Alkaline membrane electrolysis with PEM-level electrochemical performance Mikkel Rykær Kraglund a , Marcelo Carmo b , David Aili a , Günter Schiller c , Erik Christensen a , Andreas Friedrich c , Detlef Stolten b,d , Jens Oluf Jensen a [email protected]2017-06-15 / Thursday 10:20 Monday 12 th , 14:20 ICE2017 / Session 12. AEC Session 3. AEC a Department of Energy Conversion and Storage, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark b Institute of Energy and Climate Research, IEK-3: Electrochemical Process Engineering, Forschungszentrum Jülich c Institut für Technische Thermodynamik, Deutsches Zentrum für Luft- und Raumfahrt (DLR), 70569 Stuttgart, Germany d Chair for Fuel Cells, RWTH Aachen University, Germany
Transcript
Alkaline membrane electrolysis with PEM-level electrochemical performance
Mikkel Rykær Kraglunda, Marcelo Carmob, David Ailia, Günter Schillerc, Erik Christensena, Andreas Friedrichc, Detlef Stoltenb,d, Jens Oluf Jensena
a Department of Energy Conversion and Storage, Technical University of Denmark, 2800 Kgs. Lyngby, Denmarkb Institute of Energy and Climate Research, IEK-3: Electrochemical Process Engineering, ForschungszentrumJülichc Institut für Technische Thermodynamik, Deutsches Zentrum für Luft- und Raumfahrt (DLR), 70569 Stuttgart, Germanyd Chair for Fuel Cells, RWTH Aachen University, Germany
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Why alkaline membranes?
Features of alkaline electrolysis:
• Noble metal catalysts not required
• Limited to low current density
• Differential pressure operation not possible
2 Alkaline membrane electrolysis with PEM-level electrochemical performance
Alkaline membrane electrolysis combine the best of alkaline and PEM systems
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Outline
• AEM and APEM in literature
• Our alkaline membrane electrolysis results
• Membrane and electrodes
• Investigating the ohmic contribution
• Durability
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How?
Anion exchange membranes (AEM)• Without KOH
Alkaline membrane electrolysis with PEM-level electrochemical performance4
Alkaline polymer electrolyte membranes (APEM)• Ion-solvating membranes• With KOH (aq)
Two approaches
AEM APEM
H2 & O2 solubility High (H2O) Low (KOH (aq))
Ionomer/TPB Required Not needed
Corrosive electrolyte for BoP. No Yes
CCM / CCS Yes Yes
”3D” electrodes (foam) Not ideal Yes
n
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AEM-WE in literature w/o KOH
Alkaline membrane electrolysis with PEM-level electrochemical performance5
C. C. Pavel, F. Cecconi, C. Emiliani, S. Santiccioli, A. Scaffidi, S. Catanorchi and M. Comotti, Angew. Chemie Int. Ed., 2014, 53, 1378–1381.
M. Faraj, M. Boccia, H. Miller, F. Martini, S. Borsacchi, M. Geppi and A. Pucci, Int. J. Hydrogen Energy, 2012, 37, 14992–15002.
X. Wu and K. Scott, J. Power Sources, 2012, 206, 14–19.
X. Wu and K. Scott, J. Power Sources, 2012, 214, 124–129.
Y.-C. Cao, X. Wu and K. Scott, Int. J. Hydrogen Energy, 2012, 37, 9524–9528.
L. Xiao, S. Zhang, J. Pan, C. Yang, M. He, L. Zhuang and J. Lu, Energy Environ. Sci., 2012, 5, 7869.
X. Wu and K. Scott, J. Mater. Chem., 2011, 21, 12344.
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APEM-WE in literature w/ KOH
Alkaline membrane electrolysis with PEM-level electrochemical performance6
L. A. Diaz, R. E. Coppola, G. C. Abuin, R. Escudero-Cid, D. Herranz and P. Ocón, J. Memb. Sci., 2017, 535, 45–55.
J. Schauer, J. Žitka, Z. Pientka, J. Křivčík, J. Hnát and K. Bouzek, J. Appl. Polym. Sci., 2015, 132, n/a-n/a.
C. C. Pavel, F. Cecconi, C. Emiliani, S. Santiccioli, A. Scaffidi, S. Catanorchi and M. Comotti, Angew. Chemie Int. Ed., 2014, 53, 1378–1381.
