Distributed and Large Scale

Hydrogen Production Methods

George H. Miley
University of Illinois

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 1
Outline
 Comments about the “Hydrogen Economy”
 Production of Hydrogen
 Distributed and Central Plants
 Plasma production
 STAR CELL
 Jet (Torch) Production (current U of IL research)
 Hydrogen storage (comments about our
Dislocation Loop research)
 Fuel Cells (a few comments about our research)
 Direct Borohydride
 Concluding comments & questions from you
HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 2
Global Energy Systems Transition, to H2 Energy
Carrier 1850-2150

ResultingHydrogen-Carbon Ratio,
World Energy Mix, 1860-1990

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 3
Elements of a Hydrogen Energy System

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 4
Current and projected needs – would require very
significant addition of power plants for production
 contemporary hydrogen production is primarily based on fossil fuels.
Produced fertilizers, in oil refineries to lighten heavy crude oils and for
other industrial uses, primarily by steam reformation of methane..
 In the USA the hydrogen industry produces 11 million tons of
hydrogen a year with a thermal energy equivalent of 48! GW(t). In so
doing, it consumes 5% of the US natural gas usage and releases 74!
million tons of CO2.
 Transition to a Hydrogen Economy will require significant expansion in
the production and use of hydrogen. Use of hydrogen for all our
transportation energy needs would require a factor of 18 more
hydrogen than currently used. Use of hydrogen for all our non-electric
energy needs would require a factor of 40 increase. At 50% efficiency,
this represents adding 4000 new 10 GWth power plants – or use of
“Mosaic” discussed later (note numberber of new coal plants/week
in China .

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 5
Scaling
Outline
 Comments about the “Hydrogen Economy”
 Production of Hydrogen
 Distributed and Central Plants
 Plasma production
 STAR CELL
 Jet (Torch) Production (current U of IL research)
 Hydrogen storage (comments about our
Dislocation Loop research)
 Fuel Cells (a few comments about our research)
 Direct Borohydride
 Concluding comments & questions from you
HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 7
H2 production – centralized or distributed –
involves storage and distribution
Production
Mosaic for
40 million
tons?
This photovoltaic array at SunLine Transit Agency in Thousand Palms, California, is used with an electrolysis unit to create hydrogen for fuel cell-powered buses

H2 fueling stations today

 Today, there are two ways hydrogen fueling stations
can generate hydrogen on-site: through natural gas
reforming or water electrolysis.
 Nearly all of the hydrogen generated in the United
States today is produced through steam reforming of
natural gas in large industrial facilities similar to oil
refineries. However, steam reforming can also be
performed on a smaller scale on hydrogen fueling
station sites. In the steam-reforming process, natural
gas reacts with steam at high temperatures over a Solar powered
catalystto produce hydrogen gas. electrolysis station in
 Electrolysis, in contrast, generates oxygen and Thousand Palms, CA
hydrogen from water using. eectrolysis . It is a more for fueling fuel cell
expensive way to produce hydrogen, but it generates buses
no on-site emissions and may be an attractive option
in locations that have low-cost off-peak power
generation. In addition, electrolysis can be powered
by renewable fuels such as wind and solar power to
create emissions-free, renewable hydrogen.

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 10
Demonstration stations are used to
develop experience and standards
 Hydrogen Fueling Station Design Standards
 A large number of possible codes and standards can come into play for permitting
design and construction of hydrogen fueling stations. Additional federal, state, and
local requirements may also apply.
 Model code provisions related to general design issues include:
 Facilities
 Equipment
 Barrier walls
 Weather Protection
 The safety of employees and customers depends on proper design, location, and
operation of storage and dispensing equipment and the proper installation and
operation of leak detection, fire detection, and fire suppression equipment. In
addition, incompatible materials or improperly installed equipment can lead to fuel
contamination, which can degrade the performance of the fuel cells that power
hydrogen-fueled vehicles. Model code provisions related to equipment
specifications include:

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 11
U.S. DOE -Hydrogen Fueling Station
Case Studies

