bifunctional ceramic fuel cell energy system · 2016. 7. 28. · bifunctional ceramic fuel cell...
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Bifunctional Ceramic Fuel Cell Energy System
(Progress Report 2015‐2016)
Prof. Kevin HuangUniversity of South Carolina, Columbia, SC29201
Present to DOE NETL 17th Solid Oxide Fuel Cell project review meeting, July 19‐21, 2016, Pittsburgh
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About the Team
• University of South Carolina, Prof. Kevin Huang–energy storage materials, button cell testing, computational modeling
• University of Texas at Austin, Prof. John B. Goodenough– bifunctional oxygen‐electrode materials
• University of Maryland, Prof. Eric Wachsman–oxygen isotope labeled surface exchange measurement
• Atrex Energy–pilot scale battery demonstration
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Outline
• The concept• Bi‐functional oxygen‐electrode development• Button battery cell testing results• Pilot‐scale cell testing results• Summary
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About the Concept
Energy & Environ. Sci., 2011, 4, 4942–4946
arg2 arg2
Disch exCh e
xMe O MeO Overall Reaction:
H2(g)+O2‐ H2O(g)+2e‐Discharge
Charge
H2(g)+MeOx(s) H2O(g)+MeCharge
Discharge
Charge
Discha
rge
Discha
rge
Charge
Solid Oxide Metal Air Redox Battery (SOMARB)
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Modeling Predictions at 550oC
• Developing better oxygen electrode materials• Improving Fe3O4‐reduction (charging cycle) kinetics
J. Power Sources, 280 (2015), 195‐204
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The Donor (Ta, Nb, Y)‐doped SrCoO2.5+
Journal of the Electrochemical Society, 163 (5) (2016) F330‐F335
Ta‐doped SrCoO2.5+ is a promising oxygen‐electrode
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Surface Oxygen Exchange Rate Measured by Oxygen Isotopic Exchange Method
Journal of the Electrochemical Society, 10.1149/2.0211609jes
• B‐site doped SCO has a higher kex‐value than A‐site doped SCO
• For B‐site doping, Nb>Fe• For A‐site doping, La>Y• SCO based cathodes are 2 orders of magnitude
higher kex value than LSCF
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‐T‐Po2 Data of Nb‐SrCoO2.5+
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‐T‐Po2 Data of Nb‐SrCoO2.5+
• p‐type conductor• Itinerant electron hole behavior• Non‐Arrhenius behavior
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A New Defect Chemistry Model for Donor‐doped SrCoO2.5+
• BM as a reference framework for point defect assignments
• Oxygen interstitials as ionic point defect
• Itinerant d‐orbital electron holes as electronic point defect
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Defect Reactions and Equilibria
12 2 ⇄ 2 ·
·
.
2 ⇌ ·· ·
2 ·· · 2
· ·· 1
0.5
· ;
Disproportionation reaction:
Oxygen interstitial incorporation reaction:
Charge neutrality:
Co‐site conservation:
Oxygen‐site conservation:
Electron‐hole conductivity:∗
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Experimental vsModeled
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Equilibrium Constants of Defect Reactions
12 2 ⇌ 2 · 2 ⇌ ·
∆ ∆ ∆ ∆
∆ = ‐57 kJ/mol∆ = ‐95 J/mol/K
∆ = 50 kJ/mol∆ = 15.3 J/mol/K
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Concentration Contours of Nb‐SrCoO2.5+
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Thermodynamic Properties of Nb‐SrCoO2.5+
2∆
∆
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Partial Molar vs Integral Molar Properties
Oh
∆ ∆̅
Os
∆ ∆ ∆ ∆ ∆ ∆
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DFT Calculations Supporting the Formation of Oxygen Interstitials
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Evaluations of Button Cell Performance
• Fe loading : 0.056 g• Discharge/charge current:
– C/5.5: 12.7 mA (10 mA cm‐2)– C/5: 14 mA (11 mA cm‐2)– C/3: 23.4 mA (18.5 mA cm‐2)– 1C: 70. 1 mA (55.3 mA cm‐2)
• Depth of discharge (DoD) at 20%– 1 h @ C/5– 36 min @ C/3– 12 min @ 1C
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The Effect of Fe‐Bed Catalysts on Battery Performance
500 oC; 10 mA cm2 (C/5.5); 10 min discharge/charge; DoD=3%
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Evaluations at Higher DoD (Fe‐Utilization)
• 5wt% Pd‐impregnated Fe2O3‐ZrO2
• Tested at 500oC• Rate: 0.2C (11 mA/cm2 or 250 mA/g)
• DoD=20%• Charge/discharge duration: 1 hour
• Fe‐loading: 0.056 grams
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The Evaluation at Different C‐rates
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Comparison with Li‐O2 Battery
P. Adelhelm, et al. Beilstein J. Nanotechnol., 2015, 6, 1016; G. Girishkumar, et al. J Phys. Chem. Lett., 2010, 1, 2193.
Li-O2 batterySOMARB
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A Fe‐Bed Installed Commercial Scale SOFC
Cathode reaction: O2 + 4e = 2O2‐
Anode reaction: 2H2 + 2O2‐ 2H2O + 4e
Fe‐bed: H2 + FeO Fe + H2O
Cathode
Anode
Electrolyte
Iron‐bed solid‐fuel
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Installation of Fe‐bed into Pilot‐scale Cell at Atrex Energy
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Overload Tolerance Capability(Current cycling with constant H2 flow)
Fuel
cha
rgin
g
1.5W
hour
DC
cha
rgin
g(1A
)
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Fast Ramping Power Capability
• Power ramping rate: 2.5 kW/min/cell
• Scaling from single cell to 1 MW system translates to 67 MW/min power ramping capability
Fuel
cha
rgin
g
1.5W
hour
DC
cha
rgin
g(1A
)
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Theoretical FEA Analysis
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Potential Applications of Fe‐bed SOFC Technology
• Fast loading following–to compensate for variable power sources, e.g. wind and solar, as their output fluctuates
• Frequency regulation–to synchronize electricity generation and load
• Demand charge management–to reduce the peak demand
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Summary
• Donor‐doped SrCoO2.5+ is a good IT bifunctional oxygen electrode
• A new defect chemistry model has been established• Pd is an excellent catalyst for Fe3O4 reduction in H2
• Performance of solid oxide Fe‐air battery is evaluated at different DoD and C‐rates
• Internal Fe‐bed enables SOFCs to be overload‐tolerant and load‐responsive much needed for grid stability management
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Acknowledgement
• DOE‐ARPA‐e Award number DE‐AR0000492• Program director Paul Albertus, Scott Litzelman and John Tuttle for constructive discussion and guidance