The explanation of electrical properties changes under NH3 and H2 containing atmospheres in risen temperatures of ceria- and zirconia-based solid electrolytes by means of electrochemical impedance spectroscopy

doi:10.21203/rs.3.rs-4686969/v1

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Research Article

The explanation of electrical properties changes under NH₃ and H₂ containing atmospheres in risen temperatures of ceria- and zirconia-based solid electrolytes by means of electrochemical impedance spectroscopy

https://doi.org/10.21203/rs.3.rs-4686969/v1

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In the presented research, commercial powders of nominal compositions: Ce_0.8Gd_0.2O_1.9, Sc_0.1Ce_0.01Zr_0.89O_1.95, Sc_0.09Yb_0.01Zr_0.9O_1.95structural and electrochemical properties were investigated. The X-ray diffraction of the specimens at room temperature showed a cubic phase. Electrical properties studies over a wide range of frequencies (0.1 Hz to 32 MHz) and temperature (200–600 °C) were analyzed using impedance spectroscopic technique in different atmospheres (synthetic air, 3000 ppm NH₃ in argon, 10% H₂ in argon). The impedance plane plot shows semicircle arcs at different temperatures and electrical equivalent circuit have been proposed to analyze the impedance results. Basing on comparison of the spectra in different atmospheres the reactions on the three-phase boundaries were proposed as well as the conduction mechanisms of the electrolytes were described. The material based on ceria is mixed ionic-electronic conductor, while in zirconia-based materials electrical conduction is realized by oxygen ion carriers. The electrochemical properties of the powders were compared from the applicative point of view as a candidate for element in fuel cells and gas sensors.

gadolinium doped ceria

scandium doped zirconia

solid oxide electrolyte

electrochemical impedance spectroscopy

electrochemical gas sensors

Solid electrolytes are of great interest due to practical uses as ionic conductive components in high temperature electrochemical devices. Examples of devices containing elements based on solid electrolytes of fluorite structure are solid oxide fuel cells (SOFC).

One of the first ceramic material that was used as an electrolyte in SOFC was yttria-stabilized zirconia (YSZ). Zirconia (ZrO₂) crystallizes in the monoclinic system in normal conditions. In such a state, the material exhibits poor mechanical stability and low electrical conductivity. At temperatures above 1150°C ZrO₂ undergoes a phase transition to a tetragonal crystallographic system and above 2370°C to cubic phase [1]. The transition to cubic or tetragonal phase leads to significant modification of zirconia applicative properties. Firstly, the material is extremely durable and chemically resistant. Secondly, it shows ionic electrical conductivity realized by oxygen ions carriers [2, 3]. However, operating of devices constructed with elements basing on ZrO₂ at extremely elevated temperatures would not be possible.

The solution of this problem is a suitable modification of the material by decreasing the phase transition temperature. In consequence, the high-temperature crystallographic phase of the compound is stable at lower temperatures. The most popular method to achieve this aim is the addition of a precisely adjusted amount of divalent or trivalent metal atoms. The following compounds have been reported as ZrO₂ dopants: CaO, MgO, Y₂O₃, Sc₂O₃, Al₂O₃, Si₃N₄, AlN, CuO [4–20]. Such modification has a direct effect on the considerable rise of the specific electrical conductivity. This phenomenon is explained by additional oxygen vacancies creation. The Zr⁴⁺ ions are partially substituted by ions of lower valence and the oxygen vacancies are formed to preserve the charge neutrality of the system. The mentioned processes can be described by the formulas written for doping with divalent and trivalent cations descendant from oxide dopant, respectively:

$$\:\text{MeO}\underrightarrow{{\text{ZrO}}_{\text{2}}}{\text{Me}}_{\text{Zr}}^{\text{''}}\text{+}{\text{V}}_{\text{0}}^{\text{••}}\text{+}{\text{O}}_{\text{0}}^{\text{x}}$$

$$\:{\text{Me}}_{\text{2}}{\text{O}}_{\text{3}}\underrightarrow{{\text{ZrO}}_{\text{2}}}\text{2}{\text{Me}}_{\text{Zr}}^{\text{''}}\text{+}{\text{V}}_{\text{0}}^{\text{••}}\text{+3}{\text{O}}_{\text{0}}^{\text{x}}$$

Doping with tetravalent ions from MnO₂ or SiO₂ is also possible and improves mechanical stability of the materials [21–25].

