WO2018143123A1 - Carbonaceous material, electrode material using same, and battery - Google Patents
Carbonaceous material, electrode material using same, and battery Download PDFInfo
- Publication number
- 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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- Prior art keywords
- carbonaceous
- electrode
- carbonaceous material
- nonwoven fabric
- fiber nonwoven
- Prior art date
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 79
- 239000007772 electrode material Substances 0.000 title claims description 30
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 3
- 230000005284 excitation Effects 0.000 claims abstract description 3
- 238000001228 spectrum Methods 0.000 claims abstract description 3
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- 238000004458 analytical method Methods 0.000 claims description 30
- 238000002441 X-ray diffraction Methods 0.000 abstract 1
- 238000004611 spectroscopical analysis Methods 0.000 abstract 1
- 239000004745 nonwoven fabric Substances 0.000 description 94
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 229910001873 dinitrogen Inorganic materials 0.000 description 26
- 239000007788 liquid Substances 0.000 description 24
- 125000006850 spacer group Chemical group 0.000 description 24
- 229920001940 conductive polymer Polymers 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- 229920000049 Carbon (fiber) Polymers 0.000 description 20
- 239000004917 carbon fiber Substances 0.000 description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 239000010936 titanium Substances 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
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- 229910052719 titanium Inorganic materials 0.000 description 9
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- 229910052720 vanadium Inorganic materials 0.000 description 8
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
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- 239000000463 material Substances 0.000 description 6
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- 238000004080 punching Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
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- 239000011149 active material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- XRASGLNHKOPXQL-UHFFFAOYSA-L azane 2-oxidopropanoate titanium(4+) dihydrate Chemical compound N.N.O.O.[Ti+4].CC([O-])C([O-])=O.CC([O-])C([O-])=O XRASGLNHKOPXQL-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000012937 correction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
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- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 238000011088 calibration curve Methods 0.000 description 1
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- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- YECBRSTWAYLPIM-UHFFFAOYSA-N chromium;hydrochloride Chemical compound Cl.[Cr] YECBRSTWAYLPIM-UHFFFAOYSA-N 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- 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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Abstract
The carbonaceous material according to the present invention has a crystal structure in which the <002> spacing as determined via wide-angle X-ray analysis is 3.40–3.60 Å, the crystallite sizes in the c-axis direction are 15–150 Å, and the crystallite sizes in the a-axis direction are 25–75 Å, and, in a spectrum obtained via laser Raman spectroscopy at an excitation wavelength of 532 nm, the intensity ratio (ID/IG) of the peak intensity (ID) near 1360 cm–1 and the peak intensity (IG) near 1580 cm–1 is 0.2–2.0, and the Ti content as determined via ICP spectrometry is 0.1–30% by weight.
Description
本発明は、レドックス電池の電極材などに利用される炭素質材料に関するものである。
The present invention relates to a carbonaceous material used for an electrode material of a redox battery.
従来、電極は電池の性能を左右するものとして重点的に開発されている。電極には、それ自体が活物質とならず、活物質の電気化学的反応を促進させる反応場として働くタイプがある。このタイプには導電性や耐薬品性などから炭素材料がよく用いられる。特に、電力貯蔵用に開発が盛んなレドックスフロー電池の電極に、耐薬品性があり、導電性を有し、かつ通液性のある炭素繊維集合体が用いられている。
Conventionally, electrodes have been developed with emphasis on battery performance. There is a type of electrode that does not itself become an active material but acts as a reaction field that promotes an electrochemical reaction of the active material. A carbon material is often used for this type because of its conductivity and chemical resistance. In particular, 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.
レドックスフロー電池は、正極に鉄の塩酸水溶液、負極にクロムの塩酸水溶液を用いたタイプから、起電力の高いバナジウムの硫酸水溶液を両極に用いるタイプに替わり、高エネルギー密度化されてきた。さらに高い起電力を有し、安定して安価に供給可能なものとして、たとえば特許文献1のような正極にマンガン、負極にクロム、バナジウム、チタンを用いるタイプの開発もなされており、一段と高エネルギー密度化が進んでいる。
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. As a device that has a higher electromotive force and can be stably supplied at a low cost, for example, 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.
レドックスフロー電池の主な構成は、図1に示すように電解液を貯える外部タンク6、7と電解槽ECとからなる。レドックスフロー電池では、ポンプ8、9にて活物質を含む電解液を外部タンク6、7から電解槽ECに送りながら、電解槽ECに組み込まれた電極上で電気化学的なエネルギー変換、すなわち充放電が行われる。
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. In the redox flow battery, 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.
一般に、充放電の際には、電解液を外部タンクと電解槽ECとの間で循環させるため、電解槽ECは図1に示すような液流通型構造をとる。該液流通型電解槽を単セルと称し、これを最小単位として単独または多段積層して用いられる。液流通型電解槽における電気化学反応は、電極表面で起こる不均一相反応であるため、一般的には二次元的な電解反応場を伴うことになる。電解反応場が二次元的であると、電解セルの単位体積当たりの反応量が小さいという難点がある。
Generally, in order to circulate the electrolytic solution between the external tank and the electrolytic cell EC during charging and discharging, 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.
そこで、単位面積当りの反応量、すなわち電流密度を増すために電気化学反応場の三次元化が行われるようになった。図2は、三次元電極を有する液流通型電解槽の分解斜視図である。該電解槽では、相対する二枚の集電板1、1間にイオン交換膜3が配設され、イオン交換膜3の両側にスペーサ2によって集電板1、1の内面に沿った電解液の通液路4a、4bが形成されている。該通液路4a、4bの少なくとも一方には炭素繊維集合体等の電極材5が配設されており、このようにして三次元電極が構成されている。なお、集電板1には、電解液の液流入口10と液流出口11とが設けられている。
Therefore, in order to increase the reaction amount per unit area, that is, the current density, the electrochemical reaction field is three-dimensionalized. FIG. 2 is an exploded perspective view of a liquid flow type electrolytic cell having a three-dimensional electrode. In the electrolytic cell, 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.
正極電解液にオキシ硫酸バナジウム、負極電解液に硫酸バナジウムの各々硫酸酸性水溶液を用いたレドックスフロー電池の場合、放電時には、V2+を含む電解液が負極側の通液路4aに供給され、正極側の通液路4bにはV5+(実際には酸素を含むイオン)を含む電解液が供給される。負極側の通液路4aでは、三次元電極5内でV2+が電子を放出しV3+に酸化される。放出された電子は外部回路を通って正極側の三次元電極内でV5+をV4+(実際には酸素を含むイオン)に還元する。この酸化還元反応に伴って負極電解液中のSO
4 2-が不足し、正極電解液ではSO4 2-が過剰になるため、イオン交換膜3を通ってSO4 2-が正極側から負極側に移動し電荷バランスが保たれる。あるいは、H+がイオン交換膜を通って負極側から正極側へ移動することによっても電荷バランスを保つことができる。充電時には放電と逆の反応が進行する。 In the case of a redox flow battery using a sulfuric acid aqueous solution of vanadium oxysulfate as the positive electrode electrolyte and vanadium sulfate as the negative electrode electrolyte, an electrolyte containing V 2+ is supplied to theliquid 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. In the liquid passage 4a on the negative electrode side, V 2+ releases electrons in the three-dimensional electrode 5 and is oxidized to V 3+ . The emitted electrons pass through an external circuit and reduce V 5+ to V 4+ (actually oxygen-containing ions) in the three-dimensional electrode on the positive electrode side. Accompanying this redox reaction, 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. Alternatively, the charge balance can be maintained by moving H + through the ion exchange membrane from the negative electrode side to the positive electrode side. During charging, a reaction opposite to discharging proceeds.
4 2-が不足し、正極電解液ではSO4 2-が過剰になるため、イオン交換膜3を通ってSO4 2-が正極側から負極側に移動し電荷バランスが保たれる。あるいは、H+がイオン交換膜を通って負極側から正極側へ移動することによっても電荷バランスを保つことができる。充電時には放電と逆の反応が進行する。 In the case of a redox flow battery using a sulfuric acid aqueous solution of vanadium oxysulfate as the positive electrode electrolyte and vanadium sulfate as the negative electrode electrolyte, an electrolyte containing V 2+ is supplied to the
4 2 is insufficient, because SO 4 2- is excessive in the positive electrolyte through the ion-
このようなレドックスフロー電池に用いられる電極材は、特に以下に示す性能が要求される。
The electrode material used for such a redox flow battery is required to have the following performance.
