calculated from 10 photos.
  • Electrode characteristics Referring to Patent Document 2, a small cell having an electrode area of 10 cm 2 of 1 cm in the vertical direction (liquid passing direction) and 10 cm in the width direction is formed, and charging and discharging are repeated at a constant current density. Do the test.
  • a vanadium-based electrolytic solution As the electrolytic solution, a vanadium-based electrolytic solution is used.
  • As the vanadium-based electrolyte a mixture of a positive electrode electrolyte and a negative electrode electrolyte mixed with 2.0 mol / l vanadium oxysulfate and a 3 mol / l sulfuric acid aqueous solution is used with reference to Patent Document 2.
  • the amount of the electrolyte is very large relative to the cells and piping.
  • the liquid flow rate is 6.2 ml per minute and the measurement is performed at 30 ° C.
  • the charging voltage V C50 and the discharging voltage V D50 corresponding to the amount of electricity when the charging rate is 50% are obtained from the amount of electricity-voltage curve, respectively, and the cell resistance R ( ⁇ ⁇ cm 2 ) with respect to the electrode geometric area is obtained from the following equation 6. Ask for.
  • I is a current value 1A in constant current charging / discharging.
  • E is the cell open circuit voltage when the charging rate is 50%.
  • the carbonaceous material of the present invention is used for the carbon electrode material.
  • the carbon electrode material of the present invention is not limited to the carbon electrode material, and can be used for an electromagnetic wave shield, for example.
  • products using the carbonaceous material of the present invention such as a battery using the carbonaceous material of the present invention, are also included in the category of the present invention.
  • Example 1 A polyacrylonitrile fiber having an average fiber diameter of 16 ⁇ m was flame-resistant at 200 to 300 ° C. in air. Thereafter, the flame-resistant short fibers (about 80 mm in length) are used to make a felt with a felt needle SB # 40 (Foster Needle) at a punching density of 250 / cm 2 , and a basis weight of 300 g / m 2 and a thickness of 3. A 2 mm nonwoven fabric was produced.
  • the non-woven fabric was dipped in a solution of titanium tetraisopropoxide diluted to 2% with isopropyl alcohol, and excess adhering solution was squeezed with mangle to adjust the wet pickup to 100 to 200%.
  • the temperature is increased to 950 ⁇ at a heating rate of 5 ° C./min in nitrogen gas. It heated up to 50 degreeC, hold
  • the obtained carbon fiber nonwoven fabric A is heated to 1500 ⁇ 50 ° C. at a rate of 5 ° C./min in nitrogen gas, and kept at this temperature for 1 hour for graphitization to obtain a carbon fiber nonwoven fabric B. It was.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbon fiber nonwoven fabric B. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric B (carbonaceous material) was evaluated as a single layer.
  • Example 2 A polyacrylonitrile fiber having an average fiber diameter of 16 ⁇ m was flame-resistant at 200 to 300 ° C. in air. Thereafter, the flame-resistant short fibers (about 80 mm in length) are used to make a felt with a felt needle SB # 40 (Foster Needle) at a punching density of 250 / cm 2 , and a basis weight of 300 g / m 2 and a thickness of 3. A 2 mm nonwoven fabric was produced. The non-woven fabric was dipped in a solution of titanium tetraisopropoxide diluted to 1% with isopropyl alcohol, and an excess attachment solution was squeezed with a mangle to adjust the wet pickup to 100 to 200%.
  • a solution of titanium tetraisopropoxide diluted to 1% with isopropyl alcohol
  • the temperature is increased to 950 ⁇ at a heating rate of 5 ° C./min in nitrogen gas. It heated up to 50 degreeC, hold
  • the obtained carbon fiber non-woven fabric C was heated to 2000 ⁇ 50 ° C. at a temperature increase rate of 5 ° C./min in nitrogen gas, and kept at this temperature for 1 hour to perform graphitization to obtain a carbon fiber non-woven fabric D. It was.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis result, and electrode performance of the obtained carbon fiber nonwoven fabric D.
  • the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric D (carbonaceous material) was evaluated as a single layer.
  • Example 3 The carbonaceous fiber nonwoven fabric A obtained in Example 1 was heated to 2000 ⁇ 50 ° C. at a rate of temperature increase of 5 ° C./min in nitrogen gas, held at this temperature for 1 hour, graphitized, and carbonized fiber Nonwoven fabric E was obtained.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric E.
  • the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric E (carbonaceous material) was evaluated as a single layer.
  • Example 4 The carbonaceous fiber nonwoven fabric C obtained in Example 2 was heated to 2200 ⁇ 50 ° C. at a heating rate of 5 ° C./min in nitrogen gas, held at this temperature for 1 hour, graphitized, and carbonized fiber Nonwoven fabric F was obtained.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbon fiber nonwoven fabric F.
