WO2016043030A1 - 粒子状多孔質炭素材料、粒子状炭素材料集合体および粒子状多孔質炭素材料の製造方法 - Google Patents
粒子状多孔質炭素材料、粒子状炭素材料集合体および粒子状多孔質炭素材料の製造方法 Download PDFInfo
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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- 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
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- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
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- 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
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Definitions
- the present invention relates to a particulate porous carbon material that can be developed for various uses, a particulate carbon material aggregate containing the particulate porous carbon material, and a method for producing the particulate porous carbon material.
- particulate porous carbon materials include activated carbon having both relatively large macropores and micropores, such as granular activated carbon and activated carbon fiber, and mesoporous carbon produced from carbon nanotubes, mesoporous silica, and zeolite molds. Representative fine carbons are known.
- particulate porous carbon materials make use of the high surface area utilizing pores in addition to the high chemical stability, electrical conductivity, and thermal conductivity of carbon. Have been used as such.
- Patent Document 1 describes a vapor grown carbon fiber (carbon nanotube) having a branched portion.
- Patent Document 2 describes a bundle of carbon nanotubes in which one end portion is connected to each other by a carbon network.
- Carbon nanotubes having only a branched portion as described in Patent Document 1 have been densified due to high pressure due to press molding or the like, resulting in a decrease in material permeability. Moreover, since there are few branch parts and the amount and frequency of chemically bonded carbon networks are small, it is difficult to achieve high levels of electrical conductivity and thermal conductivity. Further, in the bundle-like carbon nanotubes described in Patent Document 2, since only one end is connected by a carbon network, it is difficult to maintain mechanical strength such as peeling, and pulverization and classification The carbon network was easily destroyed by receiving power during the process, and it was easy to break apart. In addition, the bundles were easily densified by the compressive force, and the material permeability tended to deteriorate.
- An object of the present invention is to provide a particulate porous carbon material having excellent electrical conductivity, thermal conductivity, pressure resistance, and strength against tension and compression.
- the present invention that solves the above problems is a particulate porous carbon material having a continuous porous structure and satisfying the following AC.
- the particulate porous carbon material of the present invention has high electrical conductivity and thermal conductivity due to the high aspect ratio branches gathering through the connecting parts, and the branches in the continuous porous structure are mutually connected. Strong resistance to deformation such as tension and compression due to the effect of supporting the structure. Therefore, the particulate porous carbon material of the present invention can be applied to various uses such as a use in which electron transfer such as electricity and an electronic material is important and a material that mediates heat exchange such as a heat dissipation material.
- FIG. 1 It is a schematic diagram of the continuous porous structure of the particulate porous carbon material of this invention. 2 is a scanning electron micrograph of a continuous porous structure of the particulate carbon material of the present invention produced in Example 1.
- FIG. 2 is a scanning electron micrograph of a continuous porous structure of the particulate carbon material of the present invention produced in Example 1.
- the particulate porous carbon material of the present invention (hereinafter sometimes simply referred to as “material”) has a continuous porous structure.
- the continuous porous structure is, for example, when a cross-section obtained by cleaving a sample sufficiently cooled in liquid nitrogen with tweezers or a particulate sample is placed on a sample stage as it is and the surface is observed with a scanning electron microscope (SEM) or the like. As illustrated in the schematic diagram of FIG. 1 and the photograph of FIG. 2, it means that a structure in which a branch part (carbon part) and a hole part (void part) are intertwined with each other is observed.
- SEM scanning electron microscope
- the voids are referred to as pores, and the material is considered to have a continuous porous structure.
- the aspect ratio of the branches forming the continuous porous structure is 3 or more.
- the carbon part forms a network structure via the joint, and each “branch” is adjacent to one joint of the carbon part forming the network structure.
- the section to the junction (other junction) or the section from one junction of the carbon part constituting the network structure to the end of the carbon part is assumed.
- the aspect ratio of the branch part is the carbon portion in the section, that is, the minimum value of the diameter of the branch part (hereinafter referred to as “the minimum diameter of the branch part”) is D, and the substantial distance (hereinafter referred to as “the length of the branch part”).
- the aspect ratio is calculated for all the branch portions, and the average value is calculated.
- the upper limit of the aspect ratio of the branch portion is not particularly limited. However, if it is too long, it is difficult to show isotropic mechanical properties, so 20 or less is preferable, and 15 or less is more preferable.
- the length of the branch part and the minimum diameter of the branch part are three-dimensionally reconstructed using CT from a transmission image obtained by photographing a particulate porous carbon material using a transmission electron microscope, an X-ray microscope, or the like. It can be obtained by thinning the image.
- the thinning process can be performed using commercially available software, for example, using Amira manufactured by FEI.
- the length of the branch portion is a substantial distance from the joint portion at one end (the branch point of the thin wire) to the joint portion at the other end in each thin line subjected to the thinning process.
- the substantial distance means the length along the path even when each thin line itself has a bent portion.
- the minimum diameter of the branch part is drawn from the position X on the thin line after the thinning process of the branch part obtained from the three-dimensional image to the surface of the branch part, and the length of the perpendicular is set to the position on the thin line.
- R (X) is expressed as a function of X
- D 2Rmin is obtained using the minimum value Rmin of R (X) between the joint at one end and the joint at the other end of the thin wire.
- a perpendicular line can be drawn in any direction of 360 ° on the plane perpendicular to the fine line, but R (X) is a perpendicular line on the plane in the perpendicular direction at the position X. It is assumed that it is an average value obtained by integrating at 10 ° / step and dividing the obtained integrated value by the number of integrations.
- the particulate porous carbon material of the present invention has a structure in which branch portions are aggregated with an aggregation number (N) of 3 or more via a junction.
- the number of branches (N) can be counted from a three-dimensional image of the particulate porous carbon material subjected to the above-described thinning process.
- the branch portion has an effect of dispersing the force received by the particulate porous carbon material from the outside, it is easy to maintain a continuous porous structure during pulverization and classification. Furthermore, since it is easy to maintain the space surrounded by the branches and easily hold other elements and molecules, the reactivity at the interface between the space and the carbon material can be improved.
- the number of branches (N) is preferably 10 or more, and more preferably 20 or more.
- the upper limit of the number of branches is not particularly limited, and can be appropriately adjusted according to the application by changing the structural period and the degree of pulverization described later. The smaller the number of branches, the more advantageous the material permeation into the continuous porous structure. In the case of an application involving material permeation, the number of branches is preferably 10,000 or less.
- the ratio (N / n) of the number of branches (N) to the number of joints (n) is 1.2 or more.
- the number n of joints can also be counted from the three-dimensional image of the particulate porous carbon material subjected to the above-described thinning process.
- N / n is 1.2 or more, it is possible to increase the efficiency of propagating the electrons and heat accompanying the adsorption, desorption, and chemical reaction generated on the surface of the branch part to others through the branch part.
- N / n is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 3.0 or more.
- the structural period of the continuous porous structure is preferably 0.002 ⁇ m to 10 ⁇ m.
- the structural period of the continuous porous structure is calculated by the following formula from the scattering angle 2 ⁇ at the position where the X-ray is incident on the sample and the scattering intensity has a peak value. If the structure period exceeds 1 ⁇ m and no X-ray scattering peak can be observed, the X-ray CT method is used to three-dimensionally image the continuous porous structure of the particulate porous carbon material and perform Fourier transform to obtain a spectrum. Similarly, the structure period is calculated. That is, the spectrum referred to in the present invention is data indicating the relationship between the one-dimensional scattering angle and the scattering intensity obtained by the Fourier transform from the X-ray scattering method or the X-ray CT method.
