QSI DSE Hydrogen PPT March 07

Hydrogen Generation via Water Electrolysis
Using Highly Efficient Nanometal Electrodes

March 2007
Robert B. Dopp
President
DoppStein Enterprises Inc.
www.doppstein.com
Overview
Overview
Introduction
Nano Realm Theory
Hydrogen Generation Theory
The Nano-effect on Hydrogen Generation
A Better Way to Build a Generator
Next Step for DSE/QSI
Conclusions
DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Introducing
Introducing Robert
Robert Dopp
Dopp
DoppStein Enterprises, Inc. of Marietta, GA

Collaborating with QuantumSphere, Inc. of Santa Ana, CA
To develop a very high rate Hydrogen Generator
using QSI-Nano Catalyst and novel designs.
My background is in air-breathing batteries.
For More Details, Visit Websites:
www.doppstein.com
www.qsinano.com

Nano
NanoNickel
NickelPowder
Powderfrom
fromQSI
QSI

Surface
Surface Atoms
Atoms
% of Atoms on the Surface of a Particle
100%
90%
80%
70%
60% <-- Higher Surface Energy

50%
40%
30%
20%
10%
0%
1 10 100 1000
Particle Diameter, nm

Nano
Nano Surface
Surface Area
Area Effect
Effect
As Particles Get Smaller

Surface Area per Gram Increases
Percent of Surface Atoms Increases
Surface Area per View Area is Unchanged
Micron & Nano Mix Increases Area/View

Surface
Surface Area
Area Effect
Effect 15
Surface area change as Loading increases

(Base is 2 um, nano is 10 nm)
4000%
3500%
3000%
2500%
2000% <--- 36.3 cm2 per geometric cm2

1500%
1000%
500%
0%
<--- 1.8 cm2 per geometric cm2
0% 2% 4% 6% 8% 10% 12% 14% 16% 18% 20%
nano Powder Loading

Electrolysis
Electrolysis Block
Block Diagram
Diagram
2H2O + 2e- --> H2 + 2OH- 2OH- --> 1/2 O2 + H2O + 2e-

Water
Water Electrolysis
Electrolysis for
for H
H22 Production
Production
Energy in Hydrogen (Use HHV Values)

BTU H2= (A* Hr * k * H2gmw) * BTU/gH2
BTU in H2 = AHr * 5.058
Energy to Make Hydrogen

BTU Used = (Amps * Cell V * Hrs)*(BTU/WHr)
BTU Used = WHr * 3.413

Water
Water Electrolysis
Electrolysis for
for H
H22 production
production
Efficiency = BTU in H2 / BTU Used to Make H2

Efficiency = 1.482 / Cell Voltage
Volume of H2 as Gallon of Gas Equivalent (gge)
gge --> kg H2 --> 125,000 BTU H2
Production Rate as gge/hr/m2 = A/cm2 * 0.405

kWhr/kg = Cell V/(SA*Hr) * (96487*2)/(3600*2.0159)
kWhr/kg (or gge) = Cell V/( cm2*Hr) * 26.59
Cost
Cost of
of Hydrogen
Hydrogen at
at 85%
85% Efficiency
Efficiency
Hydrogen Cost at 85% Efficiency
Cost of Hydrogen = (V/1000*$/kWHr)/(3600/F/2*H2gmw)*(BTU/kWHr)/(BTU/gge)
$10.00
CA Residential Rate
$9.00
$8.00
$/gge = $/kWHr * 43.08
$7.00 When H2 Generation is at 85%
$6.00
$5.00
$4.00
$3.00 GA Residential Rate

$2.00
GA Industrial Rate
$1.00 And estimated wind-assisted rate
$-
$- $0.05 $0.10 $0.15 $0.20 $0.25
Electricity Cost, $/kWHr