Zirconia-based ceramics found several practical uses. Its mechanical and chemical properties make it valuable as a prosthetic material for medicine or constructive material for industry. Moreover, high ionic electrical conductivity and temperature shock tolerance of the stabilised ZrO₂ make it suitable for application in oxygen sensors [26–30], solid oxide fuel cells [31–34], ceramic components and as catalyst or catalysts promoters in the synthesis of alcohols by hydrogenation of CO [35–38].

Scandia-stabilized zirconia is a solid electrolyte with potential application in intermediate-temperature solid oxide fuel cells (IT-SOFC) [39, 40]. The main drawback of this solid electrolyte is the complex nature of phase composition according to the phase diagram [41, 42]. The highest value of ionic conductivity was obtained for the addition of 9 mol% Sc₂O₃ [43] along with high rate of thermal degradation, due to the formation of the tetragonal structure in the cubic matrix. The solution of this problem lies in additional material doping of small amounts of ceria (1 mol%) resulting in stabilization of the material cubic structure. A number of studies in the ternary system has been carried out so far [44–60].

The operating temperatures of fuel cells containing electrolyte basing on zirconia are in the range of 900–1000°C. Although the electrochemical processes occurring in the devices run with satisfactory efficiency, the need to use such high temperatures makes it unprofitable to generate electricity. One of the problems is the rapid degradation of cell components in extreme working conditions. Therefore, research on alternative electrolytes has been of constant interest. Among the many tested oxide ceramics with fluorite structure, the highest conductivity is shown by bismuth oxide, bismuth oxide doped with yttrium and ceria doped with gadolinium in the amount of 20% at. For example, at 1000°C the reported Ce_0.8Gd_0.2O_1.9 conductivity equals to 0.1 Ω∙cm^-1 is one order of magnitude higher than that of YSZ electrolyte [61, 62].

One of the CeO₂ disadvantages is the tendency to cerium ions reduction, which results in an increase of the electronic conductivity component. Moreover, the material shows poor mechanical properties in the working conditions of large differences in oxygen chemical potentials. From the thermodynamic point of view, it appears that the introduction of Re₂O₃ admixture counteracts the reduction of Ce^{4 +} ions to the Ce^{3 +} form. Additionally, by introducing ions in the + III oxidation state to the cationic sub-network, oxygen vacancies are generated contributing to conductivity improvement.

During sintering of CeO₂ ceramic elements usually contamination with silica (SiO₂) originating from the quartz elements of the furnaces proceeds which is practically unavoidable. It results in increased resistance of grain boundaries regions. The contamination may also result in segregation of impurities at the electrode-electrolyte connection. Both phenomena cause an undesirable decrease in the conductivity of the system. The addition of Gd³⁺ ions to the CeO₂ network primarily affects grain boundary electrical properties [63, 64]. In the case of samples containing small amounts of SiO₂, higher conductivity of grain boundaries was obtained for the composition Ce_0.8Gd_0.2O_2-δ (CGO20) compared to Ce_0.9Gd_0.1O_2-δ (CGO10). On the other hand, CGO10 is characterized by a higher stability in reducing atmospheres compared to CGO20 at temperatures below 730°C. The improvement of CGO20 stability under such conditions can be obtained by codoping with small amounts of praseodymium [65].

The influence of a type admixture on the ceria sinterability can be predicted based on the so-called Vagards coefficient:

$$\:\text{X=(0.0220}{\text{r}}_{\text{i}}\text{+0.00015}{\text{z}}_{\text{i}}\text{)}$$

where r_i is the difference between the ionic radii of the dopant metal and Ce⁴⁺ for the coordination number equal to 8; z_i-charge difference between the introduced ion and Ce⁴⁺ ions. The maximum amount of modifier ions that can incorporate in network positions is inversely proportional to the X-factor [66–71].