 Although only about 60 hydrogen fueling stations have

been approved for operation in the United States,
many more are planned. The case studies presented
here are examples of operational projects throughout
the nation.
:
 Washington, District of Columbia
 Oakland, California
 White Plains, New York

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 12
Wash DC
•Step Three: Fully integrated fuel stations (which include
traditional fuels and hydrogen)
•Step Four: Mini-network "lighthouse projects" (which are semi-
commercial, public-private partnerships that involve multiple
energy companies, governments, and fleets of 100 or more
vehicles) to be developed within the next 5 years
•Step Five: Mini-networks that connect hydrogen fueling
corridors to be developed during the 2010-2020 time
period.
3355 Benning Road, NE - Washington, DC
Fuels Available: Gasoline Gaseous hydrogen (5,000 psig) Gaseous hydrogen (10,000 psig) Liquid
hydrogen.
Hydrogen Delivery: Liquid hydrogen is delivered to the station by a tanker truck.
Liquid Hydrogen Storage:stored below-grade in 1,500-gallon (400-kg) double-walled, insulated, ss
vessels at -420°F.
Vaporizer:Avaporizes the liquid h2 by raising its temperature from -420°F to ambient
Compressors: three-stage compressor takes taporized gas to 5,500 psig.;one-stage compressor goes to
11,000 psig.
Gaseous Hydrogen Storage:Gaseous hydrogen from the compressor is stored at 5,500 psig in 24 ASME
cylinders (above grade) and at 10,000 psig in three ASME cylinders (above grade).
Dispensers: one liquid hydrogen dispenser and one gaseous hydrogen dispenser with dual hoses for
dispensing at 5,000 psig and 10,000 psig (20 kg per day).
HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 13
Two extremes in size; capacity

 Distributed Units
 Electrolyzes etc for H2 filling stations
 Issues = costs, safety, complexity of running

 Central production units

 Type of power (Nuclear, renewable, etc.) /
 Distributions must be worked out

 Opportunity for hybrid electric-H2

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 14
Efforts to reduce cost of distributed
electrolysis units Example - Possible
Advanced distributed station

High-Capacity, High Pressure

Electrolysis System with
Renewable Power Sources
ELECTROLYZER DEVELOPMENT
PROJECT PARTNERS
 ELECTROLYZER DEVELOPMENT
Barriers Addressed

 Capital Cost –Increasing the Production

Capacity for a Single Module Will Take
Advantage of Economies of Scale
 System Efficiency –Demonstrate that the
Direct High Pressure Electrolysis
Maintains the High System Efficiency
Demonstrated in the Smaller Scale
Systems
 Renewable Power Integration –The Pilot
Plant System will Be Compatible with
Wind Power Input (and PV inherently) for
Performance Testing at NREL
Project Design Challenges

 Gas Exit Manifolding

 Membrane to Manifold Sealing
 Fluid and Power Penetrations
 Composite Wrapping “Heavy”
Cylinder
 Process Control of a Multiple,
High-Capacity Cell Array
 Pilot Plant Design

 20 Cell Array
 6500 psi Capable
 At Least 30 kg/day Production
 Compatible With Variable Voltage
Wind and Solar (PV) Power
 Capable of “Harvesting” Both H2
and O2
 Fully Automated Process Control
The Fully Integrated System
Block Diagram
Example of Fully Integrated Wind, Base Load Power And
Electrolyzer Hydrogen For Peak Shaving, Baseload
Firming, And Transportation Fuel Production
Hydrofiller 5000 to Produce Green
Hydrogen For Transportation Fuel Sales
Central Stations – 1 10 GW scale

 Reforming vs. dissociation of water

 Power ( Renewable, conventional coal or
FutureGen, Nuclear (fission, fusion))

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 23
H2 Production Using Renewable Energy Sources

 Harness renewable energy to power electrolysis

 Potential sources are wind, geothermal, solar, and
hydroelectric, thermochemical conversion of
biomass, photolytic and fermentative micro-organism
systems, and photoelectrochemical systems
 Advantage:
-Energy is “free” and clean
 Disadvantage:
-Technology to harness energy is expensive
Future Generation Plant/Methane Steam
Reforming