Efficiency
Efficiency as
as aa Function
Function of
of Voltage
Voltage (1.482/V)
(1.482/V)
Efficiency versus Full Cell Voltage
120%
100% 1.55 V = 96%
1.743 V = 85%
80% DoE Target 75% Efficiency
60%
Efficiency vs.
Electrolyzer
40% Cell Voltage
Electrochemical
Lowest possible
20% Voltage (1.229)
0%
0 1 2 3 4 5
Cell Voltage

Preparation
Preparation of
of Pellets
Pellets
Compressed mixture of micron and

QSI-Nano Catalyst powders to
make a 2D pellet.
All data is at ambient temperature and pressure.
QSI-Nano Electrodes Magnified View Of High Surface Area Porous

QSI-Nano Electrodes

Testing
Testing of
of Pellets
Pellets

Voltammogram
Voltammogramfrom
fromGraphite
Graphite
Horizontal Hydrogen Electrolysis Reactor
4.0
Graphite
3.5
3.0 Anodic Direction

2.5 O2 Generation
2.0
1.5
85% Efficiency
1.0
3 mA/cm2
0.5
0.0
Cathodic Direction
-0.5
H2 Generation
-1.0
-1.5
0.0001 0.001 0.01 0.1 1 10
2
Current Density, Amps/cm

Voltammogram
Voltammogramof
ofGraphite
Graphiteand
anduNi
uNipellet
pellet
4.0
Graphite
3.5
micron Ni
3.0
2.5 O2 Generation
2.0
1.5
7 mA/cm2
1.0
0.5
0.0
-0.5
H2 Generation
-1.0
-1.5
0.0001 0.001 0.01 0.1 1 10
Current Density, Amps/cm2

Voltammogram
Voltammogramfrom
fromuNi
uNi
4.0
Graphite
3.5 micron Ni
10% nano Nickel
3.0
2.5 O2 Generation
2.0
1.5
40 mA/cm2
1.0
0.5
0.0
nano Effect
H2 Generation
-0.5
-1.0
-1.5
0.0001 0.001 0.01 0.1 1 10

Voltammogram
Voltammogramfrom
fromPellet
PelletExperiments
Experiments
4.0
Graphite
3.5 micron Ni
10% nano Nickel
3.0
Complex formulation 3 nano catalysts
2.5
O2 Generation
2.0
7 mA/cm2
40 mA/cm2
3 mA/cm2
1.5
Reaches 85%
1.0 2
at 300 mA/cm
0.5
0.0
H2 Generation
-0.5
-1.0
-1.5
0.0001 0.001 0.01 0.1 1 10

Polarization
PolarizationCurve
Curvefrom
fromPellet
PelletExperiments
Experiments
4.0
3.5
3.0 O2 Generation
2.5
2.0
1.5
Graphite
85% Efficiency micron Ni
1.0 10% nano Nickel
0.5
Complex formulation 3 nano
0.0
-0.5
-1.0
H2 Generation
-1.5
0 1 2 3 4 5

Hydrogen
HydrogenProduction
ProductionRate
Ratefrom
fromPellets
Pellets
Production Rate at 85% Efficienc

0.018 65 ml/hr
0.016
Production Rate, gge/Hr/m2
0.016
0.014
0.012
nano Effect
0.010
0.008
0.006
12 ml/hr
0.004 0.003
5 ml/hr
0.002 0.0012
0.000
Graphite u Nickel QSI nNi

Hydrogen
HydrogenProduction
ProductionRate
Ratefrom
fromPellets
Pellets
Production Rate at 85% Efficiency

0.14 480 ml/hr
0.12
0.12
0.10
Triple nano
0.08
Effect
0.06
nano Effect
0.04 65 ml/hr
0.02 12 ml/hr 0.016
5 ml/hr
0.0012 0.003
0.00
Graphite u Nickel QSI nNi 3 QSI nCatalyst

