6 sofc
6 sofc
ScienceDirect
Successful Ni exsolution in
Lanthanum Strontium Titanate
confirmed by XRD, SEM, XPS.
Powder morphology not affected
by Ni doping and exsolution.
Ni nano-decoration of LaSrTiO3 by
exsolution boosts electrochemical
performances.
Exsolution is much more effective
than infiltration in decreasing
polarization.
Increasing the temperature, the
cell performances using NH3 or H2
become similar.
Article history: Hydrogen represents the most conventional fuel to feed Solid Oxide Fuel Cells (SOFCs) for
Received 29 November 2021 green energy production. However, hydrogen has some drawbacks which prevent the
Received in revised form large-scale implementation. Research identified ammonia as promising hydrogen vector.
4 February 2022 Hereby, highly dispersed Ni nanoparticle are deposited on La-doped strontium titanate by
Accepted 15 February 2022 exsolution, greatly affecting the electrochemical performance. The exsolved Ni-doped
Available online 15 March 2022 lanthanum strontium titanate (La0$45Sr0$45Ti0$90Ni0.10-dO3 e LSTNOH) was largely charac-
terized. XRD analysis detected 10 mol% of Ni doping has been successfully incorporated in
Keywords: to the perovskite structure and then released when exposed in reducing environment. SEM
Ammonia images show Ni nanoparticles highly dispersed on the surface. XPS confirms the presence
Hydrogen of Ni on the surface after the exsolution and allows to exclude other detrimental diffusion
SOFC towards the bulk. A LSTNOH derived composite based anode has been investigated through
Anode impedance spectroscopy using ammonia and hydrogen as fuel. It demonstrates best per-
formances compared to the one obtained by Ni infiltration on LSTO (La0$45Sr0$45TiO3)
* Corresponding author.
E-mail address: [email protected] (J. Cavazzani).
https://doi.org/10.1016/j.ijhydene.2022.02.133
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
13922 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 3 9 2 1 e1 3 9 3 2
LaSrTiNiO 3 composite scaffold. Polarization resistance, running on ammonia, decreases raising the
Ni exsolution temperature and the performances approach those in hydrogen.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Morphology: SEM
The nominal compositions, derived from the stoichiometry amounts, are reported for comparison. The atomic composition determined
considering only the cations are indicated below the corresponding O-containing ones. This choice permits to emphasize the surface segre-
gation phenomena often hidden by the relevant amount of oxygen.
Electrochemical performances
In Fig. 4, electrochemical performances of LSTNOH are couple Ti4þ/Ti3þ which plays an important role in the elec-
compared as a function of the content of ammonia in the flow. trical conductivity of the anode [76].
The polarization resistance diminishes increasing the fuel Full cell tests were evaluated using LSTNOH and 8YSZ
content, as expected, and 40% of NH 3 (2.9 U cm2) approaches composite as anode. The cathode is made up by a composite
to 20% of H2 (2.8 U cm2). The temperature also affects the between LSCF and GDC. GDC interlayer was deposited be-
polarization resistance. Rising the working temperature at tween the 8YSZ electrolyte and the cathode to prevent the
900 C, LSTNOH-based electrodes running on ammonia interaction between the electrolyte and LSCF [79], more details
exhibit ASR values closer to those in hydrogen (3,1 U cm2 in are reported in SM. Experimental. SEM images of cross section
NH3, 2.8 U cm2 in H2) compared to the analogous at 800 C are reported in Figure SM.2. It shows the interfaces anode/
(Fig. 3; 12.2 U cm2 in NH3, 11.3 U cm2 in H2). This behaviour is electrolyte and cathode/electrolyte. Electrolyte has high den-
consistent with titanates-based materials, their conductivity sity, as expected. Pore former (3% of carbon soot) induces
increases with the temperature in reducing conditions [57]. porosity to both electrodes although anode seems much more
All impedance spectra were fitted using the same equiva- delaminated than cathode probably due to a higher porosity.
lent circuit. In literature, the studies [76e78], regarding the EIS In the image of the anode, some pieces of electrode are
measurements of LST-based materials, use the proposed randomly distributed on the electrolyte, it is clearly caused by
model circuit. It is made up by a resistor (R1), normally the mechanical cutting to break the cell. GDC interlayer was
attributed to the electrolyte, and then the two semicircles are deposited between YSZ electrolyte and LSCF cathode, how-
described by (R-CPE)x, in series with the resistor R1. Two ever, during the thermal treatment, interlayer and cathode
different processes were identified at high frequency (HF: sinter together and they are not distinguishable.