- Structure period L, ⁇ : wavelength of incident X-ray
- the material has a structure period of 0.002 ⁇ m or more, it can be easily combined with other materials, for example, when used as a column material for separation It is preferable because excellent separation characteristics can be exhibited.
- the material has a structural period of 10 ⁇ m or less, the structure has very few defects and can be made a mechanically excellent material, and a sufficiently high surface area can be secured. Is particularly suitable for applications where reaction at is important.
- the value of the structure period can be arbitrarily selected in accordance with the application within the above range.
- the value of the structural period may vary depending on the X-ray incident direction and X-ray CT imaging direction.
- the particulate porous carbon material of the present invention preferably has a structural period falling within the above range when measured from either direction.
- the average porosity of the continuous porous structure is preferably 10 to 80%.
- the average porosity is 1 ⁇ 0.1 (nm / pixel) of a cross section in which the embedded sample is precisely formed by the cross section polisher method (CP method) or the focused ion beam method (FIB method). From an image observed at a resolution of 700,000 pixels or more with an adjusted magnification, the area of interest required for calculation is set in 512 pixels square, the area of the entire area of interest is A, and the area of the hole is B. It is calculated by the following formula.
- Average porosity (%) B / A ⁇ 100
- the average porosity of the continuous porous structure is preferably in the range of 15 to 75%, more preferably in the range of 18 to 70%.
- the continuous porous structure preferably has at least one peak diameter in the range of 5 nm to 4 ⁇ m in the pore diameter distribution curve.
- the pore diameter distribution is measured by a mercury intrusion method or a gas adsorption method.
- the mercury intrusion method can acquire a wide pore diameter distribution curve from 5 nm to 500 ⁇ m, and is therefore suitable for acquiring a pore diameter distribution in a material having a large structural period.
- the gas adsorption method is suitable for obtaining the pore diameter distribution in a small region up to about 100 nm as compared with the mercury intrusion method.
- either the mercury intrusion method or the gas adsorption method can be appropriately selected according to the structural period of the particulate porous carbon material of the present invention.
- the peak diameter of the pore diameter distribution curve in the particulate porous carbon material of the present invention is more preferably in the range of 5 nm to 3 ⁇ m, and further preferably in the range of 5 nm to 1 ⁇ m. .
- the pore diameter distribution of the continuous porous structure can be measured by measuring the pore diameter distribution of the entire material, The pore diameter distribution curve of the continuous porous structure can be approximated by the pore diameter distribution curve of the entire material.
- the particulate porous carbon material of the present invention may have a part that does not substantially have a continuous porous structure.
- the portion having substantially no continuous porous structure means that the pore diameter is a resolution when a cross section formed by the cross section polisher method (CP method) is observed at an enlargement ratio of 1 ⁇ 0.1 (nm / pixel).
- a portion where a clear hole is not observed due to the following means a portion where one side exists in an area equal to or larger than a square region corresponding to three times the structural period L calculated from the above-described X-ray analysis.
- the portion that does not have a continuous porous structure has a higher level of electrical and thermal conductivity than the portion that has a continuous porous structure due to being densely filled with carbon.
- a particulate porous carbon material having a portion that does not substantially have a continuous porous structure for example, when used as a battery material, can quickly discharge reaction heat to the outside of the system, and can provide resistance during electron transfer. Can contribute to the production of high-efficiency batteries.
- the resistance to compression fracture can be dramatically improved.
- the flow path can be complicated and disturbed by passing through a portion having no continuous porous structure, so that the fluid can be mixed efficiently. Properties can be imparted.
- the proportion of the portion having no continuous porous structure is not particularly limited and can be arbitrarily controlled depending on each application. However, when used as a battery material, 5% by volume or more is a portion having no continuous porous structure. It is preferable because electrical conductivity and thermal conductivity can be maintained at a high level.
- the proportion of the portion not having the continuous porous structure is preferably 5% by volume or more in order to exhibit the above characteristics.
- the proportion of the portion that does not have a continuous porous structure can be determined by a conventionally known analytical method, but the portion that has a continuous porous structure by measuring the three-dimensional shape by the electron tomography method or the X-ray micro CT method, etc. It is preferable to calculate from the volume of the portion that does not have.
- the term “particulate” means that the diameter of a particle obtained by a scanning electron microscope is 10 mm or less.
- the particle size of the particulate porous carbon material of the present invention is not particularly limited to 10 mm or less, and can be appropriately selected by changing the degree of pulverization according to the application, but 10 nm to 10 ⁇ m. Since particles having a particle size of, for example, a very smooth solid content forming the paste can be obtained, it is possible to prevent defects such as peeling and cracking of the paste in a process such as coating. On the other hand, a particle having a particle size of 0.1 ⁇ m or more is a preferable mode when a composite material with a resin can sufficiently exhibit the effect of improving the strength as a filler.
- the particulate carbon material is generally used as an aggregate of a number of particulate carbon materials, but in that case, not all of the aggregates need be the particulate porous carbon material of the present invention,
- the particulate porous carbon material of the present invention may be included as a part of the aggregate.
- the particulate porous carbon material of the present invention is preferably contained in an amount of 30% by weight or more of the aggregate of the particulate carbon material, more preferably 50% by weight or more, and 70% by weight or more. More preferably, it is more preferably 90% by weight or more.
- the particulate porous carbon material of the present invention includes a step (step 1) in which a carbonizable resin and a disappearing resin are mixed to form a resin mixture, and a phase-separation is performed by fixing the compatible resin mixture. It can be produced by a production method having a step (step 2) for forming, a step (step 3) for stretching, a step (step 4) for carbonization by heating and baking, and a step (step 5) for pulverization.
- Step 1 is a step in which 10 to 90% by weight of the carbonizable resin and 90 to 10% by weight of the disappearing resin are mixed to form a resin mixture.
- the carbonizable resin is a resin that is carbonized by firing and remains as a carbon material, and both a thermoplastic resin and a thermosetting resin can be used.
- a thermoplastic resin it is preferable to select a resin that can be infusibilized by a simple process such as heating or irradiation with high energy rays.
- thermosetting resin infusibilization treatment is often unnecessary, and this is also a suitable material.
- thermoplastic resins include polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, phenolic resins, wholly aromatic polyesters
- thermosetting resins include unsaturated polyester resins, alkyd resins, melamine resins, urea resins.
- thermoplastic resin Polyimide resin, diallyl phthalate resin, lignin resin, urethane resin, and the like. These may be used singly or in a mixed state, but mixing in each of the thermoplastic resin or the thermosetting resin is also a preferable aspect from the ease of molding.
- thermoplastic resin from the viewpoints of carbonization yield, moldability, and economy.
- polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, and wholly aromatic polyesters are preferably used.
- the disappearing resin is a resin that disappears following Step 2 described later, and is a resin that can be removed at the same time as the infusibilization treatment, after the infusibilization treatment, or at the same time as firing.
- the method for removing the disappearing resin is not particularly limited, and is a method of chemically removing the polymer by depolymerizing it using a chemical, a method of dissolving and removing by adding a solvent that dissolves the disappearing resin, and heating.
- a method of removing the lost resin by reducing the molecular weight by thermal decomposition is preferably used. These methods can be used alone or in combination, and when combined, they may be performed simultaneously or separately.
- a method of hydrolyzing with an acid or alkali is preferable from the viewpoints of economy and handleability.