(1)目的とする反応以外の副反応を起こさないこと(反応選択性が高いこと)、具体的には電流効率(ηI)が高いこと。
(2)電極反応活性が高いこと、具体的にはセル抵抗(R)が小さいこと。すなわち電圧効率(ηV)が高いこと。
(3)上記(1)、(2)に関連する電池エネルギー効率(ηE)が高いこと。
ηE=ηI×ηV
(4)繰り返し使用に対する劣化が小さいこと(高寿命)、具体的には電池エネルギー効率(ηE)の低下量が小さいこと。 (1) No side reaction other than the intended reaction occurs (high reaction selectivity), specifically, high current efficiency (η I ).
(2) The electrode reaction activity is high, specifically, the cell resistance (R) is small. That is, the voltage efficiency (η V ) is high.
(3) The battery energy efficiency (η E ) related to the above (1) and (2) is high.
η E = η I × η V
(4) Deterioration due to repeated use is small (long life), specifically, the amount of decrease in battery energy efficiency (η E ) is small.
(2)電極反応活性が高いこと、具体的にはセル抵抗(R)が小さいこと。すなわち電圧効率(ηV)が高いこと。
(3)上記(1)、(2)に関連する電池エネルギー効率(ηE)が高いこと。
ηE=ηI×ηV
(4)繰り返し使用に対する劣化が小さいこと(高寿命)、具体的には電池エネルギー効率(ηE)の低下量が小さいこと。 (1) No side reaction other than the intended reaction occurs (high reaction selectivity), specifically, high current efficiency (η I ).
(2) The electrode reaction activity is high, specifically, the cell resistance (R) is small. That is, the voltage efficiency (η V ) is high.
(3) The battery energy efficiency (η E ) related to the above (1) and (2) is high.
η E = η I × η V
(4) Deterioration due to repeated use is small (long life), specifically, the amount of decrease in battery energy efficiency (η E ) is small.
たとえば特許文献2には、X線広角解析より求めた<002>面間隔が3.43~3.60Åで、c軸方向の結晶子の大きさが15~33Åで、a軸方向の結晶子の大きさが30~75Åである擬黒鉛結晶構造を有し、XPS表面分析より求めた表面酸性官能基量が全表面炭素原子数の0.2~1.0%であり、表面結合窒素原子数が全表面炭素原子数の3%以下である炭素質材料をバナジウム系レドックスフロー電池の電解槽用電極材として用いることが提案されている。
For example, 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. Has a pseudo-graphite crystal structure with a size of 30 to 75 mm, the surface acidic functional group amount determined by XPS surface analysis is 0.2 to 1.0% of the total surface carbon atoms, and has surface-bound nitrogen atoms It has been proposed to use a carbonaceous material having a number of 3% or less of the total surface carbon atoms as an electrode material for an electrolytic cell of a vanadium redox flow battery.
しかしながら、特許文献2にて提案されている炭素質材料を用いたレドックスフロー電池では初期充放電時のセル抵抗が高く、電池エネルギー効率が低下するといった問題がある。そこで、本発明は、上記課題に鑑みなされ、レドックスフロー電池の電解槽用電極材として用いた場合、初期充放電時のセル抵抗を低下させ、電池エネルギー効率を向上させることが可能な炭素電極材を提供することを課題とするものである。特に、バナジウム系レドックスフロー電池に効果的に用いることができる。
However, 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. Then, 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.
本発明は上記課題を解決するために、本発明者等が鋭意検討した結果、遂に本発明を完成するに到った。すなわち、本発明は下記の通りである。
As a result of intensive studies by the present inventors in order to solve the above problems, the present invention has finally been completed. That is, the present invention is as follows.
1.X線広角解析より求めた<002>面間隔が3.40~3.60Åであり、c軸方向の結晶子の大きさが15~150Åであり、a軸方向の結晶子の大きさが25~75Åである結晶構造を有し、励起波長532nmのレーザーラマン分光測定により求めたスペクトルにおいて、1360cm-1付近のピーク強度(ID)と1580cm-1付近のピーク強度(IG)との強度比(ID/IG)が0.2~2.0であり、ICP発光分析法より得られるTi含有量が0.1~30重量%である、ことを特徴とする炭素質材料。
2.3000~7000倍の走査型電子顕微鏡観察画像において、幅または高さまたは深さが0.1~2μmの範囲の細孔が10μm2あたりに5個以上存在する、ことを特徴とする上記1に記載の炭素質材料。
3.繊維構造体からなる上記1または2に記載の炭素質材料。
4.上記1~3のいずれか1つに記載の炭素質材料を用いた電極材。例えば、レドックス電池用電極材に用いることができる。
5.上記1~4のいずれか1つに記載の炭素質材料を電極材に用いた電池。
また、本発明の炭素質材料は、例えば、電磁波シールドにも用いることができる。よって、本発明の炭素質材料を用いた製品も本発明の範疇に含まれる。 1. 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, and the crystallite size in the a-axis direction is 25 It has a crystal structure which is ~ 75 Å, 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, and the Ti content obtained by ICP emission analysis is 0.1 to 30% by weight.
2. In the scanning electron microscope observation image at a magnification of 3000 to 7000 times, 5 or more pores having a width, height or depth in the range of 0.1 to 2 μm are present per 10μm 2. 1. The carbonaceous material according to 1.
3. 3. The carbonaceous material as described in 1 or 2 above, comprising a fiber structure.
4). 4. An electrode material using the carbonaceous material according to any one of 1 to 3 above. For example, it can be used for a redox battery electrode material.
5). A battery using the carbonaceous material according to any one of 1 to 4 as an electrode material.
Moreover, the carbonaceous material of this invention can be used also for an electromagnetic wave shield, for example. Therefore, products using the carbonaceous material of the present invention are also included in the category of the present invention.
2.3000~7000倍の走査型電子顕微鏡観察画像において、幅または高さまたは深さが0.1~2μmの範囲の細孔が10μm2あたりに5個以上存在する、ことを特徴とする上記1に記載の炭素質材料。
3.繊維構造体からなる上記1または2に記載の炭素質材料。
4.上記1~3のいずれか1つに記載の炭素質材料を用いた電極材。例えば、レドックス電池用電極材に用いることができる。
5.上記1~4のいずれか1つに記載の炭素質材料を電極材に用いた電池。
また、本発明の炭素質材料は、例えば、電磁波シールドにも用いることができる。よって、本発明の炭素質材料を用いた製品も本発明の範疇に含まれる。 1. 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, and the crystallite size in the a-axis direction is 25 It has a crystal structure which is ~ 75 Å, 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, and the Ti content obtained by ICP emission analysis is 0.1 to 30% by weight.
2. In the scanning electron microscope observation image at a magnification of 3000 to 7000 times, 5 or more pores having a width, height or depth in the range of 0.1 to 2 μm are present per 10
3. 3. The carbonaceous material as described in 1 or 2 above, comprising a fiber structure.
4). 4. An electrode material using the carbonaceous material according to any one of 1 to 3 above. For example, it can be used for a redox battery electrode material.
5). A battery using the carbonaceous material according to any one of 1 to 4 as an electrode material.
Moreover, the carbonaceous material of this invention can be used also for an electromagnetic wave shield, for example. Therefore, products using the carbonaceous material of the present invention are also included in the category of the present invention.
発明者等は、電極材として用いる炭素質材料の表面に炭素酸化触媒であるTi金属を添加し熱処理を行うことにより細孔を形成できることを確認し、熱処理回数を抑制することにより低コストながら電池エネルギー効率を向上できることを確認した。ここで、炭素質材料の表面に孔を形成することにより、孔が形成された炭素質材料は無孔な材料に比べて幾何表面積の増加に伴い電解液との接触面積が増加し、かつ繊維内部の炭素結晶エッジ面を露出させることにより、電極反応活性を高めることが可能となる。これにより、初期充放電時のセル抵抗を低下でき、電池エネルギー効率を向上させることができる。
The inventors confirmed that 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. Here, by forming pores on the surface of the carbonaceous material, 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 By exposing the inner carbon crystal edge surface, 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.
よって、本発明により、レドックスフロー電池の電解槽用電極材として用いた場合、初期充放電時のセル抵抗を低下させ、電池エネルギー効率を向上させることが可能な炭素質材料を提供することができる。
Therefore, according to 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. .
