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Investigation of Perovskite Oxide SrCo0.8Cu0.1Nb0.1O3-δ as a Cathode Material for
Room Temperature Direct Ammonia Fuel Cells
Peimiao Zou [email protected] by - Professor Shanwen Tao
School of Engineering, University of Warwick
Sources: R. K. Graupner “Guanidine – Safe, Clean, and Flexible”
http://www.energy.iastate.edu/Renewable/ammonia/ammonia/2006/OregonSustainableEnergy.pdf
Compounds Density (g cm-3)
Gravimetric H2 density (% H2)
Volumetric H2 density (kg H2 l-1)
Energy density (MJ l-1)
Gaseous H2 0.00008988 100 0.00008988 0.01079 Compressed H2
(700bar) 0.039 100 0.039 5.6
Liquid H2 0.071 100 0.071 10.1 NH4OH (28%) 0.89 2.4 0.021 1.17
Liquid NH3 0.747 17.6 0.13 12.6 CO(NH2)2 1.335 10.07* 0.134 16.9
* Effective density including hydrogen from water molecules for hydrolysis.
NH3 is carbon-free
Comparison of energy density of different chemicalsComparison of energy density of different chemicals
Diagram of ‘Ammonia Economy’
Haber -Bosch process
Natural gas
Coal
Nuclear
Wind
Solar
WaveBiomass
CO 2 - free e lectricity
ArtificialPhotosynthesis
CO 2 scrubbing
Storage Delivery
Urea
Ammo niafuel cell
Ureafuel cell
Ammonia
Transportation
Nuclear H 2
)g(NH2)g(H3)g(N322
→+ )(3)(46)(2 2322 gOgNHOHgN +→+
BiosynthesisArtificialPhotosynthesis
Rong Lan, John T.S. Irvine, Shanwen Tao*, Inter. J. Hydrogen Energy, 37 (2012) 1482-1494.
Ammonia in Wastewater
Source: http://wastewater-compliance-systems.com/aquaculture/http://wastewater-compliance-systems.com/aquaculture/
Ammonia in Wastewater
Source: https://www.slideshare.net/laxer_12/ammonia-wastewater-treatment-wastewater-treatment-plant-wwtp-centrate-landfill-leachate
Reaction mechanism of ammonia fuel cellsbased on alkaline exchange membrane electrolyte
Rong Lan and Shanwen Tao, Electrochemical and Solid-State Letters, 13 (2010) B83-B86.
Hierarchical nickel-copper hydroxide nanowires
Wei Xu, Shanwen Tao, Applied Catalysis B: Environmental, 218 (2017) 470-479.
Anode - ammonia oxidation reaction
Anode - ammonia oxidation reaction
Electrodeposition of NiCu bimetal
Effects of pH value on electrochemical oxidation of ammonia
Wei Xu, Shanwen Tao, Applied Catalysis B: Environmental, 237 (2018) 1101-1109.
Cathode-oxygen reduction reaction
Raw materials:
C4H4NNbO9·xH2O
Sr(NO3)2
Co(NO3)2 · 6H2O
Cu(NO3)2 · 2.5H2O
Cubic structure
a = 3.8806(7) Å
XRD pattern of new perovskite oxide SrCo0.8Cu0.1Nb0.1O3-δ
Peimiao Zou, Shanwen Tao, ChemSusChem, 12 (2019) 2788-2794.
Fuel cell test
Cathode-SrCo0.8Cu0.1Nb0.1O3−δ /C (loading
at 18 mg/cm2)
Fumapem FAA anion exchange membrane
Anode-NiCu/C (NiCu loading at 1.2 mg/cm2)
Fuel- NH3H2O with/without 1 M NaOH
Active area- 1 cm2
Ammonia solution
Compressed air
Performance of room temperature ammonia fuel cells
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0
0.1
0.2
0.3
0.4
0.5
0.6
Volta
ge (V
)
Current density (mA/cm2)
0.02 M NH3H2O 0.1 M NH3H2O 0.2 M NH3H2O 0.6 M NH3H2O 1 M NH3H2O 3 M NH3H2O 5 M NH3H2O 35% NH3H2O
0.00
0.01
0.02
0.03
0.04
0.05
0.06
Pow
er d
ensi
ty (m
W/c
m2 )
0 1 2 3 4 5 60.0
0.1
0.2
0.3
0.4
0.5
Volta
ge (V
)Current density (mA/cm2)
0.02 M NH3H2O 0.1 M NH3H2O 0.2 M NH3H2O 0.6 M NH3H2O 1 M NH3H2O 3 M NH3H2O 5 M NH3H2O 35% NH3H2O
0.00
0.05
0.10
0.15
0.20
0.25
0.30
Pow
er d
ensi
ty (m
W/c
m2 )
Fuel-ammonia Fuel-ammonia+1 M NaOH
Wastewater 1000 ppm (i.e., 0.06 M)OCV 0.19 V
Current density 0.08 mA/cm2 Current density 1 mA/cm210 times
The SrCo0.8Cu0.1Nb0.1O3-δ/C cathode before and after the fuel cell measurements
20 30 40 50 60 70 80 90
Inte
nsity
(a.u
.)
2 theta (Degree)
SrCo0.8Cu0.1Nb0.1O3-δ electrode
SrNb0.2Co0.8O3
Reference code: 04-018-6753
(a)
20 30 40 50 60 70 80 90
SrNb0.2Co0.8O3
Reference code: 04-018-6753
PTFEReference code: 00-047-2217
Inte
nsity
(a.u
.)
2 theta (Degree)
SrCo0.8Cu0.1Nb0.1O3-δ electrode after test Carbon cloth
(b)
Before test After test
SEM/EDS analysis of the SrCo0.8Cu0.1Nb0.1O3-δ/C cathode before and after the fuel cell measurement
Before test After test
After testBefore test
For comparison-- Perovskite oxide SrFe0.8Cu0.1Nb0.1O3-δas cathode catalyst for a room temperature direct ammonia fuel cell
Peimiao Zou, Shanwen Tao, Inter. J. Hydrogen Energy, 44 (2019) 26554-26564.
Fuel-ammonia Fuel-ammonia+1 M NaOH
For comparison-- Perovskite oxide SrFe0.8Cu0.1Nb0.1O3-δas cathode catalyst for a room temperature direct ammonia fuel cell
Peimiao Zou, Shanwen Tao, Inter. J. Hydrogen Energy, 44 (2019) 26554-26564.
0 1 2 3 4 5 60.0
0.1
0.2
0.3
0.4
0.5
Volta
ge (V
)
Current density (mA/cm2)
0.02 M NH3H2O 0.1 M NH3H2O 0.2 M NH3H2O 0.6 M NH3H2O 1 M NH3H2O 3 M NH3H2O 5 M NH3H2O 35% NH3H2O
0.00
0.05
0.10
0.15
0.20
0.25
0.30Po
wer
den
sity
(mW
/cm
2 )
SrFe0.8Cu0.1Nb0.1O3-δSrCo0.8Cu0.1Nb0.1O3-δ
Conclusion
Open circuit voltage and power density of fuel cells were improved by adding 1 M NaOH
New shuttle shaped perovskite oxide
SrCo0.8Cu0.1Nb0.1O3-δ
Potential cathode for a room temperature direct ammonia fuel
cells
Thank you for your attention !