Design
Design Concerns
Concerns
QSI-Nano Catalyst Effect

Demonstrated
however . . .
Nano Catalyst Escapes from Pellet
Outgoing Hydrogen masks ions

requiring electrolyte circulation
ImagineStingray
ImagineStingraySettling
Settlinginto
intoBottom
BottomSilt
Silt

AANew
NewWay
Wayto
toElectrolyze
ElectrolyzeWater
Water--The
TheStingray
StingrayElectrode
Electrode

Voltammogram
VoltammogramCurve
Curvewith
withStingray
Stingray
4.0
Graphite
3.5 O2 Generation
micron Ni
3.0 10% nano Nickel
Complex formulation (3 nano catalysts)
2.5 Ni Foam with nNi Suspension
2.0
1.5
95%
1.0
Past 5 Amp/cm2
0.5
0.0
-0.5
-1.0
H2 Generation
-1.5
0.0001 0.001 0.01 0.1 1 10

Linear
LinearPolarization
PolarizationCurve
Curve
Developing a Fluidized Bed
42 kWh/kg

Full
FullCell
CellVoltages
Voltagesof
ofExperiments
Experiments
Eff.
5 30%
Graphite
4 Micron Nickel
40%
10% nNi in micron Nickel
Tri-nano Catalyzed
3 Fluidized Bed 50%
60%
70%
2
85%
TNV
Eo
1
1 gge/hr/m2
0
0 1 2 3 4 5
2
Current Density, Apms/cm

Hydrogen
HydrogenProduction
ProductionRate
Ratefrom
fromPellets
Pellets

0.14 480 ml/hr
0.12
0.12
0.10
Triple nano
0.08
Effect
0.06
nano Effect
0.04 65 ml/hr
0.02 12 ml/hr 0.016
5 ml/hr
0.0012 0.003
0.00
Graphite u Nickel QSI nNi 3 QSI nCatalyst

Hydrogen
HydrogenProduction
ProductionRate
Ratewith
withFBR
FBRbar
bar

3.00 9.20 l/hr
2.43
2.50
Patent Pending
2.00
Nano Fluidized
1.50
Bed (3D) Design
1.00
0.50 12 ml/hr 65 ml/hr 480 ml/hr

5 ml/hr 0.12
0.0012 0.003 0.016
0.00
Graphite u Nickel QSI nNi 3 QSI QSI nNi in
nCatalyst FBD

Hydrogen
HydrogenProduction
Productionat
at85%
85%Efficiency
Efficiency
Time to make 1 gge from 1 m2 at 85% Efficiency
10
34 Day 15 Days 3 Days 8 Hrs 25 Min
2.43
2
Prod. Rate, gge/Hr/m
0.12
0.1
0.016
0.01
0.003
0.0012
0.001
0.0001
Graphite u Nickel QSI nNi 3 QSI QSI nNi in FBD
nCatalyst

Volumetric
VolumetricConfirmation
Confirmation
Measure ml of H2 volume over time
Measure the BP and Temperature
Convert to STP
Compare to the calculated ml by:
ml H2 = ASec/F/2*22400
Remember to NOT normalize for
surface area

Volumetric
VolumetricConfirmation
Confirmation
Observed vs. Calculated H2 Output
40
Calc'ed Observed
Note:
5.6% 0.2 ml = 0.6%
35
0.3% 1 Sec = 2.6%
-1.2% 0.8%
30
-1.4%
25
20
15
10
0
1 2 3 4 5
Amp/cm^2

Next
Next Steps
Steps
Next set of experiments
KOH Concentration
Pressure
Temperature
Different QSI-Nano Catalysts
Separator
Ionic Diffusion Resistance Improvement
Thermal Stability Improvement
Build Working Prototype Model

Conclusions
Conclusions
Nano Effect Demonstrated
Superior 3D Nano Design Demonstrated
Efficiencies & Rate at a Practical Level
Easily Scalable to Large Design
How Big Could This Be? We Dont Know, but
The Future Will be Interesting

Appreciation
Appreciation
My Thanks to QuantumSphere, Inc.

