Matteo Amati |

SYNCHROTRON-BASED IN SITU CHARACTERIZATION OF PEMFC AND

SOFC COMPONENTS

Matteo Amati matteo.amati@elettra.eu

B. Bozzini, P. Bocchetta, A. Gianoncelli, L. Gregoratti, C. Mele and M. Kiskinova

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European Fuel Cell 2013 11 – 13 December, Rome, Italy

Matteo Amati |

X-ray spectroscopies in electrochemical system characterization

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Spatial resolution

X-ray spectroscopies

•  X-ray absorption spectroscopy, •  X-ray emission (fluorescence) spectroscopy •  X-ray photoelectron spectroscopy

opportunities for monitoring material changes and mass transport events occurring at submicron length scales

Matteo Amati | 4

Soft X-ray Imaging and Spectromicroscopy

Elettra

https://www.elettra.eu/

Prof. B. Bozzini Dipartimento di Ingegneria dell’Innovazione Universita del Salento, Lecce (Italy)

Matteo Amati |

TwinMic – Scanning Transmission X-ray Microscopy (STXM)

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Zone plate that forms a microprobe

Transmission Detector System

(energy res < 0.5eV)

Specimen raster-scanned across the microprobe

(spatial resolution ~ 50nm )

Fluorecence Emission Detector System

(energy res 70eV@Na)

OSA

https://www.elettra.eu/elettra-beamlines/twinmic.html

Photon energy range 400-2200 eV

CCD

Matteo Amati |

TwinMic – In situ electrochemical STXM characterizzation

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Non vacuum-compatible (aqueous solutions)

Ni / Fe Au

Nafion in aqueous solution

Bozzini et al. ChemSusChem , 7 (2010) 846

Matteo Amati |

TwinMic – In situ PEMFC durability Ni, Fe corrosion and Nafion poisoning

7 Bozzini et al. ChemSusChem , 7 (2010) 846

706/701 eV 1014 eV

40 m

m

electrode electrode electrolyte electrolyte Ni electrodes preserve pristine shape

Fe electrodes develop corrosion

morphology

Ni: narrow spreading

across interface

Fe: wide spreading

across interface

Matteo Amati |

TwinMic – In situ PEFC durability Ni, Fe corrosion and Nafion poisoning

8 Bozzini et al. ChemSusChem , 7 (2010) 846

40 m

m

Matteo Amati |

ESCAmicroscopy – Scanning PhotoElectron Microscopy (SPEM)

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SPEM actual performances § Imaging: < 50 nm

§ Microspectroscopy: 120 nm

§  Energy resolution: ~180meV

§  Standard conditions

§  Room Temperature

§  Photon Energy: 500 eV

Spatial resolution

Overall energy resolution

https://www.elettra.trieste.it/elettra-beamlines/escamicroscopy.html

N

S

Photon energy range: 350 eV (min) – 1200 eV

(undulator transmission)

Undulator

Sample

Zone Plate

OSA D  = 200-250 μm dn: 50-80 nm

Spherical grating monocromator

ESCAmicroscopy beamline layout and SPEM setup

Hemispherical electron analyzer

e-

Bozzini et al. Scientific Report 3, 2848, 2013 (2013) Bozzini et al. Electrochem Comm, Vol. 24, pp.104-107 (2012) Bozzini et al. Journal of Physical Chemistry C 116 (44), pp. 23188-23193 (2012) Bozzini et al. ChemSusChem, Vol. 4 - 8, pp. 1099-1103 (2011) Bozzini et al. Chemistry - A European Journal 18 (33), pp. 10196-10210 (2012) Ecc…

Matteo Amati |

ESCAmicroscopy – Self Driven Single Chamber SOFC In operando condition

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1x10-5 mbar of O2 P=1x10-5 mbar of H2 + O2 (1:1)

200–400 nA

B. Bozzini et al. Scientific Report 3, 2848, 2013

NiO/MnO2 Single Chamber

e2- e2- NiO

Anode

MnO2 Cathode

Matteo Amati |

ESCAmicroscopy – Self Driven Single Chamber SOFC In operando condition

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100 µm

self-driven activity of electrochemical

cell starts

Chemical reduction Ni2++H2→Ni+2H+

B. Bozzini et al. Scientific Report 3, 2848, 2013

Matteo Amati |

ESCAmicroscopy – Self Driven Single Chamber SOFC In operando condition

12 B. Bozzini et al. Scientific Report 3, 2848, 2013

Simultaneously mapping the local chemical state and

the local electrochemical

activities

64x16 µm

Matteo Amati |

Conclusion

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1.  in situ and in operando electrochemical experiments STXM and SPEM experiments can be performed under operating conditions

2.  Information regarding:

•  compositional, chemical state and overvoltage localization

•  damaging/material growth mechanisms •  behaviour of peculiar material couplings

Matteo Amati |

Acknowledgments

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STAFF: Matteo Amati Luca Gregoratti Alessandra Gianoncelli Burkhard Kaulich Maya Kiskinova Mauro Prasciolu Ivonne Sgura[ Patrizia Bocchetta Francesco Bogani Federica De Riccardis Deborah Lacitignola Claudio Mele Ivonne Sgura

PhD/PostDoc: Gian Pietro De Gaudenzi Lucia D’Urzo Ameriga Fanigliulo Giuseppe Giovannelli Hossein Hassannejad Majid Kazemian Abyaneh Cristina Lenardi Ralf Peipmann Patrizio Raffa Vincenzo Romanello Marco Serra Elisabetta Tondo

Thank you!

Matteo Amati | 15

Matteo Amati |

ESCAmicroscopy – Self Driven Single Chamber SOFC In operando condition

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Propagation of the reduction

front

H2

B. Bozzini et al. Scientific Report 3, 2848, 2013