In order to determine the possibility of using ceramics as a component of a fuel cell, it is necessary to describe its electrochemical properties. One of the parameters important from the applicative point of view is material conductivity. An exemplary comparison of results for four cerium oxide based materials at temperatures 500, 600 and 700°C is shown in Table 1 [67–74]. At 500°C, CGO10 material has the highest conductivity value, while the yttrium-dotted sample shows the highest conductivity at temperatures of 600°C and 700°C.

Table 1

Specific conductivities values of Ce(Re)O_2-δ materials according to literature [75].
Composition	σ /Ω^-1 m^-1 500°C	σ /Ω^-1 m^-1 600°C	σ /Ω^-1 m^-1 700°C
Ce_0.9Gd_0.1O_{2- δ}	9.5×10^− 1	2.53×10⁰	5.44×10¹
Ce_0.9Sm_0.1O_{2- δ}	3.3×10⁰	9.0×10^− 1	2.00×10⁰
Ce_0.9Y_0.1O_{2- δ}	8.7×10^− 1	3.44×10⁰	1.015×10¹
Ce_0.9Gd_0.1O_{2- δ}	5.3×10^− 1	1.8×10⁰	4.700×10⁰

The aim of the presented research was to compare the structural and electrochemical properties of three sintered electrolyte materials available commercially paying special attention for their potential applications in novel electrochemical devices.

2.1 Materials used

The investigations were conducted on commercially available powders provided by Terio. The declared compositions of the investigated materials are: Ce_0.8Gd_0.2O_1.9 (labeled as GDC), Sc_0.1Ce_0.01Zr_0.89O_1.91 (labeled as ScCeSZ) and Sc_0.09Yb_0.01Zr_0.9O_1.95 (labeled as ScYbSZ).

Silver paste used for EIS measurements was provided by Pelco.

2.2 Samples preparation

The powders were pressed into pellets of 5 mm diameter, 0.2 g weigh and sintered according to program recommended by the producer. In case of ScCeSZ and ScYbSZ the sintering steps were as follows: heating from 20°C to 300°C for 4 hours, holding at 300°C for 1 hour, heating from 300°C to 500°C for 2 hours, heating from 1500°C to 1660°C for 3 hours 15 minutes, holding at 1660°C for 1 hour, cooling from 1660°C to 1100°C for 2 hours 30 minutes and cooling from 1100°C to 20°C for 8 hours 20 minutes. In case of 20GDC the sintering steps were as follows: heating from 20°C to 300°C for 3 hours 20 minutes, holding at 300°C for 2 hours, heating from 300°C to 1500°C for 15 hours, holding at 1500°C for 2 hours, cooling from 1500°C to 20°C for 6 hours.

The pellets were prepared for electrochemical impedance spectroscopy (EIS) measurements by covering on both sides with Ag paste firing at 1000°C for 5 minutes.

2.3 Characterisation of sintered discs

Sintered pellets were examined by X-ray diffraction (XRD) method. The measurements were done in air at room temperature using CuK_α radiation (Philips X’Pert) within the 2Θ range 10–90° with the scan ratio of 0.008°/s.

The surface morphology of sintered materials was observed using ultrahigh-resolution scanning electron microscope (SEM) with field emission (FEG-Schottky emitter; Nova Nano-SEM 200, FEI Europe BV) cooperating with energy-dispersive spectroscopy and X-ray analyzer (EDAX EDS).

2.4 Electrochemical properties examination by electrochemical impedance spectroscopy (EIS)

The EIS measurements were performed in controlled atmospheres using a frequency analyzer (Solartron model FRA 1260) coupled with Dielectric Interface (model 1296) in temperature range 200–600°C. Frequency range was 0.1 Hz-32 MHz, the amplitude of sinusoidal voltage signal was 20 mV. The measurements were performed in the following atmospheres: synthetic air (series no 1 and 3 and 5), 3000 ppm NH₃ in argon (series no 2), 10% H₂ in argon (series no 4). The series no 3 and 5 in the synthetic air were conducted in order to determine the reversibility of the material impedance response in H₂ and NH₃ rich atmospheres. The values of the resistances were derived using Zview software (version 2.2, Scribner Associates, Inc.).