Y. Leng, G. Chen, A. J. Mendoza, T. B. Tighe, M. A. Hicknerand C.-Y. Wang, J. Am. Chem. Soc., 2012, 134, 9054–9057.
X. Li, F. C. Walsh and D. Pletcher, Phys. Chem. Chem. Phys., 2011, 13, 1162–7.
X. Wu and K. Scott, J. Mater. Chem., 2011, 21, 12344.
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Our results
Alkaline membrane electrolysis with PEM-level electrochemical performance7
Temp.: 80oC
[KOH]: 24 wt%
Zero-gap
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Relative to AEM/APEM/Classic
Alkaline membrane electrolysis with PEM-level electrochemical performance8
C. C. Pavel, F. Cecconi, C. Emiliani, S. Santiccioli, A. Scaffidi, S. Catanorchi and M. Comotti, Angew. Chemie Int. Ed., 2014, 53, 1378–1381.
L. Xiao, S. Zhang, J. Pan, C. Yang, M. He, L. Zhuang and J. Lu, Energy Environ. Sci., 2012, 5, 7869.
X. Wu and K. Scott, J. Mater. Chem., 2011, 21, 12344.
G. Schiller, R. Henne, P. Mohr and V. Peinecke, Int. J. Hydrogen Energy, 1998, 23, 761–765.
APEM / this work
Classic
APEM
AEM
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Relative to PEM
Alkaline membrane electrolysis with PEM-level electrochemical performance9
Mixed PEM data from 2010-2012.From:
M. Carmo, D. L. Fritz, J. Mergel and D. Stolten, Int. J. Hydrogen Energy, 2013, 38, 4901–4934.
Our alkaline cell
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m-PBI as ion-solvating membrane
10 Alkaline membrane electrolysis with PEM-level electrochemical performance
D. Aili, A. G. Wright, M. R. Kraglund, K. Jankova, S. Holdcroft and J. O. Jensen, J. Mater. Chem. A, 2017, 5, 5055–5066.
M. R. Kraglund, D. Aili, K. Jankova, E. Christensen, Q. Li and J. O. Jensen, J. Electrochem. Soc., 2016, 163, F3125–F3131.
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0 10 20 30 40 50
Wei
ght f
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ion
/ %
Bulk [KOH] / wt%
m-PBI
KOH
Water
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Electrode specifics
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5 cm
Zero-gap configurationClassic type Raney-electrodes
Perforated plate (pp.)
NickelRaney-Ni(Mo)
Membrane
Resin
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Specific resistance
12 Alkaline membrane electrolysis with PEM-level electrochemical performance
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Specific conductivity
13 Alkaline membrane electrolysis with PEM-level electrochemical performance
d[µm]
Rs[mΩ cm2]
σmem[mS cm-1]
Ni(f)/Zirf. 500 277
Ni(f)/PBI 40 73
R-Ni(pp)/PBI 40 40
R-Ni(pp)/PBI 80 59
Ex-situ - -
d[µm]
Rs[mΩ cm2]
σmem[mS cm-1]
Ni(f)/Zirf. 500 277 180
Ni(f)/PBI 40 73 55
R-Ni(pp)/PBI 40 40 100
R-Ni(pp)/PBI 80 59 136
Ex-situ - - 255
d[µm]
Rs[mΩ cm2]
σmem[mS cm-1]
Ni(f)/Zirf. 500 277 180
Ni(f)/PBI 40 73 55
R-Ni(pp)/PBI (a) 40 40 100
R-Ni(pp)/PBI (b) 80 59 136
”(b)-(a)” 40 19 210
Ex-situ - - 255
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Durability
14 Alkaline membrane electrolysis with PEM-level electrochemical performance
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Durability
15 Alkaline membrane electrolysis with PEM-level electrochemical performance
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Durability
16 Alkaline membrane electrolysis with PEM-level electrochemical performance
Polarization change Change in ohmic resistance
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Improving durability
17 Alkaline membrane electrolysis with PEM-level electrochemical performance
Temperature Thickness Modifying polymer
D. Aili, A. G. Wright, M. R. Kraglund, K. Jankova, S. Holdcroft and J. O. Jensen, J. Mater. Chem. A, 2017, 5, 5055–5066.
Improving electrodesReducing [KOH]
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Acknowledgements
This work is funded by DTU Energy internal project PorouZ.
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12 June 201719 Alkaline membrane electrolysis with PEM-level electrochemical performance
