JP2023079774A - Porous carbon material and method for producing the same, precursor of porous carbon material, and electrode material using porous carbon material - Google Patents
Porous carbon material and method for producing the same, precursor of porous carbon material, and electrode material using porous carbon material Download PDFInfo
- Publication number
- JP2023079774A JP2023079774A JP2021193399A JP2021193399A JP2023079774A JP 2023079774 A JP2023079774 A JP 2023079774A JP 2021193399 A JP2021193399 A JP 2021193399A JP 2021193399 A JP2021193399 A JP 2021193399A JP 2023079774 A JP2023079774 A JP 2023079774A
- Authority
- JP
- Japan
- Prior art keywords
- carbon material
- porous carbon
- precursor
- oxygen
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 93
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000007772 electrode material Substances 0.000 title claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000001301 oxygen Substances 0.000 claims abstract description 59
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 59
- 238000010304 firing Methods 0.000 claims abstract description 44
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004246 zinc acetate Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000013110 organic ligand Substances 0.000 claims abstract description 16
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 8
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 claims description 8
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 44
- 239000011701 zinc Substances 0.000 description 41
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 38
- 229910052725 zinc Inorganic materials 0.000 description 38
- 238000005259 measurement Methods 0.000 description 23
- 239000011787 zinc oxide Substances 0.000 description 22
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- 238000002447 crystallographic data Methods 0.000 description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 125000003172 aldehyde group Chemical group 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000002076 thermal analysis method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000001144 powder X-ray diffraction data Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- SBBQDUFLZGOASY-OWOJBTEDSA-N 4-[(e)-2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-OWOJBTEDSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- JMRQKWYIMBFUBZ-UHFFFAOYSA-N benzene-1,2,4-tricarbaldehyde Chemical compound O=CC1=CC=C(C=O)C(C=O)=C1 JMRQKWYIMBFUBZ-UHFFFAOYSA-N 0.000 description 1
- AEKQNAANFVOBCU-UHFFFAOYSA-N benzene-1,3,5-tricarbaldehyde Chemical compound O=CC1=CC(C=O)=CC(C=O)=C1 AEKQNAANFVOBCU-UHFFFAOYSA-N 0.000 description 1
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IQDQMRZGMILNMQ-UHFFFAOYSA-N naphthalene-2,6-dicarbaldehyde Chemical compound C1=C(C=O)C=CC2=CC(C=O)=CC=C21 IQDQMRZGMILNMQ-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
本発明は、高い比表面積値を得ることができる多孔質炭素材料およびその製造方法と、その多孔質炭素材料を用いた電極材料とに関するものである。 TECHNICAL FIELD The present invention relates to a porous carbon material capable of obtaining a high specific surface area value, a method for producing the same, and an electrode material using the porous carbon material.
一般に、電気二重層キャパシタの分極性電極として、表面積が大きく導電性に優れている点から活性炭等の多孔質材料が用いられている。 In general, a porous material such as activated carbon is used as a polarizable electrode of an electric double layer capacitor because of its large surface area and excellent conductivity.
そこで、従来より、このような活性炭に変わるものとして、本発明者等は、三次元網目構造に構成された金属錯体を合成した後、それを焼成することによって、電解質イオンの吸脱着を容易に行うことをできるようにした多孔性金属錯体の焼成体を提案している（例えば、特許文献１参照）。 Therefore, as an alternative to such activated carbon, the present inventors synthesized a metal complex having a three-dimensional network structure and then calcined it to facilitate the adsorption and desorption of electrolyte ions. We have proposed a sintered body of a porous metal complex capable of performing the above (see, for example, Patent Document 1).
しかし、上記従来の多孔性金属錯体の焼成体の場合、活性炭に替わる電極材料として有効な性能を発揮するものの、本来の性能を発揮させるために幾つかの工夫をすることで、さらに高性能となることの知見を得て、本発明者等は新たな発明を完成するに至った。 However, in the case of the conventional porous metal complex sintered body, although it exhibits effective performance as an electrode material to replace activated carbon, it is possible to achieve higher performance by making some efforts to exhibit the original performance. The inventors of the present invention have completed a new invention after obtaining the knowledge that it will become.
本発明は、簡単な作業工程で製造でき、高比表面積の多孔質炭素材料、およびその製造方法と、当該多孔質炭素材料を用いた電極材料を提供することを目的としている。 An object of the present invention is to provide a porous carbon material having a high specific surface area that can be produced by a simple work process, a method for producing the same, and an electrode material using the porous carbon material.
上記課題を解決するための本発明に係る多孔質炭素材料の製造方法は、組成に酸素を含む有機化合物を有機溶媒に溶解してなる有機リガンド液と、酢酸亜鉛を有機溶媒に溶解してなる酢酸亜鉛溶液との合成反応により、前駆体を調製し、当該前駆体を焼成することによって多孔質炭素材料を製造する方法であって、酸素元素／炭素元素の比率が、０．２５以上０．５以下の構造に特定された前駆体を調製し、当該前駆体を焼成する際、１０００℃以上の温度を所定時間以上維持することにより、酸素含有官能基を脱離させてその跡に細孔を形成して多孔質にするものである。 A method for producing a porous carbon material according to the present invention for solving the above problems comprises an organic ligand liquid obtained by dissolving an organic compound containing oxygen in its composition in an organic solvent, and zinc acetate dissolved in an organic solvent. A method for producing a porous carbon material by preparing a precursor through a synthesis reaction with a zinc acetate solution and firing the precursor, wherein the ratio of oxygen element/carbon element is 0.25 or more and 0.25 or more. When preparing a precursor specified by the structure of 5 or less and firing the precursor, by maintaining a temperature of 1000 ° C. or higher for a predetermined time or longer, oxygen-containing functional groups are eliminated and pores are left behind. is formed to make it porous.
上記多孔質炭素材料の製造方法において、酸素を含む有機化合物としてテレフタル酸を用いるものであってもよい。 In the above method for producing a porous carbon material, terephthalic acid may be used as the oxygen-containing organic compound.
上記課題を解決するための本発明に係る多孔質炭素材料は、上記の製造方法によって得られる多孔質炭素材料であって、比表面積が２４００ｍ２／ｇ以上となされたものである。 A porous carbon material according to the present invention for solving the above problems is a porous carbon material obtained by the above production method and having a specific surface area of 2400 m 2 /g or more.
上記多孔質炭素材料は、窒素吸脱着等温線より得られた結果をＢＪＨ法により算出して得られる、全比表面積に占めるメソ孔（２～５０ｎｍ）の比表面積の割合が、２０％以上となされたものであってもよい。 In the porous carbon material, the ratio of the specific surface area of mesopores (2 to 50 nm) to the total specific surface area, which is obtained by calculating the results obtained from the nitrogen adsorption-desorption isotherm by the BJH method, is 20% or more. may have been made.
上記課題を解決するための本発明の前駆体は、焼成することで多孔質炭素材料として調製することができる前駆体であって、組成に酸素を含む有機化合物を有機溶媒に溶解してなる有機リガンド液と、酢酸亜鉛を有機溶媒に溶解してなる酢酸亜鉛溶液と、の合成反応により得られ、酸素元素／炭素元素の比率が、０．２５以上０．５以下の構造に特定されたものである。 The precursor of the present invention for solving the above problems is a precursor that can be prepared as a porous carbon material by firing, and is an organic compound obtained by dissolving an organic compound containing oxygen in the composition in an organic solvent. Obtained by a synthesis reaction of a ligand liquid and a zinc acetate solution obtained by dissolving zinc acetate in an organic solvent, and having a specified structure with an oxygen element/carbon element ratio of 0.25 or more and 0.5 or less. is.
上記課題を解決するための本発明の電極材料は、上記多孔質炭素材料を含むものである。 The electrode material of the present invention for solving the above problems includes the above porous carbon material.
