CO CO OH Pt M Support CH 3 OH < 200 H 2 O/ H + 3C

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2 CO CO OH Pt M Support CH 3 OH < 200 H 2 O/ H + 3C

3 Anode CO 2 Cathode e - H 2 O + CH 3 OH Catalyst H + e - H + Catalyst O 2 H 2 O CH 3 OH+H 2 O CO 2 + 6H + + 6e - O 2 + 6H + + 6e - 3/2H 2 O

Major Developmental Issues of DMFC Anode Catalyst Anode

046 V CO 2 CH 3 OH, H 2 O Pt Ru Pt Pt Pt Bi-functional catalyst

Carbon support - surface area - pore diameter - e -

4 Major Developmental Issues of DMFC Anode Catalyst Anode Reaction: CH 3 OH + H 2 O CO 2 + 6H e - E 0 = V CO 2 CH 3 OH, H 2 O Pt Ru Pt Pt Pt Bi-functional catalyst active center e - CO 2 Pt Ru CH 3 OH, H 2 O H + 1. Carbon support - surface area - pore diameter - e - conductivity 2. Catalyst - Methanol activation - Water activation - Pt-Ru neighboring site - Stability

I-Supported catalyst development Surfactant stabilized (SS) Pt/carbon to reduce Pt

catalyst dispersion in ink SS catalyst has Excellent Pt dispersion SS catalyst has

40 nm 0 0 1 2 3 4 5 6 7 size(nm) 54.5 62.4 Pt-S/C Pt-S/C 1 Activity 40.1 35.

5 I-Supported catalyst development Surfactant stabilized (SS) Pt/carbon to reduce Pt particle size and enhance activity: C Good Pt dispersion Nano-size Pt Good catalyst dispersion in ink SS catalyst has Excellent Pt dispersion SS catalyst has highest activity Number Average=2.40 nm size(nm) Pt-S/C Pt-S/C 1 Activity JM Tanaka (Commercial) Surfactant stabilized (SS) Pt/carbon has higher activity (62.4mA/mg) than commercial catalyst(35~40ma/mg).

- -- -- 5nm Pt Particle ~5um DLS PtRuPtRu ~200nm PtRu

6 nm Pt Particle ~5um DLS PtRuPtRu ~200nm PtRu 5 nm 6um 4um PtRuPtRu PtRu steric stabilization Mechanical Coupling mixing agent catalyst utilization, % scan rate 20mV/s % Substrate Nafion 15%

7 ITRI Long-term Durability Benchmarking o Temp : 60 C 90 Voltage (V) MCL MEA 7 Vendor Y Vendor Z MCL MEA 7-G Power Density (mw/cm ) Current Density (ma/cm ) Decay rate(μv/hr) Test period ITRI MEA 0 ~ 3000 hrs D Company MEA(Gen IV) 0~3000hrs Rest/4h r Rest/12hr Rest/24hr After 3000hrs discharging, the voltage decay rate of MCL MEA is 8μV/hr,while the commercial MEA is 39 μv/hr. The performance of MCL MEA is 30% higher than commercial MEA after 2000hrs discharging

9 DMFC System Stack CO2 Exhaust Fuel Supply Power Management

10 Power Requirement Digital Video Camera Mobile Game Console Ultra Mobile PC Note PC 5 W 10 W 15 W Cellular Phone Smart Phone PDA Phone Portable Media Player Fuel Cell System Passive Type Semi-Active Type Active Type

Micro Fuel cell Developing Status Application Smart Phone Company

PEMFC Passive DMFC Passive DMFC Passive DMFC 2006 prototype 2006

MT I Hitachi MTI Passive DMFC 2009 commercialize preparation Toshiba

prototype Toshiba DMFC 2006 prototype NB Casio Maxell ITRI / SIMPLO

11 Micro Fuel cell Developing Status Application Smart Phone Company Hitachi NTT & Aquatairy ITRI Sony Samsung Fuel Cell type Passive DMFC PEMFC Passive DMFC Passive DMFC Passive DMFC 2006 prototype 2006 prototype 2006 prototype 2008 prototype 2008 prototype Status ITRI SONY MT I Hitachi MTI Passive DMFC 2009 commercialize preparation Toshiba Passive DMFC 2009 commercialize preparation Toshiba Panasonic DMFC 2006 prototype Toshiba DMFC 2006 prototype NB Casio Maxell ITRI / SIMPLO Samsung RMFC PEMFC DMFC DMFC 2007 prototype 2007prototype 2007prototype 2008 prototype ITR I Samsung