 Involves utilizing a hydrocarbon such as coal

or methane to produce H2 thermochemically
 Coal  CO + H2 then CO + H2O  H2 +
CO2
 Advantages:
-Costs comparable to thermochemical cycles like SI cycle
-Uses coal, a plentiful fossil fuel, in a near clean process
 Disadvantages:
-Expensive to start up and future of carbon sequestering
unknown
-Funding and political issues associated with plant startup
Central Plant Example --Schematic Flow Diagram of HTTR
*Fission Reactor ) Hydrogen Production System

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 26
Demo plant planned at INEEL

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 27
Use of heat vs electricity increases overall
efficiency = High Temp Electrolysis (HTE)
High Temperature Electrolysis
(HTE)
 Uses HTGR for thermal energy to drive
power cycle and heat steam for
electrolysis
 Advantage:
- 36-38% efficient without consumption of fossil fuels or
corrosive materials
 Disadvantage:
- Efficiency limited by heat cycle and temperature
Modular Hydrogen Plant Using High
Temp Electrolysis (THE)

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 30
Thermochemical Production of
H2
 Many different cycles of chemical reactions
already discovered to produce H2
 Cycles can be coupled with a Modular Helium
Reactor for heat supply for efficiency near
50%
 Some cycles better than others depending on
their characteristics (i.e. # of reactions and
elements involved, etc.)
 3 major cycles: Sulfur-Iodide, UT-3, and
Westinghouse
Thermochemical Production of
H2
 Advantages
- All chemicals are fully recycled except for H2O
- H2O is inexhaustible resource
-Essentially greenhouse gas emission free
-High efficiency since not restricted by Carnot cycle
 Disadvantages
-Require materials that can withstand high temperature
and pressure and corrosive chemical
-Most have not been tried on a large scale to determine
feasibility
Hybrid S Cycle - Chemical

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 33
 SI Cycle offer high efficiency at hi T

Figure 3. Estimated S-I process thermal-to-hydrogen efficiency vs. peak

process temperature.
Comparison of Thermal-to-Hydrogen Efficiencies
of HTE and SI Thermochemical Processes

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 35
Outline
 Comments about the “Hydrogen Economy”
 Production of Hydrogen
 Distributed and Central Plants
 Plasma production
 STAR CELL
 Jet (Torch) Production (current U of IL research)
 Hydrogen storage (comments about our
Dislocation Loop research)
 Fuel Cells (a few comments about our research)
 Direct Borohydride
 Concluding comments & questions from you
HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 36
StarCell - PLASMA
CONVERTERSYSTEM

Plasma Converter System

StarCell: How It Works
 StarCell Modules are stainless steel housings
with Carbon Molecular Sieve tube bundles inside.
 Mixed gas enters through the inlet port and
hydrogen permeates through the membrane.
 Hydrogen exits through one exit port and the
reject gas exits through another.
M&P Ceramic Membranes

Temperatures > 400°C

Steam sterilizable to > 125°C
Burst pressure > 500 psi
pH resistant
Excellent radiation resistance
Unaffected by solvents, oxidants, etc.
Rugged, reliable, long life > 5 years
StarCell Test Discussion
 Hydrogen rich gas has been produced from
waste material and purified on a commercial
scale.
 H2 Recovery rates of > 80%
 2 Stage purification from 50% to 96%
 Low gas temperature had a significant impact
on membrane performance.
 Membranes performed equally well on PCG
and bottled (baseline) gases.
 Testing validated laboratory results on
membrane performance.
 Membrane poisoning was minimal on 2 / 3
membranes after >2 months of gas exposure.
Outline
 Comments about the “Hydrogen Economy”
 Production of Hydrogen
 Distributed and Central Plants
 Plasma production
 STAR CELL
 Jet (Torch) Production (current U of IL research)
 Hydrogen storage (comments about our
Dislocation Loop research)
 Fuel Cells (a few comments about our research)
 Direct Borohydride
 Concluding comments & questions from you
HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 41
Conceptual H2 Fusion Torch Schematic
Electrical Energy
Water injection
Fusion Fuels

