12.

The Direct Methanol Fuel Cell

DMFC (1)

Use of hydrogen as fuel for transport has severe weight penalty.

Methanol has comparable energy density to petrol, (6 cf. 14 kWh kg-1)

DMFC (2)

Schematic of a Direct Methanol Fuel Cell

As opposed to Indirect where methanol is reformed to H2: CH3OH + H2O CO2 + 3H2

DMFC (3)

In the DMFC Methanol is oxidized directly at the anode (as opposed to H2 as in the PEMFC). High energy density. Liquid CH3OH is preferred over vapour due to the simplicity of design offered; existing liquid fuel distribution network. CH3OH is considered by some of have lower market entry barriers than H2 (eg. less explosive). Cheap and easy to manufacture. Low temperature operation N2 does not burn so no NOx.

DMFC (5)

Cell Reactions Anode: CH3OH(l) + H2O 6e- + 6H+ + CO2(g) PtRu catalyst E0 = 0.046V

Cathode: 1.5 O2(g) + 6e- 3H2O(l) Pt catalyst

E0 = 1.23V

Overall: CH3OH(l) + 1.5 O2(g) 3H2O(l) + CO2(g) (E=1.2 V, 90C)

DMFC (6) CH3OH CH2OH

xx

CHOH

xxx

COH

(COL) CH2O CHO

CO

HCOOH

COOH

CO2 The mechanism of methanol electro-oxidation at Pt. From V. S. Bagotzky, Yu. B. Vassilyev and O. A. Khazova, J. Electroanal. Chem., 81 (1977) 229.

DMFC (7)

DMFCs are usually based on porous carbon electrodes and the construction of the fuel cells is very similar to that of the PEMFC, differing primarily in the pattern and depth of the flow channels of the bipolar plates.

DMFC (8)

FlowField

Catalyst Layer Gases: Wettability Flooding/conductivity 3-phase interface

Gas Diffusion Layer

The structure of Gas Diffusion Electrodes (GDEs) (Porous carbon area up to 1000 m2 g-1)

DMFC (9)

Schematic of an experimental vapour-fed single cell DMFC showing the component parts.

DMFC (10)

1.0 0.8 0.6 0.4

DMFC PEMFC

Cell voltage /V

0.2 0.0

50

100 150 200 -2 Current density /mA cm

250

Typical good polarisation curves for DMFC and PEMFC operating with ambient air at 60 C & 90 C, respectively.

DMFC (11)

The Polymer Electrolyte Membrane employed (Nafion) is permeable to methanol. Methanol reacts at cathode (as well as O2) lowering the cathode potential and hence the cell voltage- BIG problem. Also swells Nafion. Consequently, major research effort on methanol-tolerant cathode catalysts for the DMFC.

11

DMFC (12)

Catalysts for Oxygen Reduction (Cathode) Ruthenium-based chalcogenides (RhRuxSy , RuSe, etc)

Transition metal macrocycles (mostly porphyrins and phthalocyanines)

Pt and its alloys with different transition metals Other noble metals such as Pd and Au

12

DMFC (13)

In Newcastle:

Catalysts based on Chevrel phase chalcogenides MxM6-xX8, M, M = Mo, Ru, Re etc, X = S, Se or Te

MoxRuySz (MoV), RhxRuySz (RhV) and RexRuySz (ReV) dispersed on porous carbon.

13

DMFC (14)

For the first time could measure methanol crossover directly!

14

DMFC (15)

Pt cathodes 0.75 mg cm-2, 2M & 4M methanol

RhRu5.9S4.7 4M methanol, 1.5 mg cm-2

4M
RhRu5.9S4.7 2M & 4M methanol, 0.75 mg cm-2 2M

Effect of anode methanol feed concentration and cathode loading on the performance of a liquid-feed DMFC operating at 90C with ambient pressure oxygen. All anodes: PtRu (1:1); 2 mg Pt cm2 (60 wt % on Vulcan XC-72R).

