JP6100516B2 - Nitrogen-containing carbon black, process for producing the same, and catalyst for fuel cell using the same - Google Patents
Nitrogen-containing carbon black, process for producing the same, and catalyst for fuel cell using the same Download PDFInfo
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- 239000006229 carbon black Substances 0.000 title claims description 33
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 title description 20
- 239000000446 fuel Substances 0.000 title description 20
- 238000000034 method Methods 0.000 title description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 47
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 150000002897 organic nitrogen compounds Chemical class 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 239000007789 gas Substances 0.000 description 19
- 229910052697 platinum Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- -1 nitrogen-containing compound Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
本発明は、窒素を含有するカーボンブラックに関する。 The present invention relates to carbon black containing nitrogen.
固体高分子型燃料電池のセル構造は、ガス流路を施したセパレーターの間にガス拡散層、触媒層、電解質膜を挟んだ構造となっている。通常、この触媒層は白金粒子及び／又は白金合金粒子（以下、「白金等粒子」という。）が担持されたカーボンブラックから構成されており、白金等粒子はカーボンブラック表面に高分散で担持されている。しかしながら、貴金属である白金を用いる従来の触媒層は非常に高価な物であり、いくつかの解決法が考案されている。 The cell structure of the polymer electrolyte fuel cell has a structure in which a gas diffusion layer, a catalyst layer, and an electrolyte membrane are sandwiched between separators provided with gas flow paths. Usually, this catalyst layer is composed of carbon black on which platinum particles and / or platinum alloy particles (hereinafter referred to as “platinum particles”) are supported, and the platinum particles are supported on the carbon black surface with high dispersion. ing. However, the conventional catalyst layer using platinum which is a noble metal is very expensive, and several solutions have been devised.
特許文献１には、白金を微粒子で担持させ白金量を低減する触媒材料が提案されており、窒素を導入したカーボンブラックにより白金微粒子をカーボン中の窒素と共有結合させ、微粒子を安定的に担持できるとされている。特許文献２には、窒素化合物含有熱硬化性樹脂を４００〜１５００℃で熱処理し、得られた窒素を導入した炭素微粒子自身が酸素還元触媒能を有し、白金代替触媒として使用できることが開示されている。しかしながら、いずれも触媒性能については改善の余地があった。 Patent Document 1 proposes a catalyst material that supports platinum in fine particles to reduce the amount of platinum, and platinum black particles are covalently bonded to nitrogen in carbon by introducing carbon black into which nitrogen is introduced, thereby stably supporting the fine particles. It is supposed to be possible. Patent Document 2 discloses that carbon fine particles into which nitrogen compound-containing thermosetting resin is heat-treated at 400 to 1500 ° C. and introduced nitrogen have an oxygen reduction catalytic ability and can be used as a platinum substitute catalyst. ing. However, all of these have room for improvement in catalyst performance.
本発明の目的は、窒素を含有したカーボンブラックと、その製造方法及びそれを含有した触媒性能の優れた燃料電池用触媒を提供することである。 An object of the present invention is to provide a carbon black containing nitrogen, a method for producing the same, and a catalyst for a fuel cell containing the same and having excellent catalytic performance.
上記の課題を解決するために、本発明においては、以下の手段を採用する。
（１）窒素含有量が０．１質量％以上で、ＪＩＳ Ｋ ６２１７−４によるＤＢＰ吸収量が１００〜２５０ｍｌ／１００ｇであることを特徴とする窒素を含有するカーボンブラック。
（２）炭化水素の熱分解反応時及び／又は燃焼反応時に窒素源を存在させることを特徴とする前記（１）に記載の窒素を含有するカーボンブラックの製造方法。
（３）炭化水素がアセチレン、窒素源が有機窒素化合物であることを特徴とする前記（２）に記載の窒素を含有するカーボンブラックの製造方法。
（４）前記（１）に記載のカーボンブラックを用いた燃料電池用触媒。
In order to solve the above problems, the following means are adopted in the present invention.
(1) A nitrogen-containing carbon black having a nitrogen content of 0.1% by mass or more and a DBP absorption amount according to JIS K 6217-4 of 100 to 250 ml / 100 g.
(2) The method for producing nitrogen-containing carbon black as described in (1) above, wherein a nitrogen source is present during a thermal decomposition reaction and / or a combustion reaction of a hydrocarbon.
(3) The process for producing nitrogen-containing carbon black as described in (2) above, wherein the hydrocarbon is acetylene and the nitrogen source is an organic nitrogen compound.
(4) A fuel cell catalyst using the carbon black described in (1).