本発明の炭素質材料は、フロータイプおよびノンフロータイプのレッドクス電池、またはリチウム、キャパシタ、燃料電池のシステムと複合化されたようなレドックス電池に好適に用いられる。
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.
以下では、本実施形態の炭素質材料について図を参照に説明する。
図2は、本実施形態の炭素質材料を電極材として使用した電解槽ECの構造の一例を示す図である。以下では、本実施形態の炭素質材料を用いた電極材を炭素電極材と称する。電解槽ECでは、相対する二枚の集電板1、1間にイオン交換膜3が配設され、イオン交換膜3の両側にスペーサ2によって集電板1、1の内面に沿った電解液の通液路4a、4bが形成されている。通液路4a、4bの少なくとも一方には本実施形態の炭素電極材5が配設されている。本実施形態の電解槽ECでは、通液路4a、4bの両方に本実施形態の炭素電極材5が配設されている。このようにして電解槽ECが構成されている。なお、集電板1には、電解液の液流入口10と液流出口11とが設けられている。 Below, the carbonaceous material of this embodiment is demonstrated with reference to figures.
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. Below, the electrode material using the carbonaceous material of this embodiment is called a carbon electrode material. In the electrolytic cell EC, anion 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. In the electrolytic cell EC of the present embodiment, 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.
図2は、本実施形態の炭素質材料を電極材として使用した電解槽ECの構造の一例を示す図である。以下では、本実施形態の炭素質材料を用いた電極材を炭素電極材と称する。電解槽ECでは、相対する二枚の集電板1、1間にイオン交換膜3が配設され、イオン交換膜3の両側にスペーサ2によって集電板1、1の内面に沿った電解液の通液路4a、4bが形成されている。通液路4a、4bの少なくとも一方には本実施形態の炭素電極材5が配設されている。本実施形態の電解槽ECでは、通液路4a、4bの両方に本実施形態の炭素電極材5が配設されている。このようにして電解槽ECが構成されている。なお、集電板1には、電解液の液流入口10と液流出口11とが設けられている。 Below, the carbonaceous material of this embodiment is demonstrated with reference to figures.
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. Below, the electrode material using the carbonaceous material of this embodiment is called a carbon electrode material. In the electrolytic cell EC, an
炭素電極材5を成す炭素質材料は、その構成組織は特に限定されないが、電極表面積を大きくできるものが好ましい。具体的には、炭素質繊維よりなる紡績糸、フィラメント集束糸、不織布、編物、織物、特殊編織物(たとえば特許文献3参照)、またはこれらの混成組織からなる炭素質繊維集合体、多孔質炭素体、炭素-炭素複合体、粒子状炭素材料等を挙げることができる。これらのうち、炭素質繊維集合体が好ましく、なかでも炭素質繊維よりなるシート状物である炭素質繊維よりなる不織布、編物、織物、特殊織編物、またはこれらの混成組織からなる炭素質繊維集合体が、取り扱いや加工性、製造性等の点からより好ましい。
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. Among these, 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.
炭素質材料の目付量は構成組織にもよるが、図2の集電板1とイオン交換膜3に挟まれたスペーサ2の厚み(以下、「スペーサ2の厚み」と言う)を0.3~3mmで使用する場合、10~1000g/m2が好ましく、構成組織が編物の場合は10~1000g/m2、織物の場合は10~800g/m2、不織布の場合は10~600g/m2が好ましい。また、炭素質材料として、片面に凹溝加工が施された不織布を使用することも通液性からより好ましい。その場合の溝幅、溝深さは少なくとも0.1mm以上が好ましい。
Although the basis weight of the carbonaceous material depends on the structure, the thickness of the spacer 2 sandwiched between the current collector plate 1 and the ion exchange membrane 3 in FIG. 2 (hereinafter referred to as “the thickness of the spacer 2”) is 0.3. when used in ~ 3 mm, 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. Moreover, it is more preferable from a liquid-permeable property to use the nonwoven fabric by which the concave groove process was given to the single side | surface as a carbonaceous material. In that case, the groove width and groove depth are preferably at least 0.1 mm.
炭素質材料の厚みは、スペーサ2の厚みより少なくとも大きいこと、不織布等の密度の低いものの場合はスペーサ2の厚みの1.5~8.0倍が好ましい。しかしながら、厚みが厚すぎるとシート状物の圧縮応力のよりイオン交換膜3を突き破ってしまうことがあるので、シート状物の圧縮応力が8MPa以下のものを使用するのが好ましい。炭素質材料によっては、目付量・厚み・圧縮応力を調整するために、炭素質材料を2層や3層など複数層積層して用いることも可能であり、また別の形態の炭素質材料との組み合わせも可能である。
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.
炭素質材料として炭素質繊維を使用する場合、その平均繊維径は0.2~20μmが好ましく、平均繊維長は30mm以上が好ましく、繊維の膜への突刺し確立を低減させるためには組織シートの端から端まで断面が出ない長繊維がより好ましい。
When carbonaceous fibers are used as the carbonaceous material, the average fiber diameter is preferably 0.2 to 20 μm, the average fiber length is preferably 30 mm or more, and 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.
本実施形態では炭素質材料は電極材として電池の中に圧接されて組み込まれ、その薄い隙間を粘度の高い電解液が流れるため、炭素質材料が脱落しないためには炭素質材料の引張強度を0.49N/cm2以上にすることが好ましい。また集電板との接触抵抗を良くするために、炭素質材料が不織布組織の場合、密度を0.01g/cm3以上に、電極面に対する反発力を0.98N/cm2以上にすることが好ましい。
In the present embodiment, 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.
炭素質材料は、X線広角解析より求めた<002>面間隔が3.40~3.60Åであり、c軸方向の結晶子の大きさが15~150Åであり、a軸方向の結晶子の大きさが25~75Åである擬黒鉛結晶構造を有する。好ましくは、前記<002>面間隔が3.45~3.52Åであり、前記c軸方向の結晶子の大きさが20~50Åであり、前記a軸方向の結晶子の大きさが25~70Åである擬黒鉛結晶構造を有する。
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. Has a pseudographite crystal structure having a size of 25 to 75 mm. Preferably, the <002> plane spacing is 3.45 to 3.52 mm, the crystallite size in the c-axis direction is 20 to 50 mm, and the crystallite size in the a-axis direction is 25 to It has a pseudographite crystal structure that is 70%.
炭素質材料のX線広角解析より求めた<002>面間隔は、黒鉛の3.35Åから3.70Åを越える不定型炭素までの様々な値をとり、その特性も大きく異なることが広く知られている。
It is widely known that the <002> plane spacing obtained from X-ray wide-angle analysis of carbonaceous materials takes various values from 3.35% to over 3.70% of amorphous carbon, and the characteristics are also greatly different. ing.
炭素質材料の結晶構造において、X線広角解析より求めた<002>面間隔が3.60Åよりも大きい場合、c軸方向の結晶子の大きさが15Åよりも小さい場合、またはa軸方向の結晶子の大きさが25Åよりも小さい場合、電池内部抵抗(セル抵抗)の内の電極材導電抵抗成分が無視できないようになる。その結果、セル抵抗が増加し、つまり電圧効率が低下し、エネルギー効率が低下する。
In the crystal structure of the carbonaceous material, when the <002> plane spacing obtained by X-ray wide-angle analysis is larger than 3.60 mm, the crystallite size in the c-axis direction is smaller than 15 mm, or in the a-axis direction When the crystallite size is smaller than 25 mm, the electrode material conductive resistance component of the battery internal resistance (cell resistance) cannot be ignored. As a result, cell resistance increases, that is, voltage efficiency decreases and energy efficiency decreases.
また、炭素質材料の結晶構造において、X線広角解析より求めた<002>面間隔が3.43Åより小さい場合、c軸方向の結晶子の大きさが65Åより大きい場合、またはa軸方向の結晶子の大きさが75Åより大きい場合、黒鉛化結晶構造に近くなるためエッジ面の露出による反応活性向上が期待できる一方で、安定構造になってしまう。そのため酸素官能基など電解液との親和性を向上させるような官能基の導入が難しく、エネルギー効率は低下する。
Further, in the crystal structure of the carbonaceous material, when the <002> plane spacing obtained by X-ray wide angle analysis is smaller than 3.43 mm, the crystallite size in the c-axis direction is larger than 65 mm, or in the a-axis direction When the crystallite size is larger than 75 mm, since it is close to a graphitized crystal structure, an improvement in reaction activity due to exposure of the edge surface can be expected, but a stable structure is obtained. Therefore, it is difficult to introduce a functional group such as an oxygen functional group that improves the affinity with the electrolytic solution, and the energy efficiency is lowered.