  • the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric F (carbonaceous material) was evaluated as a single layer.
  • Example 5 The carbonaceous fiber nonwoven fabric A obtained in Example 1 was heated to 2200 ⁇ 50 ° C. at a rate of temperature increase of 5 ° C./min in nitrogen gas, held at this temperature for 1 hour, graphitized, and carbonized fiber Nonwoven fabric G was obtained.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbon fiber nonwoven fabric G.
  • the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric G (carbonaceous material) was evaluated as a single layer.
  • Example 6 A polyacrylonitrile fiber having an average fiber diameter of 16 ⁇ m was flame-resistant at 200 to 300 ° C. in air. Thereafter, the flame-resistant short fibers (about 80 mm in length) are used to make a felt with a felt needle SB # 40 (Foster Needle) at a punching density of 250 / cm 2 , and a basis weight of 300 g / m 2 and a thickness of 3. A 2 mm nonwoven fabric was produced. The non-woven fabric was dipped in a solution obtained by diluting titanium lactate ammonium salt to 2.1% with isopropyl alcohol and water, and an excess attachment solution was squeezed with a mangle to adjust the wet pickup to 100 to 200%.
  • a solution obtained by diluting titanium lactate ammonium salt to 2.1% with isopropyl alcohol and water
  • an excess attachment solution was squeezed with a mangle to adjust the wet pickup to 100 to 200%.
  • the temperature is increased to 950 ⁇ at a heating rate of 5 ° C./min in nitrogen gas. It heated up to 50 degreeC, hold
  • the obtained carbon fiber non-woven fabric H was heated to 1500 ⁇ 50 ° C. at a rate of temperature increase of 5 ° C./min in nitrogen gas, and kept at this temperature for 1 hour for graphitization to obtain a carbon fiber non-woven fabric I. It was.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric I.
  • the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric I (carbonaceous material) was evaluated as a single layer.
  • Example 7 The carbonaceous fiber nonwoven fabric H obtained in Example 6 was heated to 2000 ⁇ 50 ° C. at a rate of temperature increase of 5 ° C./min in nitrogen gas, held at this temperature for 1 hour, graphitized, and carbonized fiber Nonwoven fabric J was obtained.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis result, and electrode performance of the obtained carbon fiber nonwoven fabric J. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric J (carbonaceous material) was evaluated as a single layer.
  • Example 8 A polyacrylonitrile fiber having an average fiber diameter of 16 ⁇ m was flame-resistant at 200 to 300 ° C. in air. Thereafter, the flame-resistant short fibers (about 80 mm in length) are used to make a felt with a felt needle SB # 40 (Foster Needle) at a punching density of 250 / cm 2 , and a basis weight of 300 g / m 2 and a thickness of 3. A 2 mm nonwoven fabric was produced. The non-woven fabric was dipped in a solution obtained by diluting titanium lactate ammonium salt to 4.2% with isopropyl alcohol and water, and an excess attachment solution was squeezed with a mangle to adjust the wet pickup to 100 to 200%.
  • a solution obtained by diluting titanium lactate ammonium salt to 4.2% with isopropyl alcohol and water
  • an excess attachment solution was squeezed with a mangle to adjust the wet pickup to 100 to 200%.
  • the temperature is increased to 950 ⁇ at a heating rate of 5 ° C./min in nitrogen gas.
  • the temperature was raised to 50 ° C., kept at this temperature for 1 hour, carbonized and cooled to obtain a carbonaceous fiber nonwoven fabric K.
  • the obtained carbonaceous fiber nonwoven fabric K is heated to 2000 ⁇ 50 ° C. at a rate of temperature increase of 5 ° C./min in nitrogen gas, and kept at this temperature for 1 hour for graphitization to obtain a carbonaceous fiber nonwoven fabric L. It was.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric L.
  • the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric L (carbonaceous material) was evaluated as a single layer.
  • Example 9 A polyacrylonitrile fiber having an average fiber diameter of 16 ⁇ m was flame-resistant at 200 to 300 ° C. in air. Thereafter, the flame-resistant short fibers (about 80 mm in length) are used to make a felt with a felt needle SB # 40 (Foster Needle) at a punching density of 250 / cm 2 , and a basis weight of 300 g / m 2 and a thickness of 3.
  • a 2 mm nonwoven fabric was produced. The nonwoven fabric was dipped in a solution obtained by diluting titanium lactate ammonium salt to 50.0% with isopropyl alcohol and water, and an excess attachment solution was squeezed with a mangle to adjust the wet pickup to 100 to 200%. Next, after drying at 120 ° C.
  • the temperature is increased to 950 ⁇ at a heating rate of 5 ° C./min in nitrogen gas. It heated up to 50 degreeC, hold
  • the obtained carbonaceous fiber nonwoven fabric M was heated to 2000 ⁇ 50 ° C. at a rate of 5 ° C./min in nitrogen gas, and kept at this temperature for 1 hour for graphitization to obtain a carbonaceous fiber nonwoven fabric N. It was.