本発明によれば、燃料電池特性の優れたカーボンブラックとそのカーボンブラックを用いた燃料電池触媒が提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the fuel cell catalyst using the carbon black excellent in the fuel cell characteristic and the carbon black can be provided.
本発明のカーボンブラックは、窒素含有量が０．１質量％以上のカーボンブラックである。窒素含有量が０．１質量％未満であると酸素還元能力が十分に発揮されない。窒素含有量の上限は特にないが、後述するその他物性等をバランスよく維持し、比較的良好な触媒性能を得る含有量としては１．０質量％までが好適である。本発明における窒素の含有量は、酸素窒素同時分析装置（ＬＥＣＯ社製ＴＣ−１３６型）によって測定することができる。 The carbon black of the present invention is a carbon black having a nitrogen content of 0.1% by mass or more. If the nitrogen content is less than 0.1% by mass, the oxygen reducing ability is not sufficiently exhibited. The upper limit of the nitrogen content is not particularly limited, but it is preferably up to 1.0% by mass as the content for maintaining the other physical properties described below in a well-balanced manner and obtaining relatively good catalyst performance. The nitrogen content in the present invention can be measured by an oxygen-nitrogen simultaneous analyzer (TC-136 type manufactured by LECO).
本発明のカーボンブラックは、ＪＩＳ Ｋ ６２１７−４によるＤＢＰ吸収量が１００〜２５０ｍｌ／１００ｇのカーボンブラックである。カーボンブラックは一次粒子が鎖状に繋がったストラクチャー構造を形成しており、ＤＢＰ吸収量が高いほどストラクチャーが発達していることを示している。固体高分子型燃料電池は、原料である水素、酸素等のガス供給と、生成物である水の排出を効率よく行うことが必要であり、そのためにはカーボンブラックは発達したストラクチャー構造を有する方が良好な性能を得ることが出来る。ＤＢＰ吸収量が１００ｍｌ／１００ｇを下回ると、ガス供給、水排出が十分にできないため、反応効率が低下する。また、２５０ｍｌ／１００ｇを超えると、触媒をバインダーとスラリー化して触媒電極を作製する工程でスラリー粘度が上昇して平滑な電極を得られず、これもまたガス供給、水排出が十分に出来ない。 The carbon black of the present invention is a carbon black having a DBP absorption amount of 100 to 250 ml / 100 g according to JIS K 6217-4. Carbon black forms a structure in which primary particles are connected in a chain form, and the higher the DBP absorption amount, the more the structure is developed. A polymer electrolyte fuel cell needs to efficiently supply gas such as hydrogen and oxygen as raw materials and discharge water as a product. For this purpose, carbon black has a developed structure. However, good performance can be obtained. When the DBP absorption amount is less than 100 ml / 100 g, the gas supply and water discharge cannot be sufficiently performed, so that the reaction efficiency is lowered. On the other hand, if it exceeds 250 ml / 100 g, the slurry viscosity rises in the process of preparing the catalyst electrode by slurrying the catalyst with a binder, and a smooth electrode cannot be obtained, and this also fails to sufficiently supply gas and discharge water. .
本発明のカーボンブラックは、炭化水素の熱分解反応時及び／又は燃焼反応時に窒素源を存在させることにより製造することが出来る。熱力学的に窒素含有化合物は高温でシアン化水素を発生しやすく、希釈されたガス雰囲気での反応時はカーボンに含有させることは難しいが、我々は高濃度の炭化水素ガスを熱分解反応及び／又は燃焼反応させる雰囲気に窒素含有化合物を導入することで、窒素をカーボンに含有できることを見いだした。また、高濃度の炭化水素ガスを用いることでカーボンブラックのストラクチャーを発達させることが可能となり、本発明に至った。 The carbon black of the present invention can be produced by the presence of a nitrogen source during the hydrocarbon pyrolysis reaction and / or the combustion reaction. Thermodynamically, nitrogen-containing compounds are prone to generate hydrogen cyanide at high temperatures, and it is difficult to incorporate carbon during reaction in a diluted gas atmosphere. It has been found that nitrogen can be contained in carbon by introducing a nitrogen-containing compound into the atmosphere for combustion reaction. Moreover, it became possible to develop the structure of carbon black by using a high-concentration hydrocarbon gas, leading to the present invention.
本発明で使用される炭化水素ガスは、ガス状、オイル状様々な炭化水素を用いることができるが、アセチレンガス、エチレンガス、ブタジエンガスを用いた場合は生成する熱量が大きく、特にアセチレンガスは自身の熱分解で連続的に分解しカーボンブラックが形成されるため、より窒素を含有しやすい。 As the hydrocarbon gas used in the present invention, various hydrocarbons such as gas and oil can be used. However, when acetylene gas, ethylene gas or butadiene gas is used, the amount of heat generated is large. Since it is continuously decomposed by its own thermal decomposition to form carbon black, it is more likely to contain nitrogen.
