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INVESTIGATING THE TECHNICAL AND COMMERCIAL MERITS OF ZINC-AIR FUEL CELLS FOR PASSENGER ELECTRIC VEHICLES
by Denis Vasilescu
October 28th 2010Masters Degree of Science in Mechanical & Aerospace Engineering
Illinois Institute of Technology
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Motivation
Tesla Roadster288 horsepower245 mile range6 hour @220/240 V 40A$109,000 MSRP
Nissan Leaf107 horsepower90 miles/hour100 mile range8 hr @220/240 V 40A
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Motivation
Chevrolet Volt150 horsepower80 hp engine50 mile range4 hr @220/240 V
Coulomb Technologies IncCT2100 ChargePoint: 208/240V 30ACT3000 ChargePoint: 500V 125A
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Motivation
Faster, more powerful charge stations?More lithium batteries per car?Change driver habits and routines?
“If I had asked people what they wanted, they would have said faster horses”
-Henry Ford
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Outline
Literature Review Technical Concept Economic Analyses Sustainability Experiments Summary
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Literature ReviewNet chemistry: the oxidation of zinc
Claim to fame: high energy density due to half the reactants available in air
Killer app: button batteries for hearing aids, watches, and calculators
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Literature Review: Mechanically Rechargeable Batteries
Developed for military electronics in the 1960s
Research for vehicle propulsion in the 1970s
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Literature Review: Mechanically Rechargeable Batteries
Commercialized in 1980s by Electric Fuel Ltd of Israel for fleet vehicles
Zinc cassettes swapped at depot in Germany, reprocessed at plant in Israel
First to implement a zinc cycle
Battery swap scheme now in use by A Better Place using lithium
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Literature Review: Mechanically Rechargeable Batteries
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Literature Review: Mechanically Rechargeable Batteries
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Literature Review: Shell-and-Tube Slurry Fuel Cells
Developed in the 1970s by French General Electric Company (CGE)
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Literature Review: Shell-and-Tube Slurry Fuel Cells
Fuel in granulated/particulate form
Constant mass of zinc within the control volume
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Literature Review: Packed Bed Tapered Fuel Cell
Developed in the 1990s through 2000s at Lawrence Livermore National Lab
Planar geometry like the mechanically-rechargeable batteries
Continuous feed of particulate zinc like the shell-and-tube fuel cell
Used a taper for gradual feed of zinc
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Literature Review: Packed Bed Tapered Fuel Cell
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Literature Review: Packed Bed Tapered Fuel Cell
Developed six generations of design
Demonstrated on a tour bus, achieved 300 mile range
IP and personnel handed over to Power Air Corp for commercialization in 2004
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Literature Review: Legacy
LLNL design by far the most researched and developed, but many questions still open-ended
How to improve power density? How to control the flows? How to manufacture? How to make the design robust? How will it be refueled? How will the oxide be reprocessed? How much will it cost? How sustainable is the whole system? Etc
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Literature Review: Thesis Contributions
Design and analyze the aspects of a holistic system using centralized reprocessing
-Technologies and mechanisms-Cost analyses-Toxins and emissions
Design and analyze a control system for the fuel cell systems
-Analytically frame the problem-Experimentally probe the physics
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Technical Concept: The Electrochemistry