15

DMFC (16)
-2

Power density /mW cm

50 40 30 20 10 0 0
Pt, (Atm. O2) 0.1 barg O2

0.5 barg O2

Rh2Ru11.8S9.4

0.5 barg air

100 200 300 -2 Current density /mA cm

400

Effect of oxidant pressure on the power characteristics of a liquid-feed DMFC operating at 90 C with 4 M methanol feed. Anode E-TEK PtRu, 60 w/o on XC-72, 2 mg cm-2 Pt. Cathode = 1.5 mg cm-2 Rh2Ru11.8S9.4, 60 w/o Ketjen 600 or 0.75 mg cm-2 Pt, 60 w/o XC16 72.

DMFC (17)

Catalysts highly active and selective.

Also an added benefit do not oxidize methanol so methanol permeation across Nafion membrane can be measured via GLC.

17

DMFC (18)

GCD Chromatograph (Pye Unicam) incorporating a flame ionizer detector and a Shimadzu Chromatopac C-E1B integrator.
Analysis was carried out on exhausts sampled from both Pt and sulfide cathode-based MEAs over a range of cell operating and polarization conditions. Each sample was mixed with a 2% n-propan-1-ol internal standard in order to normalize the signals, and then compared with a curve obtained from a range of methanol standards.

18

DMFC (19)
4M MeOH MoV

2M MeOH ReV

2M MeOH MoV

Pt

Effect of current density and anode methanol feed concentration on the concentration of methanol in the cathode exhausts of: MEA-Pt (, 2 M; , 4 M); MEA-MoV (, 2 M; , 4 M); MEA-ReV (*, 2 M). Cell operated with ambient pressure oxygen.

19

DMFC (20)

DMFC problems 60 100 C = Low temperature- poor kinetics at anode and cathode-much lower power density than H2/O2. Needs Ru co-catalyst- Pt poisons otherwise. Methanol cross over through membrane to cathode, Pt active for methanol oxidation, hence mixed potential. Durability: membrane, agglomeration of Pt

Fuel cell manufacturers

Ballard Power Systems, Inc.: Canada based, global leader in PEM (proton exchange membrane) fuel cell technology. Back up power, Distributed Generation, Vehicles (bus, material handling trucks) http://www.ballard.com/files/PDF/ProductPortfolio.pdf Intelligent Energy: UK based, H2 fuel cells. Aerospace, Military, Motive systems. http://www.intelligent-energy.com/

Fuel cell applications

Fuel Cell Applications

Transportation and Automotive Industry
Fords Adavanced Focus FCV (2002) fuel cell battery hybrid 85 kW PEM ~50 mpg (equivalent) 4 kg of compressed H2 @ 5000 psi Car companies: GM, Honda, Daimler-Chrysler, Mitsubishi etc.

Submarine Typ 212 in Docks at HDW/Kiel (Germany).

2011 buses running on route RV1 between Covent Garden and Tower Gateway Station, London

Fuel cell applications

Fuel Cell Applications

Stationary Power Supply Units More than 2500 stationary fuel cell systems have been installed all over the world In large-scale building systems,
HotModule System installed at the University Hospital in Magdeburg Molten Carbonate Fuel Cell: MCFC 342 Cells, 250 kW Electrical Power ca. 48% Electrical Efficiency Feed Gas: Natural Gas Size (L x W x H): 7,3 m x 2,5 m x 3,2 m Mass 15 t

Residential Power Units

A fuel cell installed at McDonalds restaurant, Long Island

Plug Power 7000 unit cost $5000 - $10 000.

Portable applications
portable appliances and power tools small personal vehicles Consumer electronics like laptops, mobile phones Backup power

Fuel Cell Applications

Fujitsu fuel cell powered laptop. The methanol powered laptop has a battery life of 8 to 10 hours

Toshiba fuel cell charger 2009