炭素質材料として、XPS(X線光電子分光法)表面分析より求めた炭素質材料表面の結合酸素原子数が全表面炭素原子数の0.5%以上である炭素質材料を用いるのが好ましい。結合酸素原子数が全表面炭素原子数の0.5%以上の炭素系材料を電極材に用いることにより、電極反応速度、つまり電導度を著しく高め得ることができるからである。XPS表面分析より求めた炭素質材料表面の結合酸素原子数が全表面炭素原子数の0.5%未満の酸素濃度の低い炭素質材料を用いる場合は放電時の電極反応速度が小さく、電極反応活性を高めることはできない。このように材料表面に酸素原子を多く結合させた炭素質材料を電極材として用いることにより電極反応活性、言い換えれば電圧効率が高められる理由については明らかでないが、炭素質材料と電解液との親和性、電子の授受、錯イオンの炭素材料からの脱離、錯交換反応等に表面の酸素原子が有効に働いているものと考えられる。
As 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. This is because the electrode reaction rate, that is, the conductivity can be remarkably increased by using, as the electrode material, a carbon-based material having a bond oxygen atom number of 0.5% or more of the total surface carbon atoms. When a carbonaceous material with a low oxygen concentration, in which the number of bonded oxygen atoms on the surface of the carbonaceous material obtained by XPS surface analysis is less than 0.5% of the total number of surface carbon atoms, is used, the electrode reaction rate during discharge is small, and the electrode reaction The activity cannot be increased. Although it is not clear why the electrode reaction activity, in other words, the voltage efficiency, is increased by using a carbonaceous material having many oxygen atoms bonded to the material surface as described above, the affinity between the carbonaceous material and the electrolyte is not clear. It is considered that oxygen atoms on the surface are effectively working in the properties, electron transfer, desorption of complex ions from carbon materials, complex exchange reactions, and the like.
炭素質材料として、表面に0.1~2μmの範囲の孔をその表面に有する炭素質材料を用いる。炭素質材料が前記細孔を有することにより、特許文献2に記載の表面が無細孔の炭素質材料よりも外表面積が大きく、また炭素結晶エッジ面が露出するため、電解液中の活物質であるイオンとの反応表面積が増加し反応活性が高まる。
As the carbonaceous material, a carbonaceous material having pores in the range of 0.1 to 2 μm 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.
炭素質材料は、走査型電子顕微鏡観察画像の10μm2において0.1~2μmの孔径の細孔数が5個以上であることが好ましい。5個未満の場合はほぼ細孔が存在しない状態であるため、表面積が小さくなり反応活性が低くなってしまう。
The carbonaceous material preferably has 5 or more pores having a pore diameter of 0.1 to 2 μm in 10 μm 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.
炭素質材料の原料としては、緊張下200~300℃の初期空気酸化を経たポリアクリロニトリル、等方性ピッチ、メソフェーズピッチ、セルロース、フェノール、ポリパラフェニレンベンゾビスオキサゾール(PBO)などを用いることができる。
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. .
炭素質材料の表面に孔を形成するには、炭素質材料の内部もしくは表面に触媒ガス化反応を有する金属を付与し熱処理することにより得られる。金属種としてはNa、Mg、K、Ca、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Znなどが挙げられるが、本実施形態では、少なくともTiを付与する。Tiは、比較的安価で入手しやすく、また、電解液にTiが含まれる電池の電極に用いる場合に、完全に除去せずともコンタミとして問題になら無いからである。
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. Examples of the metal species include Na, Mg, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. In this embodiment, 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.
Tiを付与する形態は金属粒子、金属キレート、金属アルコキシド、金属錯体、金属酸化物、金属化合物などが挙げられるが、炭素質材料に付与する場合において内部もしくは表面に均一分散状態で付与できることが好ましく、また炭素質材料から物理的振動や衝撃等により脱落しにくいものが好ましい。さらに、付与する金属の粒子や化合物のサイズが小さいほど均一ならびに孔径が小さい孔を形成でき反応活性が向上するために好ましい。
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.
付与するTiは、炭素質材料の含有量として0.1重量%~30重量%が好ましい。0.1重量%以下であると孔形成には不十分であり、30重量%以上であると孔形成が過剰となり繊維強度が低下し取り扱いが困難になる。
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.
Tiを付与するタイミングは不活性ガス(または窒素ガス)雰囲気下600~1250℃で炭化する工程の前でもよく、不活性ガス(または窒素ガス)雰囲気下1300~2300℃で黒鉛化をする工程の前でもよく、酸素濃度1~10%のガス雰囲気下で500~900℃の乾式酸化処理工程の前でもよい。不活性ガス(または窒素ガス)雰囲気下600~1250℃で炭化する工程の前であれば、炭素構造変化が生じやすい温度であるため孔形成に好ましく、1300~2300℃で黒鉛化をする工程の前では金属が溶融し始める温度のため反応が促進され好ましく、乾式酸化処理工程の前では酸素の介在により酸化ガス化反応が促進され好ましい。しかし酸化処理の方法は乾式酸化に限定されるものではなく、例えば電解酸化をおこなっても同様な効果が得られる。この反応機構については現在解明中であるが、不活性雰囲気下での孔形成では昇温時にHCN、NH3、COなどの反応性の高い分解ガスが触媒能を有する金属により炭素質材料の表面炭素との反応が促進され孔が形成されると推測しており、特許文献2では反応を促進される触媒を有しないため、孔が形成されにくいと考える。
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. Before the dry oxidation treatment step of 500 to 900 ° C. in a gas atmosphere having an oxygen concentration of 1 to 10%. If it is before the step of carbonizing at 600 to 1250 ° C. in an inert gas (or nitrogen gas) atmosphere, it is preferable for pore formation because it is a temperature at which the carbon structure is likely to change. In the step of graphitizing at 1300 to 2300 ° C. 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. However, the method of oxidation treatment is not limited to dry oxidation. For example, the same effect can be obtained by performing electrolytic oxidation. This reaction mechanism is currently being elucidated, but in the formation of pores in an inert atmosphere, 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.
上記の製造方法において、<002>面間隔、並びにa軸方向及びc軸方向の結晶子の大きさは、焼成(炭化)時もしくは酸化雰囲気での熱処理など炭素質材料を処理した熱履歴の中の最高熱処理温度、昇温速度、時間等により制御できる。また、表面の結合酸素原子数は、擬黒鉛結晶構造の結晶性(結晶成長度)にもよるが、主に乾式酸化処理の酸素濃度、温度、時間等を調製することで制御できる。
In the above manufacturing method, 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.
本実施形態において採用される<002>面間隔(d002)、c軸方向の結晶子の大きさ(Lc)、a軸方向の結晶子の大きさ(La)、XPS表面分析、ICP発光分析法、電子顕微鏡による10μm2あたりの細孔数、電流効率、電圧効率(セル抵抗R)、エネルギー効率および充放電サイクルの経時変化の各測定法について説明する。
<002> face spacing (d002), crystallite size in the c-axis direction (Lc), crystallite size in the a-axis direction (La), XPS surface analysis, ICP emission analysis method employed in this embodiment The measurement methods for the number of pores per 10 μm 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.
(1)<002>面間隔(d002)、結晶子の大きさ(Lc)、a軸方向の結晶子の大きさ(La)
電極材料をメノウ乳鉢を用いて、粒径10μm程度になるまで粉砕し、試料に対して約5重量%のX線標準用高純度シリコン粉末を内部標準物質として混合し、試料セルに詰め、CuKα線を線源として、ディフラクトメーター法によって広角X線を測定する。 (1) <002> spacing (d002), crystallite size (Lc), crystallite size in the a-axis direction (La)
The electrode material was pulverized with an agate mortar until the particle size became about 10 μm, and about 5 wt% of high-purity silicon powder for X-ray standard was mixed as an internal standard substance with respect to the sample, packed in a sample cell, and CuKα Wide angle X-rays are measured by a diffractometer method using a line as a radiation source.