上記多孔質炭素材料の製造方法において、組成に酸素を含む有機化合物としては、酸素含有官能基を有する芳香族炭化水素化合物を使用することができる。具体的には、カルボキシル基を有する芳香族炭化水素化合物や、アルデヒド基を有する芳香族炭化水素化合物を使用することができる。カルボキシル基を有する芳香族炭化水素化合物としては、単数または複数のベンゼン環に、単数または複数のカルボキシル基が設けられたものを使用することができる。単数のベンゼン環に、単数または複数のカルボキシル基が設けられた芳香族炭化水素化合物としては、例えば、安息香酸、または、フタル酸、イソフタル酸、テレフタル酸等のベンゼンジカルボン酸、または、１，３，５－ベンゼントリカルボン酸、１，２，４－ベンゼントリカルボン酸、１，２，３－ベンゼントリカルボン酸、または、１，２，４，５－ベンゼンテトラカルボン酸等を使用することができる。前駆体の合成や、合成された前駆体の元素比率を考慮すると、ベンゼンジカルボン酸を使用することが好ましく、テレフタル酸を使用することがより好ましい。複数のベンゼン環に、単数または複数の官能基が設けられた芳香族炭化水素化合物としては、例えば、２，６－ナフタレンジカルボン酸、４，４－ビスフェニルジカルボン酸、４，４－スチルベンジカルボン酸を使用することができる。アルデヒド基を有する芳香族炭化水素化合物としては、単数または複数のベンゼン環に、単数または複数のアルデヒド基が設けられたものを使用することができる。単数のベンゼン環に、単数または複数のアルデヒド基が設けられた芳香族炭化水素化合物としては、例えば、ベンズアルデヒド、フタルアルデヒド、イソフタルアルデヒド、テレフタルアルデヒド、１，３，５－ベンゼントリカルボアルデヒド、１，２，４－ベンゼントリカルボアルデヒドを使用することができる。複数のベンゼン環に、単数または複数のアルデヒド基が設けられた芳香族炭化水素化合物としては、例えば、２，６－ナフタレンジカルボアルデヒドを使用することができる。 In the above method for producing a porous carbon material, an aromatic hydrocarbon compound having an oxygen-containing functional group can be used as the organic compound containing oxygen in its composition. Specifically, an aromatic hydrocarbon compound having a carboxyl group or an aromatic hydrocarbon compound having an aldehyde group can be used. As the aromatic hydrocarbon compound having a carboxyl group, one having one or more carboxyl groups attached to one or more benzene rings can be used. Examples of aromatic hydrocarbon compounds in which a single benzene ring is provided with one or more carboxyl groups include, for example, benzoic acid, or benzenedicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, or 1,3 ,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, or 1,2,4,5-benzenetetracarboxylic acid or the like can be used. Considering the synthesis of the precursor and the element ratio of the synthesized precursor, benzenedicarboxylic acid is preferably used, and terephthalic acid is more preferably used. Examples of aromatic hydrocarbon compounds in which a plurality of benzene rings are provided with one or more functional groups include 2,6-naphthalenedicarboxylic acid, 4,4-bisphenyldicarboxylic acid, and 4,4-stilbenedicarboxylic acid. can be used. As the aromatic hydrocarbon compound having an aldehyde group, one having one or more aldehyde groups attached to one or more benzene rings can be used. Examples of aromatic hydrocarbon compounds in which a single benzene ring is provided with one or more aldehyde groups include benzaldehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 1,3,5-benzenetricarbaldehyde, 1, 2,4-benzenetricarbaldehyde can be used. As the aromatic hydrocarbon compound in which a plurality of benzene rings are provided with one or more aldehyde groups, for example, 2,6-naphthalene dicarbaldehyde can be used.
上記多孔質炭素材料の製造方法において、上記した組成に酸素を含む有機化合物を溶解する有機溶媒としては、例えば、ＮＭＰ（Ｎ－メチル－２－ピロリドン）、メタノール、エタノール、ＤＭＳＯ（ジメチルスルホキシド：Ｃ２Ｈ６ＳＯ）、ＤＭＦ（ジメチルホルムアミド：Ｃ３Ｈ７ＮＯ）、ＤＭＡ（ジメチルアセトアミド：Ｃ４Ｈ９ＮＯ）、ＤＥＦ（Ｎ，Ｎ－ジエチルホルムアミド）などを用いることができる。これらは、単独溶媒であってもよいし、複数種類を混合した混合溶媒であってもよい。この有機溶媒５～５００ｍｌに、上記した組成に酸素を含む有機化合物０．０５～０．５ｇを溶解することで、有機リガンド液が調製される。 In the method for producing a porous carbon material, examples of the organic solvent that dissolves the organic compound containing oxygen in the above composition include NMP (N-methyl-2-pyrrolidone), methanol, ethanol, DMSO (dimethyl sulfoxide: C2H6SO ), DMF (dimethylformamide: C3H7NO), DMA (dimethylacetamide: C4H9NO), DEF (N,N-diethylformamide) and the like can be used. These may be a single solvent, or a mixed solvent in which a plurality of types are mixed. An organic ligand liquid is prepared by dissolving 0.05 to 0.5 g of an organic compound containing oxygen in the above composition in 5 to 500 ml of this organic solvent.
上記多孔質炭素材料の製造方法において、酢酸亜鉛は、上記有機リガンド液の組成に酸素を含む有機化合物と配位結合して前駆体を合成可能な化合物として用いられる。ここで、酢酸亜鉛は、当該酢酸亜鉛の他に、酢酸亜鉛二水和物、などを含む。酢酸亜鉛を用いた場合、当該酢酸亜鉛は、弱酸性であるため、前駆体を合成する際の反応が穏やかになり、粒子の核成長が緩やかに進行する効果がある。逆に、硝酸亜鉛などの強酸を用いてしまうと、前駆体を合成する際の反応が激しくなり、粒子の核成長が早く、粒子径が小さくなってしまい、前駆体の回収が困難になる。それに比べて酢酸亜鉛を用いた場合は、大きな粒子径の前駆体が取れるので、安定的に回収し易くなる。また、酢酸亜鉛は、その組成に炭素元素が含まれているが、硝酸亜鉛は含まれていない。このように亜鉛元素に対して炭素元素が少なすぎると、後に前駆体を焼成した際に、亜鉛元素や酸素元素が分解されず、酸化亜鉛が生成されてしまうことになり、目的とする細孔の形成ができなくなってしまう。このような理由から、酢酸亜鉛を用いる。 In the method for producing a porous carbon material, zinc acetate is used as a compound capable of synthesizing a precursor by coordinating with an organic compound containing oxygen in the composition of the organic ligand liquid. Here, zinc acetate includes zinc acetate dihydrate and the like in addition to the zinc acetate. When zinc acetate is used, since zinc acetate is weakly acidic, the reaction in synthesizing the precursor is moderated, and the growth of grain nuclei proceeds gradually. Conversely, if a strong acid such as zinc nitrate is used, the reaction during synthesis of the precursor becomes violent, the nucleus growth of the particles is rapid, the particle diameter becomes small, and the recovery of the precursor becomes difficult. Compared to this, when zinc acetate is used, a precursor having a large particle size can be obtained, so that it can be collected stably and easily. Also, zinc acetate contains carbon elements in its composition, but zinc nitrate does not. If the carbon element is too small relative to the zinc element in this way, the zinc element and the oxygen element will not be decomposed when the precursor is sintered later, and zinc oxide will be generated. becomes impossible to form. For this reason zinc acetate is used.
上記多孔質炭素材料の製造方法において、酢酸亜鉛を溶解する溶媒としては、上記有機リガンド液に使用されているものと同じものが使用される。この有機溶媒１０～２００ｍｌに、上記した酢酸亜鉛０．１～０．８ｇを溶解することで、酢酸亜鉛溶液が調製される。 In the above method for producing a porous carbon material, as the solvent for dissolving zinc acetate, the same one as that used in the above organic ligand liquid is used. A zinc acetate solution is prepared by dissolving 0.1 to 0.8 g of the above zinc acetate in 10 to 200 ml of this organic solvent.
組成に酸素を含む有機化合物を有機溶媒に溶解してなる有機リガンド液と、酢酸亜鉛を有機溶媒に溶解してなる酢酸亜鉛溶液と、の合成反応により、前駆体が調製される。
この際、合成に使用する、組成に酸素を含む有機化合物、酢酸亜鉛、これらを溶解する有機溶媒、の各材料としては、合成反応によって得られる前駆体のＥＤＳ分析によるデータを結晶構造データベースと照合することにより、当該前駆体の構造を特定し、その構造から酸素元素／炭素元素の比率が、０．２５以上０．５以下となるものを使用する。この値が０．２５未満の場合、後述する酸素含有官能基が脱離した跡に、十分な細孔を形成して多孔質化を図ることができなくなる。この値が０．５を超えるものは、物として実質的に確認できないが、あまりこの数値が高すぎると、効果が飽和してしまうことが考えられる。
A precursor is prepared by a synthesis reaction between an organic ligand solution obtained by dissolving an organic compound containing oxygen in an organic solvent and a zinc acetate solution obtained by dissolving zinc acetate in an organic solvent.