3.1 Morphological features of the sintered samples

Spectra from XRD are presented in Fig. 1. GDC and ScYbSZ are single phase and crystalize in the cubic system, while ScCeSZ specimen is comprised mainly of ZrO₂ phase with CeO₂ traces.

The exemplary images of specimens’ microstructure studied by SEM technique are presented in Fig. 2. GDC surface is smooth almost without cracks. In this case, a few round small randomly situated pores are revealed. The images indicate high gas tightness and density of the material. ScCeSZ and ScYbSZ ceramics are comprised of partly grown, melted grains characterized by ovoid edges and sizes from the range 1–3 µm. Between grains small pores are visible. The specific area of ScCeSZ and ScYbSZ is significantly higher than in the case of GDC. Basing on XRD spectra the lattice parameters were calculated. The measurement of elemental compositions was performed by EDS analyzer. The calculated data form EDS and XRD and presented in Table 2. The lattice parameter of GDC is notably higher than for ScCeSZ and ScYbSZ, which remains in accordance with theoretical predictions. The elemental analysis shows a significant deficiency in oxygen in every specimen. It revealed that the concentration of oxygen vacancies is high in the lattice and would impact on materials electrical properties. Surprisingly, specimen ScCeSZ contains measurable amounts of yttrium which was not declared in the nominal composition of the material. Moreover, the amounts of scandium and cerium are much higher than it arises from the theoretical calculations. In the case of ScYbSZ the determined amount of ytterbium considerably exceeds the expected value.

Table 2

Experimental phase compositions with crystallographic data obtained from XRD analysis collated with elemental composition from EDAX EDS analysis compared with theoretical values
Specimen label	Assumed composition	Composition by XRD with lattice constant	Element	Experimental content /%wt	Theoretical content /%wt
GDC	Ce_0.8Gd_0.2O_1.9	CeO₂ 100% a = 0.54547 nm	O	12.94	17.49
			Ce	67.38	64.42
			Gd	19.67	18.09
ScCeSZ	Sc_0.1Ce_0.01Zr_0.89O_1.95	c-ZrO₂ 96.3% a = 0.51254 nm CeO₂ 3.7%	O	13.6	26.38
			Y	1.51	0.00
			Zr	72.04	68.64
			Sc	9.69	3.80
			Ce	3.16	1.18
ScYbSZ	Sc_0.09Yb_0.01Zr_0.9O_1.95	c-ZrO₂ 100% a = 0.50906 nm	O	17.05	26.20
			Zr	57.90	68.95
			Sc	2.83	3.40
			Yb	22.21	1.45

3.2 Electrochemical properties of the sintered samples

The electrochemical properties were investigated by EIS spectra analysis realized by dedicated software. The exemplary evolution of Nyquist spectra with temperature for GDC obtained during the 4th series in the H₂ rich atmosphere is presented in Fig. 3. The figure contains the results of experimental data analysis by fitting equivalent circuits method. At temperature 200°C the spectrum is comprised of two separated semicircles in high and medium frequencies and short fragment arc in low frequencies. The investigated material can be classified as polycrystalline ceramic. In such cases, the highest frequencies part of the spectrum corresponds with bulk properties and the medium frequency fragment is attributed to grain boundaries behavior. The shape of spectra indicates that the grain boundaries regions are notably more resistive than bulk regions. At 500°C the metallic electrode becomes reversible to hydrogen. Such behavior is deduced from the semicircle shape of the spectrum fragment in low frequencies. At 600°C the conductivity of the specimen becomes as high as in metallic conductors. Thus, the semicircle shape is visible in the admittance plane and equivalent circuit simulating the behavior of the specimen contains inductor.

The exemplary sets of data obtained at 450°C in different atmospheres for specimens in Nyquist plane are presented in Fig. 4.

In a typical solid oxide electrolyte conductivity is proportional to relative concentration of oxygen ions which are charge carriers in the crystallographic lattice. The conductivity is described by the equation:

$$\:\sigma\:=qc\mu\:$$

where:

q-valency of mobile ions,

c-relative concentration of mobile ions to the number of possible positions in the lattice,

µ-mobility of the ions.