電極材料をメノウ乳鉢を用いて、粒径10μm程度になるまで粉砕し、試料に対して約5重量%のX線標準用高純度シリコン粉末を内部標準物質として混合し、試料セルに詰め、CuKα線を線源として、ディフラクトメーター法によって広角X線を測定する。 (1) <002> spacing (d002), crystallite size (Lc), crystallite size in the a-axis direction (La)
The electrode material was pulverized with an agate mortar until the particle size became about 10 μm, and about 5 wt% of high-purity silicon powder for X-ray standard was mixed as an internal standard substance with respect to the sample, packed in a sample cell, and CuKα Wide angle X-rays are measured by a diffractometer method using a line as a radiation source.
曲線の補正には、いわゆるローレンツ因子、偏光因子、吸収因子、原子散乱因子等に関する補正を行わず、次の簡便法を用いる。すなわち、<002>回折に相当するピークのベースラインからの実質強度をプロットし直して<002>補正強度曲線を得る。この曲線のピーク高さの2/3の高さに引いた角度軸に平行な線が補正強度曲線と交わる線分の中点を求め、中点の角度を内部標準で補正し、これを回折角の2倍とし、CuKαの波長λとから次の数式1のBraggの式によって<002>面間隔を求める。
To correct the curve, 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 λ of CuKα.
さらに、ピーク高さの1/2の高さに引いた角度軸に平行な線が、補正強度曲線と交わる線分の長さ(半値幅β)から、次の数式2からc軸方向の結晶子の大きさLcを求める。
Further, from the length of the line segment (half-value width β) where the line parallel to the angle axis drawn to ½ the peak height intersects the correction intensity curve, The child size Lc is obtained.
また<10>回折に相当するピークのベースラインからの実質強度をプロットし直して<10>補正強度曲線を得る。ピーク高さの1/2の高さに引いた角度軸に平行な線が補正強度曲線と交わる線分の長さ(半値幅β)から、次の数式3によってa軸方向の結晶子の大きさLaを求める。
Also, the actual intensity from the baseline of the peak corresponding to <10> diffraction is re-plotted to obtain a <10> corrected intensity curve. From the length of the line segment (half-value width β) where the line parallel to the angle axis drawn to ½ of the peak height intersects the correction intensity curve, the size of the crystallite in the a-axis direction is calculated by the following Equation 3. Find La.
(2)XPS表面分析
ESCAまたはXPSと略称されているX線光電子分光法の測定に用いた装置はアルバック・ファイ5801MCを用いる。
試料をサンプルホルダー上にMo板で固定し、予備排気室にて十分に排気後、測定室のチャンバーに投入した。線源にはモノクロ化AlKα線を用い、出力は14kV、12mA、装置内真空度は10-8torrとする。
全元素スキャンを行い表面元素の構成を調べ、検出された元素ならびに予想される元素についてナロースキャンを実施し、存在比率を評価する。
全表面炭素原子数に対する表面結合酸素原子数の比を百分率(%)で算出する。 (2) XPS surface analysis 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 AlKα 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 (%).
ESCAまたはXPSと略称されているX線光電子分光法の測定に用いた装置はアルバック・ファイ5801MCを用いる。
試料をサンプルホルダー上にMo板で固定し、予備排気室にて十分に排気後、測定室のチャンバーに投入した。線源にはモノクロ化AlKα線を用い、出力は14kV、12mA、装置内真空度は10-8torrとする。
全元素スキャンを行い表面元素の構成を調べ、検出された元素ならびに予想される元素についてナロースキャンを実施し、存在比率を評価する。
全表面炭素原子数に対する表面結合酸素原子数の比を百分率(%)で算出する。 (2) XPS surface analysis 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 AlKα 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 (%).
(3)ICP発光分析法
試料中のTi(チタン)含有量の分析は次のように行う。
測定装置はアメテック社製ICP発光分析装置SPECTROBLUE用い、測定液の調製方法は以下の通りに行う。
試料0.5~1.0gを石英製三角フラスコに精密に秤量し、濃硫酸3.0mlを加えホットプレート上で加熱する。300℃まで昇温しさらに30%過酸化水素水を加え溶液が透明になるまで加熱を続け試料の分解を行う。分解後、不溶分がある場合は濾過を実施し超純水を用いて50mlに定容しこれをICP発光分析による測定検液とする。
試料中のチタン量の定量は以下のように行う。
ICP発光分析装置によりチタンの発光波長334.941nmの発光強度を測定し、検量線より溶液中のチタン濃度を求める。チタン含有量はサンプリング重量、定容体積から以下の式で表される。
サンプル重量あたりのチタン含有量(mg/kg) =処理液中のチタン濃度(mg/l)×50ml/サンプリング重量(g) (3) ICP emission analysis 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. The titanium content is expressed by the following formula from the sampling weight and the constant volume.
Titanium content per sample weight (mg / kg) = Titanium concentration in processing solution (mg / l) × 50 ml / sampling weight (g)
試料中のTi(チタン)含有量の分析は次のように行う。
測定装置はアメテック社製ICP発光分析装置SPECTROBLUE用い、測定液の調製方法は以下の通りに行う。
試料0.5~1.0gを石英製三角フラスコに精密に秤量し、濃硫酸3.0mlを加えホットプレート上で加熱する。300℃まで昇温しさらに30%過酸化水素水を加え溶液が透明になるまで加熱を続け試料の分解を行う。分解後、不溶分がある場合は濾過を実施し超純水を用いて50mlに定容しこれをICP発光分析による測定検液とする。
試料中のチタン量の定量は以下のように行う。
ICP発光分析装置によりチタンの発光波長334.941nmの発光強度を測定し、検量線より溶液中のチタン濃度を求める。チタン含有量はサンプリング重量、定容体積から以下の式で表される。
サンプル重量あたりのチタン含有量(mg/kg) =処理液中のチタン濃度(mg/l)×50ml/サンプリング重量(g) (3) ICP emission analysis 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. The titanium content is expressed by the following formula from the sampling weight and the constant volume.
Titanium content per sample weight (mg / kg) = Titanium concentration in processing solution (mg / l) × 50 ml / sampling weight (g)
ここで、電子顕微鏡による10μm2あたりの細孔数の評価は以下のように行う。
得られた炭素質材料を透過型電子顕微鏡にて観察して、4万倍の顕微鏡写真を得る。前記写真を4倍に拡大コピーし、写真の隅同士を対角線で結び対角線の交点を写真中心に設定し、電子顕微鏡のスケールマーカーを基に写真中央から10μm2をトリミングする。トリミングされた写真中に含まれる幅または高さまたは深さが0.1~2.0μmの範囲に含まれる孔をカウントする。この操作を写真10枚で行い、写真10枚より10μm2の細孔数の平均値を算出する。 Here, evaluation of the number of pores per 10 μm 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 μm 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 μm 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 μm 2 is calculated from 10 photos.
得られた炭素質材料を透過型電子顕微鏡にて観察して、4万倍の顕微鏡写真を得る。前記写真を4倍に拡大コピーし、写真の隅同士を対角線で結び対角線の交点を写真中心に設定し、電子顕微鏡のスケールマーカーを基に写真中央から10μm2をトリミングする。トリミングされた写真中に含まれる幅または高さまたは深さが0.1~2.0μmの範囲に含まれる孔をカウントする。この操作を写真10枚で行い、写真10枚より10μm2の細孔数の平均値を算出する。 Here, evaluation of the number of pores per 10 μm 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 μm 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 μm 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 μm 2 is calculated from 10 photos.
(4)電極特性
特許文献2を参考に上下方向(通液方向)に1cm、幅方向に10cmの電極面積10cm2を有する小型のセルを作り、定電流密度で充放電を繰り返し、電極性能のテストを行う。電解液は、バナジウム系電解液を用いる。バナジウム系電解液では、特許文献2を参考に正極電解液と負極電解液に2.0mol/lオキシ硫酸バナジウム、3mol/l硫酸水溶液を混合したものを用いる。電解液量はセル、配管に対して大過剰とする。液流量は毎分6.2mlとし、30℃で測定を行う。 (4) Electrode characteristics Referring toPatent 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. 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.