Interaction
Region Separation
Fusion Region Ionizes Region Side products
Separates Hydrogen
•Energy water
and Oxygen
•Plasma
HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 42
The Hydrogen Fusion Torch is a variation of the Materials Recycle
Fusion Torch invented in 1968 [ B. J. Eastlund and W. C. Gough, “The Fusion
Torch –Closing the Cycle from Use to Reuse” WASH 1132, Division of Research, USAEC,
Washington DC, May 15, 1969. ]

• Endorsed by USAEC and Nobel

Laureate Glenn Seaborg

• DOE fusion development efforts

currently focused electrical product.
But material recycling, and hydrogen
production such as discussed here,
open up a whole new horizon for
fusion applications.

• Fusion development is often

viewed as long term, but use
of the IEC concept discussed
here offers simpler ,small
devices that can be rapidly
developed.

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 43
U of Illinois Research on plasma processing --Near term – electrically
driven IEC plasma jet Is basis for plasma production of H2

Gas Feed
Line

Spherical Vacuum
Chamber
Grid

To Vacuum
Pump

High-Voltage
Feedthrough

High-Voltage
Power Supply

Basic concept of gridded IEC with “ion formed” potential

well . U of Illinois devices uses grids designed to form the
“STAR” mode (right) to direct ion beams through grid
openings – avoiding grid erosion. Grids will be removes
in future ion injection device.

HYDR*GEN Symposium, Purdue U., 44

Apriil 22, 2009
 “Jet Mode” operation of the IEC for torch uses an
enlarged grid opening to extract jet for processing.

Plasma Jet Grid View Port Opening

Jet Mode IEC Spherical IEC Space Thruster

Estimated Performance: T = 34 mN, Isp = 3000 s, Accelerating Potential: 600 V

Input Power ~750-800 W, Pjet = 500 W, ht ~ 62-68%
HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 45
Today’s Open Economy

Tomorrows Closed
Materials’
Economy with Hydrogen
Energy

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 46
Hydrogen Fusion Torch to enable the
hydrogen economy

•The hydrogen plasma torch is a natural extension of

the original fusion torch concept as applied to hydrogen
production from water.

•This approach improves efficiency of production by

using a plasma for complete dissociation plus
electrostatic separation and excess energy recovery

•Thus, the plant is a dual electrical – hydrogen

generator. Side products are helium and oxygen.

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 47
Lab demonstration of electrically driven torch
2-kW experimental unit to demonstrate the electrically driven IEC H2 plasma torch. An air plasma is used. Water
is injected into the jet plasma near the chamber exit, followed by the electrostatic separation-energy recovery
structure . Products are N2, O2, H2 and electricity

HYDR*GEN Symposium, Purdue U., 48

Apriil 22, 2009
Electrostatic separation of ions from jet plasma also enables energy recovery.
LLNL experiments demonstrate high efficiency for separation – energy
recovery

HYDR*GEN Symposium, Purdue U., 49

Apriil 22, 2009
Plasma Torch splitting efficiency
 Assuming 90% efficiency for ionization of h20
= 1853.8 / 0.9 = 2059.8 kJ/mol needed
 With 95% efficient recovery total energy
released when bonds are formed = (485.6 +
862.4) * 0.95 = 1280.6 kJ/mol
 Thus the efficiency is: 1280.6 kJ/mol / 2059.8
kJ/mol = 62.2%.
 Higher than thermal processes

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 50
P-B11 Fusion Torch to enable the
hydrogen economy

•A natural extension of the original fusion torch concept

for materials recycle as applied to hydrogen production
from water.

•Improves efficiency of production by using a plasma

for complete dissociation plus electrostatic separation
and excess energy recovery

•Dual electrical – hydrogen generator. Side products are

helium and oxygen.

HYDR*GEN Symposium,
Fuel Cell Seminar, PurdueAZ
Phoenix U.,
Apriil2008
22, 2009 51
Why IEC for p-B11?
 Non-Maxwellian – ions in potential well at ~ 80% of applied
voltage – for p-B11 requires about 150 kV (already achieved)

 Allows jet plasma reaction product exhaust (divertor) for

processing section and direct energy conversion channel.

