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. 2022 Dec 11;22(24):9707.
doi: 10.3390/s22249707.

Potentiometric Hydrogen Sensor with 3D-Printed BaCe0.6Zr0.3Y0.1O3-α Electrolyte for High-Temperature Applications

Antonio Hinojo  1 , Enric Lujan  1 , Marc Nel-Lo  1 , Jordi Abella  1 , Sergi Colominas  1
Affiliations

Potentiometric Hydrogen Sensor with 3D-Printed BaCe0.6Zr0.3Y0.1O3-α Electrolyte for High-Temperature Applications

Antonio Hinojo et al. Sensors (Basel). .

Abstract

Hydrogen is expected to play an important role in the near future in the transition to a net-zero economy. Therefore, the development of new in situ and real-time analytical tools able to quantify hydrogen at high temperatures is required for future applications. Potentiometric sensors based on perovskite-structured solid-state electrolytes can be a good option for H2 monitoring. Nevertheless, the geometry of the sensor should be designed according to the specific necessities of each technological field. Conventional shaping processes need several iterations of green shaping and machining to achieve a good result. In contrast, 3D printing methods stand out from conventional ones since they simplify the creation of prototypes, reducing the cost and the number of iterations needed for the obtainment of the final design. In the present work, BaCe0.6Zr0.3Y0.1O3-α (BCZY) was used as a proton-conducting electrolyte for potentiometric sensors construction. Two different shapes were tested for the sensors' electrolyte: pellets (BCZY-Pellet) and crucibles (BCZY-Crucible). Ceramics were shaped using extrusion-based 3D printing. Finally, parameters, such as sensitivity, response time, recovery time and the limit of detection and accuracy, were evaluated for both types of sensors (BCZY-Pellet and BCZY-Crucible) at 500 °C.

Keywords: BCZY; BaCe0.6Zr0.3Y0.1O3-α; ceramic 3D printing; perovskite; potentiometric sensor; proton-conducting materials.

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Conflict of interest statement

The authors declare no conflict of interest. The funders had no role in the design of this study; in the collection, analyses or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Figures

Figure 1
Figure 1
Schematic representation of the experimental setup used for 3D printing.
Figure 2
Figure 2
Schematic representation of the potentiometric sensors constructed with BCZY electrolyte shaped as (a) BCZY-Pellet and (b) BCZY-Crucible. WE: working electrode; RE: reference electrode.
Figure 3
Figure 3
Schematic representation of the experimental setup for electrochemical measurements. WE: working electrode; RE: reference electrode; CE: counter-electrode; PV: process value; SV: set value; and PID: proportional-integral-derivative.
Figure 4
Figure 4
X-ray diffractogram of BCZY pieces after sintering (a) BCZY-Pellet and (b) BCZY-Crucible.
Figure 5
Figure 5
Micrographs of the BCZY 3D-printed pieces after sintering: (a) BCZY-Pellet surface, (b) BCZY-Pellet cross-section, (c) BCZY-Crucible surface and (d) BCZY-Crucible cross-section.
Figure 6
Figure 6
Potential difference-over-time measurement for (a) BCZY-Pellet and (b) BCZY-Crucible.
Figure 7
Figure 7
Potential difference over the logarithm of the H2 partial pressure in the WE of (a) BCZY-Pellet and (b) BCZY-Crucible sensors.
Figure 8
Figure 8
Dynamic response–recovery curve of (a) BCZY-Pellet and (b) BCZY-Crucible.
Figure 9
Figure 9
Response and recovery times for different hydrogen partial pressures for BCZY-Pellet and BCZY-Crucible sensors.
Figure 10
Figure 10
ΔE measurement of a 0.2 mbar H2 sample at 500 °C for BCZY-Pellet and BCZY-Crucible sensors.
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