In the atmosphere rich in oxygen the reversible oxidation and reduction occurs on three-phase-boundary (gas-

metallic electrode-solid electrolyte):

$$\:{\text{O}}_{\text{2}}\text{+}{\text{2e}}^{\text{-}}\text{+}{\text{V}}_{\text{0}}^{\text{n-}}\rightleftarrows\:\text{2}{\text{O}}^{2\text{-}}$$

In the case of GDC in NH₃ rich atmosphere the reversible increase of resistance is measured, while in H₂ containing atmosphere the resistance drop is observed followed by further resistance decrease during 5th series in synthetic air. The deterioration of conducting properties of the oxide electrolytes is predictable in the conditions of atmospheres lacking in oxygen as it was demonstrated during the 2nd series. The results obtained in an atmosphere containing hydrogen exhibit that free electrons could also realize the conduction in the material.

The reactions on the three-phase boundary: hydrogen-metal-ceramic introduce permanent modifications in the material. Such an effect could be explained by reaction in which valence electrons are created accompanied by the oxygen vacancies recombination. A postulated reaction involving H₂ can be written:

$$\:{\text{H}}_{\text{2}}\text{+}{\text{2O}}^{\text{2-}}\text{+}{\text{V}}_{\text{0}}^{\text{n-}}\underrightarrow{}\text{2}{\text{(OH)}}^{\text{-}}\text{+}{\text{ne}}^{\text{-}}$$

The improved conductivity in hydrogen is due to the risen concentration of valence electrons and increased resistance in the 5th series arise from recombination of oxygen vacancies.

The resistance in both the 3rd and 5th series for the ScCeSZ specimen increases, which can be explained taking into account that the material is the oxygen ionic conductor. The comparison of spectra in both reducing atmospheres indicates that reactions run much more effective with H₂ than with NH₃. The succeeding drop of conductivity in the following 4th and 5th series in the synthetic air can be elucidated by reactions resulting in oxygen vacancies recombination:

$$\:{\text{2NH}}_{\text{3}}\text{+3}{\text{V}}_{\text{0}}^{\text{••}}\text{+}{\text{6O}}_{\text{0}}^{\text{x}}\underrightarrow{}{\text{\:6(OH)}}_{\text{O}}^{\text{•}}\text{+}{\text{N}}_{\text{2}}$$

$$\:{\text{H}}_{\text{2}}\text{+}{\text{V}}_{\text{0}}^{\text{••}}\text{+}{\text{2O}}_{\text{0}}^{\text{x}}\underrightarrow{}\text{2}{\text{(OH)}}_{\text{O}}^{\text{•}}$$

The specific conductivities were calculated using values of specimens’ resistance obtained by analysis of the spectra taking into account the pellets geometry. The collation of specific conductivities values obtained during the 1st series in the air which can be considered as reference measurements of electrical conductivity before further

modification of the materials is presented in Table 3. The results are presented in Fig. 5 as experimental points in Arrhenius coordinates along with lines derived from linear regression fitting. At 200°C and 300°C the specimen GDC shows the highest electrical conductivity. Surprisingly, the determined conductivities are a few orders lower comparing with literature data at particular temperatures presented in Table 1. The discrepancy may arise from different sintering conditions or different initial microstructure of the materials. At 400°C the conductivities for all the investigated samples are comparable. The best-conducting properties at higher temperatures are demonstrated by ScCeSZ specimen.

Table 3

Increase of specific conductivities obtained in 1 series in air with risen temperatures from EIS spectra analysis and geometry of the samples.
Temperature /°C	Specimen conduction /Ω^-1 m^-1
Temperature /°C	GDC	ScCeSZ	ScYbSZ
200	2.55×10^–10	4.57×10^–11	3.48×10^–11
300	1.51×10^− 8	7.44×10^− 9	6.42×10^− 9
400	2.04×10^− 7	4.67×10^− 7	2.07×10^− 7
450	5.61×10^− 7	1.91×10^− 6	6.88×10^− 7
500	1.38×10^− 6	5.64×10^− 6	1.97×10^− 6
550	3.01×10^− 6	1.37×10^− 5	4.74×10^− 6
600	7.32×10^− 6	2.90×10^− 5	1.04×10^− 5

Additionally, basing of slopes of fitted Arrhenius plots the activation energy values for total specific conductivities were determined and presented in Fig. 5. The values about 0.5 eV indicate the extrinsic character of the conductivity, while values about 1 eV indicate the intrinsic character of the conductivity.