At this time, the organic compound containing oxygen in the composition, zinc acetate, and the organic solvent for dissolving them, which are used in the synthesis, are selected from the data obtained by EDS analysis of the precursor obtained by the synthesis reaction and collated with the crystal structure database. By doing so, the structure of the precursor is specified, and from the structure, the ratio of oxygen element/carbon element is 0.25 or more and 0.5 or less. If this value is less than 0.25, sufficient pores cannot be formed in the traces of detachment of the oxygen-containing functional groups, which will be described later, to achieve porosity. If this value exceeds 0.5, it cannot be practically confirmed as a product, but if this value is too high, the effect may be saturated.
また、酢酸亜鉛に関しても、ＥＤＳ分析による亜鉛元素／炭素元素の比率が０．１＜Ｚｎ／Ｃとすることで、後述する亜鉛元素が離脱した跡に、十分な細孔を形成して多孔質化を図ることができる。この酢酸亜鉛を使用しているので、得られる前駆体は、純ケイ素の回折角度のピーク（２θ）が２８．２°、４７．１２°、５５．９°に測定される条件で、Ｘ線回折した際、９．９２°、１１．４７°、１１．８８°、１６．５２°、２４．２５°（何れのピークも誤差±０．３°）に相当する少なくとも５つの、亜鉛元素に由来する回折角度のピークが現れる前駆体が調製されることとなる。
さらに、得られる前駆体は、例えば、酢酸亜鉛、ＮＭＰ、テレフタル酸を用いて合成することで、上記５つの回折角度のピークを有したものとなるが、前駆体の状態では、多孔質ではない鱗片状の状態で調製される。この前駆体は、比表面積が１５ｍ２／ｇ以下となり、前駆体の状態では多孔質に形成されていない。
In addition, with respect to zinc acetate, by setting the ratio of zinc element/carbon element as determined by EDS analysis to 0.1<Zn/C, sufficient pores are formed in the traces of desorption of the zinc element described later, resulting in a porous structure. can be improved. Since this zinc acetate is used, the resulting precursor is X-ray ray At least five zinc elements corresponding to 9.92°, 11.47°, 11.88°, 16.52°, and 24.25° (all peaks with an error of ±0.3°) when diffracted. A precursor is prepared in which the derived diffraction angle peak appears.
Furthermore, the obtained precursor, for example, by synthesizing using zinc acetate, NMP, and terephthalic acid, has the above five diffraction angle peaks, but is not porous in the state of the precursor. Prepared in the scaly form. This precursor has a specific surface area of 15 m 2 /g or less, and is not porous in the precursor state.
上記前駆体は、焼成することによって多孔質炭素材料とされる。この際、焼成は、前駆体を１０００℃で焼成した際に検出されるＸ線回折の回折角度のピークが検出されなくなるまで、当該前駆体を高温で焼成する。すなわち、上記前駆体は、酢酸亜鉛溶液を用いて合成しているので、当該前駆体を７００℃程度の温度で焼成すると、前駆体に入り込んでいた酸化亜鉛や亜鉛が、当該前駆体に残ってしまい、長時間焼成しても、回折角度のピークとして検出される。確認したピークは、３１．７°、３４．３°、３６．２°、４７．４５°、５６．５°（何れのピークも誤差±０．３）である。しかし、亜鉛の沸点である９０７℃以上の温度で焼成させると、酸化亜鉛を分解し、亜鉛を蒸発させることができるので、前駆体に入り込んでいた酸化亜鉛や亜鉛を消失させ、上記したピークも無くなり、当該酸化亜鉛や亜鉛が入り込んでいた跡に、細孔が形成され多孔質になる。この際、亜鉛の沸点である９０７℃以上で焼成すれば、確実に細孔を形成して多孔質にすることができる。したがって、１０００℃で焼成すれば、前駆体に入り込んでいた酸化亜鉛や亜鉛を消失させることができる。また、１０００℃で焼成すれば、前駆体の酸素含有官能基が脱離して、さらに細孔が形成されてより一層多孔質になる。したがって、焼成条件としては、１０００℃以上で行えば良いが、亜鉛の沸点以上の１０００℃の温度であっても、回折データをワイドレンジで確認すると亜鉛が残存している場合があるので、残存している亜鉛が蒸発するためには３０分程度の時間が必要とされる。そのため、１０００℃で、時間としては、残留する亜鉛を蒸発させて酸素含有官能基を脱離させることができる条件であれば、特に限定されるものではなく、亜鉛を蒸発させた後、酸素含有官能基を確実に脱離させることを考慮すると３０分～８時間、好ましくは５時間～８時間、または前駆体１ｇ当たり３．８４時間～６１．６時間の焼成を行うことがよい。 The precursor is calcined to form a porous carbon material. At this time, the precursor is baked at a high temperature until the diffraction angle peak of X-ray diffraction detected when the precursor is baked at 1000° C. is no longer detected. That is, since the precursor is synthesized using a zinc acetate solution, when the precursor is calcined at a temperature of about 700° C., zinc oxide and zinc that have entered the precursor remain in the precursor. Even if it is baked for a long time, it is detected as a diffraction angle peak. The confirmed peaks are 31.7°, 34.3°, 36.2°, 47.45°, 56.5° (all peaks have an error of ±0.3). However, when calcined at a temperature of 907° C. or higher, which is the boiling point of zinc, zinc oxide can be decomposed and zinc can be evaporated. Pores are formed in traces where the zinc oxide or zinc has entered, resulting in a porous structure. At this time, if it is sintered at 907° C. or higher, which is the boiling point of zinc, pores can be reliably formed to make it porous. Therefore, by firing at 1000° C., zinc oxide and zinc that have entered the precursor can be eliminated. Also, if the precursor is calcined at 1000° C., the oxygen-containing functional groups of the precursor are eliminated, and pores are formed to make the material even more porous. Therefore, the firing conditions may be 1000 ° C. or higher, but even at a temperature of 1000 ° C. above the boiling point of zinc, if the diffraction data is confirmed in a wide range, zinc may remain. It takes about 30 minutes to evaporate the zinc. Therefore, at 1000 ° C., the time is not particularly limited as long as it is a condition that allows the remaining zinc to evaporate and the oxygen-containing functional group to be eliminated. Considering that the functional groups are surely eliminated, the baking should be carried out for 30 minutes to 8 hours, preferably 5 hours to 8 hours, or 3.84 hours to 61.6 hours per 1 g of the precursor.
焼成は、不活性ガス雰囲気（窒素ガスもしくはアルゴンガス雰囲気）にて行うものであってもよい。この際、不活性ガス雰囲気は、０．１～１．０リットル／分のガス流量で焼成雰囲気を置換しながら行うものであってもよい。また、焼成時に所定の温度から５～１０℃／分程度の昇温速度で昇温して所定温度にして焼成を行うものであってもよい。さらに、焼成は、減圧雰囲気下で行うものであってもよい。焼成する炉は、炉心管タイプ、ボックス炉、ロータリーキルン炉などを用いることができる。 Firing may be performed in an inert gas atmosphere (nitrogen gas or argon gas atmosphere). At this time, the inert gas atmosphere may be performed while replacing the firing atmosphere with a gas flow rate of 0.1 to 1.0 liter/minute. Further, the temperature may be increased from a predetermined temperature at a rate of about 5 to 10° C./min during firing to reach the predetermined temperature, and the firing may be performed. Furthermore, the firing may be performed under a reduced pressure atmosphere. As a furnace for firing, a furnace core tube type, a box furnace, a rotary kiln furnace, or the like can be used.
