Microsoft PowerPoint _SP8_GSC (NXPowerLite)3.ppt
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1
2 Agenda 1. 1) 2) 3) 2. 1) 2) 3.
3 1-1) 1) ダイハツが 考 える 燃 料 電 池 自 動 車 FCV FCV Environmental Showcase of G8 Summit
4 1-2) 燃 料 としての 水 加 ヒドラジンとは 主 要 用 途 電 気 化 学 反 応 式 100% 水 加 ヒドラジン (N 2 H 4 H 2 O) 脱 酸 素 剤 発 泡 剤 還 元 剤 無 水 ヒドラジン (N 2 H 4 ) ロケット 燃 料 性 状 無 色 の 液 体 油 状 発 煙 性 液 体 凝 固 点 沸 点 引 火 点 IARCによる 発 がん 性 リスク 評 価 74 60% 以 下 では 引 火 しない 2B 人 体 へ 影 響 があるかもしれない (ガソリンと 同 等 のクラス) 38 引 火 性 の 高 い 液 体 毒 性 LD50=129 mg/kg LD50=60mg/kg 日 本 での 毒 劇 物 取 締 法 劇 物 毒 物 N 2 H 4 + O 2 N 2 + 2H 2 O E 0 = 1.61 V
5 1-3) これまでの 燃 料 電 池 自 動 車 開 発 の 歴 史 日 本 初 のFCV
6 1-3) これまでの 燃 料 電 池 自 動 車 開 発 の 歴 史 1972 DHFCV (Japan s first) was developed by AIST with Daihatsu & Panasonic. K. Yamada et al., J. Power Sources 115 (2003) 236. K. Yamada et al., Electrochem. Com. 5 (2003) 892. K. Yamada et al., J. Power Sources 122 (2003) 132. U. Martinez et al., ECS Trans. 33 (2010) J.-S. Chinchira et al. J. Am. Chem. Soc. 133 (2011) T. Sakamoto et al., Catal. Today 164 (2011) 181. U. Martinez et al., PCCP. (2012). T. Sakamoto et al., J. Power Sources 234 (2013) 252. (NiLa) T. Sakamoto et al., J. Power Sources 247 (2014) 605. fcc Ni K. Asazawa et al., Angew. Chem. Int. Ed. 46 (2007) 8024 K. Asazawa et al., J. Power Sources 191 (2009) 362. K. Asazawa et al., J. Electrochem. Soc. 156 (2009) B Press release of DHFCs technology hcp LaNi 5
7 Agenda 1. 1) 2) 3) 2. 1) 2) 3.
8 2-1) スタック 開 発 と 車 両 開 発 Stack of first generation Dr. Fan Joint research with Dr. Chinbay Fan s Group Gas Technology Institute 370 cm 2 X 50 cells (5 kw) stack@2008/june 8/54
9 2-1) スタック 開 発 と 車 両 開 発 President Mr. Mitsui's test-ride event at 2012/September President Mr. Masanori Mitsui Year FC Power Stack Volume Weight 2011 ProtoIV 5.7kW 115L 160kg 2012 ProtoV 11kW 55L 68kg
10 2-1) スタック 開 発 と 車 両 開 発 Test-ride in SPring-8 at 2013/September
11 2-1) スタック 開 発 と 車 両 開 発 Air cleaner KOH tank KOH pump Fuel circulation pump Hydrazine hydrate fuel tank Fluid level sensor Humidifie r Fuel cell stack Cell monitor Gas Liquid Separator Hydrazine sensor Compressor Lithium ion battery Inter cooler
12 Agenda 1. 1) 2) 3) 2. 1) 2) 3.
13 2-2) 2) 電 極 触 媒 の 開 発 16ch Combi-array Catalyst Powder Computational Material Design Discussion & Hypothesis High-speed survey of functional materials Analysis Synthesis Evaluation Mass production Visualization Ultra high vol TEM Synchrotron radiation XAFS Circulation of catalyst research with joint research
14 2-2) 2) 電 極 触 媒 の 開 発 Characterization of catalyst Synchrotron analysis at SPring-8 (SPring-8 8 ; Super Photon ring 8 GeV) XAFS Hard X-ray X PES Soft X-ray X PES BL14B1 BL14B2 BL01B1 BL28B2 BL46XU BL47XU BL27SU Various analyses using synchrotron have been carried out.