Most ideal specific energy is the Gibbs free energy of zinc oxide, 1352 Wh/kg
Ideal efficiency, ε = ΔG/ ΔH = 91.4%. 80-90% for Li-ion and 55-80% NiMH
Practical specific energies depend on packaging and controls
Observed ZAFCs: 110-330 Wh/gObserved Li-ion: 160-190 Wh/gObserved NiMH: 70-80 Wh/kg
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Technical Concept: The Electrochemistry
Zinc, immersed in alkaline electrolyte, undergoes intermediary reactions
Zinc hydroxide formation
Decomp. (I)
Decomposition (II)
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Technical Concept: The Electrochemistry
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Technical Concept: Fuel Cell Architecture
Three feeds: zinc, air, and electrolyte
Observe that high flow rates aid in chemical rates, but also convect heat away
Geometry is not all together homogenous
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Technical Concept: Fuel Cell Architecture
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Technical Concept: Fuel Cell Architecture
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Technical Concept: Fuel Cell Architecture
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Technical Concept: Fuel Cell Architecture
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Technical Concept: Fuel Cell Architecture
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Technical Concept: Fuel Cell Architecture
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Technical Concept: Fuel Cell Architecture
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Technical Concept: Fluids Management System
Determine optimal values of electrolyte flow rate and air flow rate experimentally rather than analytically
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Technical Concept: Fluids Management System
Air convected in between cells using fan
Cathode characteristicslimit power
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Technical Concept: Fluids Management System
Fuel and waste storage system
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Technical Concept: Refueling Scheme
Centralized Reprocessing: Pump in zinc metal fuel at a gas station
Pump out zinc oxide waste
Zinc oxide shipped from station to rail depot to freight car to depot to reprocessing plant
Reprocessing plant uses renewable energy
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Technical Concept: Refueling Scheme
Solar Generation
Rail DepotRail Depot
Service Station
Plant
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Technical Concept: Refueling Scheme
Existing gas stations to be retrofit for ZAFCs by converting two underground tanks and associated pumps and meters
If metering keeps atomic flow rates equal, customer is only charged the price of electricity and shipping
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Economic Analyses: Capital Costs for EV
Onboard systems: Fuel Cell
Multiple cells (12)Cathode
Fluids Management System2 pumps, air fan, hydrocyclone, storage tank
Power Electronics & DriveDC motor, controller, pedal assembly
Secondary Battery PackNiMH pack for peak powerCharger, mating electronics
Zinc & Electrolyte
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Economic Analyses: Capital Costs for EV
How much zinc to carry depends on fuel economy. Use EPA highway and city dynamometer tests
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Economic Analyses: Capital Costs for EV
City fuel economy summary
Total Secondary Energy Spent (Wh) 4169.536
Estimated ZAFC Energy Expenditure (Wh) 5486.232
Zinc Required for Test (kg) 4.058
Miles Driven (mi) 10.257
Zinc Required for 300 mi (kg) 118.689
Energy Required for 300 mi (Wh) 160467.847
Energy Required for 300 mi (J) 577684247.439
Energy Density of Gasoline (MJ/kg) 44.400
Mass of Gasoline Equivalent (kg) 13.011
Density of Gasoline (kg/m^3) 719.700
Volume of Gasoline Equivalent (m^3) 0.018
Volume of Gasoline Equivalent (gal) 4.776
MPG equivalent (mpg) 62.817
Total Secondary Energy Spent (Wh) 2186.584
Estimated ZAFC Energy Expenditure (Wh) 2877.084