このようにして構成された多孔質炭素材料は、組成に酸素を含む有機化合物を有機溶媒に溶解してなる有機リガンド液と、酢酸亜鉛を有機溶媒に溶解してなる亜鉛イオン溶液と、の合成反応により、当該合成反応によって得られる前駆体のＥＤＳ分析によるデータを結晶構造データベースと照合することにより、酸素元素／炭素元素の比率が、０．２５以上０．５以下の構造に特定された、三次元網目構造で骨格形成がされた前駆体を調製し、この前駆体に取り込まれている酸化亜鉛や亜鉛や酸素が無くなるまで焼成することにより、酸化亜鉛や亜鉛や酸素を消失させ、当該酸化亜鉛や亜鉛や酸素が入り込んでいた跡に、細孔を形成して多孔質化を図ることができる。しかも、酸化亜鉛や亜鉛や酸素を消失させることができる高温で焼成するため、余計な不純物等も同時に消失させることができるので、焼成後の水洗の必要も無くすことができ、焼成工程後に得られた焼成体をそのまま使用することができることとなり、簡単な作業工程で多孔質炭素材料を得ることができる。 The porous carbon material thus constructed is produced by synthesizing an organic ligand solution obtained by dissolving an organic compound containing oxygen in its composition in an organic solvent, and a zinc ion solution obtained by dissolving zinc acetate in an organic solvent. By comparing the data obtained by EDS analysis of the precursor obtained by the synthesis reaction from the reaction with the crystal structure database, the structure was identified as having an oxygen element/carbon element ratio of 0.25 or more and 0.5 or less. A precursor having a skeleton formed with a three-dimensional network structure is prepared, and the zinc oxide, zinc, and oxygen are eliminated by firing until the zinc oxide, zinc, and oxygen incorporated in this precursor are eliminated, and the oxidation is performed. Porosity can be achieved by forming pores in the traces of zinc, zinc, and oxygen that have entered. Moreover, since it is fired at a high temperature that can eliminate zinc oxide, zinc, and oxygen, unnecessary impurities can be eliminated at the same time, so the need for washing with water after firing can be eliminated, and the resulting product can be obtained after the firing process. The sintered body can be used as it is, and a porous carbon material can be obtained by a simple working process.
しかも、このようにして構成された多孔質炭素材料は、元々、三次元網目構造で骨格形成された前駆体から、酸化亜鉛や亜鉛や酸素の部分を消失させて、当該酸化亜鉛や亜鉛や酸素が入り込んでいた跡に、細孔を形成しているため、静電容量の高い高性能な電極材料とすることができる。また、このようにして形成される細孔は、上記酸化亜鉛や亜鉛や酸素が抜けた跡に形成されるものが多くなるため、ＩＵＰＡＣで定義されるメソ孔（２～５０ｎｍ）を多く形成できることとなり、全比表面積に占めるメソ孔の比表面積の割合を２０％以上にすることができる。さらに、このメソ孔は、多孔質ではない前駆体の状態から、酸化亜鉛や亜鉛や酸素の部分を消失させる１０００℃の高温で、かつ、上記した長時間の焼成を行うことで、指数関数的またはｎ次関数（ｎ＞１）的に酸化亜鉛や亜鉛や酸素を消失させて、その跡に細孔を形成することができるので、比表面積を２５００ｍ２／ｇ以上とし、そのうち、メソ孔の比表面積を１４００ｍ２／ｇ以上とした超高性能な多孔質炭素材料を得ることができる。 Moreover, the porous carbon material thus constructed is obtained by removing the zinc oxide, zinc, and oxygen from the precursor that originally had the skeleton of the three-dimensional network structure, and removing the zinc oxide, zinc, and oxygen from the precursor. Since pores are formed in the traces of intrusion, a high-performance electrode material with high capacitance can be obtained. In addition, many of the pores formed in this way are formed at the traces of zinc oxide, zinc, and oxygen that have escaped, so many mesopores (2 to 50 nm) defined by IUPAC can be formed. Thus, the ratio of the specific surface area of the mesopores to the total specific surface area can be 20% or more. Furthermore, the mesopores are formed exponentially by firing at a high temperature of 1000 ° C. for a long time to eliminate zinc oxide, zinc and oxygen from the state of the precursor that is not porous. Alternatively, zinc oxide, zinc, and oxygen can be eliminated in an n-th order function (n>1), and pores can be formed in the traces, so the specific surface area is set to 2500 m 2 /g or more, and among them, mesopores An ultra-high-performance porous carbon material having a specific surface area of 1400 m 2 /g or more can be obtained.
以上述べたように、本発明によると、組成に酸素を含む有機化合物を有機溶媒に溶解してなる有機リガンド液と、酢酸亜鉛を有機溶媒に溶解してなる亜鉛イオン溶液との合成反応によって得られる前駆体のＥＤＳ分析によるデータを、結晶構造データベースと照合することにより、酸素元素／炭素元素の比率が、０．２５以上０．５以下の構造に特定された前駆体を調製し、当該前駆体を焼成する際、１０００℃以上の温度を所定時間以上維持することにより、酸素元素を脱離させてその跡に細孔を形成して多孔質化を図った多孔質炭素材料を得ることができる。このようにして構成された多孔質炭素材料は、酢酸亜鉛に由来する酸化亜鉛および亜鉛や、酸素を含む有機化合物に由来する酸素を消失させて当該酸化亜鉛や亜鉛や酸素の跡に細孔を形成した高比表面積の多孔質炭素材料となるため、静電容量の高い高性能な電極材料とすることができる。 As described above, according to the present invention, an organic ligand solution obtained by dissolving an organic compound containing oxygen in its composition in an organic solvent and a zinc ion solution obtained by dissolving zinc acetate in an organic solvent are synthesized. Data obtained by EDS analysis of the precursor obtained is collated with the crystal structure database to prepare a precursor specified to have a structure in which the ratio of oxygen element/carbon element is 0.25 or more and 0.5 or less, and the precursor When the body is sintered, a temperature of 1000° C. or higher is maintained for a predetermined period of time or longer to desorb oxygen elements and form pores in the traces thereof to obtain a porous carbon material that is made porous. can. The porous carbon material thus configured eliminates zinc oxide and zinc derived from zinc acetate and oxygen derived from an organic compound containing oxygen to form pores in traces of the zinc oxide, zinc, and oxygen. Since the formed porous carbon material has a high specific surface area, it can be a high-performance electrode material having a high capacitance.
以下、本発明に係る実施の形態について説明する。 BEST MODE FOR CARRYING OUT THE INVENTION Embodiments according to the present invention will be described below.
［実施例１，２、比較例１］
（前駆体の調製）
酢酸亜鉛・二水和物をＮＭＰ（Ｎ－メチル－２－ピロリドン）に溶解させたものを亜鉛イオン溶液として調製した。
４，４－スチルベンジカルボン酸をＮＭＰ（Ｎ－メチル－２－ピロリドン）に溶解させたものを有機リガンド液として調製した。
テレフタル酸をＮＭＰ（Ｎ－メチル－２－ピロリドン）に溶解させたものを有機リガンド液として調製した。
質量比にて、４，４－スチルベンジカルボン酸／酢酸亜鉛・二水和物＝４．９となるように、上記亜鉛イオン溶液と、上記有機リガンド液とを混合し、合成反応により実施例１に係る前駆体を得た。
質量比にて、テレフタル酸／酢酸亜鉛・二水和物＝３．０となるように、上記亜鉛イオン溶液と、上記有機リガンド液とを混合し、合成反応により実施例２に係る前駆体を得た。
[Examples 1 and 2, Comparative Example 1]
(Precursor preparation)
A zinc ion solution was prepared by dissolving zinc acetate dihydrate in NMP (N-methyl-2-pyrrolidone).
An organic ligand solution was prepared by dissolving 4,4-stilbenedicarboxylic acid in NMP (N-methyl-2-pyrrolidone).
An organic ligand solution was prepared by dissolving terephthalic acid in NMP (N-methyl-2-pyrrolidone).
The zinc ion solution and the organic ligand liquid were mixed so that the mass ratio of 4,4-stilbenedicarboxylic acid/zinc acetate dihydrate=4.9, and the synthetic reaction of Example 1 was obtained.
The zinc ion solution and the organic ligand liquid were mixed so that the mass ratio of terephthalic acid/zinc acetate dihydrate=3.0, and the precursor according to Example 2 was produced by a synthesis reaction. Obtained.