- the resin that is susceptible to hydrolysis by acid or alkali include polyester, polycarbonate, and polyamide.
- a method of removing by adding a solvent that dissolves the disappearing resin a method of dissolving and removing the disappearing resin by continuously supplying a solvent to the mixed carbonizable resin and the disappearing resin, or by a batch method
- a suitable example is a method of mixing and dissolving and removing the disappearing resin.
- the disappearing resin suitable for the method of adding and removing the solvent include polyolefins such as polyethylene, polypropylene, and polystyrene, acrylic resins, methacrylic resins, polyvinyl pyrrolidone, aliphatic polyesters, polycarbonates, and polyvinyl alcohol. It is done. Among them, an amorphous resin is more preferable because of its solubility in a solvent, and examples thereof include polystyrene, methacrylic resin, polycarbonate, polyvinyl pyrrolidone, and polyvinyl alcohol.
- a method of removing the lost resin by reducing the molecular weight by thermal decomposition a method in which the mixed carbonizable resin and the lost resin are heated in a batch manner to thermally decompose, or a continuously mixed carbonized resin and the lost resin are removed.
- a method of heating and thermally decomposing while continuously supplying to a heat source a method in which the mixed carbonizable resin and the lost resin are heated in a batch manner to thermally decompose, or a continuously mixed carbonized resin and the lost resin are removed.
- the disappearing resin is preferably a resin that disappears by thermal decomposition when carbonizing the carbonizable resin by firing in Step 3 described later, and is large during the infusibilization treatment of the carbonizable resin described later.
- a thermoplastic resin that does not cause a chemical change and has a carbonization yield of less than 10% after firing is preferable.
- Specific examples of such disappearing resins include polyolefins such as polyethylene, polypropylene and polystyrene, acrylic resins, methacrylic resins, polyacetals, polyvinylpyrrolidones, aliphatic polyesters, aromatic polyesters, aliphatic polyamides, polycarbonates and the like. These may be used alone or in a mixed state.
- step 1 the carbonizable resin and the disappearing resin are mixed to form a resin mixture (polymer alloy).
- “Compatibilized” as used herein refers to creating a state in which the phase separation structure of the carbonizable resin and the disappearing resin is not observed with an optical microscope by appropriately selecting the temperature and / or solvent conditions.
- the carbonizable resin and the disappearing resin may be compatible by mixing only the resins, or may be compatible by adding a solvent.
- a system in which a plurality of resins are compatible includes a phase diagram of an upper critical eutectic temperature (UCST) type that is in a phase separation state at a low temperature but has one phase at a high temperature, and conversely, a phase separation state at a high temperature.
- UCT upper critical eutectic temperature
- LCST lower critical solution temperature
- the solvent to be added is not particularly limited, but the absolute value of the difference from the average value of the solubility parameter (SP value) of the carbonizable resin and the disappearing resin, which is a solubility index, is within 5.0. It is preferable. Since it is known that the smaller the absolute value of the difference from the average value of SP values, the higher the solubility, it is preferable that there is no difference. Further, the larger the absolute value of the difference from the average SP value, the lower the solubility, and it becomes difficult to take a compatible state between the carbonizable resin and the disappearing resin. Therefore, the absolute value of the difference from the average value of SP values is preferably 3.0 or less, and most preferably 2.0 or less.
- carbonizable resins and disappearing resins are polyphenylene oxide / polystyrene, polyphenylene oxide / styrene-acrylonitrile copolymer, wholly aromatic polyester / polyethylene as long as they do not contain solvents.
- examples include terephthalate, wholly aromatic polyester / polyethylene naphthalate, wholly aromatic polyester / polycarbonate.
- combinations of systems containing solvents include polyacrylonitrile / polyvinyl alcohol, polyacrylonitrile / polyvinylphenol, polyacrylonitrile / polyvinylpyrrolidone, polyacrylonitrile / polylactic acid, polyvinyl alcohol / vinyl acetate-vinyl alcohol copolymer, polyvinyl Examples include alcohol / polyethylene glycol, polyvinyl alcohol / polypropylene glycol, and polyvinyl alcohol / starch.
- the method of mixing the carbonizable resin and the disappearing resin is not limited, and various known mixing methods can be adopted as long as uniform mixing is possible. Specific examples include a rotary mixer having a stirring blade and a kneading extruder using a screw.
- the temperature (mixing temperature) when mixing the carbonizable resin and the disappearing resin is equal to or higher than the temperature at which both the carbonizable resin and the disappearing resin are softened.
- the softening temperature may be appropriately selected as the melting point if the carbonizable resin or disappearing resin is a crystalline polymer, and the glass transition temperature if it is an amorphous resin.
- the mixing temperature is preferably 400 ° C. or lower from the viewpoint of preventing deterioration of the resin due to thermal decomposition and obtaining a precursor of a porous carbon material having excellent quality.
- Step 1 90 to 10% by weight of the disappearing resin is mixed with 10 to 90% by weight of the carbonizable resin. It is preferable that the carbonizable resin and the disappearing resin are within the above-mentioned range since an optimum pore size and porosity can be arbitrarily designed. If the carbonizable resin is 10% by weight or more, it is possible to maintain the mechanical strength of the carbonized material and improve the yield. Further, if the carbonizable material is 90% by weight or less, it is preferable because the lost resin can efficiently form voids.
- the mixing ratio of the carbonizable resin and the disappearing resin can be arbitrarily selected within the above range in consideration of the compatibility of each material. Specifically, in general, the compatibility between resins deteriorates as the composition ratio approaches 1: 1, so when a system that is not very compatible is selected as a raw material, the amount of carbonizable resin is increased. It is also preferable to improve the compatibility by reducing it so that it approaches a so-called uneven composition.
- a solvent when mixing the carbonizable resin and the disappearing resin. Addition of a solvent lowers the viscosity of the carbonizable resin and the disappearing resin to facilitate molding, and facilitates compatibilization of the carbonizable resin and the disappearing resin.
- the solvent here is not particularly limited as long as it is a liquid at room temperature that can dissolve and swell at least one of carbonizable resin and disappearing resin. Any resin that dissolves the resin is more preferable because the compatibility between the two can be improved.
- the addition amount of the solvent should be 20% by weight or more based on the total weight of the carbonizable resin and the disappearing resin from the viewpoint of improving the compatibility between the carbonizable resin and the disappearing resin and reducing the viscosity to improve the fluidity. preferable. On the other hand, from the viewpoint of costs associated with recovery and reuse of the solvent, it is preferably 90% by weight or less based on the total weight of the carbonizable resin and the disappearing resin.
- Step 2 is a step of forming a fine structure by phase-separating the resin mixture in a state of being dissolved in Step 1, and immobilizing the fine structure.
- the method for phase separation of the mixed carbonizable resin and the disappearing resin is not particularly limited.
- a thermally induced phase separation method in which phase separation is induced by a temperature change or a phase separation is induced by adding a non-solvent.
- Non-solvent induced phase separation methods reaction induced phase separation methods that induce phase separation using chemical reactions, and methods that cause phase separation using changes in light, pressure, shear, electric field, and magnetic field, and the like.
- the heat-induced phase separation method and the non-solvent-induced phase separation method are preferable because the conditions for inducing phase separation can be easily controlled, and the phase separation structure and size can be controlled relatively easily.
- phase separation methods can be used alone or in combination.
