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1 NEDO
2 1
3 NEDOPEFC 22 FCCJ1923 FCCJPEFC MEA 2 PEFC PEFC NEDO NEDO FCCJ 2
4 MEA TEC10E50ENR211NR212MEA TEC10E50E NR211NR212MEAI-VORRECA 3I-V RDE ECATEC10E50EECARDEECA MEAECAPt TEC10E50EMEA I-VECAORR OCV MEA 1 I-V 2 ECA 3 4 ORR RDE 10 3
5 GDLMEA MEA MEA 22NEDO 1721NEDOWG_MEA F-4PEFC DuPont Nafion Dispersions DuPont NR211 and NR212 SGL GROUP THE CARBON COMPANY SIGRACET locale=en 4
6 1cm1cm MEA10mg 1cm1cm MEAMEA cm1cm 3cm5cm MEA 3cm5cm 3cm5cm 3cm5cm 3cm5cm 5cm5cmJARI JARI1 PEFC JARI JARIPEFC Uf70% Uox40% JARI 22NEDO 52 3F16 PEFC 19 A3 "Study of fuel cell structure and heating method Development of JARI s standard single cell" Y.Hashimasa et.al, Journal of Power Sources 155 (2006)
7 100mgcm 2 1cm1cm 50mg 1cm1cm 1cm1cm 1cm1cm 3 MEA 0.5mm0.55mm 0.3mm 1cm1cm 6 1cm1cm kPa-G 1 150NmL/min NmL/min NmL/min NmL/min MAX510A 03V 1cm1cm 6
8 OCV3cm5cm 3cm5cm 3cm5cm 16 MEA 1.0mm1.0mm 0.5mm 3cm5cm kPa-G 3~1500 NmL/min 6~3000 NmL/min kPa-G 3~1500 NmL/min 6~3000 NmL/min N 2 H cm5cm 3cm5cm N 2 Air
9 5cm5cm8cm8cmMEAJARI JARI2g JARI JARI JARI 1 MEA 1.0mm1.0mm 1.0mm 5cm5cm 12 JARI JARI JARI 8
10 MEAMEA TEC10E50ENR211NR212MEA Nafion 2g 50100mg MEA TEC10E50ENR211NR212MEA 1cm1cm JARI TEC10E50E DuPont Nafion NR211(t 25m) SGL SGL24-BCH 0.2A/cm V 0.78V 1.0A/cm V 0.61V m 2 /g-pt 65 m 2 0.9V 68 A/g-Pt 106 A/g-Pt 9
11 1cm1cm 3cm5cm JARI H 2 H NmL/min 5@1A/cm NmL/min 5%@0.2A/cm NmL/min 70%@1A/cm 2 Air Air 332 NmL/min 5%@1A/cm NmL/min 5%@0.2A/cm NL/min 40%@1A/cm (RH 81%) 80 (RH 100%) or 65 (RH 53%) 77 (RH 88%) 75 (RH 81%) 80 (RH100%) or 65 (RH 53%) 60 (RH 42%) MEA 0.5V 20h 0.5V 20h 1000 ma/cm 2 V2mV/h 0.5V20h 8065 MEA cm1cm0.5V20h 1.20 (A/c) A B C D E h 10
12 I-V 1cm1cm 3cm5cm JARI H 2 2% 5% 70% Air 2% O 2 5% O 2 40% O *80 (RH 100%) 40~80 (RH 16%~100%) 77 (RH 88%) *80 (RH 100%) 40~80 (RH 16%~100%) 60 (RH 42%) ** 2,4,6,10,20,50,75,100 ma/cm 2 (5min) 200,400,600,800,1000, 1500,2000mA/cm 2 (10min) 25,50,75,100 ma/cm 2 (5min) 200,400,600,800,1000, 1200 ma/cm 2 (10min) 25,50,75,100 ma/cm 2 (5min) 200,400,600,800,1000, 1200 ma/cm 2 (10min) * 80 - ** 20mA/cm 2 210mA/cm O 2 O 2 8.4% IR-free (V) 1.17 V (80 o C, H 2 /Air) y = ALn(x) + B I-V E rev(ph 2,PO2,T) = (T298) 2.303RT 4F log PH 2 PH 2 2 PO 2 PO 2 PH 2 =PO 2 =101.3kPa T=80 o C (353 K), (PH 2 /P*H 2 )=1.0, (PO 2 /P*O 2 )=0.21 PH 2 PO (A/cm 2 ) Handbook of Fuel Cells - Fundamentals, Technology and Applications, Edited by Wolf Vielstich, Hubert A. Gasteiger, Arnold Lamm, Vol. 3: Fuel Cell Technology and Applications, John Wiley & Sons, Ltd., p.597 (2003) IR-freeTafel V A/cm 2 cm 2 IR-free 11