本発明に用いる窒素源については、窒素ガス、アンモニア、ヒドラジン、ピリジン、ピロリジン、ピペリジン、アニリン等の窒素を含む物質である。中でも、窒素環芳香族化合物は、カーボンブラックへの窒素の含有が容易であるので好ましい。 The nitrogen source used in the present invention is a substance containing nitrogen such as nitrogen gas, ammonia, hydrazine, pyridine, pyrrolidine, piperidine, aniline. Among these, a nitrogen ring aromatic compound is preferable because it is easy to contain nitrogen in the carbon black.
本発明の燃料電池用触媒は、本発明のカーボンブラックをそのまま用いても良いし、カーボンブラック表面に白金等の粒子を高分散で析出（担持）させたものでもよい。燃料電池性能の長期安定性の面から、白金等の粒子はカーボンブラック表面に強く担持されていることが好ましく、白金等の粒子の大きさとしては１０〜５０Åが好ましい。 The fuel cell catalyst of the present invention may use the carbon black of the present invention as it is, or may be one in which particles such as platinum are precipitated (supported) with high dispersion on the surface of the carbon black. From the viewpoint of long-term stability of the fuel cell performance, it is preferable that the particles such as platinum are strongly supported on the surface of carbon black, and the size of the particles such as platinum is preferably 10 to 50 mm.
本発明の燃料電池用触媒の評価は、固体高分子型燃料電池の場合には、以下のようにして行うことができる。燃料電池用触媒を四フッ化樹脂粉末と混合し、アルコールを加えてペースト状にしたものをカーボンペーパーの片面に塗布し触媒層を形成する。そして、触媒層の表面にナフィオン溶液を均一に塗布し電極とする。ナフィオン膜（パーフルオロスルホン酸電解質膜）の両面に、電極を接するように重ね合わせ、ホットプレスで熱圧着させ、電解質膜−電極接合体（ＭＥＡ）を得る。ＭＥＡをセパレーター、続いて集電板で挟み込めば単セルが完成し、電子負荷装置、ガス供給装置を接続すれば燃料電池の評価を行うことができる。また、市販されている燃料電池単セル評価装置を用いれば上記評価をより簡便に行うことができる。 The evaluation of the fuel cell catalyst of the present invention can be performed as follows in the case of a polymer electrolyte fuel cell. A fuel cell catalyst is mixed with tetrafluoride resin powder, and a paste obtained by adding alcohol is applied to one side of carbon paper to form a catalyst layer. And a Nafion solution is uniformly apply | coated to the surface of a catalyst layer, and it is set as an electrode. An electrode is placed on both sides of a Nafion membrane (perfluorosulfonic acid electrolyte membrane) so that the electrodes are in contact with each other and thermocompression bonded by a hot press to obtain an electrolyte membrane-electrode assembly (MEA). A single cell is completed if the MEA is sandwiched between a separator and a current collector, and a fuel cell can be evaluated by connecting an electronic load device and a gas supply device. Moreover, if the commercially available fuel cell single cell evaluation apparatus is used, the said evaluation can be performed more simply.
実施例１〜６ 比較例１〜３
炉長４ｍ、炉直径０．５ｍの竪型炉の頂部に、炭化水素ガス及び酸素ガスを混合して導入する供給ノズル(直径３７ｍｍ)と、窒素源の供給ノズル(直径１０ｍｍ)を設け、炭化水素ガスとしてアセチレンガスを、窒素源として１３０℃まで加熱し気化したピリジンを各ノズルより表１の条件で供給し、アセチレンガスの反応熱及び酸素ガスによる燃焼熱を利用してカーボンブラックを製造した。さらに、実施例６として、２５０℃で気化したアニリンガスを用いた以外は実施例１と同様の条件でカーボンブラックを試作した。また、比較例３として、内径９０ｍｍ、均熱ゾーンが３００ｍｍの管状炉を使用して、反応温度１０００℃、表１のガス条件でカーボンブラックを試作した。
Examples 1-6 Comparative Examples 1-3
At the top of a vertical furnace with a furnace length of 4 m and a furnace diameter of 0.5 m, a supply nozzle (diameter 37 mm) for introducing a mixture of hydrocarbon gas and oxygen gas and a nitrogen source supply nozzle (diameter 10 mm) are provided. Acetylene gas as hydrogen gas and pyridine heated to 130 ° C. and vaporized as nitrogen source were supplied from each nozzle under the conditions shown in Table 1, and carbon black was produced using the reaction heat of acetylene gas and the combustion heat of oxygen gas. . Further, as Example 6, a carbon black was prototyped under the same conditions as in Example 1 except that aniline gas vaporized at 250 ° C. was used. Further, as Comparative Example 3, carbon black was prototyped using a tubular furnace having an inner diameter of 90 mm and a soaking zone of 300 mm under the reaction temperature of 1000 ° C. and the gas conditions shown in Table 1.