- Specific methods for use in combination include, for example, a method in which non-solvent induced phase separation is caused through a coagulation bath and then heated to cause heat-induced phase separation, or a temperature in the coagulation bath is controlled to control a non-solvent induced phase.
- Examples thereof include a method of causing separation and thermally induced phase separation at the same time, a method of bringing the material discharged from the die into cooling and causing thermally induced phase separation, and then contacting with a non-solvent.
- the term “not accompanied by a chemical reaction” means that the carbonized resin or the disappearing resin mixed does not change its primary structure before and after mixing.
- the primary structure refers to a chemical structure constituting a carbonizable resin or a disappearing resin. Since there is no chemical reaction during phase separation, the mechanical and chemical properties of the carbonizable resin and / or disappearing resin are not impaired. Since it is possible to mold without changing, this is a preferred embodiment. In particular, when a fine structure is formed by phase separation without immobilizing a crosslinking reaction, and it is fixed, a significant increase in elastic modulus and a decrease in elongation are not observed with the crosslinking reaction. Since a simple structure can be maintained, the fiber and film manufacturing process passability is excellent without thread breakage or film breakage.
- Step 3 is a step of stretching the precursor that has been phase-separated in Step 2 to form a co-continuous phase separation structure. This step makes it possible to orient the phase separation structure formed in step 2 in the stretching direction, and further by firing, the porous carbon material in which the aspect ratio of the branch portion of the continuous porous structure is 3 or more Can be obtained.
- Stretching can be performed by appropriately using conventionally known means, but a typical example is a method of stretching between rollers with a difference in speed. As this method, the roller itself is heated and stretched, a contact type or non-contact type heater, a hot water / solvent bath, a steam heating facility, a laser heating facility, etc. are provided between the rollers, and the precursor fiber is formed. Examples of the method include heating and stretching.
- press molding is also preferable for the purpose of giving the same effect as stretching.
- Either of the stretching methods may be selected or used in combination. For example, a precursor once stretched between rollers may be pressed between rollers.
- the heating temperature is preferably equal to or higher than the glass transition temperature of the carbonizable resin and / or the disappearing resin from the viewpoint of ensuring molecular mobility and smoothly stretching. Moreover, both the carbonizable resin and the loss
- the upper limit of the heating temperature is not particularly set, but when the carbonizable resin or disappearing resin is a crystalline polymer, it is preferably below the melting point.
- the heating temperature is preferably 300 ° C. or less from the viewpoint of preventing the carbonization reaction.
- the stretching may be performed up to the limit of the stretching ratio at which it breaks at a time, but in order to obtain a highly oriented precursor, it is preferably performed in multiple steps. Since the polymer chain has a molecular weight distribution, a component that relaxes in a short time and a component that relaxes in a longer time are often mixed, and the component that can be relaxed in a short time is first stretched at a high draw ratio. It is also preferable to keep it.
- the high draw ratio here refers to a ratio of 90% or more of the draw ratio calculated from the secondary yield point elongation after obtaining the SS curve for the precursor before drawing and the low stress extension region. Say to set the draw ratio.
- the precursor stretched at a ratio of 90% or more of the stretch ratio calculated from the secondary yield point elongation yields a uniform material free from thick and thin unevenness, and is excellent in quality.
- the lower limit of the draw ratio is not particularly limited, but it is preferable that the draw ratio is equal to or higher than the ratio at which the draw tension is generated in the draw because the process can be easily drawn and the material can be drawn efficiently.
- the magnification at which stretching tension is generated refers to the minimum magnification in which the precursor of the present invention undergoing stretching is in tension and is not relaxed. For example, the precursor is contracted during the stretching process. If it is, the stretching ratio can be made less than 1 because tension is generated due to shrinkage stress.
- the precursor subjected to stretching in the step 3 is further subjected to a heat treatment step.
- the heat treatment suppresses shrinkage associated with relaxation of the molecular chains oriented by stretching, and the precursor can be subjected to carbonization while maintaining a highly oriented state.
- a conventionally known method can be used.
- a method of heating the wound precursor in an oven or the like is preferable.
- a method of heating the roller surface itself or a method of heat treatment by providing a contact or non-contact heater, hot water / solvent bath, steam heating equipment, laser heating equipment, etc. between the rollers is also preferably used. It is done.
- the heating temperature in the heat treatment induces crystallization from the viewpoint of ensuring molecular mobility and smoothly relaxing the molecular chain, and particularly when the carbonizable resin and / or the disappearing resin is a crystalline polymer.
- the temperature is preferably equal to or higher than the glass transition temperature of the carbonizable resin and / or the disappearing resin.
- heating to a temperature higher than the higher one of the glass transition temperature of the carbonizable resin and the disappearing resin ensures the molecular mobility of the carbonizable resin and the disappearing resin and smoothly relaxes the molecular chain. This is a more preferable embodiment.
- the upper limit of the heating temperature in the heat treatment is not particularly set, but when the carbonizable resin or the disappearing resin is a crystalline polymer, it is preferably below its melting point.
- the heating temperature is preferably 300 ° C. or less from the viewpoint of preventing the carbonization reaction.
- the length of the precursor during heat treatment does not change in the range of 0.8 to 1.2 times. It is preferable to be limited to Limiting the length means suppressing a dimensional change during heat treatment, specifically winding around a metal roll, limiting the length using a clip, pinning the pin to limit the length, a metal frame And heat treatment in a state where the speed is limited between rollers.
- the heat-treated precursor is partially relaxed in orientation, and when a crystalline polymer is contained in the resin mixture, it becomes possible to prevent macro contraction by progressing crystallization, and in the stretching process,
- the oriented molecular chain can be fixed.
- the length limit is preferably 0.8 times or more because it can be greatly relaxed around a micromolecular chain while minimizing the relaxation of the structure in which the phase separation state is oriented, and is preferably 1.2 times or less. It is preferable that the oriented phase separation state is maintained at a high level without being relaxed and can be relaxed around a micro molecular chain.
- the precursor stretched in step 3 is removed of the disappearing resin before being subjected to the carbonization step (step 4).
- the method for removing the lost resin is not particularly limited as long as the lost resin can be decomposed and removed. Specifically, a method of chemically removing and reducing the molecular weight of the disappearing resin using an acid, alkali or enzyme, a method of removing by adding a solvent that dissolves the disappearing resin, an electron beam, a gamma ray, A method of removing the lost resin by depolymerization using radiation such as ultraviolet rays or infrared rays is preferable.
- the disappearing resin when the disappearing resin can be thermally decomposed, heat treatment can be performed in advance at a temperature at which 80% by weight or more of the disappearing resin disappears, or in the carbonization step (step 4) or an infusibilization treatment described later.
- the lost resin can be removed by pyrolysis and gasification. From the viewpoint of increasing the productivity by reducing the number of steps, it is more preferable to select a method in which the lost resin is thermally decomposed and gasified and removed simultaneously with the heat treatment in the carbonization step (step 4) or infusibilization treatment described later. It is. In particular, it is preferable to remove the lost resin simultaneously with the carbonization in the carbonization step (step 4) because the cost can be reduced by reducing the number of steps and the yield can be improved.
- the precursor stretched in step 3 is preferably pulverized before being subjected to the carbonization step (step 4), and is preferably in the form of particles in advance.
- the pulverization in step 5 is not necessary.
- the pulverization treatment can be performed by the same method as in step 5 described later.
- Step 4 The precursor stretched in Step 3 or the precursor that has been subjected to the removal treatment of the disappearing resin as necessary is subjected to an infusibilization treatment before being subjected to the carbonization step (Step 4). It is preferable.