13 SAMPLE STD (A/cm 2 ) (V) (cm 2 ) IR-free (V) (A/cm 2 ) (V) (cm 2 ) IR-free (V) V I-V SAMPLE STD IR-freeV SAMPLE STD y = Ln(x) y = Ln(x) Tafel A/cm 2 A/cm 2 V SAMPLE STD A/cm 2 A/cm 2 12 V
14 1cm1cm 3cm5cm JARI H 2 70 NmL/min 200 NmL/min 200 NmL/min N NmL/min NmL/min NmL/min 40* 80 40* 80 40* 80 40* (RH 100%) 80 (RH 100%) ECA 80 40* (RH 100%) 80 (RH 100%) or 65 (RH 53%) * (RH 100%) 80 (RH 100%) ECA 80 ECA * 40ECA V50mV/s5 5210C/cm 2 ECA ECA ECARDEECAMEAECA PtRDE ma 40 50mV/s5 Pt 0.39 mg/cm cm 2 C/cm 2 C 0 Pt 278 cm 2 ECA 71.2 m 2 /g-pt Pt C cm V VS. RHE 0.90V ECA 73.4 m 2 /g-pt p "Pt Utilization Analysis Using CO Adsorption" K. Shinozaki, T. Hatanaka, and Y. Morimoto, ECS Transactions, 11 (1) (2007) 13
15 1cm1cm 3cm5cm JARI H 2 70 NmL/min 200 NmL/min 200 NmL/min N NmL/min 500 NmL/min 200 NmL/min (RH 100%) 80 (RH 100%) 65 (RH 53%) 80 (RH 100%) V vs. RHE 0.5mV/s V / V 0V ma/cm ma/cm y = 4.45x / V 0V V vs. RHE V0.5mV/s V vs. RHE 2.17 ma/cm = mcm 2 p
16 1cm1cm JARI H 2 70 NmL/min 70% O NmL/min 8.4% 150kPa 150kPa (RH 100%) 80 (RH 100%) 0 ma/cm 2 (O 2 2min) 1000, 200, 100, 80, 60, 40, 20 ma/cm 2 (15min) 10, 6, 4, 2 ma/cm 2 (5min) 0 ma/cm 2 (O 2 2min) 1000, 200, 100, 80, 60, 40, 20 ma/cm 2 (15min) 1000 (ma/cm 2 ) min 20mA/cm 2 IR-free0.9V 10mA/cm 2 1cm1cm p Polymer Electrolyte Fuel Cell Degradation, Edited by Matthew M. Mench,Emin Caglan Kumbur, T. Nejat Veziroglu, Academic Press (2011); p , Specific (i s ) and Mass Activity (i m ) 15
17 ORR34ECACOC 5 COCIR-freeTafel 34 IR-free0.9V0.9V0.85V 0.8V IR-free 0.9V1cm 2 1g A/g-Pt A/g Pt IR-free 0.9V1cm 2 ECA1cm 2 A/cm 2 -Pt A/cm 2 Pt Pt 0.30mg-Pt/cm 2 ECA 73.4 m 2 /g-pt COC 2.17 ma/cm 2 = A/cm 2 (A/cm 2 ) + COC(A/cm 2 ) (V) (cm 2 ) IR-free (V) IR-free V y = Ln(x) A/cm A/cm 2 0.9V 0.024( ) 80 A/g-Pt A/m 2 -Pt 110 A/cm 2 -Pt 16
18 MEA FCCJ 1cm1cm I-V ECA An:H 2 70NmL/min, Ca:N 2 166NmL/min* Tcell=80, Tda=Tdc=80 JARI I-V ECA AnH 2 200NmL/min, Ca:N 2 800NmL/min* Tcell=80, Tda=Tdc= I-VECAORR 500cycle1 1,000cycle21,000cycle ECA50 60,000cycle * CO 2 N 2 CO 2 30s 1s 1s 1.5V 2s/cycle 1.0V p NEDO MEA P10 Analysis of Durability of MEAs in Automotive PEMFC Applications Randal L. Perry DuPont, 2012 Annual Merit Review Proceedings FC089, May 16, Membrane and Catalyst Performance Targets for Automotive Fuel Cellsby FCCJ Membrane, Catalyst, MEA WG A.Ohma, K.Shinohara, A.Iiyama, T.Yoshida,and A.Daimaru ECS Transactions, 41 (1) (2011) 17
19 ECA m 2 /g-pt ECA ECAm 2 /g-pt ECA 60 ECA y = Ln(x) ECA 34 y = a Ln(x) + b y = 50 x 3,500