（前駆体のＯ／Ｃの元素比率）
上記した実施例１および実施例２の各前駆体を、下記装置によりＥＤＳ分析を行い、図１に示すように、このデータを結晶構造データベースと照合して前駆体の構造単位を特定した。実施例１はＣ１６Ｈ１０Ｏ４Ｚｎ、実施例２はＣ８Ｈ４Ｏ４Ｚｎと特定でき、その構造からＯ／Ｃの元素比率を求めた。その結果、実施例１はＯ／Ｃ＝０．２５、実施例２はＯ／Ｃ＝０．５であることを確認した。
また、上記した実施例１および実施例２の各前駆体は、図２に示すように、純ケイ素の回折角度のピーク（２θ）が２８．２°、４７．１２°、５５．９°に測定される条件で、Ｘ線回折した際、９．９２°、１１．４７°、１１．８８°、１６．５２°、２４．２５°（何れのピークも誤差±０．３°）に相当する少なくとも５つの、亜鉛元素に由来する回折角度のピークが現れる前駆体であることも確認した。
測定機種：ＪＥＭ－２１００Ｆ（日本電子株式会社製）
測定条件：加速電圧２００ｋＶ
(Precursor O/C element ratio)
Each of the precursors of Examples 1 and 2 described above was subjected to EDS analysis using the following equipment. As shown in FIG. 1, this data was collated with a crystal structure database to identify the structural units of the precursor. Example 1 was identified as C 16 H 10 O 4 Zn, and Example 2 was identified as C 8 H 4 O 4 Zn. As a result, it was confirmed that Example 1 had O/C=0.25 and Example 2 had O/C=0.5.
In addition, as shown in FIG. 2, each of the precursors of Examples 1 and 2 described above has diffraction angle peaks (2θ) of pure silicon of 28.2°, 47.12°, and 55.9°. Equivalent to 9.92°, 11.47°, 11.88°, 16.52°, and 24.25° (each peak has an error of ±0.3°) when X-ray diffraction is performed under the conditions of measurement. It was also confirmed that the precursor exhibits at least five diffraction angle peaks derived from zinc element.
Measurement model: JEM-2100F (manufactured by JEOL Ltd.)
Measurement conditions: acceleration voltage of 200 kV
（前駆体の焼成）
上記の方法で調製した実施例１および実施例２の前駆体を、それぞれ焼成して多孔質炭素材料を得た。
(Baking of precursor)
The precursors of Examples 1 and 2 prepared by the above method were fired to obtain porous carbon materials.
上記前駆体の焼成条件は、窒素ガス雰囲気にて、ガス流量０．２リットル／分、室温２５℃から昇温速度１０℃／分で昇温し、１０００℃到達後、その温度で５時間の焼成を行った。 The firing conditions for the precursor are as follows: in a nitrogen gas atmosphere, at a gas flow rate of 0.2 liter/minute, the temperature is raised from room temperature of 25°C at a temperature elevation rate of 10°C/minute, and after reaching 1000°C, the temperature is maintained for 5 hours. Firing was performed.
（焼成過程でのＸ線回折）
上記の前駆体から多孔質炭素材料を得るまでの焼成工程において、当該焼成工程の途中でサンプリングを行い、各焼成工程における実施例１および実施例２の各多孔質炭素材料のＸ線回折を行った。測定機種、測定条件などは下記の通りである。結果を図３ないし図５に示す。また、比較例１として、組成に酸素元素を含まないｓｉｇｍａ‐ａｌｄｒｉｃｈ社製商品名「ＢａｓｏｌｉｔｅＺ１２００」を使用して同様のＸ線回折を行った。図３に対応する結果を図６に、図５に対応する結果を図７（ｂ）に示す。図７（ａ）は亜鉛部分の回折データを示している。なお、図１および図６において、対照物質として酸化亜鉛の測定データを併記する。
測定機種：smart Lab SE （株式会社リガク社製）、多目的高温装置
測定条件：サンプルを０．０２g、白金ホルダーにセットし、Smart Lab SEの多目的高温ユニットに組み込む。昇温プログラムは、窒素ガス雰囲気（０．２リットル／分）のもと、１０℃／分で昇温し、５０℃、１００℃、１５０℃、…、１１００℃と５０℃ずつ、その各温度に到達すると、X線の測定を開始する。測定角度の範囲は２θ＝２°～4０°
スキャンスピード１０°／ｍｉｎ
Ｘ線源；Ｃｕ（Ｋα）
(X-ray diffraction in the firing process)
In the firing process until the porous carbon material is obtained from the above precursor, sampling was performed during the firing process, and X-ray diffraction was performed on each of the porous carbon materials of Examples 1 and 2 in each firing process. rice field. The measurement model, measurement conditions, etc. are as follows. The results are shown in FIGS. 3-5. In addition, as Comparative Example 1, similar X-ray diffraction was performed using Sigma-Aldrich's trade name "Basolite Z1200" which does not contain an oxygen element in its composition. The results corresponding to FIG. 3 are shown in FIG. 6, and the results corresponding to FIG. 5 are shown in FIG. 7(b). FIG. 7(a) shows the diffraction data of the zinc portion. 1 and 6 also show measurement data for zinc oxide as a control substance.
Measurement model: smart Lab SE (manufactured by Rigaku Co., Ltd.), multi-purpose high temperature device Measurement conditions: 0.02 g of sample is set in a platinum holder and incorporated into the multi-purpose high temperature unit of Smart Lab SE. The temperature raising program is to raise the temperature at 10 ° C./min under a nitrogen gas atmosphere (0.2 liters / min), 50 ° C., 100 ° C., 150 ° C., ..., 1100 ° C. and 50 ° C. When it reaches , it starts measuring X-rays. The range of measurement angles is 2θ = 2° to 40°
X-ray source; Cu(Kα)
（焼成過程での示唆熱分析および熱重量分析）
上記の前駆体から多孔質炭素材料を得るまでの焼成工程において、当該焼成工程の途中でサンプリングを行い、各焼成工程における実施例１および実施例２の各多孔質炭素材料の示唆熱分析および熱重量分析を行った。測定機種、測定条件などは下記の通りである。結果を図８に示す。
示唆熱分析
測定機種：DTG-60 （株式会社島津製作所）
測定条件：サンプルを5ｍｇ程度、白金ホルダーにセットし、窒素ガス雰囲気（０．２リットル／分）のもと、１０℃／分で昇温し、３０～３８度（２θ）において、低角側から酸化亜鉛の反射面（ミラー指数）（１００）、（００２）、そして（１０１）面が確認できなくなるまで高温にして焼成した。
熱重量分析
測定機種：上と同じ
測定条件：上と同じ
(Suggestive thermal analysis and thermogravimetric analysis in the firing process)
In the firing process until the porous carbon material is obtained from the above precursor, sampling was performed during the firing process, and suggestive thermal analysis and thermal analysis of each porous carbon material of Examples 1 and 2 in each firing process. A gravimetric analysis was performed. The measurement model, measurement conditions, etc. are as follows. The results are shown in FIG.
Suggestive thermal analysis measurement model: DTG-60 (Shimadzu Corporation)
Measurement conditions: About 5 mg of sample is set in a platinum holder, heated at a rate of 10°C/min under a nitrogen gas atmosphere (0.2 liter/min), and at 30-38° (2θ), low angle side. It was fired at a high temperature until the reflective surfaces (Miller index) (100), (002) and (101) surfaces of zinc oxide could not be observed.