- the infusible treatment method is not particularly limited, and a known method can be used.
- Specific methods include a method of causing oxidative crosslinking by heating in the presence of oxygen, a method of forming a crosslinked structure by irradiating high energy rays such as electron beams and gamma rays, and impregnating a substance having a reactive group, Examples thereof include a method of forming a crosslinked structure by mixing, and a method of causing oxidative crosslinking by heating in the presence of oxygen is preferable because the process is simple and the production cost can be kept low. These methods may be used singly or in combination, and each may be used simultaneously or separately.
- the heating temperature in the method of causing oxidative crosslinking by heating in the presence of oxygen is preferably 150 ° C. or more from the viewpoint of efficiently proceeding with the crosslinking reaction, from weight loss due to thermal decomposition, combustion, etc. of carbonizable resin.
- the temperature is preferably 350 ° C. or lower from the viewpoint of preventing the deterioration of the yield.
- the oxygen concentration during the treatment is not particularly limited, but it is a preferable aspect to supply a gas having an oxygen concentration of 18% or more, particularly air as it is, because manufacturing costs can be kept low.
- the method for supplying the gas is not particularly limited, and examples thereof include a method for supplying air directly into the heating device and a method for supplying pure oxygen into the heating device using a cylinder or the like.
- the carbonizable resin is irradiated with an electron beam or gamma ray using a commercially available electron beam generator or gamma ray generator. And a method of inducing cross-linking.
- the lower limit of the irradiation intensity is preferably 1 kGy or more from the efficient introduction of a crosslinked structure by irradiation, and is preferably 1000 kGy or less from the viewpoint of preventing the material strength from being lowered due to the decrease in molecular weight due to cleavage of the main chain.
- a crosslinkable compound having a carbon-carbon double bond in the structure.
- Any known crosslinking compound can be used, but ethylene, propene, isoprene, butadiene, styrene, ⁇ -methylstyrene, divinylbenzene, acrylic acid, methacrylic acid, monoallyl isocyanurate, diallyl isocyanurate And triallyl isocyanurate, and the like.
- a crosslinkable compound having two or more carbon-carbon double bonds in the molecule is preferable because the crosslinking reaction can be efficiently advanced.
- a method of forming a crosslinked structure by impregnating and mixing a substance having a reactive group is a method in which a low molecular weight compound having a reactive group is impregnated in a resin mixture, and a crosslinking reaction is advanced by irradiation with heat or high energy rays. And a method in which a low molecular weight compound having a reactive group is mixed in advance and the crosslinking reaction is advanced by heating or irradiation with high energy rays.
- step 4 the precursor itself stretched in step 3 or, if necessary, the precursor subjected to the above-described decomposition treatment and / or infusibilization treatment is calcined and carbonized to obtain a porous carbon material. It is.
- firing is preferably performed by heating to 500 ° C. or higher in an inert gas atmosphere.
- the inert gas refers to one that is chemically inert during heating, and specific examples include helium, neon, nitrogen, argon, krypton, xenon, carbon dioxide, and the like.
- nitrogen and argon is a preferable embodiment from an economical viewpoint.
- the carbonization temperature is 1500 ° C. or higher, it is preferable to use a rare gas element such as argon, helium, neon, krypton, or xenon from the viewpoint of suppressing nitride formation, and argon is particularly preferable from the viewpoint of cost. preferable.
- the carbonization temperature is 500 ° C. or higher because a carbon network is efficiently formed in the entire porous carbon material including the branches constituting the continuous porous structure.
- the carbonization temperature referred to in the present invention indicates the maximum temperature in the carbonization treatment in Step 4, and does not limit the treatment at a lower temperature.
- the flow rate of the inert gas may be an amount that can sufficiently reduce the oxygen concentration in the heating device, and an optimal value can be selected as appropriate depending on the size of the heating device, the amount of raw material supplied, the heating temperature, and the like. preferable.
- the upper limit of the flow rate is not particularly limited, but is preferably set appropriately in accordance with the temperature distribution and the design of the heating device, from the viewpoint of economy and the temperature change in the heating device being reduced. Further, if the gas generated during carbonization can be sufficiently discharged out of the system, a porous carbon material excellent in quality can be obtained, which is a more preferable embodiment. From this, the generated gas concentration in the system is 3,000 ppm. It is preferable to determine the flow rate of the inert gas so as to be as follows.
- the upper limit of the carbonization temperature is not limited, but 3000 ° C. or less is preferable from the viewpoint of sufficient carbonization.
- the heating method in the case of continuous carbonization it is a production method that the material is taken out while being continuously supplied using a roller, conveyor, rotary kiln, etc. into a heating device maintained at a constant temperature. It is preferable because it is possible to increase the property. Further, in the heating for performing the carbonization treatment, heating while mixing the materials is also preferable for uniformly performing the heat treatment and improving the quality of the materials. When it is difficult to mix materials such as fibers and films, it is preferable to devise so that an inert gas stream is uniformly applied to the entire material because it is effective for uniform heat treatment and high quality.
- the lower limit of the rate of temperature rise and the rate of temperature drop when performing batch processing in the heating device is not particularly limited, but productivity can be increased by shortening the time required for temperature rise and temperature drop, and 1 ° C. It is preferable that the speed is at least 1 minute.
- the upper limit of the temperature increase rate and the temperature decrease rate is not particularly limited, it is preferable to make it slower than the thermal shock resistance of the material constituting the heating device.
- the holding time at the carbonization temperature can be arbitrarily set. However, the longer the holding time, the smaller the disturbance of the carbon network, and the shorter the holding time, the larger the disturbance of the carbon network. Therefore, it is preferable to set appropriately according to the intended use, but it is preferable because the retention time of 5 minutes or more can efficiently reduce the disturbance of the carbon network.
- the holding time is preferably set to 1200 minutes at the longest because energy consumption is suppressed and the porous carbon material of the present invention can be efficiently obtained.
- Step 5 is a step of pulverizing the porous carbon material obtained in Step 4. By further pulverizing the porous carbon material obtained in step 4, the particulate porous carbon material can be produced.
- the pulverization treatment a conventionally known method can be selected, and it is preferable that the pulverization treatment is appropriately selected according to the particle size and the processing amount after the pulverization treatment.
- the pulverization method include a ball mill, a bead mill, a jet mill, and the like.
- the precursor is a fiber as a coarse pulverization
- the fiber length is shortened in advance using a cutter or the like. Is also preferable.
- the pulverization may be continuous or batch, but is preferably continuous from the viewpoint of production efficiency.
- the filler to be filled in the ball mill is selected as appropriate, but for applications where mixing of metal materials is not preferred, it is made of a metal oxide such as alumina, zirconia or titania, or stainless steel, iron or the like as a core, nylon or polyolefin It is preferable to use a material coated with fluorinated polyolefin or the like. For other uses, metals such as stainless steel, nickel and iron are preferably used.
- the grinding aid is arbitrarily selected from water, alcohol or glycol, ketone and the like.
- the alcohol ethanol and methanol are preferable from the viewpoint of availability and cost, and in the case of glycol, ethylene glycol, diethylene glycol, propylene glycol and the like are preferable.
- glycol ethylene glycol, diethylene glycol, propylene glycol and the like are preferable.
- a ketone acetone, ethyl methyl ketone, diethyl ketone and the like are preferable.
- the grinding aid is preferably removed by washing and drying after grinding.
