WO2023199935A1 - Méthode de fabrication de matériau carboné contenant des cristaux de graphite - Google Patents

Méthode de fabrication de matériau carboné contenant des cristaux de graphite Download PDF

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Publication number
WO2023199935A1
WO2023199935A1 PCT/JP2023/014834 JP2023014834W WO2023199935A1 WO 2023199935 A1 WO2023199935 A1 WO 2023199935A1 JP 2023014834 W JP2023014834 W JP 2023014834W WO 2023199935 A1 WO2023199935 A1 WO 2023199935A1
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iron
ions
carbon material
raw material
carbon
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PCT/JP2023/014834
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English (en)
Japanese (ja)
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棟▲ヨン▼ 柳
実 矢田
佳英 渡邉
正人 山口
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日本製紙株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation

Definitions

  • the present disclosure relates to the production of a graphite crystal-containing carbon material, and more specifically, to a method of producing a graphite crystal-containing carbon material using a carbon raw material containing a cellulose polysaccharide, and materials such as precursors related thereto.
  • Graphite is a carbon material with excellent properties such as lubricity, conductivity, heat resistance, and chemical resistance. Because of these excellent characteristics, graphite is used in a wide range of applications, including battery components, circuit paints, brake pads, oil seals, fireproof materials, and heat dissipation materials.
  • Biomass is a term originally used to express the mass of biological resources (bio), but now it is a comprehensive concept that also broadly refers to resources derived from living organisms (excluding fossil resources). It is also used as a term to represent.
  • the temperature at which biomass can be fired using devices such as rotary kilns and continuous firing furnaces that are commonly used for firing biomass is generally 1400° C. or lower, and graphitization usually does not proceed sufficiently at this temperature. It is also said that in order to obtain a carbon material containing graphite crystals, a temperature of 2500° C. or higher, especially 2800° C. or higher is required (for example, Patent Document 1).
  • graphite crystal-containing carbon material As mentioned above, in order to obtain a carbon material containing graphite crystals (hereinafter also referred to as “graphite crystal-containing carbon material” in the present disclosure), firing at a high temperature of 2500°C or higher is generally required. This requires a burden on equipment capable of such high-temperature firing. Furthermore, firing at high temperatures consumes a large amount of energy, and from the viewpoint of reducing energy consumption, it is desirable to suppress the firing temperature as much as possible. Therefore, in order to achieve sufficient graphitization by firing at a low temperature, it is also possible to use a metal catalyst. However, for example, it is difficult to uniformly disperse the catalyst by simply mixing a metal catalyst with woody biomass containing cellulose polysaccharides, and therefore it is difficult to uniformly obtain a fired product. It wasn't easy.
  • one of the issues to be solved is to obtain a carbon material containing graphite crystals by using biomass as a raw material and subjecting it to uniform firing treatment under low temperature conditions.
  • the invention presented in this disclosure can be understood as several aspects from a multifaceted perspective, and includes aspects that can be implemented as means for solving the problems, for example, as described below.
  • the invention presented in this disclosure is also referred to as the "present invention.”
  • One or more metal ions selected from the group consisting of iron ions, nickel ions, chromium ions, and cobalt ions are added to the first carbon raw material containing a cellulosic polysaccharide having an anionic functional group.
  • the first carbon raw material is one or more selected from the group consisting of papermaking pulp, regenerated cellulose fiber, and chemically modified products of papermaking pulp or regenerated cellulose fiber. The manufacturing method described in ].
  • a graphite crystal-containing carbon material can be obtained by using biomass as a raw material and performing uniform firing treatment under low temperature conditions.
  • a graphite crystal-containing carbon material is obtained even by firing at a low temperature condition below 2500° C. using a cellulose polysaccharide complex as a raw material. be able to.
  • one embodiment of the present invention refers to any one embodiment out of multiple embodiments included in the scope of the present invention, and refers to any one embodiment of the multiple embodiments included in the scope of the present invention. This does not negate or limit the existence of such embodiments, and therefore the present invention is not limited to that one embodiment.