for Providing Funding and Materials
for this Research
www.qsinano.com
(714) 545-NANO (6266)

About QuantumSphere, Inc
QuantumSphere is a manufacturer of nanoscale catalyst materials for applications in portable power, renewable energy,
electronics, aerospace, defense and other markets demanding advanced materials. QuantumSpheres proprietary
technology enables the production of ultra-pure, highly uniform nanometals and alloys under 100 nanometers in high
volume at commercial prices with the potential to be utilized in a large number of new applications. QuantumSphere has
also created an extensive intellectual property portfolio around its process capabilities and end-use commercial
applications. QuantumSphere seeks to leverage its market position to manufacture and ship QSI-Nano catalyst
materials and electrode devices for clean-energy applications such as high-performance batteries and micro fuel cells for
portable power, and hydrogen generation through electrolysis, among others. The current global catalyst market is in
excess of $10 billion, annually.
QuantumSphere also works closely with industry experts, national labs, and leading universities to validate QSI-Nano
catalyst materials and generate licensing rights to intellectual property for high-value commercial applications.
For more information visit www.qsinano.com or contact Kevin Maloney at kmaloney@qsinano.com or phone 714-545-
6266.
About DoppStein Enterprises, Inc.

Robert Dopp is President of DoppStein Enterprises, Inc., Marietta, GA, where he consults to fuel cell, battery and
materials companies. He offers a depth of knowledge in battery systems with freedom and flexibility from his
independent laboratory. His proficiencies include fuel cells, hydrogen generation and water desalination. He is one
of the foremost authorities on Zinc Air with 36 patents and 6 pending in energy related fields. Robert was principal
engineer at Rayovac Corporation for 18 years on the Zinc Air project with a variety of leadership responsibly. As
Director of Research for Electric Fuel Corporation working from his personal laboratory directing research in Biet
Shemish, Israel, he was instrumental in developing components resulting in batteries with over four times the
energy density of alkaline cylindrical cells. Since being independent, he has worked in many aspects of the
electrochemical world.
For more information, visit www.doppstein.com or contact Robert Dopp at rbdopp@doppstein.com or phone at
770-649-1933

QSI DSE Hydrogen PPT March 07

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Hydrogen Generation via Water Electrolysis

Using Highly Efficient Nanometal Electrodes

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

DoppStein Enterprises, Inc. of Marietta, GA

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

60% <-- Higher Surface Energy

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

As Particles Get Smaller

Surface Area per View Area is Unchanged

Micron & Nano Mix Increases Area/View

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Surface area change as Loading increases

2000% <--- 36.3 cm2 per geometric cm2

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

2H2O + 2e- --> H2 + 2OH- 2OH- --> 1/2 O2 + H2O + 2e-

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Energy in Hydrogen (Use HHV Values)

Energy to Make Hydrogen

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Efficiency = BTU in H2 / BTU Used to Make H2

Production Rate as gge/hr/m2 = A/cm2 * 0.405

$3.00 GA Residential Rate

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

100% 1.55 V = 96%

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Compressed mixture of micron and

QSI-Nano Electrodes Magnified View Of High Surface Area Porous

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

3.0 Anodic Direction

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Current Density, Amps/cm2

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Current Density, Amps/cm2

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Current Density, Amps/cm2

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Production Rate at 85% Efficienc

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Production Rate at 85% Efficiency

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

QSI-Nano Catalyst Effect

Outgoing Hydrogen masks ions

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Current Density, Amps/cm2

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Developing a Fluidized Bed

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Production Rate at 85% Efficiency

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Production Rate at 85% Efficiency

0.50 12 ml/hr 65 ml/hr 480 ml/hr

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

Measure ml of H2 volume over time

Measure the BP and Temperature

Compare to the calculated ml by:

Remember to NOT normalize for

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com

DoppStein Enterprises, Inc. 770-649-1933 www.doppstein.com