- the pulverization efficiency decreases due to heat generated by the pulverization process, it is also preferable to cool the equipment.
- the cooling method is not particularly limited, it is possible to exemplify using cooling air, cold water, etc. Among them, it is preferable to cool using cold water from the viewpoint of heat exchange efficiency.
- the particulate porous carbon material that has been subjected to the pulverization treatment is a material that is classified and has a uniform particle size.
- Particulate porous carbon material with uniform particle size can form a uniform structure with, for example, fillers and additives to the paste, which makes it possible to stabilize the filling efficiency and paste application process. It is preferable because production efficiency can be increased and cost reduction can be expected.
- About a particle size it is preferable to select suitably according to the use of the particulate porous carbon material after a grinding process.
- step 5 is not necessary.
- Evaluation method Continuous porous structure Observation was performed by placing the particulate porous carbon material on a sample stage for a scanning electron microscope. A secondary electron image was obtained while scanning the sample surface at an acceleration voltage of 1 kV and a current value of 10 ⁇ A. At this time, it was determined that the observation sample had a continuous porous structure when it was observed that the hole and the branch were intertwined in the depth direction.
- [Structural period of continuous porous structure] A particulate porous carbon material was sandwiched between sample plates, and the positions of the light source, the sample, and the two-dimensional detector were adjusted so that information with a scattering angle of less than 10 degrees was obtained from the X-ray source obtained from the CuK ⁇ ray light source. From the image data (luminance information) obtained from the two-dimensional detector, the central portion affected by the beam stopper is excluded, a moving radius is provided from the beam center, and a luminance value of 360 ° is obtained for each angle of 1 °. The scattering intensity distribution curve was obtained by summing up. From the scattering angle 2 ⁇ at a position having a peak in the obtained curve, the structural period of the continuous porous structure was obtained by the following equation.
- Average porosity (%) B / A ⁇ 100 [Obtain pore diameter distribution curve]
- the adsorbed gas component was removed by vacuum drying the particulate porous carbon material at 300 ° C. for 5 hours. Thereafter, a pore diameter distribution curve was obtained using Autopore IV9500 manufactured by Shimadzu Corporation.
- a three-dimensional image of the particulate porous carbon material was obtained by the continuous section method using an ion beam.
- the obtained three-dimensional image was thinned using Amira manufactured by FEI, and thin line data and the number of joints were obtained. Further, from the thinning processing data obtained, the path of the thin line corresponding to the other joint from one joint of the branch part is divided into 10 parts, and the void surface from the midpoint position X of each path divided in the three-dimensional image A perpendicular line was drawn, and a distance R (X) until the perpendicular line hits the gap was calculated.
- R (X) was an average value obtained by scanning 360 ° with a perpendicular drawn around a thin line in 10 ° steps.
- D 2R min calculated from a value R min that minimizes R (X), and a distance L that is the total of the paths from the junction to the junction used to calculate R (X).
- the ratio (L / D) was calculated. This aspect ratio (L / D) was similarly analyzed for 10 branches, and the average value was taken as the aspect ratio.
- N the number of branches (N) and the number of junctions (n) included in the three-dimensional image are counted, and N is set as the number of branches, and N and the number of junctions (n).
- the ratio (N / n) was calculated.
- the particulate porous carbon material was placed on an observation stage for an electron microscope, and images were taken at five locations at an enlargement ratio at which 10 or more particles could be recognized individually. Ten particles were extracted from the photographed image, the area of each particle was determined, and the particle diameter was converted from the area as a circle having the same area. This operation was performed for 50 extracted particles, and the average value was defined as the average particle size.
- Example 1 Separable flask containing 37.5 g of polyacrylonitrile (MW 150,000) manufactured by Polyscience, 37.5 g of polyvinyl pyrrolidone (MW 40,000) manufactured by Sigma-Aldrich, and 425 g of dimethyl sulfoxide (DMSO) manufactured by Waken Pharmaceutical as a solvent. Then, a uniform and transparent solution was prepared at 150 ° C. while stirring and refluxing for 3 hours. At this time, the concentration of polyacrylonitrile and the concentration of polyvinylpyrrolidone were each 7.5% by weight.
- DMSO dimethyl sulfoxide
- the solution After cooling the obtained DMSO solution to 25 ° C., the solution is discharged at a rate of 3 ml / min from a 0.6 mm ⁇ 1-hole cap and led to a pure water coagulation bath maintained at 25 ° C., and then 6 m / min.
- the yarn was taken up at a speed and deposited on the bat to obtain a raw yarn. At this time, the air gap was 3 mm, and the immersion length in the coagulation bath was 15 cm.
- the obtained raw yarn was translucent and caused phase separation.
- the obtained yarn is dried for 1 hour in a circulation drier kept at 25 ° C. to dry the moisture on the surface of the yarn, followed by vacuum drying at 25 ° C. for 5 hours.
- Raw material yarn was obtained.
- the obtained yarn was drawn at a draw ratio of 4 in a heater having a slit width of 10 mm and a slit length of 30 cm maintained at 120 ° C.
- the raw yarn wound around a stainless steel mold was placed as a precursor in an electric furnace maintained at 235 ° C., and infusible treatment was performed by heating in an oxygen atmosphere for 1 hour.
- the raw yarn that had been infusibilized changed to black.
- the obtained infusible raw yarn is fixed to a carbon mold and subjected to carbonization under the conditions of a nitrogen flow rate of 1 liter / minute, a heating rate of 10 ° C./minute, an ultimate temperature of 900 ° C., and a holding time of 10 minutes.
- a porous carbon fiber was obtained.
- the obtained porous carbon fiber was coarsely pulverized using a mortar and then pulverized for 2 hr by a ball mill.
- the continuous porous structure shown in FIG. 2 was observed, the structural period of the continuous porous structure was 0.086 ⁇ m, and the average porosity was 55%.
- the average particle size was 10 ⁇ m.
- the aspect ratio of the branches was 6.1.
- the number N of branches was 262
- the number n of joints was 80
- the value of N / n was 3.3.
- the obtained pulverized product was excellent in electrical conductivity and thermal conductivity, and also excellent in resistance to compression.
- Example 2 A porous carbon fiber and a pulverized product thereof were obtained in the same manner as in Example 1 except that the draw ratio was changed to 2.0 times.
- the resulting pulverized product had a structural period of 0.085 ⁇ m and an average porosity of 54%.
- the average particle size was 7 ⁇ m.
- the aspect ratio of the branches was 4.2, the number of branches N was 204, the number of junctions n was 52, and the value of N / n was 3.9.
- the obtained pulverized product was excellent in electrical conductivity and thermal conductivity, and also excellent in resistance to compression.
- Example 3 A porous carbon fiber and a pulverized product thereof were obtained in the same manner as in Example 1 except that the pulverization time was 4 hours.
- the resulting pulverized product had a structural period of 0.087 ⁇ m and an average porosity of 55%.
- the average particle size was 3 ⁇ m.
- the aspect ratio of the branches was 5.9, the number N of branches was 104, the number of junctions n was 61, and the value of N / n was 1.7.
- the obtained pulverized product was excellent in electrical conductivity and thermal conductivity, and also excellent in resistance to compression.
- Example 4 A porous carbon fiber and a pulverized product thereof were obtained in the same manner as in Example 1 except that the pulverization time was 10 hours.
- the resulting pulverized product had a structural period of 0.087 ⁇ m and an average porosity of 55%.
- the average particle size was 1 ⁇ m.