  • the term “embodiment” may include one or more embodiments unless otherwise specified.
  • AA to BB indicates “more than or equal to AA and less than or equal to BB” (herein, “AA” and “BB” indicate arbitrary numerical values). ). Furthermore, unless otherwise specified, the units for both the lower limit and the upper limit are the same as the unit immediately after the latter (ie, "BB” here). Moreover, the expression “X and/or Y” means both X and Y, or either one of them.
  • a method for manufacturing a graphite crystal-containing carbon material is provided.
  • a carbon raw material containing a cellulosic polysaccharide having an anionic functional group is referred to as a first carbon raw material.
  • the first carbon raw material supported with metal ions capable of catalyzing the graphitization of carbon is referred to as a second carbon raw material.
  • the second carbon raw material may be prepared from the first carbon raw material, or may be obtained and prepared in the form of a second carbon raw material.
  • the prepared second carbon raw material is subjected to heat treatment under predetermined temperature conditions in an inert gas atmosphere to graphitize it, thereby obtaining a graphite crystal-containing carbon material.
  • the second carbon raw material can also be called a precursor of a graphite crystal-containing carbon material.
  • Graphite crystal is an elemental mineral consisting of carbon, and the crystal form is a hexagonal system or hexagonal plate crystal.
  • the structure of graphite crystal is a tortoise-shell-shaped layered material, in which carbon atoms are connected by strong covalent bonds (sp2-like) in the plane of each layer, but weak van der Waals forces exist between the layers (interplane). are combined.
  • the electronic state is semimetallic. Applications include bearings, sliding parts such as carbon brushes, heat diffusion sheets, internal parts of high-temperature furnaces, crucibles, electrodes for electric furnaces (artificial graphite electrodes), electrodes for electrolysis, insoluble anodes, and batteries. It is used in conductive materials, negative electrode materials for secondary batteries, and friction materials such as brake pads.
  • General artificial graphite is produced by crushing, separating, and blending coal coke, which is the main raw material, and kneading it with pitch coke or coal tar pitch, which acts as an adhesive.Then, it is fired at about 1000°C and soaked in coal tar pitch. repeat. Thereafter, it is heat-treated at about 2700°C to 3000°C to graphitize it. In terms of energy consumption, such conventional methods require high-temperature firing during production, resulting in high production costs.
  • cellulose polysaccharide refers to a fibrous polymer containing a structure in which D-glucopyranose is linked through ⁇ 1,4 bonds, and includes cellulose and modified products thereof. Modified cellulose products are included in cellulose polysaccharides as long as they maintain a structure in which D-glucopyranose is linked by ⁇ 1,4 bonds in the molecule.
  • Cellulose is usually linear, but "cellulose polysaccharides” may have side chains or branches.
  • Examples of carbon materials containing cellulose polysaccharides include regenerated cellulose fibers such as cotton, paper pulp, and rayon, as well as chemically modified products thereof. Materials containing cellulose polysaccharides may be used alone or in combination of two or more. Cotton, paper pulp, regenerated cellulose fibers, etc. may contain anionic functional groups in advance due to trace amounts of carboxyl groups being introduced during purification processes such as bleaching, or due to the coexistence of hemicellulose.
  • Cellulose polysaccharides having anionic functional groups may be used as they are, or may be chemically modified to have anionic functional groups added to them.
  • chemical modification method a known method for imparting an anionic functional group can be used.
  • Chemical modification methods include, for example, carboxyl methylation, TEMPO oxidation, phosphoryl esterification, and sulfonation, and general oxidation methods such as ozone treatment, hydrogen peroxide treatment, and Fenton reaction are There are many things that can be done.
  • a cellulosic polysaccharide having an anionic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group can be prepared.
  • the cellulose polysaccharide having an anionic functional group may have other substituents, characteristic groups, or functional groups in addition to the anionic functional group.
  • An example of a preferred embodiment of the chemical modification technique may be TEMPO oxidation.
  • Cellulosic polysaccharides are treated in the presence of a catalytic amount of 2,2,6,6-tetramethyl-1-piperidine-N-oxyradical (TEMPO) and sodium hypochlorite, an inexpensive oxidizing agent.
  • TEMPO 2,2,6,6-tetramethyl-1-piperidine-N-oxyradical
  • sodium hypochlorite an inexpensive oxidizing agent.
  • carboxyl groups can be efficiently introduced onto the surface of the cellulosic polysaccharide.
  • a cellulose polysaccharide into which a carboxyl group has been introduced can be modified freely using the carboxyl group as a starting point.
  • Carboxyl groups are suitable for supporting metal ions through ion exchange treatment, which will be explained later, and from this point of view, a material containing a cellulose-based cellulose polysaccharide chemically modified by TEMPO oxidation may be a suitable material.
  • a single type of cellulose polysaccharide or a material containing cellulose polysaccharide may be used, or a plurality of types may be used in combination.
  • Materials containing cellulose polysaccharides include paper pulp, regenerated cellulose fibers, and Chemical modifications thereof may be suitable.
  • carbon material precursors other than cellulose polysaccharides may be used in combination.
  • Precursors that can be used in combination include biomass materials and non-biomass materials.
  • biomass-based materials include polysaccharides such as hemicellulose, chitin, and chitosan, and lignin.
  • non-biomass materials include synthetic polymers such as phenol resin and polyacrylonitrile.
  • the amount of the biomass material to be blended is not particularly limited, but may be preferably 200 parts by weight or less, more preferably 100 parts by weight or less, based on 100 parts by weight of the carbon material containing cellulose polysaccharide. From the viewpoint of sustainability, the amount of the non-biomass material used in combination may be preferably 50 parts by weight or less and 25 parts by weight or less based on 100 parts by weight of the carbon material containing cellulose-based polysaccharides. .
  • examples of the anionic functional group include a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
  • the cellulose polysaccharide may have one or more anionic functional groups.
  • the anionic functional group includes, for example, a carboxy group.
  • the content of anionic functional groups in the first carbon raw material may preferably be 0.01 to 2.00 mmol/g.
  • the anionic functional group is contained in the first carbon raw material in such a range, metal ions are sufficiently supported, which contributes to smooth graphitization.
  • the lower limit of the content of anionic functional groups in the first carbon raw material is as follows. More preferably, it is 0.02 mmol/g or more, still more preferably 0.03 mmol/g or more, and still more preferably 0.05 gmmol/g or more.
  • the upper limit of the content of anionic functional groups in the first carbon raw material is not particularly limited and may be arbitrary from the viewpoint of sufficiently supporting metal ions and smoothly proceeding with graphitization, but 2. Even if it is contained in an amount of 00 mmol/g or more, the effect becomes less improved as the amount increases.
  • the content of anionic functional groups may be set to 1.90, 1.80, or 1.70 mmol/g or less, for example. Good too.
  • a predetermined transition metal is supported on a cellulosic polysaccharide and then heat-treated, whereby the transition metal acts as a catalyst and produces a carbon material containing graphite crystals.
  • transition metals having this type of catalytic action include iron, nickel, chromium, and cobalt, with iron being preferred from the viewpoint of low toxicity.
  • iron ion sources include iron(II) chloride, iron(III) chloride, iron(II) sulfate, iron(III) sulfate, iron(II) phosphate, iron(III) phosphate, and iron nitrate. (II), iron (III) nitrate, etc., hydrates thereof, and organic complex iron salts such as Prussian blue. From the viewpoint of ease of solution preparation when carrying iron ions on the first carbon material containing cellulosic polysaccharide, iron(II) chloride, iron(III) chloride, iron(II) sulfate is preferably used. , iron (III) sulfate, iron (II) nitrate, iron (III) nitrate and their hydrates, and soluble Prussian blue that partially contains potassium ions, ammonium ions, etc., and the like.
  • the number of metal ions supported on the carbon raw material containing cellulosic polysaccharide may be one or two or more.
  • a carbon raw material in which metal ions are supported on a carbon raw material containing a cellulosic polysaccharide i.e., a second carbon raw material (or also referred to as a precursor of a graphite crystal-containing carbon material)
  • an inert gas atmosphere is prepared. Heat treatment is performed below.
  • the heat treatment is preferably performed under an inert gas atmosphere.
  • inert gases include helium, argon, nitrogen, and the like. Among them, nitrogen is more preferable from the viewpoint of industrial cost.
  • the heat treatment device is not particularly limited as long as it can heat to a predetermined temperature, for example 600 to 1400° C., but preferably a gas displacement furnace is used.
  • the gas displacement furnace is preferably a batch type or continuous gas displacement furnace, and more preferably a continuous gas displacement furnace.
  • the heat treatment temperature may preferably be 600°C or higher and lower than 1400°C.
  • the lower limit of the heat treatment temperature may be more preferably 700°C or higher, and still more preferably 800°C or higher.
  • the upper limit of the heat treatment temperature does not need to be particularly limited, but from the viewpoint of general heat treatment equipment constraints and energy saving, it is preferably less than 1400°C, more preferably 1200°C or less, More preferably, the temperature may be 1100°C or below 1000°C.
  • metal ions acting as catalysts can be uniformly dispersed, so that graphitization can be performed under low temperature conditions as a heat treatment for graphitization as described above.
  • the graphite crystal-containing carbon material obtained can be homogeneous.
  • the heat treatment time is preferably 0.1 to 4 hours, more preferably 0.5 to 3 hours.
  • a graphite crystal-containing carbon material can be obtained in the form of a black carbide.
  • the residual rate (weight ratio) of the black carbide after heat treatment is preferably 1 to 40%, more preferably 10 to 30%, based on the dry weight of the raw material before heat treatment, that is, the dry weight of the second carbon raw material. It's possible.
  • X-ray diffraction (hereinafter referred to as XRD), Raman spectrum, etc. can be used.
  • XRD X-ray diffraction
  • the interlayer distance d002 is commonly used as an index of graphitization.
  • the interlayer distance (d002) is preferably in the range of 3.3 ⁇ or more and 4.0 ⁇ or less, and more preferably in the range of 3.3937 ⁇ or more and 3.4635 ⁇ or less.
  • the thickness (Lc) of the mesh plane group is preferably in the range of 10 nm or more and 200 nm or less, and more preferably in the range of 30 nm or more and 187 nm or less.
  • TEMPO oxidized pulp (anionic functional group content: 1.6 mmol/g, cation is sodium ion) was used as a raw material containing cellulosic polysaccharide (first carbon raw material). 100 ml of 0.1 mol/L hydrochloric acid was added to 3 g of dry weight of TEMPO oxidized pulp, held for 30 minutes, filtered, and thoroughly washed with ion-exchanged water to exchange cations with protons.
  • iron (II) chloride tetrahydrate as an iron ion source, add 100 ml of its 2% aqueous solution, hold for 30 minutes, filter and wash thoroughly with ion-exchanged water to remove iron ions from the cations. It was replaced with (II).
  • the obtained pulp was light brown in color, and some of the iron ions (II) were oxidized to iron ions (III).
  • the obtained pulp was used as a second carbon raw material carrying iron ions.
  • the obtained pulp (i.e., the second carbon raw material) was dried at 105°C for 1 hour, and then heat-treated at 900°C for 2 hours in a nitrogen atmosphere using a batch gas replacement furnace to obtain black carbide. Ta.
  • the residual ratio of black carbide to the dry weight of the pulp was 24%.
  • Example 4 Rayon nonwoven fabric (fiber diameter 3.3 dtex, anionic functional group content 0.015 mmol/g) was used as the raw material containing cellulosic polysaccharide (first carbon raw material), and iron (II) sulfate was used as the iron ion source.
  • Example 5 A rayon nonwoven fabric (fiber diameter: 3.3 dtex, anionic functional group content: 0.015 mmol/g) with a dry weight of 3 g was added to 100 ml of 5% hydrogen peroxide solution and immersed for 15 minutes at room temperature. After sufficiently squeezing, Fenton reaction was performed by immersing in 100 ml of 2% iron (II) sulfate heptahydrate aqueous solution for 30 minutes, and by thorough washing, an oxidized rayon nonwoven fabric was obtained (anionic functional group amount 0.12 mmol/g).