Zinc Required for Test (kg) 2.128
Miles Driven (mi) 7.450
Zinc Required for 300 mi (kg) 85.688
Energy Required for 300 mi (Wh) 115849.693
Energy Required for 300 mi (J) 417058896.588
Energy Density of Gasoline (MJ/kg) 44.400
Mass of Gasoline Equivalent (kg) 9.393
Density of Gasoline (kg/m^3) 719.700
Volume of Gasoline Equivalent (m^3) 0.013
Volume of Gasoline Equivalent (gal) 3.448
MPG equivalent (mpg) 87.010
Highway fuel economy summary
Full tank = 160kWh, 119 kg ZnFuel economy = 87 MPGe city, 63 MPGe highway
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Economic Analyses: Capital Costs for EVEV capital cost summary
Subsystem ItemMaterial Cost Rate
AmountLabor Cost Rate
Time Quantity Total Cost
12-Celled Zinc-Air Fuel Cell
Glass-filled Nylon Channel Plate
$0.56 /g 93 g$100.0
0/hr 1 hr 12 $1,824.96
1/4" Acrylic Front Plate $0.21 /in^2 72 in^2 $60.00 /hr 1 hr 12 $901.44
1/4" Acrylic Back Plate $0.21 /in^2 72 in^2 $60.00 /hr 1 hr 12 $901.44
Cobalt Based Catalyzed Carbon Air Cathode
$0.05 /cm^2 151 cm^2 12 $90.78
Copper Anode Current Collector
$0.54 /in^2 23.5 in^2 12 $152.77
RTV Silicone Sealant $1.60 /oz 1 oz 12 $19.20
Fluid Management System
Zinc Peristaltic Pump $242.35 1 1 $242.35
Electrolyte Centrifugal Pump $314.48 1 1 $314.48
Air Fan $28.99 1 1 $28.99
Hydrocyclone $0.00 1 1 $0.00
PVC Tubing $10.95 /ft 12 ft 1 $131.40
Power Electronics
DC Brush Motor$1,775.0
01 1 $1,775.00
Motor Controller$1,850.0
01 1 $1,850.00
Hall Effect Accelerator Pedal $140.00 1 1 $140.00
Dashboard Display Module $260.00 1 1 $260.00
Secondary Battery SystemLead-Acid Battery $26.95 1 16 $431.20
Charge Pump 1 1 $0.00
Fuel Supply
Zinc Pellets $1.03 /lb 262 lb 1 $270.22
Potasium Hydroxide $27.90 /kg 7.12 kg 1 $198.62
Water $0.01 /gal 3.81 gal 1 $0.02
Total $9,532.87
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Economic Analyses: Capital Costs for Station
Summary of capital costs to station owner
Subsystem Item Material Cost Rate Amount Labor Cost Rate Time Quantity Total Cost
Underground Tank Retrofit
Underground Tank Corrosion Lining
$0.04 /ft^2 483.00 ft^2 1 $17.88
6" Diameter 20' Auger $3,250.00 1.00 1 $3,250.00
Nozzle-and-Metering Unit
Fuel/Waste Metering Peristaltic Pump
$242.35 2.00 1 $484.70
Pumping Nozzle $116.67 2.00 1 $233.34
Lost Revenue Gasoline $3.00 /gal 1428.57 gal 1 $4,285.71
Installation Skilled professional $100.00 /hr 24 hr 5 $12,000.00
Total $20,271.63
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Economic Analyses: EV Maintenance Costs
Cathode seals may wear out, need replacement
Electrolyte must be topped off if hydrocyclone isn’t 100% efficient
Maintenance Event Time Between EventsExpected Number of Events per Year
Cost Per Event Yearly Cost
Cathode Replacement 12000 hr 0.73 $90.78 $66.27
Secondary Battery Replacement 5 years 0.20 $431.20 $86.24
Electrolyte Top Off (99% Efficient) 300 miles 33.33 $1.99 $66.33
Total $218.84
Secondary batteries will wear out
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Economic Analyses: Cost to Reprocess Zinc
Set up daily cash flow charts for the station and the plant
Service Station Cash Flow: Day 1
Item Value Unit
Volume of Oxide Tank 5000 gallons
Volume of Zinc Oxide 14.01359441 m^3
Mass of Oxide 78560.21026 kg
Mass of Zinc 63114.6049 kg
Freight Cars for Shipping 4
Number of Barrels per Car 50
Volume per Barrel 0.070067972 m^3
Mass per Barrel 392.8010513 kg
Shipping Rate to Chicago $119.08 /barrel
Distance to Chicago 45.7 miles
Shipping Cost to Chicago -$23,816.00
Account Balance -$23,816.00
Zinc Plant Cash Flow: Day 2
Item Value Unit
Mass of Zinc to be Produced 63114.6049 kg
Energy Required to Produce 29786.57881 kWh
Cost to Produce using Coal -$2,382.93
Cost to Produce using Solar -$10,127.44
Market Value of Zinc $143,318.20
Credit to Station for Oxide using Coal -$117,896.98
Credit to Station for Oxide using Solar -$109,378.02
Account Balance using Coal -$117,896.98
Account Balance using Solar -$109,378.02
Look at solar energy versus coal
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Economic Analyses: Cost to Reprocess Zinc