- the aspect ratio of the branches was 6.3, the number N of branches was 35, the number n of joints was 27, and the value of N / n was 1.3.
- the obtained pulverized product had good electrical conductivity, thermal conductivity and resistance to compression.
- AN copolymer consisting of 98% by mole of acrylonitrile (hereinafter abbreviated as AN), 2% by mole of methacrylic acid (hereinafter abbreviated as MAA), 99% by mole of methyl acrylate (hereinafter abbreviated as MMA), acrylic A block copolymer consisting of 40 mol% AN and 60 mol% MMA with respect to 100 parts by weight of a mixture of both copolymers consisting of 40 mol% of a thermally decomposable copolymer of 1 mol% of methyl acid (hereinafter abbreviated as MA)
- DMF dimethylformamide
- the mixed solution was extruded from a nozzle and spun by a dry-wet spinning method to obtain a fiber, which was stretched twice in warm water, and further stretched twice in hot water. Thereafter, the film was further stretched 1.5 times between heated rolls, and the total stretching ratio was 6 times.
- the obtained fiber was continuously treated in a 250 ° C. flameproofing furnace and then continuously treated in a 600 ° C. firing furnace to obtain carbon fibers.
- the obtained fiber was crushed and the structure was observed, but fibrillar carbon fibers gathered together, and no branching portion was observed in the fibril. Moreover, the obtained crushed product was inferior in electrical conductivity and thermal conductivity, and its form was easily destroyed by compression.
Abstract
Description
A:連続多孔構造を形成する枝部のアスペクト比が3以上である。
B:枝部が接合部を介して集合数(N)3以上で集合している。
C:枝部の集合数(N)と接合部の数(n)の比(N/n)が1.2以上である。
本発明の粒子状多孔質炭素材料(以下、単に「材料」という場合がある。)は、連続多孔構造を有する。連続多孔構造とは、例えば液体窒素中で充分に冷却した試料をピンセット等により割断した断面あるいは粒子状試料をそのまま試料台に乗せて走査型電子顕微鏡(SEM)などによって表面観察した際に、図1の模式図および図2の写真に例示される通り、枝部(炭素部)と孔部(空隙部)がそれぞれ連続しつつ絡み合った構造が観察されることを言う。なお、本発明の粒子状多孔質炭素材料のうち小さいものにおいては、枝部と枝部の間に形成された空隙に分岐点が数か所しか存在しない場合があり得るが、本明細書においてはその場合でも当該空隙を孔部と称し、当該材料は連続多孔構造を有しているものと考える。
0.002μm以上の構造周期を持つ材料であれば、容易に他素材との複合化が可能であるほか、例えば分離用カラム材料として用いる際にも優れた分離特性を発揮できるため、好ましい。また10μm以下の構造周期を持つ材料であれば、構造体として欠陥が非常に少なく、力学的に優れた材料とすることが可能になるほか、十分に高い表面積を確保することができるため、表面での反応が重要な用途について、特に好適である。構造周期の値は、上記範囲の中で用途に合わせて任意に選択することができる。
平均空隙率は、高いほど他素材との複合の際に充填効率を高められるほか、ガスや液体の流路として圧力損失が小さく、流速を高めることができる一方、低いほど圧縮や曲げに対する耐性、力学特性を向上させられることから、取り扱い性や加圧条件での使用に際して有利となる。これらのことを考慮し、連続多孔構造の平均空隙率は15~75%の範囲であることが好ましく、18~70%の範囲がさらに好ましい。
本発明の粒子状多孔質炭素材料は、一例として、炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程(工程1)と、相溶した状態の樹脂混合物を相分離させ、固定化する工程(工程2)と、延伸する工程(工程3)と、加熱焼成により炭化する工程(工程4)と、粉砕する工程(工程5)とを有する製造方法により製造することができる。
工程1は、炭化可能樹脂10~90重量%と、消失樹脂90~10重量%と相溶させ、樹脂混合物とする工程である。
工程2は、工程1において相溶させた状態の樹脂混合物を相分離させて微細構造を形成し、当該微細構造を固定化する工程である。
工程3は、工程2において相分離させて共連続相分離構造を形成させた前駆体を延伸する工程である。本工程により工程2で形成された相分離構造を延伸方向に配向させることが可能になり、さらに焼成を経ることで、連続多孔構造の枝部のアスペクト比が3以上の配向した多孔質炭素材料を得ることができる。
工程3において延伸が施された前駆体は、さらに熱処理工程に供されることが好ましい。熱処理は、延伸によって配向した分子鎖が緩和することに伴う収縮を抑制し、高度に配向した状態を保ったまま前駆体を炭化に供することができる。
工程3において延伸された前駆体は、炭化工程(工程4)に供される前に消失樹脂の除去を行うことも好ましい。消失樹脂の除去の方法は特に限定されるものではなく、消失樹脂を分解、除去することが可能であれば良い。具体的には、酸、アルカリや酵素を用いて消失樹脂を化学的に分解、低分子量化して除去する方法や、消失樹脂を溶解する溶媒を添加して溶解除去する方法、電子線、ガンマ線や紫外線、赤外線などの放射線を用いて解重合することで消失樹脂を除去する方法などが好適である。
工程3において延伸された前駆体は、炭化工程(工程4)に供される前に粉砕処理し、あらかじめ粒子状としておくことも好ましい。この場合、工程5の粉砕は不要となる。粉砕処理は、後述する工程5と同様の方法で行うことができる。
工程3において延伸された前駆体、あるいは当該前駆体に必要に応じてさらに上記の消失樹脂の除去処理を行ったものは、炭化工程(工程4)に供される前に不融化処理が行われることが好ましい。不融化処理の方法は特に限定されるものではなく、公知の方法を用いることができる。具体的な方法としては、酸素存在下で加熱することで酸化架橋を起こす方法、電子線、ガンマ線などの高エネルギー線を照射して架橋構造を形成する方法、反応性基を持つ物質を含浸、混合して架橋構造を形成する方法などが挙げられ、中でも酸素存在下で加熱することで酸化架橋を起こす方法が、プロセスが簡便であり製造コストを低く抑えることが可能である点から好ましい。これらの手法は単独もしくは組み合わせて使用しても、それぞれを同時に使用しても別々に使用しても良い。