  • the obtained carbonaceous fiber nonwoven fabric N is immersed in a solution obtained by diluting titanium lactate ammonium salt to 50.0% with isopropyl alcohol and water, and an excess attachment solution is squeezed with a mangle and a wet pickup is 100 to 100%. It was adjusted to 200%. Next, it was dried at 120 ° C., heated to 950 ⁇ 50 ° C. at a rate of 5 ° C./min in nitrogen gas, kept at this temperature for 1 hour, carbonized, and cooled. Furthermore, the temperature was raised to 2000 ⁇ 50 ° C. at a rate of temperature rise of 5 ° C./min in nitrogen gas, and this temperature was maintained for 1 hour for graphitization to obtain a carbonaceous fiber nonwoven fabric O.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric O.
  • the spacer thickness was set to 0.6 mm, and the carbon fiber non-woven fabric O (carbonaceous material) was evaluated as a single layer.
  • Example 10 The carbonaceous fiber nonwoven fabric H obtained in Example 6 was heated to 2200 ⁇ 50 ° C. at a rate of temperature increase of 5 ° C./min in nitrogen gas, held at this temperature for 1 hour, graphitized, and carbonized fiber Nonwoven fabric Z was obtained.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric Z.
  • the spacer thickness was set to 0.6 mm, and the carbon fiber nonwoven fabric Z (carbonaceous material) was evaluated as a single layer.
  • Example 11 The carbonaceous fiber nonwoven fabric K obtained in Example 8 was heated to 2200 ⁇ 50 ° C. at a rate of 5 ° C./min in nitrogen gas, held at this temperature for 1 hour, graphitized, and carbonized fiber Nonwoven fabric P was obtained.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric P.
  • the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric P (carbonaceous material) was evaluated as a single layer.
  • Example 12 to 22 The carbonaceous fiber nonwoven fabrics obtained in Examples 1 to 12 were further subjected to dry oxidation at 700 ⁇ 50 ° C. in air until the mass yield was 90 to 95% to obtain carbonaceous fiber nonwoven fabrics.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbon fiber nonwoven fabric. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbon fiber non-woven fabric (carbon material) was evaluated as a single layer.
  • a polyacrylonitrile fiber having an average fiber diameter of 16 ⁇ m was flame-resistant at 200 to 300 ° C. in air. Thereafter, the flame-resistant short fibers (about 80 mm in length) are used to make a felt with a felt needle SB # 40 (Foster Needle) at a punching density of 250 / cm 2 , and a basis weight of 300 g / m 2 and a thickness of 3.
  • a 2 mm nonwoven fabric was produced. The nonwoven fabric was adjusted to a thickness of 0.9 ⁇ 0.1 mm at a pressure of 45 kgf / cm 2 at 210 ⁇ 10 ° C. and then increased to 950 ⁇ 50 ° C. at a rate of 5 ° C./min in nitrogen gas.
  • Comparative Example 2 The carbonaceous fiber nonwoven fabric Q obtained in Comparative Example 1 was heated to 1800 ⁇ 50 ° C. at a rate of temperature increase of 5 ° C./min in nitrogen gas, held at this temperature for 1 hour, graphitized, and carbonized fiber Nonwoven fabric S was obtained.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric S.
  • the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric S was evaluated as a single layer.
  • Comparative Example 3 The carbonaceous fiber nonwoven fabric Q obtained in Comparative Example 1 was heated to 2000 ⁇ 50 ° C. at a rate of 5 ° C./min in nitrogen gas, held at this temperature for 1 hour, graphitized, and carbonized fiber Nonwoven fabric T was obtained.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis result, and electrode performance of the obtained carbonaceous fiber nonwoven fabric T.
  • the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric T was evaluated as a single layer.
  • Comparative Example 4 The carbonaceous fiber nonwoven fabric Q obtained in Comparative Example 1 was heated to 2000 ⁇ 50 ° C. at a rate of 5 ° C./min in nitrogen gas, held at this temperature for 1 hour, graphitized, and carbonized fiber A nonwoven fabric U was obtained.
  • Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 ⁇ m 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric U. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric U was evaluated as a single layer.
  • the carbon electrode material for a redox battery of the present invention is a cell at the time of initial charge / discharge by enhancing electrode reaction activity while not containing acetylene black, ketjen black, etc., which are said to be conductive graphite powder or conductive additive. It is possible to reduce resistance and improve battery energy efficiency.
  • the carbon electrode material of the present invention is suitably used for flow type and non-flow type Redox batteries, or redox batteries that are combined with lithium, capacitor, and fuel cell systems to improve battery performance. It becomes possible and can contribute greatly to the industry.