Service Station Cash Flow: Day 3
Item Value Unit
Plant Credit from Coal $117,896.98
Plant Credit from Solar $109,378.02
Account Balance using Coal $94,080.98
Account Balance using Solar $85,562.02
Zinc Plant Cash Flow: Day 4
Item Value Unit
Mass of Zinc Sold 63114.6049 kg
Volume of Zinc Sold 8.839580518 m^3
Freight Cars for Shipping 4
Number of Barrels per Car 50
Volume per Barrel 0.044197903 m^3
Mass per Barrel 315.5730245 kg
Shipping Rate to Joliet $114.00 /barrel
Distance to Joliet 45.7 miles
Shipping Cost to Joliet -$22,800.00
Account Balance using Coal -$140,696.98
Account Balance using Solar -$132,178.02
Service Station Cash Flow: Day 5
Item Value Unit
Debit to Plant for Zinc -$143,318.20
Account Balance using Coal -$49,237.22
Account Balance using Solar -$57,756.18
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Economic Analyses: Cost to Reprocess Zinc
Zinc Plant Cash Flow: Day 6
Item Value Unit
Credit from Station $143,318.20
Account Balance using Coal $2,621.22
Account Balance using Solar $11,140.18Service Station Cash Flow: Day 6
Item Value Unit
Mass of Zinc Obtained 63114.60 kg
Zinc Usage per EV 118.69 kg
Break-Even Cost per EV using Coal -$92.59
Break-Even Cost per EV using Solar -$108.61
Resale Profit 10.00 %
EV Tank Refill Price using Coal $101.85
EV Tank Refill Price using Solar $119.47
Refueling Cost per Exchanged Zinc using Coal $0.86 /kg
Refueling Cost per Exchanged Zinc using Solar $1.01 /kg
The rail shipping costs dominate the final price to the customer
Cost of solar versus coal close to each other
Total cost to fill up tank with reprocessed zinc = $102/$119
Competitive at $10/gal
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Economic Analyses: Ownership Cost Comparison
Compare the costs of owning a conventional pick-up, a conventional economy car, a hybrid, or a ZAFC EV
Vehicle MSRP RebateFederal Tax Credit
City MPG
Hwy MPG
Avg MPG
Fuel Consumption per Year
Annual Fuel Cost
Annual Maintenance Cost
Cost Over Entire Ownership
Savings Over Entire Ownership
2004 Chevrolet S-10 $24,660 $0 $0 17.0 23.0 20.0 435 gal $1,521.74 $0.00 $44,905.69 $0.00
2008 Honda Civic $17,760 $0 $0 25.0 36.0 30.5 278 gal $972.22 $0.00 $31,016.63 $13,889.06
2008 Toyota Prius $22,875 $0 $0 48.0 45.0 46.5 222 gal $777.78 $0.00 $34,871.71 $10,033.98
ZAFC Powered S-10 $32,967 $0 $7,500 87.0 62.8 74.9 3966.7 kg $2,380.00 $218.84 $57,370.70 ($12,465.01)
ZAFC Powered Civic $26,067 $0 $7,500 87.0 62.8 74.9 3966.7 kg $2,380.00 $218.84 $49,362.97 ($4,457.28)
At $3.50/gallon gasoline, $0.60/kg zinc, 10 year ownership, 10,000 miles driven per year, i = 1.5%
ZAFC EV not cost competitive at all
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Economic Analyses: Ownership Cost Comparison
If everything stays the same except shipping rates go down by 10x, cost of refueling by solar is $0.28/kg zinc
ZAFC EV is cost competitive at $3.50/gallon
Vehicle MSRP RebateFederal Tax Credit
City MPG
Hwy MPG
Avg MPG
Fuel Consumption per Year
Annual Fuel Cost
Annual Maintenance Cost
Cost Over Entire Ownership
Savings Over Entire Ownership
2004 Chevrolet S-10 $24,660 $0 $0 17.0 23.0 20.0 435 gal $1,521.74 $0.00 $44,905.69 $0.00
2008 Honda Civic $17,760 $0 $0 25.0 36.0 30.5 278 gal $972.22 $0.00 $31,016.63 $13,889.06
2008 Toyota Prius $22,875 $0 $0 48.0 45.0 46.5 222 gal $777.78 $0.00 $34,871.71 $10,033.98
ZAFC Powered S-10 $32,967 $0 $7,500 87.0 62.8 74.9 3966.7 kg $1,110.67 $218.84 $43,785.38 $1,120.31
ZAFC Powered Civic $26,067 $0 $7,500 87.0 62.8 74.9 3966.7 kg $1,110.67 $218.84 $35,777.65 $9,128.04
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Sustainability: Safety
Zinc is a mild irritant, partially flammable, dust can cause nausea
Zinc oxide is a mild irritant, not flammable
Potassium hydroxide is a harsh irritant to skin in high molarity and poses the risk of burns
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Sustainability: Availability Zinc is plentiful around the world, including the United
States
United States produces 150,000 metric tons of surplus zinc ore each year