~105e103 Hz) and at medium frequency (MF: ~10e1 Hz). No The IeV and IeP curves are reported in Supplementary
electrochemical processes appear at low frequency (LF: 101 e Materials in Figure. SM. 3 and results are summarized in Table
102 Hz). The latter are typically attributed to diffusion phe- SM.3. A power density peak about 3.7 mW/cm 2 was reached at
nomena. The choice of the composite (50:50) with YSZ can be 780 C using 40% of ammonia. In the same condition,
considered a strategic help in this sense, thanks to the high hydrogen exhibits 11.7 mW/cm2. Inferior power density using
ionic conductivity of YSZ. Thus, the ionic conductivity related ammonia instead pure hydrogen can be attributed to a lower
resistance can be neglected in comparison with the other H2 concentration in the atmosphere because the presence of
resistance contribution [77]. In EIS spectra, no new process N2 produced during the decomposition of ammonia [22,55,56].
appears when electrode is working with ammonia at Pure hydrogen (wet) test was also carried out reaching a power
800e900 C temperature range. The fitting results (Table SM.2) density of 15.5 mW/cm2 (see Table SM.3). Considering results
suggest that both processes are thermally activated as they in hydrogen (40% vs pure), Open Circuit Voltage (OCV) slightly
become less intense with rising the temperature. The fuel decreases from 1049 V in pure H2 to 1016 V in 40% of H2. This
composition also affects the polarization resistance of the light variation of the OCV is mainly caused the difference of
processes but less markedly. In the light of this results, the the hydrogen partial pressure (pH) in the anode compartment:
semicircles in HF region can be attributed to a not perfect rising the pH, the higher content of H2 in the flow (the flow of
electronic transfer through the electrolyte and electrode air at cathode is kept constant at 100 sccm) leads to an
interface [78]. As long as, the semicircle in MF region may be increment of the OCV, according with Nernst equation. While,
assigned to the cyclic reduction and oxidation of titanate the slope variation with the current density, between the
measurements in hydrogen, may represent that the H2 con-
tent is limiting step for the overall reaction. However, further
studies should be brought for better understating the reasons.
More interested is the different OCV using ammonia or
hydrogen (40%), here OCV changes from 0,867 V in NH 3 to
1016 V in H2. Analogously to the power density, OCV is
affected by the atmosphere of the anode: the lower partial
pressure of hydrogen due to the presence of nitrogen in the
mixture diminishes the OCV in ammonia fuelled cell [22].
Beyond N2, also the steam: both the one coming from the inlet
gases, because the fuel passes though the bubbler, but even
the one produced by the electrochemical reaction. Observing
the slope of the IeV curve for the ammonia, the initial slope
undergoes a change at about 5 mA/cm2: for lower values of
density current the losses mainly involves those connected to
activation processes and ohmic resistance. But for higher
current densities, losses are likely due to mass transport, in
agreement with what discussed above regards the reduction
in concentration leading to insufficient supply of reactants to
the electrode surface. In the light of these considerations, to
Fig. 4 e EIS spectra of LSTNOH composite using increasing achieve best performances using ammonia it is possible to use
content of NH3 at 900 C. 20% of H2 in Ar is also reported as other flow rate (fuel was kept at 100 sccm): by decreasing the
reference. “Wet” indices the fuels contain 3% of water. flow it is possible to prolong the permeation time of the gas
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 3 9 2 1 e1 3 9 3 2 13929
inside the porous structure of the electrode and thus the electrochemical oxidation of hydrogen to achieve best
contact between the fuels (ammonia but also hydrogen) and performances.
the electrocatalyst material of the anode [37]. In general, the
cell performances are strongly affected by the thickness of the
electrolyte, hereby about 1.5 mm. Diminishing the electrolyte Declaration of competing interest
thickness will improve significantly the power density; further
work is in course to this purpose. The authors declare that they have no known competing
Recently, Song et al. [56] studied LSTN-based material financial interests or personal relationships that could have
infiltrated on SDC (Samarium-doped Ceria) scaffold achieving appeared to influence the work reported in this paper.
best performances at 800 C in hydrogen and ammonia,
338 mW/cm2 and 161 mW/cm2 respectively. Their much more
competitive results can be in part justified by the thinner Appendix A. Supplementary data
electrolyte (350 mm). Moreover, perovskite infiltration exhibits
a promising solution that could be investigated in a subse- Supplementary data to this article can be found online at 10.
quent work. Molouk et al. [39] focused their work on Ni-YSZ 1016/j.ijhydene.2022.02.133
and Ni-GDC. Ni-based cermets demonstrate an interesting
catalytic activity towards the ammonia cleavage in hydrogen
and nitrogen. Since the basic sites promote the ammonia
references
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