 Simple construction and small high power density units.

 Electrically driven version allows early market penetration (also

waste processing market = syngas production from garbage and
food wastes) while still developing fusion technology for p-B11

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009

52
IEC Can Match Fusion Cross Sections Requirements

<σv>(E) vs kV
Region of
Interest = 150-250 kV

Cross Sections from John Santarius, Fusion Technology Institute, University of Wisconsin
HYDR*GEN Symposium, Purdue U., 53
Apriil 22, 2009
IEC Ion Physics – the key is a deep potential
well to trap ions

1. Ions form deep

potential well (Φ ~ Einjection )
2. Electrons confined by the
electrostatic potential
3. Ion distribution is strongly
non-thermal
4. Ions coming to edge of well
fall into the interior
5. Ion density strongly peaks at
r=0
6. Ion convergence allows
attractive reactor

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009

Diagram from US patent application 11/527,906, “Method and Apparatus for Controlling Charged Particles”, R.W. Bussard, (2006). 54
Ion- injected IEC provides way to
increase potential well depth and volume

Present single gun device - sketch of

injector gun is shown att he right

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 55
Vision --The IEC p-B11 H2 Fusion Torch
Industrial Process of the Future

Boron and Hydrogen Fuel

• Energy
• Plasma

Plasma Processing Separates

Water into Elements

Energy conversion provides

Electricity and portable
Fuels

Demonstrate p-B11 IEC is the

key for development

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 56
Outline
 Comments about the “Hydrogen Economy”
 Production of Hydrogen
 Distributed and Central Plants
 Plasma production
 STAR CELL
 Jet (Torch) Production (current U of IL research)
 Hydrogen storage (comments about our
Dislocation Loop research)
 Fuel Cells (a few comments about our research)
 Direct Borohydride
 Concluding comments & questions from you
HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 57
H2 Storage

 Key System Component – both at

production plant, filling station and in
mobile applications (e.g. automotive)
 Various approaches
 High pressure tanks
 Cryogenic liquid

 Hydrides

 Other research: e.g. carbon nano-tubes

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 58
 Our Dislocation-Loop-Cluster Studies
(Current research –new concept)

A B

b
H

Pd
 a 
b  [110] b  2.75Å
2
Pd [1 1 2]
Thermal Desorption demonstrates loop absorption
Cluster regions can have hydrogen densities approaching
1024/cc. SQUID magnetic measurements: H/D loaded
Pd/PdO has type-II superconductor performance.
 Our Dislocation-Loop-Cluster Studies
(Current research –new concept)

Manufactured by repeated electro

absorption – desorption plua low
temperature annealing – stress induced
progressively produces more dislocation
void regions which act as traps to form
Bose-Einstein cluster state of H
Thermal Desorption demonstrates loop absorption
Cluster regions can have hydrogen densities approaching 1024/cc.
SQUID magnetic measurements: H/D loaded Pd/PdO has type-II
superconductor performance.
Cluster Parameters
 Extrapolating the results of thermal desorption measurements for various
residual hydrogen concentrations, it is possible to estimate a radius RH of
residual hydrogen distribution with respect to dislocation cores. When
<x>=H/Pd = 6x10-4 .
 The binding energy of hydrogen within the Pd estimated. Using Garlic-
Gibson kinetics for the kinetic parameters of second-order thermal activation
processes in the thermal desorption analysis (TDA). The activation energy
of desorption (effective binding energy of hydrogen atoms within the lattice)
is ~ 0.65  0.10 eV.
Consistent with the result of Kirchheim for hydrogen trapping at dislocation
core sites in cycled Pd.
Indicate all residual hydrogen is bound solely inside the deepest core sites,
or say, inside the dislocation loops, with minimal radius RH = 2.75 Å, close to
the Burgers vector b [101]=2.75 Å.
 Depending on average residual concentration <x> and dislocation density
Nd, the effective loading ratio inside the loops in a Pd f.c.c. lattice is
determined by the simple formula: xeff = 2<x>/Nd<x>/b2. Accordingly to this
formula at Nd ~ (1.0-2.0)x1011 cm-2 and <x> ~ (4-6) x10-4 xeff would be in
the range of 1.0<xeff <3.0, suggesting superstoichiometric hydride formation
in the deep dislocation cores.
Experimental Magnetic Moment
Measurements show superconducting state

2.E-06
1.E-06
Moment [emu]

5.E-07
0.E+00
-5.E-07 Pd/PdO:Hx
-1.E-06 Pd/PdO
Pd/PdO:Hx - Pd/PdO
-2.E-06
-2.E-06
-3.E-06
0 20 40 60 80
Temperature [K]

The magnetic moment of H2- cycled PdHx(fg) samples in the

temperature range of 2  T < 50 K is significantly lower than M(T)
for the original Pd/PdO.
Summary- clusters lead to localized SC –
verifying extremely high density state in loop
 These results show that an anomalous
diamagnetic response in these electrodes
occurs at temperatures below 30 K. This is
attributed to the appearance of superconductivity
in Pd hydride phase inside the deep dislocation
cores .
 This interpretation is also consistent with the
temperature and field dependencies of
corresponding magnetization curves.
 Both the shape and field behavior of the
magnetization curves have the characteristics of
a non-linear, irreversible magnetization function
of a type-II superconductor.
 New Nano-Structured
electrodes under development

 Objective – mimic dislocation loop

structure obtained from cycling, but –
 Increase the density (#/cc) of loops
Nano-Structure Film Electrodes

 Recently a new type of electrode, the NSF electrode,

is being developed to create cluster formation in
nanostructures . The concept is to mimic the
dislocation loops , but have a larger volumetric
concentration than in the cycled electrode.
 Palladium is deposited on a nickel substrate using an electroless
deposition technique originally developed by R.N. Rhonda of the
International Nickel Plating Company.
 Auger spectroscopy confirmed the deposited palladium on Ni
microstructure completely and thinly. Roughly 0.05g of palladium is
deposited on each 25cm2 electrode at a thickness of roughly 50 nm.
 The structures provided with the nano thin layer coatings are thought to
provide the conditions needed for cluster formation. More needs to be
studied to understand the true promise of this new electrode design.
Nano-Structure Electrodes

Zoom-in view
Showing Pd
nanostructures on
the Ni Foam

Ni felt Ni Foam
Cluster type electrodes have
four major applications
Hydrogen Storage
LENR fusion power cells
ICF hot fusion targets
Superconducting wires
Outline
 Comments about the “Hydrogen Economy”
 Production of Hydrogen
 Distributed and Central Plants
 Plasma production
 STAR CELL
 Jet (Torch) Production (current U of IL research)
 Hydrogen storage (comments about our
Dislocation Loop research)
 Fuel Cells (a few comments about our research)
 Direct Borohydride
 Concluding comments & questions from you
HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 68
 UIUC Fuel Cell Research

Comments about -- NaBH4/H2O2

and NaBH4/Air
Fuel Cells

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009

69
NaBH4/H2O2 FC Schematic

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 70
All liquid NaBH4 / H2O2
Fuel Cell Reactions

 Anode Reaction:

NaBH4 + 2H2O  NaBO2 + 8H+ + 8e- (-0.45 V)

 Cathode Reaction (assuming H+ charge carrier; alternately OH- is used in

some designs):

4H2O2 + 8H+ +8e-  8H2O (1.78 V)

 Overall Reaction:

NaBH4 + 2H2O + 4H2O2  NaBO2 + 8H2O (2.23 V)

The only waste products are water and sodium metaborate, which can be
recycled to produce new sodium borohydride either at a central plant
(currently feasible) or in the fuel cell itself (currently under development).

HYDR*GEN Symposium, Purdue U., 71

Apriil 22, 2009
 The NaBH4 / O2 (Air) Fuel Cell
Has Similar Reactions

 The anode and overall reactions are the same

 Cathode reaction:

O2 + 4H+ + 4e- +  2H2O

Slight efficiency loss due to higher overpotential on the air side

HYDR*GEN Symposium, Purdue U., 72

Apriil 22, 2009
R&D Background in DBFCs at UIUC

Agencies Achievements Images

2003.10 ~ 2007.12
World’s 1st NaBH4/H2O2 DBFC

2004.11 ~ 2006.6
World’s 1st 1 kW DBFC
World’s 1st Rechargeable DBFC

2006.11 ~ 2009.3
World’s 1st Gelled Fuel DBFC

5 Years of Cumulated Experience

HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 73
Competition
Competitive Advantages of DBFC vs other Fuel Cells

High Mass Productivity Low

Safe

Easy
DBFC
Operation

Logistics
Safety

DFAFC

DMFC

PEMFC

Difficult
Danger

Low Unit Price High

HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 74
Direct NaBH4/Air Fuel Cells for Automobiles Approach DOE 2015 Targets

Parameter Value
 Power density of 2200 W/L Mass of liquid fuel 100 kg
Size of liquid fuel tank 20 gal
 Specific power of 2000 Parasitic Mass 20 kg
W/kg Total Fuel System Mass 120 kg
Energy Density of Fuel System 2.2 kWh/kg
 75% fuel cell efficiency Vehicle Power Consumption 20 kW
Vehicle Speed 75 mph
 System cost: $20/kWe Vehicle Range 500 mi

 Durability, transient
response time, cold startup
time, and temperature
survivability conditions can
currently all be met, unlike
gaseous H2 systems.

75
Fuel cost = key issue - Progress in NaBH4 Production
and Recycling Will Lower Costs

 NaBH4 currently costs $50-$60 per kg, yielding an TOTAL energy

cost of $0.66 per kW-hr
 Much of the cost of NaBH4 is in electrolyzing Na+ from NaCl
 Millennium Cell (Eatontown, NJ) is working on a process to reduce
the cost of NaBH4 by extracting Na+ from the NaOH that is produced
during NaBH4 production and recycling the NaBO2 product of the fuel
cell
 NPL is working on an electrolytic process
 Under laboratory conditions, NaBH4 has been produced for ~ $0.07
per kilogram, which in a NaBH4/H2O2 fuel cell, would yield an energy
cost under $0.3 per kW-hr, comparable to the cost of gasoline
NaOH

NaBH4
NaBH4 plant Fuel Cell
NaBO2
HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 76
STID Unitized Regenerative Cell – for use
with wind or solar power stations
 The STID design uses novel
catalysts and a new chemical
pathway to achieve
regeneration
 Currently, the only unitized
hydrogen based liquid
regenerative cell in
development.
 Roundtrip efficiencies of 75%
with cycle life of >10000 have
been demonstrated.
 A complete NaBH4
regenerative fuel cell system
Current state-of-the-art 16-W
would mitigate the need to regenerative test cell.
consider borohydride fuel
economics

77
STID Performance Characteristics
Energy Power Density Power Density
Cycle Life
Density (Peak) (Nominal)

Prototype 110 W-hr/kg 400 W/kg 110 W/kg >10000

In 5 Months 200 W-hr/kg 800 W/kg 220 W/kg >10000

 Because the cell uses a permeable membrane, it will self

discharge after a certain amount of time (~15 hrs)
 Because of this discharge/recharge cycle, the cell is
ideal for periodic applications such as satellite power and
load leveling

78
Outline
 Comments about the “Hydrogen Economy”
 Production of Hydrogen
 Distributed and Central Plants
 Plasma production
 STAR CELL
 Jet (Torch) Production (current U of IL research)
 Hydrogen storage (comments about our
Dislocation Loop research)
 Fuel Cells (a few comments about our research)
 Direct Borohydride
 Concluding comments & questions from you
HYDR*GEN Symposium, Purdue U.,
Apriil 22, 2009 79
Concluding remarks
 The hydrogen economy is a noble goal
 There are road blocks to be overcome
 To get there we need to take small steps forward
 Some steps undertaken by my research group
(hydrogen torch and borohydride fuel cell) are
hopefully examples
 Contributions by many research teams world wide are
moving us ahead towards this goal

HYDR*GEN Symposium, Purdue U.,

Apriil 22, 2009 80
George H. Miley
[email protected]

HYDR*GEN Symposium, Purdue U., 81

Apriil 22, 2009