Zinc consumption down since 2009 in all countries except China and India
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Sustainability: Availability
London Metals Exchange highest 2009 price = 94¢/lb
US yearly surplus of ore, if refined based on zinc content, can produce enough zinc for 1,206,000 ZAFC EVs
Total hybrid and EV sales by 2014 expected to be 1.5 million vehicles; surplus can allocate to compete with that
In order to produce 600 million ZAFC Evs (replacing the global automobile fleet), 75 million metric tons are needed, or 37.5% of known world zinc reserves
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Sustainability: Availability Lithium not as plentiful or evenly distributed; vast majority in
Bolivia, Chile, and Argentina. No US surplus, net importer
Total yearly US lithium consumption can only produce 800,000 Tesla Roadsters. Depleting total US reserves can only build 9 million Roadsters
Zinc: abundant, evenly distributed, surplus Lithium: rare, single source, material deficit
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Sustainability: Emissions
Electric vehicle itself has zero emissions
There are emissions associated with refining the surplus ore into zinc metal for the vehicles, the manufacture of the vehicles themselves, and the logistics of reprocessing zinc oxide back into zinc metal
Determine emissions of these subsystems of the zinc economy using Economic Input-Output Life Cycle Assessment (EIOLCA), a mathematical model using real price and cost information from the US economy in previous years across multiple industries
Essentially a set of operations on very large matrices of industrial data and their interdependencies, with economic activity ($) as the input
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Sustainability: Emissions
Refining the US surplus of zinc ore into zinc metal for ZAFC EVs-150,000 tonnes @ $0.94/lb = $63,955,500 economic activity
Manufacturing 603,000 ZAFC EVs-Half the processed surplus for vehicle supply, half for station supply-603,000 * MSRP of $22,875 = $13 billion in activity
SectorTotal (T CO2 Equivalent)
CO2 Fossil (T CO2 Equivalent)
CO2 Process (T CO2 Equivalent)
CH4 (T CO2 Equivalent)
N2O(T CO2 Equivalent)
HFC/PFCs (T CO2 Equivalent)
Total for all sectors 68200.0 51000.0 8060.0 3240.0 429.0 5480.0
SectorTotal (T CO2 Equivalent)
CO2 Fossil (T CO2 Equivalent)
CO2 Process (T CO2 Equivalent)
CH4 (T CO2 Equivalent)
N2O(T CO2 Equivalent)
HFC/PFCs (T CO2 Equivalent)
Total for all sectors 7760000.0 5680000.0 1120000.0 577000.0 180000.0 201000.0
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Sustainability: Emissions
The logistics of moving material in between reprocessing plants and service stations
- The cost to the station owner amounts to $108.61 per tank-$65,491,830
Total carbon dioxide equivalent is 7.905 megatonnes, or 13 tonnes per vehicle including their manufacture, but 240 kg per vehicle without
SectorTotal (T CO2 Equivalent)
CO2 Fossil (T CO2 Equivalent)
CO2 Process (T CO2 Equivalent)
CH4 (T CO2 Equivalent)
N2O(T CO2 Equivalent)
HFC/PFCs (T CO2 Equivalent)
Total for all sectors 78700.0 73500.0 1760.0 3010.0 309.0 181.0
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Sustainability: Emissions
In comparison, the US automobile fleet (~200 million cars) produced 3,277 megatonnes of CO2 or 16.4 tonnes per vehicle if manufacturing is considered
Without manufacturing, US autos produced 0.819 megatonnes or 8.9 tonnes per vehicle
ZAFCs are slightly cleaner, but not much due to unsustainable manufacturing
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Experiments
Implement a test version of the control system
Design experiments that vary the flow rates and measure specific energy indirectly through voltage measurements
Determine characteristics if not the actual optimum values
“Re-invent the wheel” for LLNL design
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Experiments: Prelab Activities
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Experiments: Prelab Activities
