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Start: July 2009 End: September 2013 % complete: ~90%

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Barrier 2020 Target

A: Durability 5,000 h for Transportation 60,000 h for Stationary

B: Cost $30/kW for transportation $1000-1700/kW for Stationary (2-10 kW)

Total project funding: •! DOE share: $6,000,000* •! Cost share: $788,850

Funding received in FY12: $1475K*

Planned Funding for FY13: $1690K*

*Includes $400K to LANL (sub)

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4

Approach

Core Project Objectives

1. Identify fundamental classes of contamination

2. Develop and validate test methods

3. Identify severity of contaminants

4. Identify impact of operating conditions

5. Identify poisoning mechanisms

6. Develop models/predictive capability

7. Provide guidance on future material selection

Status

Complete

Complete

Complete

In progress

In progress

In progress

Future work

2010-2011

2012-2013

End of FY2013

Dissemination of information on NREL Website: http://www.nrel.gov/hydrogen/contaminants.html

^%

Approach – FY12-FY13 Milestones&FY

1 3

1 Study the effect of three model compounds on ORR activity, quantifying performance loss and recovery in ex-situ experiments.

01/2013 100%

2 Quantify the extent of in-situ voltage losses due to specific contamination mechanisms (ion exchange effects in membranes and poisoning of catalysts) for two model compounds

06/2013 80%

3 Identify the impact of fuel cell operating conditions (e.g., RH, temperature, and contaminant concentration) on voltage loss and recovery for two system contaminant extracts

8/2013 70%

FY 1

2

1 Perform parametric in-situ studies on three variety of PPA plastic to understand the mechanism of performance loss (> 50 mV loss) and recovery during fuel cell operation.

05/2012 100%

2 Down-select 20% of all materials and model compounds for in-depth parametric studies 07/2012 100%

3 Quantify the impact of two model compounds (with different functional groups) on fuel cell performance via ion exchange effects in membranes and adsorption on electrodes.

09/2012 100%

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9

Technical Progress – In-situ Studies of Individual Organic Model Compounds

Standard Operation Conditions (SOC) = Tcell=80 °C , RH%=32/32, Stoich.=2/2, Back pressure=150/150 kPa, i = 0.2 A/cm2

Model compounds result in different contamination effects

o Voltage loss, o HFR effects o Recoverability

DGMEE

DGMEA BA

2,6-DAT

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12

• Ion-exchange and absorption are two mechanisms that lead to membrane conductivity loss

– Amine functional group ion-exchanges and expels water. – Alcohol and acetate functional groups absorb into the membrane and expel water.

• Ion-exchange mechanism has stronger impact

Technical Progress – Membrane Conductivity Loss Mechanisms

Ion-exchange Membrane Conductivity Loss

2,6-DAT DGMEE

DGMEA

BA

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Interactions: Participate in the DOE Durability working group Ballard Power Systems and Nuvera Inc. on material selection and testing protocols

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21

Technical Progress – Parametric Studies of Structural Materials (in process)

Factors Pt loading [mg/cm2]

Extraction sol’n concentration

RH [%] Temp. [oC] Current density [A/cm2]

Hi 0.4 1X 65 80 0.2 Lo 0.1 0.1X 32 40 0.06

Cell voltage loss (∆V)

.

Cell voltage profile during infusion

HFR

Cell Voltage

(HH) (HL)

Results for EMS-4

- A partial factorial [22 + 1 ] test is complete. - ∆V is influenced by Pt loading and extract

solution concentration. - High Pt loading, low concentration would

relieve voltage degradation. - Voltage loss can be partially recovered via

water infusion.

DI water infusion Extract sol’n infusion

∆VHH

∆VHL

∆VHH = Vi - Vmin

DI water infusion

22

Technical Progress – Recoverability of Organic Model Compounds (ex-situ cyclic voltammetry)

• Physisorbed aliphatic organic compounds are recoverable • Aromatics with amine group are more difficult to recover • Some organics can under go redox reactions and their products can have a different effects • Ex-situ data supports in-situ data

0

10

20

30

40

50

60

70

80

90

100

Nim

, %

2,6-DAT BA DEGEEDGMEA

2,6 DAT

-600

-500

-400

-300

-200

-100

0

100

200

300

400

500

0 200 400 600 800 1000 1200

Cur

rent

den

sity

, µA

/cm

2

Potential, mV

baseline20mMrecovery

BA

-1000

-900

-800

-700

-600

-500

-400

-300

-200

-100

0

100

200

300

400

500

0 200 400 600 800 1000 1200

Cur

rent

den

sity

, µA

/cm

2

Potential, mV

baseline20mMrecovery

DGMEA

-500

-400

-300

-200

-100

0

100

200

300

400

0 200 400 600 800 1000 1200

Cur

rent

den

sity

, µA

/cm

2

Potential, mV

baseline20mMrecovery

DGMEE

-600

-500

-400

-300

-200

-100

0

100

200

300

400

0 200 400 600 800 1000 1200

Cur

rent

den

sity

, µA

/cm

2

Potential, mV

Baseline full20mMrecovery

Normalized Mass Activity

blue = Contamination at 20 mM; green = recovery 0

102030405060708090

100

NE

CA

, %

DGMEE2,6-DAT BA DGMEA

Normalized ECA

FL%

A. Schematic of channel and adsorption on Pt

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B. Model development & outcome W5! FH7%GN;%PJ%()?%*93%G/J%%

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""V membrane* =iR

(a) Experimental data

(c) Prediction for ionomer contamination

(b) Prediction line

(d) Prediction for Pt contamination

##$$@ RH=60%, I=10A

E. Compare model with DEGEE infusion data

##$$iR corrected V

D. Predicting %% V with Butler-Volmer & Conductivity

Tcell= 80!2!stoich.=2.0/2.0 P=150/150 kPa i=0.2 A/cm2, RH=32/32%

C leachate=256ppm, feed rate = 0.03 cm3/min

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C. Outcome

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MC5 TFHS

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(Nafion® ionomer degradation product) (3M ionomer degradation product)

F^%

UVV4'/$F&g&2/%#40/9&)#9#$K'.&f&3'$7+&Materials chosen based on:

1.! Physical properties o! Operating conditions (0-100% RH, -40-90˚C)

2.! Commercial availability 3.! Cost 4.! Input from OEMs and fuel cell system

manufacturers o! GM (active project collaborator) o! Ballard Power Systems o! Nuvera

1.!Balance of Plant Materials (BoP) Focus –!Liquid path 90% •! Structural plastics •! Adhesives •! Lubricants

–! Gas path 5% •! General silicone material

2.!By-products of membrane degradation 5%

Material Selection Prioritization: based on wetted surface area, total mass/volume, proximity to MEAs, function, cost, and performance implications 1.! Structural materials 2.! Coolants 3.! Elastomers for seals 4.! Elastomers for (sub)gaskets 5.! Assembly aids (adhesives, lubricants) 6.! Hoses 7.! Membrane degradation products 8.! Fuel Impurities 9.! Ions from catalyst alloys

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