Regenerative Fuel Cells for Energy Storage

April 2011
Corky Mittelsteadt

April 2011

Outline
1. Regenerative Fuel Cells at Giner 2. Regenerative Systems for Energy Storage
1. 2. 3. 4. 5. Economics Electrolyzer Optimization Fuel Cell Optimization What to do with O2? High Pressure Electrolysis vs. External Pumping

3. The Three Questions

April 2011

RFC System Challenges

Lines to Gas Storage Oxygen High Pressure Sep. HPS-501

O2 Storage OST-531

H2 Storage HST-321 Water Pistons OWP-531 & HWP-331

User Interface

Fuel Cell FC-601 Electrolyzer EM-210

Demineralizers DM-204, 205 Hydrogen High Pressure Sep. HPS-301

Regenerative Fuel Cell System at NASA Glenn Research Center (above) Regenerative Fuel Cell System for HighAltitude Airships at Giner (left)

Existing state of the art regenerative fuel cell systems require two separate stacks and significant auxiliary support hardware
April 2011 3

Fuel Cell vs. Electrolyzer: Stack Comparison

Fuel Cell Stack Electrolyzer Cell Stack

Membrane Catalyst Bipolar Plates End Plates

April 2011

Never on at the Same Time Combine Them

Membrane Catalyst Bipolar Plates End Plates

4

Issues Motivating WaMM Development

Unitized Regenerative Fuel Cell: Fuel Cell Mode:
Could save volume/weight of extra stack, however, water management becomes difficult. Almost impossible to avoid liquid water flooding the cathode in pressurized systems operating at low stoich. Systems must operate at lower pressure/high recirculation rates to remove water.
Complicated in low gravity Parasitic Efficiency Loss

Electrolyzer Mode:

Solution: keep water in the vapor phase

April 2011

The same features required in a fuel cell to evacuate product water will also stop feed water from reaching the electrode during electrolysis

Single Cell Operation

Fuel Cell: Electrolyzer:
Cathode Anode

Feed H2 p++H2O Feed O2 Vapor H Vapor H2O2O

Product H2 Product O2 Vacuum

MEA
Cathode Anode

WaMM Liquid H2O

April 2011

System Implications
Vapor fed electrolyzer produces >99.9% dry product gases: no liquid gas phase separators required Electrolyzer feed water can be static feed for further system simplification: no liquid recirculation pumps required Fuel cell feed gases can be static feed: no gas recirculation pumps required Fuel cell is humidified in situ by product water: no external humidifiers required Because water permeable plate is relatively insusceptible to impurities in feed water, water purity constraints can be relaxed: no deionization beds required
H2 Tank
Recirculation Pumps H2 Humidifier O2 Humidifier O2Separator H2Separator
H2O Tank Deionizer Recirculation Pump O2 Tank H2 Tank H2 Phase Separator O2 Phase Separator

Vacuum Pump O2 Tank Piston H2O Tank

Fuel Cell

Electrolyzer

URFC

Traditional RFC System

April 2011

WaMM-Based URFC System

7

URFC: Electrolyzer Performance

2.1 2 1.9 1.8 1.7 1.6 1.5 1.4 0 200 400 600 mA/cm2 800 1000 1200 60C 80C N117 Liquid Feed 80C 95C

Performance is comparable to a standard N117 electrolyzer at moderate currents

April 2011

URFC: Fuel Cell Testing

1.1 1 0.9 0.8 0.7 0.6 0.5 0.4 0 200 400 600 mA/cm2 800 1000

Discreet 2.0 stoich fuel 100% RH fuel cell Dead-ended Fuel Cell with 50% RH central chamber Gen 2 Regenerative System

April 2011

URFC: Mode Cycling

Single Cycle

Because system is vapor based, it can change modes very quickly Turn around time around 5 seconds
Voltage

1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 14:48:30 14:49:00 14:49:30 14:50:00 14:50:30 Time (hh:mm:ss)

Fast Mode Cycling: 200 mA/cm2 URFC

1.8 1.6 1.4

Voltage

1.2 1 0.8 0.6 0.4 14:45 14:50 Time (hh:mm) 14:55

April 2011

10

Outline
1. Regenerative Fuel Cells at Giner 2. Regenerative Systems for Energy Storage
1. 2. 3. 4. 5. Economics Electrolyzer Optimization Fuel Cell Optimization What to do with O2? High Pressure Electrolysis vs. External Pumping