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  • Geology (AREA)
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  • Electric Double-Layer Capacitors Or The Like (AREA)
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  • Nonwoven Fabrics (AREA)

Abstract

La matière carbonée de l'invention présente un espacement de plan ＜００２＞ obtenu par diffraction des rayons X compris entre 3,40 et 3,60Å, possède une structure telle que la dimension d'une cristallite dans une direction axiale (c) est comprise entre 15 et 150Å, et la dimension d'une cristallite dans la direction axiale (a) est comprise entre 25 et 75Å, présente un rapport d'intensité (ID/IG) entre une intensité de pic (ID) à proximité de １３６０ｃｍ－１, et une intensité de pic (IG) à proximité de １５８０ｃｍ－１, comprise entre 0,2 et 2,0, dans un spectre obtenu au moyen d'une mesure par spectroscopie de Raman au laser de longueur d'onde d'excitation de 532nm, et présente une teneur en Ti obtenue par spectrométrie à plasma à couplage inductif comprise entre 0,1 et 30% en masse.
PCT/JP2018/002710 2017-01-31 2018-01-29 Matière carbonée, matériau d'électrode mettant en œuvre celle-ci, et batterie WO2018143123A1 (fr)

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CN113493193A (zh) * 2020-03-20 2021-10-12 国家能源投资集团有限责任公司 无定形碳材料及其制备方法、钠离子电池负极和钠离子电池
CN113574707A (zh) * 2019-03-13 2021-10-29 东洋纺株式会社 碳电极材料和氧化还原电池

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WO2020158797A1 (fr) * 2019-01-29 2020-08-06 昭和電工株式会社 Électrode, son procédé de production et batterie

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JP2000357520A (ja) * 1999-06-11 2000-12-26 Toyobo Co Ltd バナジウム系レドックスフロー電池用炭素電極材
JP2000357522A (ja) * 1999-06-11 2000-12-26 Toyobo Co Ltd レドックスフロー電池用炭素電極材
WO2005045115A1 (fr) * 2003-11-10 2005-05-19 Teijin Limited Tissu non tisse de fibre de carbone et ses procedes de production et d'utilisation
WO2017022564A1 (fr) * 2015-07-31 2017-02-09 東洋紡株式会社 Matériau d'électrode de carbone pour des batteries redox

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JP2000357520A (ja) * 1999-06-11 2000-12-26 Toyobo Co Ltd バナジウム系レドックスフロー電池用炭素電極材
JP2000357522A (ja) * 1999-06-11 2000-12-26 Toyobo Co Ltd レドックスフロー電池用炭素電極材
WO2005045115A1 (fr) * 2003-11-10 2005-05-19 Teijin Limited Tissu non tisse de fibre de carbone et ses procedes de production et d'utilisation
WO2017022564A1 (fr) * 2015-07-31 2017-02-09 東洋紡株式会社 Matériau d'électrode de carbone pour des batteries redox

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113574707A (zh) * 2019-03-13 2021-10-29 东洋纺株式会社 碳电极材料和氧化还原电池
CN113574707B (zh) * 2019-03-13 2024-01-12 东洋纺Mc株式会社 碳电极材料和氧化还原电池
CN113493193A (zh) * 2020-03-20 2021-10-12 国家能源投资集团有限责任公司 无定形碳材料及其制备方法、钠离子电池负极和钠离子电池

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