Thermogravimetric analysis measurement model: Same as above Measurement conditions: Same as above
（窒素吸脱着測定（比表面積/細孔分布測定））
上記Ｘ線回折や示唆熱分析とは別に、多孔質炭素材料を焼成する前にあらかじめ前駆体を複数個に分けておき、焼成工程の各段階で一つ毎に取り出して焼成工程の経過測定用サンプルとした。
上記の方法で調製した前駆体と、焼成後の多孔質炭素材料と、その焼成工程のサンプルとは、それぞれを２００℃で２４時間減圧乾燥させ、室温雰囲気中で多孔質炭素材料および各サンプルに吸着した水分を脱着させた後、当該多孔質炭素材料および各サンプルのそれぞれの粉末０．０２ｇをサンプル管に入れ、液体窒素雰囲気下で比表面積/細孔分布測定装置（BELLSORP-mini II：マイクロトラックベル株式会社製）によって窒素吸脱着等温曲線を測定した。また、同装置の解析プログラム（I型（ISO9277）ＢＥＴ自動解析）により比表面積を算出した。さらに、得られた窒素吸脱着等温線をＢＪＨ(Barrett-Joyner-Halenda)法により処理してＩＵＰＡＣで定義されているメソ孔（２～５０ｎｍ）のサイズの比表面積を算出した。また、全比表面積に占めるメソ孔の比表面積の割合を算出した。
前駆体から多孔質炭素材料を得るまでの各工程における比表面積の変化を表１および図９に示す。なお、表１において、対照物質として活性炭（クラレケミカル社製：ＹＰ５０Ｆ）の測定データを併記する。また、比較例１として、組成に酸素元素を含まないｓｉｇｍａ‐ａｌｄｒｉｃｈ社製商品名「ＢａｓｏｌｉｔｅＺ１２００」を使用して同様の比表面積の測定を行った。図９に対応する結果を図１０に示す。
(Nitrogen adsorption/desorption measurement (specific surface area/pore distribution measurement))
Apart from the above X-ray diffraction and suggestive thermal analysis, the precursor is divided into a plurality of pieces in advance before firing the porous carbon material, and each one is taken out at each stage of the firing process to measure the progress of the firing process. was taken as a sample.
The precursor prepared by the above method, the porous carbon material after firing, and the sample in the firing process were each dried under reduced pressure at 200 ° C. for 24 hours, and the porous carbon material and each sample were dried in a room temperature atmosphere. After desorbing the adsorbed moisture, 0.02 g of each powder of the porous carbon material and each sample was put into a sample tube, and a specific surface area/pore size distribution measuring device (BELLSORP-mini II: micro A nitrogen adsorption/desorption isotherm was measured using Trackbell Co., Ltd.). In addition, the specific surface area was calculated by the analysis program of the same device (type I (ISO9277) BET automatic analysis). Further, the obtained nitrogen adsorption-desorption isotherm was processed by the BJH (Barrett-Joyner-Halenda) method to calculate the specific surface area of the mesopore size (2 to 50 nm) defined by IUPAC. Also, the ratio of the specific surface area of mesopores to the total specific surface area was calculated.
Table 1 and FIG. 9 show changes in the specific surface area in each step from the precursor to the porous carbon material. In Table 1, measurement data of activated carbon (YP50F manufactured by Kuraray Chemical Co., Ltd.) is also shown as a control substance. In addition, as Comparative Example 1, the specific surface area was similarly measured using Sigma-Aldrich's product name "Basolite Z1200" which does not contain oxygen element in its composition. Results corresponding to FIG. 9 are shown in FIG.
（焼成過程の考察）
図９の結果から、前駆体の状態では多孔質ではなかったが、１０００℃以下では、温度の上昇に伴って指数関数的に比表面積が増加していることが確認できる。また、この比表面積の増加に伴って、図３および図４に示すように、亜鉛のピークの減少や図８に示すように亜鉛元素の質量の減少が確認できることから、酸化亜鉛の還元と亜鉛の昇華とともに多孔質化して比表面積が増加していることが確認できる。
また、１０００℃を超えた時点で、図４に示すように亜鉛に関するピークは略無くなり、１０００℃の持続時間が長くなるに連れて、図５に示すように、－Ｃ－Ｏ、＞Ｃ＝Ｏ、－ＣＯＯ結合に起因して存在していたピークが減少してＣ－Ｃ、Ｃ＝Ｃ結合に起因するピークのみに集束していくことが確認できる。また、この－Ｃ－Ｏ、＞Ｃ＝Ｏ、－ＣＯＯ結合に起因して存在していたピークが減少することと引き換えに、図９に示すように、比表面積が増加していることから、１０００℃以上の焼成では、酸素含有官能基が脱離した跡に細孔が形成され、それによって比表面積が増加していることが確認できる。
なお、図４では、亜鉛に関するピークは略無くなっているが、図１１に示すように、ワイドレンジで確認した場合、実施例２に示す多孔質炭素材料は、亜鉛のピークが確認できるが、３０分経過すれば、確認されなくなった。このことから１０００℃で３０分以上の加熱時間を維持すれば、酸化亜鉛の還元と亜鉛の昇華に起因する比表面積の増加を確実に図ることができる。ただし、酸素含有官能基の脱離に起因する比表面積の増加については、図９に示すように、５時間焼成した場合でも、勾配は緩やかだが上昇傾向にあるので、１０００℃で約８時間程度の焼成を維持すれば、酸素含有官能基の脱離に起因する比表面積の増加を確実に図ることができる。
因みに、組成に酸素元素を含まない比較例１の前駆体の場合、図７（ａ）に示すように、１０００℃の段階で亜鉛のピークが残っているが、３時間後以降は略確認されなくなる。また、組成に酸素元素を含まないため、図７（ｂ）に示すように、Ｃ－Ｃ、Ｃ＝Ｃ結合に起因するピークのみが確認されるだけである。それを裏付けるように、比表面積の変化は、図１０に示すように、多孔質状態から一旦熱収縮して比表面積が減少するが、そこから亜鉛の昇華によって細孔が形成されて多孔質化するが、１０００℃を超えて以降は、上記した亜鉛のピークが消える３時間後には略比表面積の増加も横ばいとなり、酸素元素の脱離による細孔の形成は確認されない。なお、比較例１の前駆体は、１０００℃以降の比表面積の増加だけをみると、実施例１よりも増加しているが、これは、元々多孔質であった前駆体が熱収縮していたためで、酸素の脱離による細孔の形成によるものではないことは、上記した図７（ｂ）からも明らかである。
(Consideration of firing process)
From the results of FIG. 9, it can be confirmed that although the precursor was not porous, the specific surface area increased exponentially as the temperature increased at 1000° C. or lower. In addition, as the specific surface area increases, it can be confirmed that the zinc peak decreases as shown in FIGS. 3 and 4 and the mass of zinc element decreases as shown in FIG. It can be confirmed that the specific surface area increases as the material becomes porous as it sublimes.
Moreover, when the temperature exceeds 1000° C., the peak related to zinc almost disappears as shown in FIG. It can be confirmed that the peaks due to the O,--COO bonds are reduced and the peaks due to the C--C, C=C bonds are converged. In addition, in exchange for the decrease in the peaks that existed due to the -C-O, >C=O, and -COO bonds, the specific surface area increased as shown in FIG. It can be confirmed that in the firing at 1000° C. or higher, pores are formed after the oxygen-containing functional groups are detached, thereby increasing the specific surface area.
In FIG. 4, the peak related to zinc is almost absent, but when confirmed in a wide range as shown in FIG. Minutes passed and it was no longer confirmed. Therefore, if the heating time is maintained at 1000° C. for 30 minutes or longer, the specific surface area can be reliably increased due to the reduction of zinc oxide and the sublimation of zinc. However, regarding the increase in the specific surface area due to elimination of the oxygen-containing functional groups, as shown in FIG. 9, even when calcined for 5 hours, the gradient is gentle but there is an upward trend, so about 8 hours at 1000 ° C. If the sintering is maintained, the specific surface area can be reliably increased due to elimination of the oxygen-containing functional groups.
Incidentally, in the case of the precursor of Comparative Example 1, which does not contain an oxygen element in its composition, as shown in FIG. Gone. Moreover, since the composition does not contain an oxygen element, only peaks due to CC and C═C bonds are confirmed as shown in FIG. 7(b). As shown in FIG. 10, the change in the specific surface area is, as shown in FIG. However, after the temperature exceeds 1000° C., the increase in the specific surface area levels off 3 hours after the zinc peak disappears, and the formation of pores due to desorption of oxygen elements is not confirmed. The precursor of Comparative Example 1 has an increase in specific surface area after 1000° C., which is higher than that of Example 1. It is also clear from FIG.