3. The Three Questions

April 2011

11

Cost of Electrolysis is Becoming Competitive

Table 1 COSTS OF HYDROGEN FROM PEM ELECTROLYSIS Based on US Department of Energys H2A Model Item Capital Cost Fixed O&M Power Cost ($0.039/kWh) Other Variable Costs (utilities etc.) High Pressure Storage (pumps and tanks) Total Cost Miles travelled kg H2/gallon of gasoline Total Cost in gallons of gasoline equivalent
April 2011

Cost $/kg $0.79 $0.49 $1.95 $0.01 $1.80 $5.04 50/30 $3.02

12

Regenerative Systems Can Make Renewables More Competitive But Efficiency is Extremely Important
100 MW Installed Wind, 33 MW Electrolyzer, 22,500 kg Storage, 25 MW Fuel Cell Windmill Cost ($1000/kW 20 Year Amortization at 5%) Annual Storage H2 Cost (20 Year Amortization) Annual Electrolyzer and Fuel Cell System Cost ($500 kW electrolyzer, $500/kW fuel cell) (20 Year Amortization) Annual Operating, Maintenance, Refurbishment $1.5 MM Annual Off-Peak Power Yield (GW) Annual On-Demand Power Yield (50% Efficiency) Annual Value of Off-Peak Power @ 3.0/kWh Annual Value of Peak Power @ 15/kWh $ $ Windmill Only Windmill with 50% Efficient Regenerative System $ $ $ $ 8,024 181 2,648 2,705 205 50.6 $ $ 7,190 7,588 Windmill with 40% Efficient Regenerative System $ 8,024 $ 181

$ $ $ $

8,024 2,000 307 0 10,731 -

$ 2,648 $ 2,705 205 40.5 $ 7,190 $ 6,071

Annual Profit April 2011

707

1,220

$ (297) 13

Follows analysis by Dunn and Shimko 2010 DOE Merit Review

Dont Just Take our Word for it

Kevin Harrison 2010 DOE Merit Review, http://www.hydrogen.energy.gov/pdfs/review10/pd031_harrison_2010_o_web.pdf

April 2011 14

By Increasing Efficiency and Lowering Part Counts Electrolysis Cost has Been Dramatically Lowered
Part Count Required to Generate 10 Nm3 H2/hr
6000 5000

Number of Parts

4000 3000 2000 1000 0

EP1 (2006)

EP2 (2008)

EP3 (2011)

EP4 (2014)

April 2011

15

Outline
1. Regenerative Fuel Cells at Giner 2. Regenerative Systems for Energy Storage
1. 2. 3. 4. 5. Economics Electrolyzer Optimization Fuel Cell Optimization What to do with O2? High Pressure Electrolysis vs. External Pumping

3. The Three Questions

April 2011

16

Optimizing Performance For Electrolyzers

Similar to fuel cells, the majority of efficiency losses are due to slow oxygen kinetics and membrane resistance

For cell operating at 1000 psi and 80C with Nafion 117

April 2011

17

Improvements in Lowering Permeability can Greatly Improve Operating Efficiency

1100 EW Ionomer 60 58 56 54 52 50 48 46 44 42 40 60 58 56 54 52 50 48 46 44 42 40 2x Cond/Perm Improvement 60 58 56 54 52 50 48 46 44 42 40 5 x Cond/Perm Improvement

Efficiency kWh/kg H2

2 mil 10 mil

5 mil 20 mil

Efficiency kWh/kg H2

2 mil 10 mil

5 mil 20 mil

Efficiency kWh/kg H2

2 mil 10 mil

5 mil 20 mil

50 0 10 00 15 00 20 00 25 00 30 00

50 0 10 00 15 00 20 00 25 00 30 00

Current Density mA/cm2

Current Density mA/cm2

Operation at 80C and 1000 psi Using Current PFSAs Thick Membranes is Required for High Pressure Operation
April 2011 18

50 0 10 00 15 00 20 00 25 00 30 00
Current Density mA/cm2

Membranes and Catalysts that can Tolerate High Temperatures Can Greatly Improve Efficiency
2.4
60