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Experiments: Optimization Trails
Experiments varying electrolyte flow rate versus voltage were mired by leaks, slow flows, low power under loads
Experimental work took a detour to explore the nature of hindered flow
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Experiments: Pressure Differential
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Experiments: Pressure DifferentialHigh pressure drops given slow flow rate
Back-calculate k from data finds it to be 10-7cm2, more like very fine sand not gravel
Trial #
Pump Power Setting (W)
Volume of Beaker Filled (milliliters)
Elapsed Time (seconds)
Calculated Flow Rate (m^3/s)
Calculated Pressure Drop ΔP (Pa)
Theoretical Fuel Cell ΔP (Pa)
1 1.17E-01 900 223 4.04E-06 2.55E+04 2.54E-01
2 1.17E-01 900 197 4.57E-06 2.22E+04 2.87E-01
3 1.17E-01 900 240 3.75E-06 2.77E+04 2.36E-01
4 1.17E-01 1000 294 3.40E-06 3.09E+04 2.14E-01
5 1.09E-01 900 225 4.00E-06 2.39E+04 2.51E-01
6 1.09E-01 900 258 3.49E-06 2.79E+04 2.19E-01
7 1.09E-01 900 429 2.10E-06 4.87E+04 1.32E-01
8 1.09E-01 900 335 2.69E-06 3.73E+04 1.69E-01
9 4.11E-02 1000 551 1.81E-06 1.93E+04 1.14E-01
10 4.11E-02 900 552 1.63E-06 2.18E+04 1.02E-01
11 4.11E-02 930 480 1.94E-06 1.79E+04 1.22E-01
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Experiments: Post MortemDecision to open up the fuel cell
5 Failure modes discovered: serpentine channel clog, cathode seal rupture, catalyst damaged, copper patina, zinc fusion
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Experiments: Post Mortem
Serpentine channel for electrolyte inflow almost entirely clogged with black RTV silicone sealant
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Experiments: Post Mortem
Seal between zinc chamber and air chamber using the air cathode broke along the bottom
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Experiments: Post Mortem
Catalyst side of the air cathode punctured and scarred
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Experiments: Post Mortem
Copper anode current collector panel, on the taper, covered with patina
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Experiments: Post Mortem
Zinc pellets fused into solid wedges at the bottom, possibly herniating the cathode
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Experiments: SEM Analysis
All failures likely the result of poor assembly practices except zinc pellets fusing
Possibly zinc ions, zinc oxide, or zinc hydroxide plating back on to the pellets
Send the fused pellet to the scanning electron microscope to identify the material of fused surfaces
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Experiments: SEM Analysis
Fused zinc pellets, adjacent to the air cathode, x90
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Experiments: SEM Analysis
Fused zinc pellets, adjacent to the air cathode, x1,000
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Experiments: SEM Analysis
Fused zinc pellets, adjacent to the air cathode, x10,000
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Experiments: SEM Analysis
Spectrometry finds that the octahedrons are 27.7% atomically zinc, 72.3% atomically oxygen; 2.6 O per 1 Zn
Spectrometry finds the dendrites are 57% atomically oxygen and 40% atomically zinc; 1.4 O per 1 Zn
Could be explained by complexes or hydrates
Is zinc fusion the result of a series of unfortunate events, or is this a fundamental aspect of the chemistry?
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Summary of Achievements
Designed, analyzed the aspects of a holistic system using centralized reprocessing
-Technologies and mechanisms-Cost analyses-Toxins and emissions
Designed, analyzed a control system for the fuel cell systems
-Analytically frame the problem-Experimentally probe the physic
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Final Remarks
Zinc economy: centralized reprocessing cost prohibitive and unsustainable without control over logistics and emissions
Fuel cell control: quality engineering and deeper electrochemistry need to be addressed