（三電極法による電極試験片の作製）
実施例２で得られた多孔質炭素材料を活物質として用い、当該活物質と、導電助剤（アセチレンブラック）と、結着剤（ＰTFE（ポリテトラフルオロエチレン））とを、８：１：１の重量比で混練した。この混練物をチタンメッシュに塗布乾燥させて電極試験片を調製した。この電極試験片を作用極とし、Ａｇ/ＡｇＣｌを参照電極とし、白金を対極とし、１Ｍ希硫酸を電解液として三電極法による三極セルを構成した。
(Preparation of electrode test piece by three-electrode method)
Using the porous carbon material obtained in Example 2 as an active material, the active material, a conductive agent (acetylene black), and a binder (PTFE (polytetrafluoroethylene)) were mixed at a ratio of 8:1: It was kneaded at a weight ratio of 1. This kneaded product was applied to a titanium mesh and dried to prepare an electrode test piece. Using this electrode test piece as a working electrode, Ag/AgCl as a reference electrode, platinum as a counter electrode, and 1M dilute sulfuric acid as an electrolyte, a three-electrode cell was constructed by a three-electrode method.
（電極試験片の容量測定）
上記で調製したそれぞれの電極試験片の活物質重量あたり、５０ｍＡ／ｇとなるように定電流を流して、参照電極に対して電位を０～０．８Ｖまで充電し、到達後、０．８～０Ｖまで放電し、その放電電気量から静電容量を算出した。静電容量は、電気化学計測器（ＶＳＰ３００ Ｂｉｏｌｏｇｉｃ社製）を用いて測定した。また、比較対象として、実施例２で得られた多孔質炭素材料を、活性炭（クラレケミカル社製：ＹＰ５０Ｆ）に変更して調製した電極試験片を用いて同様の測定を行った。その結果を表２および図１２に示す。
(Capacitance measurement of electrode test piece)
A constant current is passed so that the weight of the active material of each electrode test piece prepared above is 50 mA / g, and the potential is charged to 0 to 0.8 V with respect to the reference electrode. The battery was discharged to 0 V, and the capacitance was calculated from the amount of discharged electricity. The capacitance was measured using an electrochemical measuring instrument (VSP300 manufactured by Biological). For comparison, the same measurement was performed using an electrode test piece prepared by changing the porous carbon material obtained in Example 2 to activated carbon (manufactured by Kuraray Chemical Co., Ltd.: YP50F). The results are shown in Table 2 and FIG.
（電気容量維持率の測定）
上記の容量測定を、５０、１００、２００、５００、１０００、２０００、５０００ｍＡ／ｇでそれぞれ行い、各電流密度における容量をプロットした。結果を図１３に示す。
(Measurement of electric capacity retention rate)
The above capacity measurements were performed at 50, 100, 200, 500, 1000, 2000 and 5000 mA/g, respectively, and the capacity at each current density was plotted. The results are shown in FIG.
以上の結果から、本発明に係る多孔質炭素材料は、電極材料として、従来の活性炭を大きく上回る静電容量を得ることができ、電極材料として非常に高性能であることが確認できた。 From the above results, it was confirmed that the porous carbon material according to the present invention, as an electrode material, can obtain a capacitance that greatly exceeds that of conventional activated carbon, and has extremely high performance as an electrode material.
なお、本発明は、その精神または主要な特徴から逸脱することなく、他のいろいろな形で実施することができる。そのため、上述の実施例はあらゆる点で単なる例示に過ぎず、限定的に解釈してはならない。本発明の範囲は特許請求の範囲によって示すものであって、明細書本文には、なんら拘束されない。さらに、特許請求の範囲に属する変形や変更は、全て本発明の範囲内のものである。 In addition, the present invention can be embodied in various other forms without departing from its spirit or essential characteristics. Therefore, the above-described embodiments are merely illustrative in all respects and should not be construed in a restrictive manner. The scope of the present invention is indicated by the claims, and is not restricted by the text of the specification. Furthermore, all modifications and changes within the scope of the claims are within the scope of the present invention.
上記課題を解決するための本発明に係る多孔質炭素材料の製造方法は、テレフタル酸を有機溶媒に溶解してなる有機リガンド液と、酢酸亜鉛を有機溶媒に溶解してなる酢酸亜鉛溶液との合成反応により、前駆体を調製し、当該前駆体を焼成することによって多孔質炭素材料を製造する方法であって、酸素元素／炭素元素の比率が、０．２５以上０．５以下の構造に特定された前駆体を調製し、当該前駆体を焼成する際、１０００℃以上の温度を所定時間以上維持することにより、酸素含有官能基を脱離させてその跡に細孔を形成して多孔質にするものである。 A method for producing a porous carbon material according to the present invention for solving the above-mentioned problems is to use an organic ligand liquid obtained by dissolving terephthalic acid in an organic solvent and a zinc acetate solution obtained by dissolving zinc acetate in an organic solvent. A method for producing a porous carbon material by preparing a precursor by a synthesis reaction and firing the precursor, wherein the ratio of oxygen element/carbon element is 0.25 or more and 0.5 or less. When the specified precursor is prepared and the precursor is calcined, a temperature of 1000 ° C. or higher is maintained for a predetermined time or longer to eliminate the oxygen-containing functional groups and form pores in the traces to form pores. Quality.
以上述べたように、本発明によると、テレフタル酸を有機溶媒に溶解してなる有機リガンド液と、酢酸亜鉛を有機溶媒に溶解してなる亜鉛イオン溶液との合成反応によって得られる前駆体のＥＤＳ分析によるデータを、結晶構造データベースと照合することにより、酸素元素／炭素元素の比率が、０．２５以上０．５以下の構造に特定された前駆体を調製し、当該前駆体を焼成する際、１０００℃以上の温度を所定時間以上維持することにより、酸素元素を脱離させてその跡に細孔を形成して多孔質化を図った多孔質炭素材料を得ることができる。このようにして構成された多孔質炭素材料は、酢酸亜鉛に由来する酸化亜鉛および亜鉛や、酸素を含む有機化合物に由来する酸素を消失させて当該酸化亜鉛や亜鉛や酸素の跡に細孔を形成した高比表面積の多孔質炭素材料となるため、静電容量の高い高性能な電極材料とすることができる。 As described above, according to the present invention, an EDS of a precursor obtained by a synthetic reaction between an organic ligand liquid obtained by dissolving terephthalic acid in an organic solvent and a zinc ion solution obtained by dissolving zinc acetate in an organic solvent By collating the analytical data with the crystal structure database, when preparing a precursor specified to have a structure in which the oxygen element/carbon element ratio is 0.25 or more and 0.5 or less, and calcining the precursor By maintaining a temperature of 1000° C. or higher for a predetermined period of time or longer, it is possible to obtain a porous carbon material in which oxygen elements are desorbed and pores are formed in the traces of the desorbed carbon material. The porous carbon material thus configured eliminates zinc oxide and zinc derived from zinc acetate and oxygen derived from an organic compound containing oxygen to form pores in traces of the zinc oxide, zinc, and oxygen. Since the formed porous carbon material has a high specific surface area, it can be a high-performance electrode material having a high capacitance.
Claims (6)
酸素元素／炭素元素の比率が、０．２５以上０．５以下の構造に特定された前駆体を調製し、当該前駆体を焼成する際、１０００℃以上の温度を所定時間以上維持することにより、酸素含有官能基を脱離させてその跡に細孔を形成して多孔質にすることを特徴とする多孔質炭素材料の製造方法。 A precursor is prepared by a synthetic reaction between an organic ligand liquid obtained by dissolving an organic compound containing oxygen in an organic solvent and a zinc acetate solution obtained by dissolving zinc acetate in an organic solvent, and the precursor is calcined. A method for producing a porous carbon material by
By preparing a precursor specified to a structure in which the ratio of oxygen element/carbon element is 0.25 or more and 0.5 or less, and maintaining the temperature of 1000 ° C. or more for a predetermined time or more when firing the precursor 3. A method for producing a porous carbon material, characterized in that oxygen-containing functional groups are eliminated and pores are formed in the traces thereof to make the porous carbon material porous.
比表面積が２４００ｍ２／ｇ以上となされた多孔質炭素材料。 A porous carbon material obtained by the production method according to claim 2,
A porous carbon material having a specific surface area of 2400 m 2 /g or more.