2.2
Energy Requirement kWh/kg H 2

2
Voltage

55

1.8

50

1.6 30C 1.4 0 1000 2000 3000 Current Density mA/cm2 60C 80C 100C

30C 45 0 1000

60C

80C 2000

100C 3000

Current Density mA/cm2

April 2011

19

Outline
1. Regenerative Fuel Cells at Giner 2. Regenerative Systems for Energy Storage
1. 2. 3. 4. 5. Economics Electrolyzer Optimization Fuel Cell Optimization What to do with O2? High Pressure Electrolysis vs. External Pumping

3. The Three Questions

April 2011

20

Due to Crossover, Fuel Cells Generally do not Benefit From Nerstian Boost of High Pressure
Effect of Pressure on Cell Efficiency 25

kWh/kg H2

20 15 10 0 200 400

H2/O2 80C
600 800 1000 1200

Current Density mA/cm2 20psia 50psia 100psia 200psia

April 2011

21

Outline
1. Regenerative Fuel Cells at Giner 2. Regenerative Systems for Energy Storage
1. 2. 3. 4. 5. Economics Electrolyzer Optimization Fuel Cell Optimization What to do with O2? High Pressure Electrolysis vs. External Pumping

3. The Three Questions

April 2011

22

If Operating on Air, Fuel Cells Need a Thin Membrane

26 24 22 26 24 22

kWhr/kg Hydrogen

kWhr/kg Hydrogen

20 18 16 14 12 10 0
0.5 mils 1 mils 2 mils 5 mils

20 18 16 14 12 10 0
0.5 mils 1 mils 2 mils 5 mils

90C Anode/Cathode: 20/20 psia 1.1/2.0 Stoich 100/20% Inlet RH

500 1000 Current Density mA/cm2

500 1000 Current Density mA/cm2

With current PFSA membranes it is not possible to operate high pressure electrolysis with a thin membrane
April 2011 23

With Focus on Efficiency it is Difficult to Operate with Air

1.10
Single Cell Voltage

1.00 0.90 0.80 0.70 0.60 0.50 0

Pt Black H2/ O2 H2 /O2 Pt on C H2 /Ai r P t on C

200 400 600 800 C urrent Density (mA/cm2)

1000

Further improvements in catalysts still needed. 3M and Argonne catalysts look promising.

April 2011

24

Outline
1. Regenerative Fuel Cells at Giner 2. Regenerative Systems for Energy Storage
1. 2. 3. 4. 5. Economics Electrolyzer Optimization Fuel Cell Optimization What to do with O2? High Pressure Electrolysis vs. External Pumping

3. The Three Questions

April 2011

25

Increasing Electrolyzer Pressure Leads to System Simplification but not Necessarily Lower Cost
Complete Cost of Generating H2 for Storage at 5000 psi as a Function of Electrolyzer Operating Parameters
$11.00

$10.00

2000 PSI 300 PSI

5000 PSI

$9.00

cost of hydrogen ($/kg) 2

$8.00

$/kg H

$7.00

$6.00

$5.00

$4.00

$3.00

23 bar; & 10.75kA/m

23 bar; & 21.5kA/m

23 bar; & 32.25kA/m

23 bar; & 43kA/m

23 bar; & 53.75kA/m

23 bar; & 64.5kA/m

23 bar; & 75.25kA/m

$0.07 $0.06 $0.05

23 bar; & 86kA/m

138 bar; & 10.75kA/m

138 bar; & 21.5kA/m

$0.04$/kWh

138 bar; & 32.25kA/m

138 bar; & 43kA/m

138 bar; & 53.75kA/m

$0.03

345 bar; & 10.75kA/m

345 bar; & 21.5kA/m

45 bar; & 32.25kA/m

$0.02

Current Density A/cm2

electrolyzer outlet pressure & current density

April 2011

345 bar; & 43kA/m

26

Outline
1. Regenerative Fuel Cells at Giner 2. Regenerative Systems for Energy Storage
1. 2. 3. 4. 5. Economics Electrolyzer Optimization Fuel Cell Optimization What to do with O2? High Pressure Electrolysis vs. External Pumping

3. The Three Questions

April 2011

27

The Three Questions

1. Is this technology feasible for cost effective storage of renewable electricity? Dependent on scale and duty cycle. Fuel cell and electrolyzer duty cycle need to be closely matched For air operating it is difficult to match fuel cell and electrolyzer membranes 2. What are the materials and systems barriers to developing this technology? Membranes with lower gas permeability Lower Cost Catalysts 3. What are the manufacturing issues that need to be addressed to be cost effective? Continuing to lower part count and component cost

Efficiency is still key for cost competitiveness.

April 2011 28