15 Agenda 1. 1) 2) 3) 2. 1) 2) 3.
16 2-2) 2) 電 極 触 媒 の 開 発 ; カソード 触 媒 Development of Pt-free catalysts J. Ozaki 2000 P. Atanassov M. Yuasa 2010 K. Stevenson P. Zelenay R.Jasinski(1964) R. Jasinsky: Nature, Vol. 201, p (1964)
17 2-2) 2) 電 極 触 媒 の 開 発 ; カソード 触 媒 N Fe C Template: amorphous silica infused with Fe salt Precursor ( 前 駆 体 ) pyrolyzed with Heat Treatment 熱 処 理 silica etched by HF and removed P. Atanassov, et. al., Electrochem. Commun. 22 (2012) 53 AAPyr 600, 800, 900 Phen 800, 900, 1000
18 2-2) 2) 電 極 触 媒 の 開 発 ; カソード 触 媒 Rotating Ring Disk Electrode (RRDE) MEA Voltage (V) FeAAPyr FeAAPyr (600 ) Catalytic activity FeAAPyr (800 ) FeAAPyr (900 ) High 触 媒 担 持 量 :0.51ug/mm2 温 度 :30 FeAAPyr(900 ) FePhen(900 ) Current density (ma/cm2) Half wave potential (V vs Half wave potential RHE) (V vs RHE)* Power density (mw/cm2) アノード 触 媒 :Ni エア:0.5L/min 燃 料 :HH10wt% KOH1mol/L 燃 料 流 量 :2mL/min 電 極 面 積 :4cm2 セル 温 度 :80 FePhen (900 ) FePhen (800 ) FeAAPyr (600 ) Pt/C FePhen (1000 ) High Catalytic activity FeAAPyr (800 ) Potential (V vs 10^-5A SPring-8 FeAAPyr (900 ) Ref:Pt/C:TEC10V50E 田 中 貴 金 属
19 2-2) 2) 電 極 触 媒 の 開 発 ; カソード 触 媒 HAXPES BL46XU (Hard X-ray Photoelectron Spectroscopy) ~ 数 nm Surface ~ 数 十 nm Total Kobayashi, K. Nucl Instrum Meth A 2005, 547, 98. N Fe C XPS(1.5keV) X-ray energy / ev HAXPES Fe C O N
20 2-2) 2) 電 極 触 媒 の 開 発 ; カソード 触 媒 Intensity (a.u.) FePhen (600 ) Graphitic Pyrrolic Quaternary Nx-Me Pyridinic Nitrile Intensity (a.u.) FeAAPyr (900 ) Graphitic Quaternary Pyrrolic Nx-Me Pyridinic Nitrile Binding energy (ev) Binding energy (ev) BE*.(eV) N N Structure name Graphitic Quaternary Pyrrolic Nx-Me Pyridinic Nitrile FeAAPyr FePhen Pyrrolic N N
21 2-2) 2) 電 極 触 媒 の 開 発 ; カソード 触 媒 XAFS BL14B2 (X-ray Adsorption Spectroscopy) 1. Measure initial catalyst state 2. Supply 1M KOH saturated by air 3. Set potential -0.6, -0.4, -0.2, 0, 0.25 V vs Hg/HgO (0.32, 0.52, 0.72, 0.92, 1.17 V vs RHE) O 2 OH- Fe RE Hg/HgO CE Pt Graphite plate N C Air 1M KOH P PE film Sample vs. Hg/HgO Fe
22 Agenda 1. 1) 2) 3) 2. 1) 2) 3.
23 2-2) 2) 電 極 触 媒 の 開 発 ; アノード 触 媒 Ni
24 2-2) 2) 電 極 触 媒 の 開 発 ; アノード 触 媒 Zn La Zn La Ni 0.0 Ni Ni 0.87 Zn 0.13 NiLa NiZn
25 2-2) 2) 電 極 触 媒 の 開 発 ; アノード 触 媒 Cell voltage (V) Test conditions Cathode; Fe-Phen Membrane; A201 Tokuyama Cell temperature; 80 ºC MEA Performance Ni 0.83 Zn 0.17 Ni 0.9 La Ni (Inco 210H) Current density (ma/cm 2 ) NiZn and NiLa show higher performance than the Ni in the anode. Fe-Phen has demonstrated satisfactory performance in the cathode Power density (mw/cm 2 ) Fuel; 20% N 2 H 4 H 2 O + 1M KOH Air gas humidified at 50 ºC Pressure; 10 kpa@a, 60 kpa@c Flow rate; 2 cc/min@a, 0.5 L/min@C
26 2-2) 2) 電 極 触 媒 の 開 発 ; アノード 触 媒 In-situ electrochemical cell CE (Pt coil) Electrolyte tank RE (Hg/HgO) Outlet Potentiostat PC Detector X-ray Circulation pomp Inlet X-ray WE (Carbon plate) Catalyst coated on carbon paper Joint research Current (ma) Ni/C Ni 0.87 Zn 0.13 /C CV in 1 M KOH Hydrazine oxidation Dr. Matsumura Potential (V vs. RHE) CV spectra using in-situ cell Dependence on potential of catalyst is analyzed by in-situ XAFS
27 2-2) 2) 電 極 触 媒 の 開 発 ; アノード 触 媒 XANES and RSF spectra of Ni-K edge at dry condition Normalized intensity (a.u.) Fourier transform intensity (a.u.) Ni-O Ni-Ni Ni-Ni Ni/C on CP Ni 0.87 Zn 0.13 /C on CP Ni foil Ni(OH) 2 NiO Ni-Ni Ni-O E (ev) Distance (Å) NiZn/C Ni-K Ni/C
28 2-2) 2) 電 極 触 媒 の 開 発 ; アノード 触 媒 In-situ XAFS spectra 1 M KOH Ni/C V V V 1 M KOH Ni 0.87 Zn 0.13 /C V V V Ni foil Normalized intensity (a.u.) E (ev) 1 M KOH M HH Fourier transform intensity (a.u.) Distance (Å) 1 M KOH M HH E (ev) Distance (Å)
29 3. 結 論 1. 水 加 ヒドラジンを 燃 料 とした 燃 料 電 池 自 動 車 の 走 行 試 験 を 実 施 まだまだ スタートラインに 立 ったばかり 2. 放 射 光 解 析 により 触 媒 の 活 性 種 や 反 応 メカニズムについて 知 見 を 得 ることができた 今 後 は 得 られた 知 見 を 材 料 設 計 へフィー ドバックし さらなる 性 能 向 上 を 目 指 す 燃 料 電 池 開 発 には 多 くの 知 見 経 験 技 術 が 必 要 どれだけ 多 くの 協 力 を 得 られるか がポイント
30 "CAFE" Creation of Anion Fuel-cell for the Earth Project Many laboratories of universities, public research institutes, and private enterprises in and outside Japan are taking part in this CAFE project. Please join our CAFE Project! We appreciate if you visit to Daihatsu for technical discussion!!
31 Acknowledgement Thank you for your attention.
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