JP5689379B2 - 触媒担持用担体、触媒担持体、電極及び電池 - Google Patents
触媒担持用担体、触媒担持体、電極及び電池 Download PDFInfo
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- JP5689379B2 JP5689379B2 JP2011157904A JP2011157904A JP5689379B2 JP 5689379 B2 JP5689379 B2 JP 5689379B2 JP 2011157904 A JP2011157904 A JP 2011157904A JP 2011157904 A JP2011157904 A JP 2011157904A JP 5689379 B2 JP5689379 B2 JP 5689379B2
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Classifications
-
- 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
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- Fuel Cell (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Description
30.93gのアクリロニトリルと4.07gのメタクリル酸とを、蒸留水中、窒素雰囲気下において70℃で4時間重合した。得られた反応溶液をロータリーエバポレーターで濃縮し真空乾燥機で乾燥し、ポリアクリロニトリル−ポリメタクリル酸共重合体を得た。
次に、原料の炭素化を行った。すなわち、上述のように不融化処理した1.5gの原料を石英ボートに載せ、イメージ炉にて、20分間窒素パージし(窒素流量:0.7L/分)、加熱により50℃/分の昇温速度で室温から1000℃まで昇温した。その後、この原料を1000℃で1時間保持し、炭素化材料を得た。
次に、金属除去処理(酸処理)を行った。すなわち、上述のように粉砕した1gの炭素化材料に100mLの濃塩酸を加え、1時間攪拌した。次いで、炭素化材料を沈殿させ、溶液を除去した後、濃塩酸と蒸留水とを1:1(体積比)で混合した溶液を100mL加え、1時間攪拌した。炭素化材料を沈殿させ、溶液を除去した後、蒸留水を100mL加え、1時間攪拌した。こうして、炭素化材料から金属(Co)を除去した。その後、この炭素化材料を蒸留水で洗浄し、吸引ろ過し、真空乾燥機で乾燥した。
次に、熱処理を行った。すなわち、上述のように酸処理を施した炭素化材料を石英ボートに載せ、イメージ炉にて、20分間窒素パージし(窒素流量:0.7L/分)、加熱により50℃/分の昇温速度で室温から700℃まで昇温した。その後、この炭素化材料を700℃で1時間保持した。
次に、担体に対して10重量%の白金(Pt)を使用して触媒担持処理を行った。すなわち、0.265gの塩化白金酸(白金を0.1g含有)を100gの蒸留水中に溶解し、白金含有溶液を調製した。次いで、この白金含有溶液に、上述のようにして得られた1gの炭素化材料からなる担体(IK(Co)1000℃AW)を加え、100℃で3時間還流した。その後、炭素化材料を蒸留水で洗浄し、吸引ろ過で回収した。さらに、真空乾燥後、水素雰囲気中で650℃にて還元処理した炭素化材料を、白金を担持した炭素化材料からなる触媒担持体(Pt/IK(Co)1000℃AW)として得た。
上述の実施例1〜4及び比較例1〜5で得られた触媒担持用担体の各々について、粉末X線回折法による解析を行い、当該担体の炭素構造に含まれる黒鉛類似構造成分及びアモルファス成分の割合を評価した。
上述の実施例1〜4及び比較例1〜5で得られた触媒担持用担体の各々について、ラマン分光法による解析を行い、炭素材料の構造の乱れや欠陥を評価した。すなわち、ラマンシフトが1580cm−1付近に現れるピーク(Gバンド)の強度に対する、1360cm−1付近に現れるピーク(Dバンド)の強度の比(I1360/I1580)を評価した。ラマンスペクトルは、HORIBA顕微レーザーラマン分光測定装置(LabRAM、HORIBA Jobin Yvon)を用いて、532nmの励起波長で、露光5秒×積算5回の条件で測定することにより得た。
上述の実施例1〜4及び比較例1〜5で得られた触媒担持体の各々について、触媒の担持量を評価した。すなわち、上述のとおり1gの担体に対して0.1gの白金(Pt)を使用して触媒担持処理を行うことにより、当該担体に対して実際に担持された白金の量(重量%)を触媒担持量とした。具体的には、10mgの触媒担持体をるつぼに入れ、マッフル炉を用いて、700℃で3時間空気中にて灰化した後、王水4mLを加えて加熱して白金を溶出し、蒸留水で希釈後ICP(Inductively Coupled Plasma)発光分光分析により白金を定量した。
上述の実施例1〜4及び比較例1〜5で得られた触媒担持体の各々について、電圧を繰り返し印加する条件下における耐久性を評価した。まず、触媒担持体を含む触媒スラリーを調製した。具体的に、触媒担持体5mgに、5重量%Nafion(登録商標)溶液(Aldrich製)50μL、エタノール150μL、蒸留水150μLを加え、ガラスビーズを加え、10分間超音波処理し、均一な触媒スラリーを得た。
図2には、実施例1〜4及び比較例1〜5で得られた触媒担持用担体及び触媒担持体を上述のように評価した結果を示す。すなわち、図2には、各実施例及び比較例で使用した触媒担持用担体の種類、当該触媒担持用担体のX線回折(XRD)により得られた黒鉛類似構造成分の割合(%)及びアモルファス成分の割合(%)、当該触媒担持用担体のラマン分光測定により得られたD/G強度比(I1360/I1580)、当該触媒担持体に触媒(Pt)を担持してなる触媒担持体の耐久率(%)、当該触媒担持体における触媒(Pt)担持量(重量%)を示す。
Claims (6)
- 窒素含有有機物と、マンガン、鉄及びコバルトからなる群より選択される1種又は2種以上の金属とを含む原料を炭素化して得られた炭素化材料に、金属除去処理を施し、さらに300℃以上の熱処理を施して得られた
ことを特徴とする電極触媒担持用担体。 - X線回折図形における回折角26°付近のピークが、20〜45%の黒鉛類似構造成分と、55〜80%のアモルファス成分と、を含む
ことを特徴とする請求項1に記載された電極触媒担持用担体。 - ラマンスペクトルにおける1360cm−1バンドの1580cm−1バンドに対する強度比(I1360/I1580)が0.3以上、1.0以下である
ことを特徴とする請求項1又は2に記載された電極触媒担持用担体。 - 請求項1乃至3のいずれかに記載された電極触媒担持用担体と、
前記電極触媒担持用担体に担持された貴金属触媒と、
を有する
ことを特徴とする電極触媒担持体。 - サイクリックボルタンメトリーにおいて、0〜1.6Vの範囲で電位を50サイクル連続的に掃引した場合に、5サイクル目の1.5V印加時の電流値に対する50サイクル目の1.5V印加時の電流値の割合が90%以上である
ことを特徴とする請求項4に記載された電極触媒担持体。 - 窒素含有有機物と、マンガン、鉄及びコバルトからなる群より選択される1種又は2種以上の金属とを含む原料を炭素化して得られた炭素化材料に、金属除去処理を施し、さらに300℃以上の熱処理を施して得られ、酸素還元活性を有する
ことを特徴とする炭素化材料。
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