特許文献2を参考に上下方向(通液方向)に1cm、幅方向に10cmの電極面積10cm2を有する小型のセルを作り、定電流密度で充放電を繰り返し、電極性能のテストを行う。電解液は、バナジウム系電解液を用いる。バナジウム系電解液では、特許文献2を参考に正極電解液と負極電解液に2.0mol/lオキシ硫酸バナジウム、3mol/l硫酸水溶液を混合したものを用いる。電解液量はセル、配管に対して大過剰とする。液流量は毎分6.2mlとし、30℃で測定を行う。 (4) Electrode characteristics Referring to
(a)電流効率:ηI
充電に始まり、放電で終わる1サイクルのテストにおいて、電流密度を電極幾何面積当たり100mA/cm2(1000mA)として、1.5Vまでの充電に要した電気量をQ1クーロン、1.0Vまでの定電圧放電で取り出した電気量をそれぞれQ2とし、次の数式4から電流効率ηIを求める。 (A) Current efficiency: η I
In a one-cycle test starting with charging and ending with discharging, the current density is 100 mA / cm 2 (1000 mA) per electrode geometric area, and the amount of electricity required for charging up to 1.5 V is Q 1 coulomb and up to 1.0 V. the quantity of electricity taken out at a constant voltage discharge and Q 2 respectively, determine the current efficiency eta I from the following equation 4.
充電に始まり、放電で終わる1サイクルのテストにおいて、電流密度を電極幾何面積当たり100mA/cm2(1000mA)として、1.5Vまでの充電に要した電気量をQ1クーロン、1.0Vまでの定電圧放電で取り出した電気量をそれぞれQ2とし、次の数式4から電流効率ηIを求める。 (A) Current efficiency: η I
In a one-cycle test starting with charging and ending with discharging, the current density is 100 mA / cm 2 (1000 mA) per electrode geometric area, and the amount of electricity required for charging up to 1.5 V is Q 1 coulomb and up to 1.0 V. the quantity of electricity taken out at a constant voltage discharge and Q 2 respectively, determine the current efficiency eta I from the following equation 4.
(b)セル抵抗:R
負極液中のバナジウム系電解液ではV3+をV2+に、マンガン系電解液ではTi4+をTi3+に完全に還元するのに必要な理論電気量Qthに対して、放電により取り出した電気量の比を充電率とし、次の数式5にて充電率を求める。 (B) Cell resistance: R
To V 2+ to V 3+ are vanadium electrolytic solution in negative electrode solution, the theoretical quantity of electricity Q th required to completely reduce the Ti 4+ to Ti 3+ in manganese electrolyte, the quantity of electricity taken out by the discharge The charging rate is obtained by the following equation (5).
負極液中のバナジウム系電解液ではV3+をV2+に、マンガン系電解液ではTi4+をTi3+に完全に還元するのに必要な理論電気量Qthに対して、放電により取り出した電気量の比を充電率とし、次の数式5にて充電率を求める。 (B) Cell resistance: R
To V 2+ to V 3+ are vanadium electrolytic solution in negative electrode solution, the theoretical quantity of electricity Q th required to completely reduce the Ti 4+ to Ti 3+ in manganese electrolyte, the quantity of electricity taken out by the discharge The charging rate is obtained by the following equation (5).
充電率が50%のときの電気量に対応する充電電圧VC50、放電電圧VD50を電気量-電圧曲線からそれぞれ求め、次の数式6より電極幾何面積に対するセル抵抗R(Ω・cm2)を求める。
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 (Ω · cm 2 ) with respect to the electrode geometric area is obtained from the following equation 6. Ask for.
(c)電圧効率:ηV
上記の方法で求めたセル抵抗(R)を用いて次の数式7の簡便法により電圧効率ηVを求める。ここで、Iは定電流充放電における電流値0.4Aである。 (C) Voltage efficiency: η V
Using the cell resistance (R) obtained by the above method, the voltage efficiency η V is obtained by the simple method of the following formula 7. Here, I is a current value of 0.4 A in constant current charge / discharge.
上記の方法で求めたセル抵抗(R)を用いて次の数式7の簡便法により電圧効率ηVを求める。ここで、Iは定電流充放電における電流値0.4Aである。 (C) Voltage efficiency: η V
Using the cell resistance (R) obtained by the above method, the voltage efficiency η V is obtained by the simple method of the following formula 7. Here, I is a current value of 0.4 A in constant current charge / discharge.
(d)エネルギー効率:ηE
前述の電流効率ηIと電圧効率ηVを用いて、次の数式8によりエネルギー効率ηEを求める。 (D) Energy efficiency: η E
Using the above-described current efficiency η I and voltage efficiency η V , energy efficiency η E is obtained by the followingformula 8.
前述の電流効率ηIと電圧効率ηVを用いて、次の数式8によりエネルギー効率ηEを求める。 (D) Energy efficiency: η E
Using the above-described current efficiency η I and voltage efficiency η V , energy efficiency η E is obtained by the following
電流効率、電圧効率が高くなる程、エネルギー効率は高くなり、従って充放電におけるエネルギーロスが小さく、優れた電極であると判断される。
The higher the current efficiency and voltage efficiency, the higher the energy efficiency. Therefore, the energy loss during charging and discharging is small, and it is judged that the electrode is an excellent electrode.
以上の実施形態では、本発明の炭素質材料を炭素電極材に用いた場合の実施形態について説明した。本発明の炭素電極材は、炭素電極材に限定されず、例えば、電磁波シールドにも用いることが可能である。また、本発明の炭素質材料を用いた電池など、本発明の炭素質材料を用いた製品も本発明の範疇に含まれる。
In the above embodiment, the embodiment in which the carbonaceous material of the present invention is used for the carbon electrode material has been described. 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. In addition, 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.
次に、本発明を実施例を用いてさらに詳しく説明するが、本発明は以下の実施例に限定されない。
(実施例1)
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。チタンテトライソプロポキシドをイソプロピルアルコールで2%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Aを得た。 EXAMPLES Next, although this invention is demonstrated in more detail using an Example, this invention is not limited to a following example.
Example 1
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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%. Next, after drying at 120 ° C. and adjusting the thickness to 0.9 ± 0.1 mm at a pressure of 45 kgf / cm 2 at 210 ± 10 ° 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 | maintained at this temperature for 1 hour, carbonized, cooled, and obtained the carbonaceous fiber nonwoven fabric A.
(実施例1)
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。チタンテトライソプロポキシドをイソプロピルアルコールで2%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Aを得た。 EXAMPLES Next, although this invention is demonstrated in more detail using an Example, this invention is not limited to a following example.
Example 1
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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%. Next, after drying at 120 ° C. and adjusting the thickness to 0.9 ± 0.1 mm at a pressure of 45 kgf / cm 2 at 210 ± 10 ° 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 | maintained at this temperature for 1 hour, carbonized, cooled, and obtained the carbonaceous fiber nonwoven fabric A.
得られた炭素質繊維不織布Aを窒素ガス中で5℃/分の昇温速度で1500±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Bを得た。
得られた炭素質繊維不織布Bの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布B(炭素質材料)を単層で評価した。 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 μm 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.
得られた炭素質繊維不織布Bの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布B(炭素質材料)を単層で評価した。 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 μm 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.
(実施例2)
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。チタンテトライソプロポキシドをイソプロピルアルコールで1%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Cを得た。
得られた炭素質繊維不織布Cを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Dを得た。
得られた炭素質繊維不織布Dの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布D(炭素質材料)を単層で評価した。 (Example 2)
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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%. Next, after drying at 120 ° C. and adjusting the thickness to 0.9 ± 0.1 mm at a pressure of 45 kgf / cm 2 at 210 ± 10 ° 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 | maintained at this temperature for 1 hour, carbonized, and cooled, and the carbonaceous fiber nonwoven fabric C was obtained.
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 μm 2 by SEM, ICP emission analysis result, and electrode performance of the obtained carbon fiber nonwoven fabric D. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric D (carbonaceous material) was evaluated as a single layer.
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。チタンテトライソプロポキシドをイソプロピルアルコールで1%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Cを得た。
得られた炭素質繊維不織布Cを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Dを得た。
得られた炭素質繊維不織布Dの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布D(炭素質材料)を単層で評価した。 (Example 2)
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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%. Next, after drying at 120 ° C. and adjusting the thickness to 0.9 ± 0.1 mm at a pressure of 45 kgf / cm 2 at 210 ± 10 ° 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 | maintained at this temperature for 1 hour, carbonized, and cooled, and the carbonaceous fiber nonwoven fabric C was obtained.
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 μm 2 by SEM, ICP emission analysis result, and electrode performance of the obtained carbon fiber nonwoven fabric D. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric D (carbonaceous material) was evaluated as a single layer.