得られたカーボンブラックについて、（１）窒素含有量：カーボンブラックの前処理として２５０℃、窒素雰囲気で１８時間乾燥処理を行った後、酸素窒素同時分析装置（ＬＥＣＯ社製「ＴＣ−１３６型」）により窒素含有量を測定した。（２）ＤＢＰ吸収量：ＪＩＳ Ｋ ６２１７−４によるＤＢＰ吸収量を測定した。（３）全細孔容積：全自動ガス吸脱着測定装置（コールター社製 ＯＭＮＩＳＯＲＰ−３６０ＣＸ）を用いて、窒素ガス（流量＝０．３ｍｌ／ｍｉｎ）で連続容量法による吸脱着測定を行い、全細孔容積を算出した。 About the obtained carbon black, (1) Nitrogen content: As a pretreatment of carbon black, after drying for 18 hours in a nitrogen atmosphere at 250 ° C., an oxygen-nitrogen simultaneous analyzer (“TC-136 type” manufactured by LECO) ) To measure the nitrogen content. (2) DBP absorption: DBP absorption according to JIS K 6217-4 was measured. (3) Total pore volume: Using a fully automatic gas adsorption / desorption measuring device (OMNISORP-360CX, manufactured by Coulter, Inc.), adsorption / desorption measurement by a continuous volume method was performed with nitrogen gas (flow rate = 0.3 ml / min). The pore volume was calculated.
得られた燃料電池用触媒１ｇに５質量％ナフィオン（パーフルオロスルホン酸、デュポン社製）を２５００ｍｇ混合してペーストとし、カーボンペーパーに塗布した後、８０℃で乾燥して酸素極とした。次に、Ｐｔ−ブラックを燃料極に用い、ナフィオン膜を挟んで酸素極と重ね合わせて１３５℃で１０分間、９．８ＭＰａでプレスし、１．７ｃｍ×１．７ｃｍの膜・電極接合体（ＭＥＡ）を得た。のセパレーター、集電板で挟み込み一体化して、燃料電池を構成した。この燃料電池に反応ガスとして燃料極に水素（１００ｍｌ／ｍｉｎ）、酸素極に酸素を供給（１００ｍｌ／ｍｉｎ）し、電流密度１０ｍＡ／ｃｍ２におけるセル電圧を測定した。 2500 g of 5% by mass of Nafion (perfluorosulfonic acid, manufactured by DuPont) was mixed with 1 g of the obtained fuel cell catalyst to obtain a paste, which was applied to carbon paper and dried at 80 ° C. to obtain an oxygen electrode. Next, Pt-black was used as the fuel electrode, and the Nafion membrane was sandwiched between the oxygen electrode and pressed at 135 ° C. for 10 minutes at 9.8 MPa, and a 1.7 cm × 1.7 cm membrane / electrode assembly ( MEA) was obtained. A fuel cell was constructed by sandwiching and integrating the separator and current collector plate. In this fuel cell, hydrogen (100 ml / min) was supplied to the fuel electrode as a reaction gas, oxygen was supplied to the oxygen electrode (100 ml / min), and the cell voltage at a current density of 10 mA / cm 2 was measured.
表１から、本発明の窒素を含有するカーボンブラックは、比較例に比べて、ＤＢＰ吸収量が高く、かつ反応ガス及び水が通過出来る細孔が多く存在することが判る。そのため本発明の窒素を含有するカーボンブラックは、酸素還元能力が高い、すなわちセル電圧が高く、電池性能が良好となっていることがわかる。 From Table 1, it can be seen that the nitrogen-containing carbon black of the present invention has a higher DBP absorption and more pores through which the reaction gas and water can pass than the comparative example. Therefore, it can be seen that the nitrogen-containing carbon black of the present invention has a high oxygen reducing ability, that is, a high cell voltage and good battery performance.
本発明のアセチレンブラックは、固体高分子型燃料電池の触媒として利用することができる。
The acetylene black of the present invention can be used as a catalyst for a polymer electrolyte fuel cell.
Claims (1)
An organic nitrogen compound is present during the thermal decomposition reaction and / or combustion reaction of acetylene, the nitrogen content is 0.1% by mass or more, and the DBP absorption according to JIS K 6217-4 is 100 to 250 ml / 100 g A method for producing nitrogen-containing carbon black.
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