  • anionic functional group amount 0.12 mmol/g
  • Example 2 Thereafter, heat treatment was performed in the same manner as in Example 1 to obtain a black carbide.
  • the residual rate of black carbide based on the dry weight of the rayon nonwoven fabric was 18%.
  • TEMPO oxidized pulp (anionic functional group content: 1.6 mmol/g, cation is sodium ion) was used as a raw material containing cellulosic polysaccharides. 100 ml of 0.1 mol/L hydrochloric acid was added to 3 g dry weight of TEMPO oxidized pulp, held for 30 minutes, filtered, and thoroughly washed with ion-exchanged water to exchange cations with protons.
  • TEMPO oxidized pulp (anionic functional group content: 1.6 mmol/g, cation is sodium ion) was used as a raw material containing cellulosic polysaccharides. After adding 100 ml of 0.1 mol/L hydrochloric acid to 3 g dry weight of TEMPO oxidized pulp and holding for 30 minutes, the mixture was filtered and thoroughly washed with ion-exchanged water to exchange cations with protons.

Abstract

L'un des problèmes abordés par la présente invention est d'obtenir un matériau carboné contenant des cristaux de graphite à l'aide d'une biomasse en tant que matériau et d'effectuer un traitement de cuisson uniforme sur la biomasse dans une condition de basse température.　La présente invention comprend : la préparation d'un second matériau carboné dans lequel un ou plusieurs ions métalliques choisis dans le groupe constitué par un ion fer, un ion nickel, un ion chrome et un ion cobalt sont supportés sur un premier matériau carboné contenant un polysaccharide à base de cellulose qui a un groupe fonctionnel anionique ; et le chauffage du second matériau carboné dans une atmosphère de gaz inerte à une condition de température non inférieure à 600°C mais inférieure à 1400°C.
PCT/JP2023/014834 2022-04-13 2023-04-12 Méthode de fabrication de matériau carboné contenant des cristaux de graphite WO2023199935A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001294757A (ja) * 2000-04-12 2001-10-23 Japan Science & Technology Corp リグニンを原料とするグラファイト
JP2009268960A (ja) * 2008-05-06 2009-11-19 Toyota Industries Corp 触媒前駆体、触媒材料および触媒製造方法
JP2012204302A (ja) * 2011-03-28 2012-10-22 Kyoto Univ 燃料電池用電極触媒の製造方法
JP2013035743A (ja) * 2011-07-12 2013-02-21 Institute Of National Colleges Of Technology Japan 炭素質複合体及びその製造方法
KR20150076492A (ko) * 2013-12-27 2015-07-07 한국과학기술원 다공성 금속산화물의 제조방법 및 이에 따라 제조되는 다공성 금속산화물
JP2016005843A (ja) * 2009-02-27 2016-01-14 ビーエーエスエフ コーポレーション 金属−炭素含有体を調製する方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001294757A (ja) * 2000-04-12 2001-10-23 Japan Science & Technology Corp リグニンを原料とするグラファイト
JP2009268960A (ja) * 2008-05-06 2009-11-19 Toyota Industries Corp 触媒前駆体、触媒材料および触媒製造方法
JP2016005843A (ja) * 2009-02-27 2016-01-14 ビーエーエスエフ コーポレーション 金属−炭素含有体を調製する方法
JP2012204302A (ja) * 2011-03-28 2012-10-22 Kyoto Univ 燃料電池用電極触媒の製造方法
JP2013035743A (ja) * 2011-07-12 2013-02-21 Institute Of National Colleges Of Technology Japan 炭素質複合体及びその製造方法
KR20150076492A (ko) * 2013-12-27 2015-07-07 한국과학기술원 다공성 금속산화물의 제조방법 및 이에 따라 제조되는 다공성 금속산화물

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