(実施例3)
実施例1で得られた炭素質繊維不織布Aを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Eを得た。
得られた炭素質繊維不織布Eの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布E(炭素質材料)を単層で評価した。 (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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric E. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric E (carbonaceous material) was evaluated as a single layer.
実施例1で得られた炭素質繊維不織布Aを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Eを得た。
得られた炭素質繊維不織布Eの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布E(炭素質材料)を単層で評価した。 (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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric E. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric E (carbonaceous material) was evaluated as a single layer.
(実施例4)
実施例2で得られた炭素質繊維不織布Cを窒素ガス中で5℃/分の昇温速度で2200±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Fを得た。
得られた炭素質繊維不織布Fの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布F(炭素質材料)を単層で評価した。 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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbon fiber nonwoven fabric F. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric F (carbonaceous material) was evaluated as a single layer.
実施例2で得られた炭素質繊維不織布Cを窒素ガス中で5℃/分の昇温速度で2200±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Fを得た。
得られた炭素質繊維不織布Fの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布F(炭素質材料)を単層で評価した。 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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbon fiber nonwoven fabric F. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric F (carbonaceous material) was evaluated as a single layer.
(実施例5)
実施例1で得られた炭素質繊維不織布Aを窒素ガス中で5℃/分の昇温速度で2200±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Gを得た。
得られた炭素質繊維不織布Gの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布G(炭素質材料)を単層で評価した。 (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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbon fiber nonwoven fabric G. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric G (carbonaceous material) was evaluated as a single layer.
実施例1で得られた炭素質繊維不織布Aを窒素ガス中で5℃/分の昇温速度で2200±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Gを得た。
得られた炭素質繊維不織布Gの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布G(炭素質材料)を単層で評価した。 (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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbon fiber nonwoven fabric G. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric G (carbonaceous material) was evaluated as a single layer.
(実施例6)
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。チタンラクテートアンモニウム塩をイソプロピルアルコールおよび水で2.1%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Hを得た。
得られた炭素質繊維不織布Hを窒素ガス中で5℃/分の昇温速度で1500±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Iを得た。
得られた炭素質繊維不織布Iの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布I(炭素質材料)を単層で評価した。 (Example 6)
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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%. Next, after drying at 120 ° C. and adjusting the thickness to 0.9 ± 0.1 mm at a pressure of 45 kgf / cm 2 at 210 ± 10 ° 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 | maintained at this temperature for 1 hour, carbonized, cooled, and the carbonaceous fiber nonwoven fabric H was obtained.
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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric I. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric I (carbonaceous material) was evaluated as a single layer.
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。チタンラクテートアンモニウム塩をイソプロピルアルコールおよび水で2.1%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Hを得た。
得られた炭素質繊維不織布Hを窒素ガス中で5℃/分の昇温速度で1500±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Iを得た。
得られた炭素質繊維不織布Iの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布I(炭素質材料)を単層で評価した。 (Example 6)
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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%. Next, after drying at 120 ° C. and adjusting the thickness to 0.9 ± 0.1 mm at a pressure of 45 kgf / cm 2 at 210 ± 10 ° 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 | maintained at this temperature for 1 hour, carbonized, cooled, and the carbonaceous fiber nonwoven fabric H was obtained.
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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric I. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric I (carbonaceous material) was evaluated as a single layer.
(実施例7)
実施例6で得られた炭素質繊維不織布Hを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Jを得た。
得られた炭素質繊維不織布Jの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布J(炭素質材料)を単層で評価した。 (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 μm 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.
実施例6で得られた炭素質繊維不織布Hを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Jを得た。
得られた炭素質繊維不織布Jの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布J(炭素質材料)を単層で評価した。 (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 μm 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.
(実施例8)
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。チタンラクテートアンモニウム塩をイソプロピルアルコールおよび水で4.2%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Kを得た。
得られた炭素質繊維不織布Kを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Lを得た。
得られた炭素質繊維不織布Lの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布L(炭素質材料)を単層で評価した。 (Example 8)
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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%. Next, after drying at 120 ° C. and adjusting the thickness to 0.9 ± 0.1 mm at a pressure of 45 kgf / cm 2 at 210 ± 10 ° C., 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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric L. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric L (carbonaceous material) was evaluated as a single layer.
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。チタンラクテートアンモニウム塩をイソプロピルアルコールおよび水で4.2%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Kを得た。
得られた炭素質繊維不織布Kを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Lを得た。
得られた炭素質繊維不織布Lの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布L(炭素質材料)を単層で評価した。 (Example 8)
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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%. Next, after drying at 120 ° C. and adjusting the thickness to 0.9 ± 0.1 mm at a pressure of 45 kgf / cm 2 at 210 ± 10 ° C., 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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric L. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric L (carbonaceous material) was evaluated as a single layer.
(実施例9)
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。チタンラクテートアンモニウム塩をイソプロピルアルコールおよび水で50.0%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Mを得た。
得られた炭素質繊維不織布Mを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Nを得た。
得られた炭素質繊維不織布Nに対し、チタンラクテートアンモニウム塩をイソプロピルアルコールおよび水で50.0%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却した。さらに窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Oを得た。
得られた炭素質繊維不織布Oの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布O(炭素質材料)を単層で評価した。 Example 9
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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. and adjusting the thickness to 0.9 ± 0.1 mm at a pressure of 45 kgf / cm 2 at 210 ± 10 ° 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 | maintained at this temperature for 1 hour, carbonized, and cooled, and the carbonaceous fiber nonwoven fabric M was obtained.
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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric O. In the electrode performance evaluation, 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.
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。チタンラクテートアンモニウム塩をイソプロピルアルコールおよび水で50.0%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Mを得た。
得られた炭素質繊維不織布Mを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Nを得た。
得られた炭素質繊維不織布Nに対し、チタンラクテートアンモニウム塩をイソプロピルアルコールおよび水で50.0%に希釈した溶液に該不織布を浸漬し、マングルにて余分な添着溶液を絞りウェットピックアップが100~200%になるように調整した。次に120℃で乾燥し、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却した。さらに窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Oを得た。
得られた炭素質繊維不織布Oの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布O(炭素質材料)を単層で評価した。 Example 9
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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. and adjusting the thickness to 0.9 ± 0.1 mm at a pressure of 45 kgf / cm 2 at 210 ± 10 ° 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 | maintained at this temperature for 1 hour, carbonized, and cooled, and the carbonaceous fiber nonwoven fabric M was obtained.
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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric O. In the electrode performance evaluation, 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.
(実施例10)
実施例6で得られた炭素質繊維不織布Hを窒素ガス中で5℃/分の昇温速度で2200±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Zを得た。
得られた炭素質繊維不織布Zの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布Z(炭素質材料)を単層で評価した (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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric Z. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbon fiber nonwoven fabric Z (carbonaceous material) was evaluated as a single layer.
実施例6で得られた炭素質繊維不織布Hを窒素ガス中で5℃/分の昇温速度で2200±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Zを得た。
得られた炭素質繊維不織布Zの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布Z(炭素質材料)を単層で評価した (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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric Z. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbon fiber nonwoven fabric Z (carbonaceous material) was evaluated as a single layer.
(実施例11)
実施例8で得られた炭素質繊維不織布Kを窒素ガス中で5℃/分の昇温速度で2200±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Pを得た。
得られた炭素質繊維不織布Pの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布P(炭素質材料)を単層で評価した。 (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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric P. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric P (carbonaceous material) was evaluated as a single layer.
実施例8で得られた炭素質繊維不織布Kを窒素ガス中で5℃/分の昇温速度で2200±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Pを得た。
得られた炭素質繊維不織布Pの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布P(炭素質材料)を単層で評価した。 (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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric P. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric P (carbonaceous material) was evaluated as a single layer.
(実施例12~実施例22)
実施例1~実施例12で得られた炭素質繊維不織布をさらに空気中700±50℃で質量収率90~95%になるまで乾式酸化処理を行い、炭素質繊維不織布を得た。
得られた炭素質繊維不織布の面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布(炭素質材料)を単層で評価した。 (Examples 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 μm 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.
実施例1~実施例12で得られた炭素質繊維不織布をさらに空気中700±50℃で質量収率90~95%になるまで乾式酸化処理を行い、炭素質繊維不織布を得た。
得られた炭素質繊維不織布の面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布(炭素質材料)を単層で評価した。 (Examples 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 μm 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.