GSM Video call present Battery + 1000mW fuel cell ITRI DMFC Application for Mobile Communication/Entertainment Mp Gam Load (ma)

5 750 3 225 0.8 1 225 e 490 1.8 1 490 VOD 390 1.4 0.5 180 DSC 250 0.9 0.5 125 Bell 350 1.3 0.05 20 etc 120 17.

12 GSM Video call present Battery mW fuel cell ITRI DMFC Application for Mobile Communication/Entertainment Mp Gam Load (ma) Power (W) Operation (hr) Capac. require ITRI MCL 500mW Fuel Cell size : 48*48*86 mm 3 Call IMB e VOD DSC Bell etc Tota l Ref: Samsung 2008 FC EXPO repor 4 Lithium battery packs required for 24 hrs. operation of 4G mobile device. hr. 7 hrs to 24 hrs

14 ye Test sales Start of sales Commercial sales Start of sales Commercial sales Mass-production Commercial sales Test sales Industrial co-generation systems Source QR-4534, Nikkei Mechanical, 2002

15 Is Slim Fuel Cell Possible?

16 Niche Applications for DMFC Leisure Toshiba Military Samsun g SONY 4500 Products shipped 2007 USD $1995 Remote surveillance DMFC meets US army requirements of 4Kg, 20W, 96hrs. (US army 13-20Kg) Market is there Only Cost and Size

17 Prototype below 50W Motolora Motolora Toshiba Toshiba Planar design NEC NEC

18 Prototype 50/500W ISE ISE Some Some are are Stack Stack design design Others: Others: Samsung, NEC, NEC, Toshiba Casio Casio Ballard Ballard

19 3C ( ) Toshiba PDA Cellular phone Samsung Motorola MTI

20 3C ( ) Casio Smart Fuel Cell Samsung Fraunhofer Institute

Possible Grand Challenges (2014) Auto charge of LEV (Light

wh/l fuel Reliable Power (worry-free) Scenario 2L fuel run for 100

Worry free of battery recharge <NT15/L fuel High water retention

high environment tolerance Water back diffusion control to enhance

21 Possible Grand Challenges (2014) Auto charge of LEV (Light Electric Vehicle) by Fuel Cell Hybrid Power 50 Km/L fuel, 1000 wh/l fuel Reliable Power (worry-free) Scenario 2L fuel run for 100 km applied in Green LEV (power chair, wheelchair, e-bike) Approach Worry free of battery recharge <NT15/L fuel High water retention designed MEA in elevated temperature Durable MEA and membrane with high environment tolerance Water back diffusion control to enhance system efficiency Energy requirement Power chair = 20Wh/km Pedlect bike ~5 Wh/km

PEMFC classification by working temperature Advantages Membrane Draw back efficiency ~ 40% Excellent performance Nafion Not

excellent performance Good to excellent performance Simple water management Good performance Simple design Nafion Hydro- Carbon/

Bulky & complex fuel processing High Equipment cost and complicated control Source: Motorola Three temperature zones determined

22 PEMFC classification by working temperature Advantages Membrane Draw back efficiency ~ 40% Excellent performance Nafion Not practical fuel storage (High pressure or metal hydride) Gas/ MeOH Gas/ MeOH Gas/ MeOH efficiency ~ 35% efficiency ~ 45% Good to excellent performance Good to excellent performance Simple water management Good performance Simple design Nafion Hydro- Carbon/ Sulfonate PBI/H 3 PO 4 Bulky & complex fuel processing High Equipment cost and complicated control Acid management and corrosion Bulky & complex fuel processing High Equipment cost and complicated control Source: Motorola Three temperature zones determined by CO tolerance: 10-20ppm@ ppm@ ppm@200 Membrane requirement vs. operation temperature: water( ) vs. H 3 PO 4 (>150 )

