Multi-Wall Carbon Nanotubes in Fuel Cells

EMTEC 3rd MEA Manufacturing Symposium

August 22, 2007

Dayton Marriott

Stewart McKenzie

Columbian Chemicals

Director Business Development

Nanotechnology and Energy Systems

Carbon Black: Formation and Fundamental Properties

Feed Oil

Combustion Gas

Water

Blast Air Feed Oil

Four Fundamental PropertiesFineness - Particle Size Structure - Aggregate Size/Shape Porosity - Pore Size Surface Chemistry - Surface Activity

NanoTechnology & Materials Development

Carbon Nanotechnology

Fuel Cell Catalysts& Components

Nano-Composite Materials

NanoCarbides

Carbon Nanotubes

ConesFullerenes C2n

Diamond

Graphite

Properties of carbon combined with nanotubes

high electron mobilityhigh thermal conductivity

high strength low mass density

Carbon Black

Carbon: A Versatile Element

•NanoBlackTM Multi-Wall Carbon Nanotubes

•DURA-lyst® CNT Pt/CNT electrocatalysts

• DURA-lyst® Pt Alloy electrocatalysts /CNT

•Ultra Durable (UD) CNT Supports

•NanoPaper

•Nano-STM Metal Nano Carbides

Columbian Nanotechnology Fuel Cell Materials

Substrate

A. Oberlin, M. Endo and T. Koyama, Journal of Crystal Growth, 32, 335-349 (1976).

A. Oberlin, M. Endo and T. Koyama, Journal of Crystal Growth, 32, 335-349 (1976).

Hydrocarbon Supply

Metal catalystHydrocarbon Supply

Metal catalystHydrocarbon Supply

Metal catalystHydrocarbon Supply

Metal catalystHydrocarbon Supply

Metal catalystHydrocarbon Supply

Metal catalystHydrocarbon Supply

Metal catalystHydrocarbon Supply

Metal catalystHydrocarbon Supply

Metal catalyst

Growth Model

Two Forms of NanoBlackTM

NanoBlackTM Platelet NanoBlackTM Tubular

Orientation of graphitic planes in nanostrucutres are system specific: dependent upon feed gas composition, synthesis temperature, catalyst composition.

Portfolio of NanoBlackTM Products

Tubular (II) Platelet (┴) Single Wall Nanotubes

High Surface Area (HSF) Spiral (S)

NanoBlack™ “Fluidized Bed” Reactor Pilot Production

Pilot Production Capacity

~ 4 metric tons per year

NanoBlackTM for Conductive Applications

Diameter Distribution

0

2

4

6

8

10

12

14

16

18

20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

Size, nm

Freq

uenc

y (n

=87

)

Unique Properties of NanoBlackTM

• Extremely High Aspect Ratio (>1000)

• Exceptional Mechanical Strength

• High Thermal and Electrical Conductivity

• High Surface Area/Surface Activities

• Chemical Stability

• Strength to Weight Characteristics

Carbon Black vs Nanotubes

50 nm

Carbon Oxidation Rates Reduced by Graphitization

70

80

90

100

0 100 200 300 400

Time (minutes)

Wei

gh

t (%

)

Carbon Black

Graphitized Black

Accelerated Test

Heat Treatment of Carbon Black

Accelerated Durability Testing

0.4

0.5

0.6

0.7

0.8

0 300 600 900 1200 1500 1800

Cycles (0.6 - 1.2 V)

2255 O2 2255HD 02 2255 Air 2255HD, Air

Voltage Cycling 30 ms

(0.6 and 1.2 V)

Cel

l Vo

ltag

e @

1A

/cm

2 (V

olt

s)

Supports for Fuel Cell Catalyst

Pt particles size is around 2-2.4nm and a CV surface area of 90 m2/g

Improvement in Performance and Cost

DURA-lyst® Ultra Durable (UD)

15% Pt/C 15% Pt/CNT

DURA-lyst® Advanced Electrocatalysts•Series 1100: 10-50% Pt

•Series 2200: 10-70% Pt

•High Durability (HD): 10-50 % Pt

•Ultra Durability (UD): 10-30 %Pt

•Q4, 2007 DURA-lyst® CNT (UD)

Product DURA-lyst®

1140DURA-lyst®

2255DURA-lyst®

2255HD

Pt Loading (%) 40 55 50+

Particle Size (nm) 2.1 2.3 2.5

Surface Area (m2/g-Pt)

80 90 75

NanoBlack™ Improves GDL Surface Morphology

Reference GDL Competitor’s product

Columbian GDL Smooth and crack-free surface morphology

Smooth and crack free surface minimizes electrical resistance

NanoBlack™ GDL

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8

Current Desity (A/ cm2)

Cell

Volta

ge (V

)

0

2

4

6

8

10

12

14

16

18

20

Cell

Resi

stan

ce (m

Ohm

)

competitor

Columbian

Resistance (competitor)

Resistance (Columbian)

H2/Air 70C, 100% RH, s1.2/2.0, ambient

0

0.2

0.4

0.6

0.8

1

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

Current Desity (A/cm2)

Cel

l Vol

tage

(V)

0

10

20

30

40

50

60

70

80

90

100

Cel

l Res

ista

nce

(mO

hm)

CCC

Competitor

Resistance CCC

Resistance competitor

H2/Air 95C, 50/0% RH, s1.2/2.0, 25psi B.P.

NanoBlack™ GDL performance is as good as competitive product under wet condition,

Columbian GDL’s is significantly better than competitive product under dry conditions.

Unique High Strength Carbon Paper

Microporous Paper Composition:92 % NanoBlackTM

8 % UHMWPE

Thickness: 100umResistivity: 4.34 ohm-cmThermal Conductivity: 7 W/m-K

Very Good Physical PropertiesHigh Tensile Strength

40X Magnification

40,000X Magnification

Metal Nano Carbides (MNC)

NanoBlack™ NanoCarbide

Summary: NanoBlack ™ An Enabling Technology

•NanoBlack™ Cost Effective Multi-wall CNT

•DURA-lyst® Advanced Electrocatalysts

•Advanced Materials

―DURA-lyst®/NanoBlack™ (UD) electrocatalysts

―DURA-lyst®/NanoBlack™ alloy electrocatalysts

―BPP materials development

―GDL materials development

―NanoPaper

―NanoCarbides