(比較例1)
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。該不織布を、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Qを得た。
得られた炭素質繊維不織布Qを窒素ガス中で5℃/分の昇温速度で1500±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Rを得た。得られた炭素質繊維不織布Rの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布Rを単層で評価した。 (Comparative Example 1)
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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. Warm, hold at this temperature for 1 hour, carbonize and cool to obtain carbonaceous fiber nonwoven fabric Q.
The obtained carbon fiber non-woven fabric Q was heated to 1500 ± 50 ° C. at a temperature increase rate 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 R. It was. Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric R. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric R was evaluated as a single layer.
平均繊維径16μmのポリアクリロニトリル繊維を空気中200~300℃で耐炎化した。その後、該耐炎化繊維の短繊維(長さ約80mm)を用いてフェルト針SB#40(Foster Needle社)、パンチング密度250本/cm2でフェルト化して目付量300g/m2、厚み3.2mmの不織布を作製した。該不織布を、210±10℃で45kgf/cm2のプレス圧にて厚みを0.9±0.1mmに調整後、窒素ガス中で5℃/分の昇温速度で950±50℃まで昇温し、この温度で1時間保持し炭化を行って冷却し、炭素質繊維不織布Qを得た。
得られた炭素質繊維不織布Qを窒素ガス中で5℃/分の昇温速度で1500±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Rを得た。得られた炭素質繊維不織布Rの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布Rを単層で評価した。 (Comparative Example 1)
A polyacrylonitrile fiber having an average fiber diameter of 16 μm 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. Warm, hold at this temperature for 1 hour, carbonize and cool to obtain carbonaceous fiber nonwoven fabric Q.
The obtained carbon fiber non-woven fabric Q was heated to 1500 ± 50 ° C. at a temperature increase rate 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 R. It was. Table 1 shows the interplanar spacing, crystallite size, number of pores per 10 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric R. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric R was evaluated as a single layer.
(比較例2)
比較例1で得られた炭素質繊維不織布Qを窒素ガス中で5℃/分の昇温速度で1800±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Sを得た。
得られた炭素質繊維不織布Sの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布Sを単層で評価した。 (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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric S. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric S was evaluated as a single layer.
比較例1で得られた炭素質繊維不織布Qを窒素ガス中で5℃/分の昇温速度で1800±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Sを得た。
得られた炭素質繊維不織布Sの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布Sを単層で評価した。 (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 μm 2 by SEM, ICP emission analysis results, and electrode performance of the obtained carbonaceous fiber nonwoven fabric S. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric S was evaluated as a single layer.
(比較例3)
比較例1で得られた炭素質繊維不織布Qを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Tを得た。
得られた炭素質繊維不織布Tの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布Tを単層で評価した。 (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 μm 2 by SEM, ICP emission analysis result, and electrode performance of the obtained carbonaceous fiber nonwoven fabric T. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric T was evaluated as a single layer.
比較例1で得られた炭素質繊維不織布Qを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Tを得た。
得られた炭素質繊維不織布Tの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布Tを単層で評価した。 (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 μm 2 by SEM, ICP emission analysis result, and electrode performance of the obtained carbonaceous fiber nonwoven fabric T. In the electrode performance evaluation, the spacer thickness was set to 0.6 mm, and the carbonaceous fiber nonwoven fabric T was evaluated as a single layer.
(比較例4)
比較例1で得られた炭素質繊維不織布Qを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Uを得た。
得られた炭素質繊維不織布Uの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布Uを単層で評価した。 (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 μm 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.
比較例1で得られた炭素質繊維不織布Qを窒素ガス中で5℃/分の昇温速度で2000±50℃まで昇温し、この温度で1時間保持し黒鉛化を行って炭素質繊維不織布Uを得た。
得られた炭素質繊維不織布Uの面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布Uを単層で評価した。 (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 μm 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.
(比較例5~比較例8)
実施例1~実施例4で得られた炭素質繊維不織布をさらに空気中700±50℃で質量収率90~95%になるまで乾式酸化処理を行い、炭素質繊維不織布を得た。
得られた炭素質繊維不織布の面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布を単層で評価した。 (Comparative Example 5 to Comparative Example 8)
The carbonaceous fiber nonwoven fabrics obtained in Examples 1 to 4 were further subjected to a dry oxidation treatment 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 μm 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 carbonaceous fiber nonwoven fabric was evaluated as a single layer.
実施例1~実施例4で得られた炭素質繊維不織布をさらに空気中700±50℃で質量収率90~95%になるまで乾式酸化処理を行い、炭素質繊維不織布を得た。
得られた炭素質繊維不織布の面間隔、結晶子サイズ、SEMによる10μm2あたりの細孔数、ICP発光分析結果、電極性能を表1に示す。電極性能評価において、スペーサ厚は0.6mmに設定し、炭素質繊維不織布を単層で評価した。 (Comparative Example 5 to Comparative Example 8)
The carbonaceous fiber nonwoven fabrics obtained in Examples 1 to 4 were further subjected to a dry oxidation treatment 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 μm 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 carbonaceous fiber nonwoven fabric was evaluated as a single layer.
本発明のレドックス電池用炭素電極材は、導電性を高める黒鉛粉末や導電助剤といわれるアセチレンブラック、ケッチェンブラック等を未含有でありながら、電極反応活性を高めることにより初期充放電時のセル抵抗を低下させ、電池エネルギー効率を向上させることを可能とするものである。そして、本発明の炭素電極材はフロータイプおよびノンフロータイプのレッドクス電池、またはリチウム、キャパシタ、燃料電池のシステムと複合化されたようなレドックス電池に好適に用いられ、電池性能を向上させることが可能となり、産業界へ多大に寄与できる。
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.
1 集電板
2 スペーサ
3 イオン交換膜
4a,4b 通液路
5 電極材
6 正極電解液タンク
7 負極電解液タンク
8,9 ポンプ
10 液流入口
11 液流出口
12,13 外部液路
DESCRIPTION OFSYMBOLS 1 Current collector plate 2 Spacer 3 Ion exchange membrane 4a, 4b Liquid passage 5 Electrode material 6 Positive electrode electrolyte tank 7 Negative electrode electrolyte tank 8, 9 Pump 10 Liquid inlet 11 Liquid outlet 12, 13 External liquid path
2 スペーサ
3 イオン交換膜
4a,4b 通液路
5 電極材
6 正極電解液タンク
7 負極電解液タンク
8,9 ポンプ
10 液流入口
11 液流出口
12,13 外部液路
DESCRIPTION OF
Claims (5)
- X線広角解析より求めた<002>面間隔が3.40~3.60Åであり、c軸方向の結晶子の大きさが15~150Åであり、a軸方向の結晶子の大きさが25~75Åである結晶構造を有し、
励起波長532nmのレーザーラマン分光測定により求めたスペクトルにおいて、1360cm-1付近のピーク強度(ID)と1580cm-1付近のピーク強度(IG)との強度比(ID/IG)が0.2~2.0であり、
ICP発光分析法より得られるTi含有量が0.1~30重量%である、ことを特徴とする炭素質材料。 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, and the crystallite size in the a-axis direction is 25 Having a crystal structure of ~ 75Å,
In the spectrum obtained by laser Raman spectroscopy of the excitation wavelength 532 nm, 1360 cm -1 vicinity of the peak intensity (ID) and 1580 cm -1 vicinity of the peak intensity (IG) and the intensity ratio of (ID / IG) is 0.2 to 2 0.0,
A carbonaceous material characterized in that the Ti content obtained by ICP emission analysis is 0.1 to 30% by weight. - 3000~7000倍の走査型電子顕微鏡観察画像において、幅または高さまたは深さが0.1~2μmの範囲の細孔が10μm2あたりに5個以上存在する、ことを特徴とする請求項1に記載の炭素質材料。 2. A scanning electron microscope observation image of 3000 to 7000 times, wherein there are 5 or more pores in a range of 0.1 to 2 μm in width, height, or depth per 10 μm 2. The carbonaceous material described in 1.
- 繊維構造体からなる請求項1または2に記載の炭素質材料。 The carbonaceous material according to claim 1 or 2, comprising a fiber structure.
- 請求項1~3のいずれか1項に記載の炭素質材料を用いた電極材。 An electrode material using the carbonaceous material according to any one of claims 1 to 3.
- 請求項1~4のいずれか1項に記載の炭素質材料を電極材に用いた電池。
A battery using the carbonaceous material according to any one of claims 1 to 4 as an electrode material.
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