23 Proton transfer mechanism Vehicular mechanism Proton combined with water to form H 3 O + and move with water flow Proton can easily transfer from one H 2 O molecule to another Sulfonic acids offer H + to help the transportation Proton conductivity decreases Low RH (usually elevated temperature) Grotthuss mechanism An excess proton or protonic defect diffuses through the hydrogen bond network Brönsted acid base pairs (Ionic liquids): No water is needed Proton conductivity usually less than 10-3 S/cm when the temperature is below 130 but increase dramatically with increasing temperature

24 MEA Cost Reduction and Performance Improvement 1. Material of MEA is the major cost of DMFC fuel cell system. 2. MEA cost can be reduced by improve MEA power density, lower catalyst loading and recycle Pt catalyst. 16% 15% Catalyst - Pt Separator - Nafion % Catalyst - PtRu, JM Carbon paper, SGL Material cost of MEA 38% Material Cost, USD/W catalyst loading, mg/cm MEA Power, mw/cm 2 cost down miniaturizatio n Q material cost, US$/cm Improvement of catalyst utilization Bad dispersion, (~2 m) 10% utilization Good dispersion,(~100nm) 40% utilization Present Status ~ 58% MEA material cost is attributed to catalyst, 3 mg/cm 2, 100 mw/cm 60, 4 X 4 (ITRI) 2009 Target MEA Power Density: 120 mw/cm 2 Loading: 1 mg/cm 2 Cost: USD 3/W System NB Application 15W Energy Density 1000Wh/l Target Price USD150-

25 MEMS 1 10 /

Jen-Luan Chen, Chen, Chih-Yuan Chih-Yuan Chen, Chen, Chih-Jer Chih-Jer Shih Shih MEA MEA (MRL): (MRL): Li-Duan Li-Duan Tsai, Tsai, Kan-Lin Kan-Lin Hsueh, Hsueh, Chiou-Ping Chiou-Ping Hwang,

26 DMFC Development Team Project Project Coordination Coordination Dr. Dr. Jing-Pin Jing-Pin Pan Pan and and Mrs. Mrs. Yat-Fang Yat-Fang Tao Tao Catalyst Catalyst (UCL): (UCL): Manyin Manyin Lo, Lo, Chun-Chieh Chun-Chieh Huang Huang Membrane Membrane (MRL): (MRL): Jong-Pyng Jong-Pyng Chen, Chen, Jen-Luan Jen-Luan Chen, Chen, Chih-Yuan Chih-Yuan Chen, Chen, Chih-Jer Chih-Jer Shih Shih MEA MEA (MRL): (MRL): Li-Duan Li-Duan Tsai, Tsai, Kan-Lin Kan-Lin Hsueh, Hsueh, Chiou-Ping Chiou-Ping Hwang, Hwang, Fu-Chi Fu-Chi Wu, Wu, Chin-Hsing Chin-Hsing Chen, Chen, Du-Yuan Du-Yuan Yu, Yu, Wen-Yi Wen-Yi Chen Chen System System (MRL): (MRL): Chiou-Chu Chiou-Chu Lai, Lai, Yuh-Fwu Yuh-Fwu Chou, Chou, Ku-Yin Ku-Yin Ka, Ka, Sheng-Yong Sheng-Yong Shen, Shen, Peggy Peggy Huwang Huwang

27 / Du Pont CWRU (USA) (ITRI) IP / / / /

28 Taiwan Seashore Scenery

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24-2_cover_OK 2 08 Flexible All Solid State Thin Film Li-ion Battery 1 1 2 1 1 2 ( 300Wh/kg) (3.4~3.8 V) ( 1000 cycles) (LiCoO 2 ) (LiPON) (Mica) 26mAhcm -2 mm -1 30 85% LED Abstract With the ever-changing technology,