20 MEA FCCJ 1cm1cm I-V ECA An:H 2 70NmL/min, Ca:N 2 166NmL/min Tcell=80, Tda=Tdc=80 JARI I-V ECA AnH 2 200NmL/min, Ca:N 2 800NmL/min Tcell=80, Tda=Tdc= I-VECAORR 500cycle1 1,000cycle 2 1,000cycle CVECA50 400,000cycle 3s 3s 1.0V 30s 6s/cycle 0.6V p NEDO MEA2 79 p.4433p11 Analysis of Durability of MEAs in Automotive PEMFC Applications Randal L. Perry DuPont, 2012 Annual Merit Review Proceedings FC089, May 16, Membrane and Catalyst Performance Targets for Automotive Fuel Cellsby FCCJ Membrane, Catalyst, MEA WG A.Ohma, K.Shinohara, A.Iiyama, T.Yoshida,and A.Daimaru ECS Transactions, 41 (1) (2011) 19
21 ECA m 2 /g-pt ECA ECAm 2 /g-pt ECA ECA y = Ln(x) ECA 34 y = a Ln(x) + b y = 50 x 7,100 20
22 3cm5cm I-VECA H NmL/min*, Air 997 NmL/min* 3cm5cm * 0.2A/cm 2 5 H NL/min, Air NL/min JARI Tcell=90, Tda=Tdc=61 RH30 OCV I-VECA OCV NR211NR212OCV 3cm5cm (ma/cm 2 ) NR211 NR212 HC h NR NR p "DOE Fuel Cell Program: Durability Technical Targets and Testing Protocols" Nancy Garland, Thomas Benjamin and John Kopasz ECS Trans. 2007, Volume 11, Issue 1, Pages
23 3cm5cm MPLGDLSGL24- BCH I-VECA Air 2,000NmL/min, Air 2,000NmL/min 3cm5cm N 2 800NmL/min, N 2 800NmL/min JARI Tcell= 80, Wet : Tda=Tdc= 90 RH 150 2min Dry : Tda=Tdc= Dry RH 0% 2min 1000cycle67h I-VECA 10 20,000cycle FCCJDOE MPL NR211t 25mNR212t 50m (ma/cm 2 3cm5cm ) NR2119, NR211 NR212 NR NR21220,000 NR ,000 10,000 15,000 20,000 25,000 p "DOE Fuel Cell Program: Durability Technical Targets and Testing Protocols" Nancy Garland, Thomas Benjamin and John Kopasz ECS Trans. 2007, Volume 11, Issue 1, Pages
24 RDE RDEECAORR M HClO 4 O 2 100, 400, 900, 1600, 2500 rpm * *FCCJp CV ECA CV 0.05~1.20V, 50mV/s mV/s0.9V0.85V Koutecky-Levich0.9V0.85V A/g-PtA/cm 2 ORR 3.25RDE (ECA 81.4 m 2 /g-pt) [ma] ma 100rpm 400rpm 900rpm 1600rpm 2500rpm [V/vs.RHE] V vs.rhe -1 [ma -1 ] Koutecky-Levich Plot 0.9V0.85V y = -12.5x - y = -12.0x /2 [ (rad s -1 ) -1/2 ] 0.9V3.25gPt ma A g= 270 A/g-Pt 0.9V (270 A/g-Pt)(81.4m 2 /g-pt) = 3.32 A/m 2 -Pt = 332A/cm 2 -Pt 0.85V3.25gPt ma A g= 708 A/g-Pt 0.85V (708 A/g-Pt)(81.4m 2 /g-pt) = 8.70 A/m 2 -Pt = 870A/cm 2 -Pt p , p Polymer Electrolyte Fuel Cell Degradation Edited by Matthew M. Mench,Emin Caglan Kumbur, T. Nejat Veziroglu, Academic Press (2011); p , Electrochemical Half Cells 23
25 RDE YES NO RDE RDEECA RDEORR MEA NO TEM-EDX YES TEM-EDX MEA 2 SEM 1cm 2 Pt MEA i/carbon i/catalyst AFM MEA NO FIB/SEM EPMA/SEM YES YES I-V, ORR, ECA, MEA IR ORR //ECA NO NO I-V YES EPMA/SEM SEM FIB/SEM MEA YES MEA MEA NO NO Pt TEM YES TEMFIB/SEM SEM 24 FIB/SEM
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e - カーボンブラック Pt 触媒 プロトン導電膜 H 2 厚さ = 数 10μm H + O 2 H 2 O 拡散層 触媒層 高分子 電解質 触媒層 拡散層 マイクロポーラス層 マイクロポーラス層 ガス拡散電極バイポーラープレート ガス拡散電極バイポーラープレート 1 1~ 50nm 0.1~1
Development History and Future Design of Reduction of Pt in Catalyst Layer and Improvement of Reliability for Polymer Electrolyte Fuel Cells 6-43 400-0021 Abstract 1 2008-2008 2015 2 1 1 2 2 10 50 1 5
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