組成に酸素を含む有機化合物を有機溶媒に溶解してなる有機リガンド液と、
酢酸亜鉛を有機溶媒に溶解してなる酢酸亜鉛溶液と、
の合成反応により得られ、
ＥＤＳ分析によるデータを結晶構造データベースと照合することにより、酸素元素／炭素元素の比率が、０．２５以上０．５以下の構造に特定されたことを特徴とする多孔質炭素材料の前駆体。 A precursor that can be prepared as a porous carbon material by firing,
an organic ligand liquid obtained by dissolving an organic compound containing oxygen in its composition in an organic solvent;
a zinc acetate solution obtained by dissolving zinc acetate in an organic solvent;
obtained by the synthesis reaction of
A precursor of a porous carbon material characterized in that a structure having a ratio of oxygen element/carbon element of 0.25 or more and 0.5 or less is specified by collating EDS analysis data with a crystal structure database.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021193399A JP7293320B2 (en) | 2021-11-29 | 2021-11-29 | Porous carbon material, method for producing the same, precursor of porous carbon material, and electrode material using porous carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021193399A JP7293320B2 (en) | 2021-11-29 | 2021-11-29 | Porous carbon material, method for producing the same, precursor of porous carbon material, and electrode material using porous carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2023079774A true JP2023079774A (en) | 2023-06-08 |
| JP7293320B2 JP7293320B2 (en) | 2023-06-19 |
Family
ID=86647290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021193399A Active JP7293320B2 (en) | 2021-11-29 | 2021-11-29 | Porous carbon material, method for producing the same, precursor of porous carbon material, and electrode material using porous carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7293320B2 (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014218603A (en) * | 2013-05-09 | 2014-11-20 | 独立行政法人産業技術総合研究所 | Porous metal coordination polymer compound and production method of porous carbon material |
| CN104229768A (en) * | 2014-07-01 | 2014-12-24 | 江西师范大学 | Method for preparing porous carbon with three-dimensional structure |
| CN105129768A (en) * | 2015-08-14 | 2015-12-09 | 安徽大学 | Method for preparing nitrogen-doped porous carbon material on the basis of folic acid |
| JP2019172496A (en) * | 2018-03-28 | 2019-10-10 | 旭化成株式会社 | Method for producing nitrogen-containing carbon material |
| KR20200021217A (en) * | 2018-08-20 | 2020-02-28 | 주식회사 엘지화학 | Metal Organic Framework, Method for Preparing the Same and Method for Preparing Porous Carbon Structure Using the Same |
| US20200259168A1 (en) * | 2017-09-28 | 2020-08-13 | Lg Chem, Ltd. | Carbon-sulfur composite, preparation method therefor, and lithium secondary battery comprising same |
| JP2020189760A (en) * | 2019-05-20 | 2020-11-26 | 学校法人 関西大学 | Method for producing porous carbon material |
| JP7048693B1 (en) * | 2020-10-01 | 2022-04-05 | 星和電機株式会社 | Porous carbon material and its manufacturing method, precursor of porous carbon material, and electrode material using porous carbon material |
| JP7086152B2 (en) * | 2020-10-01 | 2022-06-17 | 星和電機株式会社 | Porous carbon material and its manufacturing method, precursor of porous carbon material, and electrode material using porous carbon material |
-
2021
- 2021-11-29 JP JP2021193399A patent/JP7293320B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014218603A (en) * | 2013-05-09 | 2014-11-20 | 独立行政法人産業技術総合研究所 | Porous metal coordination polymer compound and production method of porous carbon material |
| CN104229768A (en) * | 2014-07-01 | 2014-12-24 | 江西师范大学 | Method for preparing porous carbon with three-dimensional structure |
| CN105129768A (en) * | 2015-08-14 | 2015-12-09 | 安徽大学 | Method for preparing nitrogen-doped porous carbon material on the basis of folic acid |
| US20200259168A1 (en) * | 2017-09-28 | 2020-08-13 | Lg Chem, Ltd. | Carbon-sulfur composite, preparation method therefor, and lithium secondary battery comprising same |
| JP2019172496A (en) * | 2018-03-28 | 2019-10-10 | 旭化成株式会社 | Method for producing nitrogen-containing carbon material |
| KR20200021217A (en) * | 2018-08-20 | 2020-02-28 | 주식회사 엘지화학 | Metal Organic Framework, Method for Preparing the Same and Method for Preparing Porous Carbon Structure Using the Same |
| JP2020189760A (en) * | 2019-05-20 | 2020-11-26 | 学校法人 関西大学 | Method for producing porous carbon material |
| JP7048693B1 (en) * | 2020-10-01 | 2022-04-05 | 星和電機株式会社 | Porous carbon material and its manufacturing method, precursor of porous carbon material, and electrode material using porous carbon material |
| JP7086152B2 (en) * | 2020-10-01 | 2022-06-17 | 星和電機株式会社 | Porous carbon material and its manufacturing method, precursor of porous carbon material, and electrode material using porous carbon material |
Non-Patent Citations (1)
| Title |
|---|
| WANG, CHENGWEI ET AL.: "Facile One-Pot Synthesis of Highly Porous Carbon Forms for High-Performance Supercapacitors Using Te", APPLIED MATERIALS & INTERFACES, vol. 7, JPN6022021491, 2015, pages 8952 - 8960, ISSN: 0004961049 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7293320B2 (en) | 2023-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102086658B1 (en) | Biomass carbon-MOF composite, preparation method thereof and super capacitor electrode comprising the same | |
| Sakthivel et al. | Bimetallic vanadium cobalt diselenide nanosheets with additional active sites for excellent asymmetric pseudocapacitive performance: comparing the electrochemical performances with M–CoSe 2 (M= Zn, Mn, and Cu) | |
| JP6071261B2 (en) | Porous carbon material, method for producing the same, and electric double layer capacitor using the same | |
| CA2899131C (en) | Carbon material for catalyst support use | |
| Sofi et al. | Cu 2+-BTC based metal–organic framework: a redox accessible and redox stable MOF for selective and sensitive electrochemical sensing of acetaminophen and dopamine | |
| Wang et al. | Toward Metal–Organic‐Framework‐Based Supercapacitors: Room‐Temperature Synthesis of Electrically Conducting MOF‐Based Nanocomposites Decorated with Redox‐Active Manganese | |
| Hao et al. | Synthesis and electrochemical capacitive properties of nitrogen-doped porous carbon micropolyhedra by direct carbonization of zeolitic imidazolate framework-11 | |
| Ellis et al. | Growth of ZIF-8 on molecularly ordered 2-methylimidazole/single-walled carbon nanotubes to form highly porous, electrically conductive composites | |
| Ng et al. | Enhancing the performance of 3D porous N-doped carbon in oxygen reduction reaction and supercapacitor via boosting the meso-macropore interconnectivity using the “exsolved” dual-template | |
| JPH0857317A (en) | Platinum alloy catalyst and its manufacturing process | |
| Wu et al. | Three-dimensional Co 3 O 4/flocculent graphene hybrid on Ni foam for supercapacitor applications | |
| JP6196579B2 (en) | Platinum hollow nanoparticles, particle-supported catalyst body, and method for producing the catalyst body | |
| JP5611349B2 (en) | Catalysts for electrochemical reactions | |
| US20160104900A1 (en) | Porous carbon catalyst, method for producing same, electrode and battery | |
| Naveen et al. | Novel synthesis of highly porous three-dimensional nickel cobaltite for supercapacitor application | |
| JP2014218603A (en) | Porous metal coordination polymer compound and production method of porous carbon material | |
| Han et al. | A good-performance glucose sensor fabricated via rationally designing a new cobalt–metal–organic framework precursor | |
| JP7048693B1 (en) | Porous carbon material and its manufacturing method, precursor of porous carbon material, and electrode material using porous carbon material | |
| KR101492433B1 (en) | Method for preparing mesoporous poly(styrene-co-methacrylic acid) spherical granule, and spherical granule, graphene and supercapacitor produced therefrom | |
| JP7293320B2 (en) | Porous carbon material, method for producing the same, precursor of porous carbon material, and electrode material using porous carbon material | |
| JP7086152B2 (en) | Porous carbon material and its manufacturing method, precursor of porous carbon material, and electrode material using porous carbon material | |
| JP2017016853A (en) | Carrier material for electrode and production method therefor | |
| KR101735337B1 (en) | Three-dimensional mesoporous graphene derived from Ni(II) complexes and preparation method thereof | |
| Asiwal et al. | Fabrication of anhydride core-based conductive layered Ni-MOF nanoflakes for high performance supercapacitors | |
| Li et al. | In situ synthesis of well crystallized rhodium sulfide/carbon composite nanospheres as catalyst for hydrochloric acid electrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20211129 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230110 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230227 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230606 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230607 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7293320 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |