DIRECT CARBON (COAL) CONVERSION BATTERIES AND FUEL CELLS

Presented to

Fourth Annual SECA Meeting April 15-16, 2003 Seattle WA

by

John F. Cooper and Roger Krueger

Chemistry and Materials Science Directorate Lawrence Livermore National Laboratory Livermore CA 94550 Tel. 925-423-6649 Fax 925-422-0049 email Cooper3@LLNL.gov
JFC:Jun-03
This work was performed under the auspices of the U.S. Department of Energy by University of California, Lawrence Livermore National Laboratory under Contract No. W-7405-Eng-48.

Topics
Concept Thermodynamic and Chemical Basis Technical Approach and Results The Synthesis of Carbon Electrochemical Fuels Conclusions

JFC:Jun-03

Direct Carbon Conversion Fuel Cell and Battery: Electricity From C/O2 Electrochemical Reaction
T = 675 C

Electric energy +
Air in

Carbon

Cathode: O2 +2CO2 + 4e- = 2CO32Anode:

Net reaction: C+O2 = CO2

Air out

C + 2CO32- = 3CO2 +4e

CO2
High fuel cell efficiency: 80% of H298 (HHV), High fuel cell efficiency: 80% of H298 (HHV), H298 = 32.8 MJ/kg-C [9.1 kWh/kg-C], S ~~0, fixed C and CO2 activities H = 32.8 MJ/kg-C [9.1 kWh/kg-C], S 0, fixed C and CO activities High specific energy battery: 3-4 kWh/kg (~3.5 kWh/liter) at 100-133 W/kg High specific energy battery: 3-4 kWh/kg (~3.5 kWh/liter) at 100-133 W/kg Fixed C, CO2 activities make possible invariant EMF and full fuel utilization Fixed C, CO activities make possible invariant EMF and full fuel utilization
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298

Boudouard corrosion is expected only at low polarization: C + CO2 = 2CO Boudouard corrosion is expected only at low polarization: C + CO2 = 2CO

Routes to Power Production at Efficiencies > 70%

Electrochemical conversion

Petro-coke Natural gas Petroleum Coal, lignite

Pyrolysis

C & H2

Air

Electric power Sequester or reuse

CO2

H2

Fuel cells [or turbines, refinery, etc.]

70 80 % efficiency, HHV

The pyrolysis of CHx => C + (x/2)H2 consumes 3-8% of fuel value; no ash The pyrolysis of CHx => C + (x/2)H2 consumes 3-8% of fuel value; no ash H2 co-product has multiple uses: fuel cells, chemical value, combustion H2 co-product has multiple uses: fuel cells, chemical value, combustion
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The Carbon Air Technology Evolved from LLNL Internal Research

Area Nanostructures Particle anodes Anode R&D: rates and structure Angled cell Rigid anode
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Contribution Defined approach relating structure to rate; first full-cell experiments ever Particles + melt mimic rigid electrode Experimental slurries in full cells Structure, conductivity effects studied; Carbon anode mechanism proposed; Data base of diverse fuels from slurry cells in full-cell configuration Developed cell enabling scale up, refueling, controlled wetting of carbon

Sponsor/Year
CEES 1999
Gas analysis O2/CO2 controlled atmosphere

CEES 1999 LDRD, IL-10479 LDRD, FY00-02

1.4 1.2 C ell Potential (V) 1.0 0.8 0.6 0.4 0.2 0.0 0

Au Ref

+
Porous alumina

Current collector

Carbon paste

Molten salt

60 50 40 30 20
Ac Blk- s m all cell 800 C Pet C oke- s m all cell 800 C Ac Blk- lg cell 850 C Pet C oke- lg cell 850 C

Power (m W /cm )

10 0 120
2

40

80 C urrent (m A /cm )

160

LDRD FY01-02 IL-10848

Air fill

Cathode lead Anode lead Alumina tube Carbon fill Separator Anode collector Cathode collector

Allows stacking and refueling of small FY2002-3 assemblies; discovery of low-T IL-11101 materials; DOE NA22, ARL, ARO

10 cm

AA

Comparison of Fuels for Fuel Cells

Fuel Theoretical limit == Theoretical limit G(T)/Hostd
o

Utilization efficiency, 1.0 0.80 0.80

V(i)/V(i=0) = v 0.80 0.80 0.80

Actual efficiency Total efficiency == (G/Hostd)()( v) 0.80 0.57 0.45

C CH4 H2
a

1.003 0.895 0.70

(electrical energy out) / /(HHV thermal value of fuels in) (electrical energy out) (HHV thermal value of fuels in)

Efficiency of aafuel cell Efficiency of fuel cell

[G(T)/H][][V/V]= [theoretical eff][utilization][voltage efficiency] [G(T)/H][][V/V]= [theoretical eff][utilization][voltage efficiency]

--where G(T) - -nFV H-TS --where G(T) nFV H-TS

Fundamental advantages derive from thermodynamics of the C/O2 reaction and fixed activities of the reactants
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Technical background

Past efforts limited by ash entrainment, electrode fabrication and logistics

History Jacques [1898]: 15 kW coal batteries ~102 papers in 20th century

C + 2KOH + O2 = K2CO3 + H2O Efficiency not driver, CO2 not pollution >98% utilization at 750 C Power levels => 0.8 kW/m2 @ 1 kA/m2 Fundamental studies of ground C slurries Suggested nano-scale disorder might enhance rate
Jacques [1898]

Weaver [1980]: found reactive cokes Vutetakis [1985]

Barriers to electricity direct from coal Ash entrained into melt Electrode fabrication, distribution costs Resistance of rigid electrode,high polarization Relation to Molten Carbonate Fuel Cell Similar cathode, melt No H2 or steam corrosion JFC:Jun-03 tolerant of S (no anode catalyst) More

Weaver [1981]

At Temperatures of 400-1100 C, the Only Reaction is C + O2 CO2

Conditions T = 700 C, graphite, carbonate T = 400-900 C, graphite, CO32T = 700-800 C, rigid reactive carbons and coke T = 700 C, CO32Large volume, free slurry T = 900-1100 C, NaAlF4 + Al2O3, turbo & graphite
JFC:Jun-03

Method used W, dV/dt ~ I/nF

Results n=4 u not reported n=4 u ~ 1.0 n=4 u ~ 1.0 n=4 u poor n=4 u ~ 1.0

Reference Tamaru & Kamada [1937] Hauser [1964] Weaver [1977-9] Vutetakis [1984] Thonstad [1970]

dV/dt; [CO]/[CO2] dV/dt; W

d[CO2]/dt = I/nF

d[CO2]/dt = I/nF anode CO ~ 0: no Boudouard rxn

Studies with 60 cm2 Angled Cell Anticipate Fuel Cell

Cathode lead Anode lead Alumina tube Carbon fill Separator Anode collector Air flow tube Excess melt reservoir Cathode collector Sump

Cell in heater
JFC:Jun-03

60 cm2 angled cell

Tilted orientation allows control of wetting Fuel cell option for exchange of electrolyte Basis of patent-pending

Voltage Stability, 80% Efficiency and Successful Scale-up of Powder-fed Fuel Cell
Cell Potential (V) -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0
1.4 Cell Potential (V) 1.2 1.0 0.8 0.6 0.4 0.2 0.0
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Ac Blk- small cell 800 C Pet Coke- small cell 800 C Ac Blk- lg cell 850 C Pet Coke- lg cell 850 C

Voc = 1.13 V

Stable voltage Stable voltage during 30 h test at during 30 h test at constant load constant load
Cathode lead Anode lead Alumina tube Carbon fill
2

T = 800 C 0.90-0.98 V, constant current, 75 mA (27 mA/cm )

Separator Anode collector Air fill Cathode collector

10

20 Time (hrs)

30
60 50 40 30 20 10 0 120 160 Power (mW/cm )

40

80 Current (mA/cm )
2

Scale up 2.8 to 60 cm22 Scale up 2.8 to 60 cm

Demonstrated >100 mA/cm2 at 80% Efficiency With Carbon Black Fuels

-1.2
120 mA/cm at 0.8 V
2

120 100 80 60 40 20 0 0 50 100 150 2 Current Density (mA/cm ) 200 Power Density (mW /cm )

-1.0 Cell Potential (V) -0.8 -0.6 -0.4 -0.2 0.0

Furnac e Blac k 800 C day 1 700 C day 3 Green Needle Petroleum Coke 800 C

Performance sustained until fuel consumed (> 3 days) Performance sustained until fuel consumed (> 3 days)
Data: N.Cherepy JFC:Jun-03

New Rigid Block Materials: Half-Cell Research

Const I

Luggin probe Anode

SS cathode

Measures anode polarization against Au/0.28CO2, 0.14O2

JFC:Jun-03

Enhanced Performance with Composite Plates at 650-700 C

1.10 1.00

Properties of composites Properties of composites With separator, cathode at With separator, cathode at 700 C: 700 C: 1 kW/m22@ 80% 1 kW/m @ 80% efficiency efficiency 4.5 kW/m22peak power 4.5 kW/m peak power Ongoing tests on 50 cm22 Ongoing tests on 50 cm
Density: >25 % theoretical Density: >25 % theoretical Conductivity > 25 -1cm-1 Conductivity > 25 -1cm-1

Ea vs Au/CO2,air

0.90 0.80 0.70 0.60 0.50 0 100 200 300 400 500 600
650 C 675 C 700C 725 C 750 C

Current density, mA/cm2

Recently studied class of high-density C composite plates yielded twice previously achieved power at 100 C lower T. Expected 80% efficiency at 50-500 mA/cm2
JFC:Jun-03

Experimental Approach: Rigid Plate Anode with Flow Field and Improved Diagnostics
Au ref

CO2 Overflow

Va prob

Vc prob

Air/CO2 flow field

Au ref

Independent reference electrodes and voltage probes Precise control over gas composition and flow Isolation of reaction zone in rigid carbon block
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DOE/NETL Project, FY 2003

The synthesis of carbon electrochemical fuels

JFC:Jun-03

Extraction and Use of Carbon from Coal

Solvent-extraction of ash-free carbons Direct Carbon Conversion Fuel cell Electric power _ + Clean coal Air in
Coal residuals, Ash, pyrite, mid BTU gas pyrite
> 95 % 90 > 75 % 72 80 %
Air out

Coal

CO 2 out

Solvent extraction yields coal with 0.01% ash

Recycles benign solvents, negligible loss (0.7 %) per cycle Unconverted coal retains thermal value
JFC:Jun-03

A. Stiller, J. Zondlo, WVU; B. K. Parekh, U. Kentucky

Hydraulic Cleaning of Coal

Air

Coal

Bake out Mid BTU Gas, steam

Pulverization and Hydraulic Separation from Ash & Pyrite

65 kWh/ton (98 % retention of heating value) Net coal-to-electricity efficiency 78 %

Hydraulic separation of C (<1 % S, ash) from pyrite, ash

Total cost $60/ton => 0.8 /kWh for fuel But: high ash requires further cleaning or periodic electrolyte exchange
JFC:Jun-03

Ref.: B. K. Parekh, U. Kentucky

Clean Carbon Fuels from Hydropyrolysis

Biochar or Lignite + lime

CH4
_ + Electric power out
Air in

Reactive C
H2-coal

heat

pyrolysis
Air out

H2

CO2 out

Un-reacted chars, Sulfur, toxic ash

H2 slip stream (6%)

Net reaction: C+O2 = CO2

Fuel Cells, turbines, refinery, etc.

Extraction of Carbon from Coal Seam by in situ methanation ?

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How Often Must Electrolyte Be Replaced?

Interval between electrolyte replacement/recycle
0.5% ash hydraulic cleaned coal 200 days (twice yearly) 0.05% ashsolvent extracted coal 5.5 years (life of cell) 0.01% ashpyrolyzed oil N/A

For 0.5% ash cleaned coal For common fuels under consideration, cost of electrolyte exchange is insignificant Lowest recycle cost if Na/K eutectic is used: $2.5/kW per exchange, assuming 20 /lb salt 200 days between exchange => 0.05 /kWh
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Summary: Efficient Processes for Cleaning Coal

UK: hydraulic separation
grind to 30 m; baking to remove mid-BTU gas; low-ash product

UK-process: extraction of pitch with anthracene oil

425 C, 200 atm; no hydrogenation; 40-70% yield; 0.05-0.1 % ash

WVU-process: extraction of pitch with n-methyl pyrrolidone

Ambient pressure, 200 C; 40-50% yield; 0.05-0.1 % ash Process
UK-hydro UK-solvent WVU-solvent
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Efficiency
98% > 90% > 90%

Yield
100% 40-70% 40-50%

%Ash
0.5-1 0.05 0.05

%S
1-2 0.5 0.5-1

Cost
$60/ton, $3/GJ 0.8 -fuel/kWh $200/ton, 2.4 -fuel/kWh $78-140/ton, 1-2 -fuel/kWh

Initial Hardware Cost Estimates

Stack cost ~ $250/m2 at 2 kW/m2
Component or factor Zirconia fabric Basis Zircar, Inc. retail price $200/m2 Nickel felt Eltech, Inc. $20/m2 retail price Stainless steel lid Ni plated SS frame, $5/lb Graphite base, collector $1.00/lb design Assembly 20% parts G&A, profit 20% parts and labor Total Cost $/kW 100 10 38 10 32 48 $237

JFC:Jun-03

Acknowledgments
LLNL Collaborators
J. F. Cooper, Chemistry, Electrochemical Engineering Nerine Cherepy, Chemistry Larry Hrubesh, Physics Ton Tillotson (advanced composite materials) Roger Krueger, Sr. Techn. Associate Prof. Rob Selman IIT (Molten Carbonate Fuel Cell) Dr. Kim Kinoshita (LBL, ret.; Carbon properties) Meyer Steinberg (BNL) fossil fuel to carbon processing MesoSystems Technology (Kennewick WA). Thermal engineering

Consultants and advisors

LDRD and CEES; DOE NA-22; ARL; ARO; DOE/NETL

JFC:Jun-03