工程4は、工程3において延伸された前駆体そのもの、あるいは必要に応じてさらに上記の分解処理および/または不融化処理に供された前駆体を焼成し、炭化して多孔質炭素材料を得る工程である。
工程5は、工程4で得られた多孔質炭素材料を粉砕する工程である。工程4で得られた多孔質炭素材料をさらに粉砕することで、粒子状多孔質炭素材料を製造することができる。
〔連続多孔構造〕
粒子状多孔質炭素材料を走査型電子顕微鏡用試料台に乗せて観察を行った。加速電圧1kV、電流値10μAにて試料表面を走査しながら二次電子像を得た。このとき、観察試料において、奥行き方向に孔部と枝部がそれぞれ連続しつつ絡み合っている様子が観察された場合、連続多孔構造を有していると判断した。
粒子状多孔質炭素材料を試料プレートに挟み込み、CuKα線光源から得られたX線源から散乱角度10度未満の情報が得られるように、光源、試料及び二次元検出器の位置を調整した。二次元検出器から得られた画像データ(輝度情報)から、ビームストッパーの影響を受けている中心部分を除外して、ビーム中心から動径を設け、角度1°毎に360°の輝度値を合算して散乱強度分布曲線を得た。得られた曲線においてピークを持つ位置の散乱角度2θより、連続多孔構造の構造周期を下記の式によって得た。
〔平均空隙率〕
後述のアスペクト比、枝部の集合数(N)、枝部の集合数(N)と接合部の数(n)の比と同様に、イオンビームによる連続切片法により得られた粒子状多孔質炭素材料の断面を走査型二次電子顕微鏡にて材料中心部を1±0.1(nm/画素)となるよう調整された拡大率で、70万画素以上の解像度で観察した画像から、計算に必要な着目領域を512画素四方で設定し、着目領域の面積A、孔部分の面積をBとして、下記の式で算出した。
〔細孔直径分布曲線の取得〕
粒子状多孔質炭素材料を300℃、5時間の条件で真空乾燥を行うことで吸着したガス成分を除去した。その後、島津製作所製オートポアIV9500を用いて細孔直径分布曲線を取得した。
イオンビームによる連続切片法で粒子状多孔質炭素材料の三次元像を得た。得られた三次元像に対してFEI社製Amiraを用いて細線化処理を施し、細線データ及び接合部の数を得た。また得られた細線化処理データから、枝部の一の接合部から他の接合部に相当する細線の経路を10分割し、三次元像内で分割した各経路の中点位置Xから空隙表面に対して垂線をひき、この垂線が空隙に突き当たるまでの距離R(X)を算出した。このときR(X)は、10°ステップで細線を中心として引いた垂線を360°を走査した平均値とした。ここでR(X)が最小となる値Rminから算出されるD=2Rmin、R(X)の算出に用いた接合部から接合部までの経路の合計である距離Lを用いて、アスペクト比(L/D)を算出した。このアスペクト比(L/D)を10の枝部に対して同様の解析を実施し、その平均値をアスペクト比とした。
粒子状多孔質炭素材料を電子顕微鏡用観察ステージに乗せ、粒子を個別に10以上認識できる拡大率で5か所の撮影を行った。撮影を行った画像内から粒子10個を抽出し、それぞれの粒子の面積を求め、該面積から粒子直径を同一の面積を持つ円として換算した。該操作を抽出した粒子50個分について実施し、その平均値を平均粒径とした。
37.5gのポリサイエンス社製ポリアクリロニトリル(MW15万)と37.5gのシグマ・アルドリッチ社製ポリビニルピロリドン(MW4万)、及び、溶媒として425gの和研薬製ジメチルスルホキシド(DMSO)をセパラブルフラスコに投入し、3時間攪拌および還流を行いながら150℃で均一かつ透明な溶液を調整した。このときポリアクリロニトリルの濃度、ポリビニルピロリドンの濃度はそれぞれ7.5重量%であった。
延伸倍率を2.0倍に変更したこと以外は実施例1と同様の方法で多孔質炭素繊維及びその粉砕品を得た。得られた粉砕品の構造周期は0.085μm、平均空隙率は54%であった。また平均粒径は7μmであった。また枝部のアスペクト比は4.2、枝部の集合数Nは204、接合部の数nは52であり、N/nの値は3.9であった。得られた粉砕品は、電気伝導性、熱伝導性に優れ、また圧縮に対する耐性も優れたものであった。
粉砕した時間を4hrとしたこと以外は、実施例1と同様の方法で多孔質炭素繊維及びその粉砕品を得た。得られた粉砕品の構造周期は0.087μm、平均空隙率は55%であった。また平均粒径は3μmであった。また枝部のアスペクト比は5.9、枝部の集合数Nは104、接合部の数nは61であり、N/nの値は1.7であった。得られた粉砕品は、電気伝導性、熱伝導性に優れ、また圧縮に対する耐性も優れたものであった。
粉砕した時間を10hrとしたこと以外は、実施例1と同様の方法で多孔質炭素繊維及びその粉砕品を得た。得られた粉砕品の構造周期は0.087μm、平均空隙率は55%であった。また平均粒径は1μmであった。また枝部のアスペクト比は6.3、枝部の集合数Nは35、接合部の数nは27であり、N/nの値は1.3であった。得られた粉砕品の電気伝導性、熱伝導性及び圧縮に対する耐性は、良好であった。
アクリロニトリル(以下ANと略記する)98モル%、メタアクリル酸(以下MAAと略記する)2モル%からなるAN共重合体60重量%と、メチルアクリレート(以下MMAと略記する)99モル%、アクリル酸メチル(以下MAと略記する)1モル%の熱分解性共重合体40重量%とからなる両共重合体の混合物100重量部に対して、AN40モル%、MMA60モル%からなるブロック共重合体からなる相溶剤5重両部を混合し、溶剤としてジメチルホルムアミド(以下DMFと略記する)に、三者の混合物の溶液濃度が26重量%になるように溶解し、混合溶液とした。
Claims (9)
- 連続多孔構造を有する粒子状多孔質炭素材料であって、下記A~Cを満たす粒子状多孔質炭素材料。
A:前記連続多孔構造を形成する枝部のアスペクト比が3以上である。
B:前記枝部が接合部を介して集合数(N)3以上で集合している。
C:前記枝部の集合数(N)と前記接合部の数(n)の比(N/n)が1.2以上である。 - 前記連続多孔構造の構造周期が0.002μm~10μmである、請求項1に記載の粒子状多孔質炭素材料。
- 前記連続多孔構造の平均空隙率が10~80%である、請求項1または2に記載の粒子状多孔質炭素材料。
- 前記N/nが1.5以上である、請求項1~3のいずれかに記載の粒子状多孔質炭素材料。
- さらに、連続多孔構造を有しない部分を有する、請求項1~4のいずれかに記載の粒子状多孔質炭素材料。
- 10nm~10μmの粒径を有する、請求項1~5のいずれかに記載の粒子状多孔質炭素材料。
- 請求項1~6のいずれかに記載の粒子状多孔質炭素材料を含む粒子状炭素材料集合体。
- 工程1:炭化可能樹脂10~90重量%と、消失樹脂90~10重量%と相溶させ、樹脂混合物とする工程;
工程2:工程1で得られた樹脂混合物を相分離させて微細構造を形成し、当該微細構造を固定化して前駆体とする工程;
工程3:工程2で得られた前駆体を延伸する工程;
工程4:延伸された前駆体を炭化し、多孔質炭素材料とする工程;
工程5:工程4で得られた多孔質炭素材料を粉砕する工程
をこの順に有し、工程3と工程4の間、または工程4と同時に前記消失樹脂の除去を行う粒子状多孔質炭素材料の製造方法。 - 工程1:炭化可能樹脂10~90重量%と、消失樹脂90~10重量%と相溶させ、樹脂混合物とする工程;
工程2:工程1で得られた樹脂混合物を相分離させて微細構造を形成し、当該微細構造を固定化して前駆体とする工程;
工程3:工程2で得られた前駆体を延伸する工程;
をこの順に有し、
その後、延伸された前駆体を粉砕する工程を有し、
さらに
工程4:粉砕された前駆体を炭化する工程;
を有し、工程3と工程4の間、または工程4と同時に前記消失樹脂の除去を行う粒子状多孔質炭素材料の製造方法。
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EP3196164A4 (en) | 2018-03-28 |
JP6657952B2 (ja) | 2020-03-04 |
KR20170059995A (ko) | 2017-05-31 |
CN107074545B (zh) | 2020-05-19 |
TWI665158B (zh) | 2019-07-11 |
US20170291820A1 (en) | 2017-10-12 |
JPWO2016043030A1 (ja) | 2017-06-29 |
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