The presented results indicate that investigated materials’ electrical properties are consistent with Arrhenius law in the synthetic air and in NH₃ rich atmospheres at investigated temperatures. In atmosphere containing H₂ in all cases, the shift in the plot is denoted. The result can be explained by a rapid change in the effectiveness of the reactions (6) and (8) above the temperatures 500°C, 450°C and 400°C for GDC, ScCeSZ and ScYbSZ respectively.

From the commercial zirconia and ceria based powders dedicated as solid electrolytes for SOFC the dense sintered bodies were prepared. The materials were examined by SEM, XRD and EDS techniques. Material based on ceria is characterized by different microstructure than zirconia based ceramics. In the first case, the dense, flat surface without characteristic grains was revealed, while the zirconia ceramics shows typical polycrystalline structure comprised of round, partly separated grains. All the samples show a deficiency in oxygen. Samples based on zirconia some disagreements between declared and experimental elemental composition were observed.

According to EIS studies conducted in oxidizing and reducing atmospheres, the zirconia samples are oxygen ionic conductors, whereas mixed-ionic electronic conduction is showed in ceria. Thus, GDC would be the most appropriate to be used as an anode element in SOFC devices working at temperatures above 500°C. In such condition the effectiveness of hydrogen oxidation significantly increases. Moreover, GDC exhibits significant and reversible electrochemical response to NH₃ in the whole investigated temperature range. Therefore, it may be perspective as material for working element of ammonia gas sensors.

The utmost electrochemical response was recorded in case of ScCeSZ material for exposition on NH₃ above 400°C. However, the reaction was only partially reversible, which limits its usability as ammonia sensor element without further modification.

On the other hand, ScYbSZ shows the highest stability of electrical properties in reducing atmospheres below 400°C, as well as, noticeable reversible response for H₂ above 400°C. On this account, it may be interesting candidate for working phase of H₂ sensor or solid electrolyte for IT-SOFC devices.

To sum up, the presented studies are crucial for evaluation of potential usage of investigated materials as well as for determinations its optimal working conditions i.e. temperature and atmosphere composition. Nevertheless, further research of preparation and ceramic composition effect on the observed electromechanical properties is apparently required.

YSZ stands for yttria stabilized zirconia

CGO10 stands for Ce_0.9Gd_0.1O_2-_d

CGO20 stands for Ce_0.8Gd_0.2O_2-_d

GDC stands for Ce_0.8Gd_0.2O_1.9

ScCeSZ stands for Sc_0.1Ce_0.01Zr_0.89O_1.91

ScYbSZ stands for Sc_0.09Yb_0.01Zr_0.9O_1.95

EIS stands for electrochemical impedance spectroscopy

SOFC stands for solid oxide fuel cell

IT-SOFC stands for intermediate-temperature solid oxide fuel cells

Additional information

OriginPro8 graphics program provided by OriginLab Corporation was used to create the artwork.

Author Contribution

M.D. performed all the experiments, analyzed data and edited the manuscript.

Acknowledgments

This work was supported by the subsidy of the Ministry of Education and Science for the AGH University of Science and Technology in Kraków (Project No. 16.16.160.557)

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The explanation of electrical properties changes under NH₃ and H₂ containing atmospheres in risen temperatures of ceria- and zirconia-based solid electrolytes by means of electrochemical impedance spectroscopy

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Abstract

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1. Introduction

2. Experimental section

2.1 Materials used

2.2 Samples preparation

2.3 Characterisation of sintered discs

2.4 Electrochemical properties examination by electrochemical impedance spectroscopy (EIS)

3. Results and discussion

3.1 Morphological features of the sintered samples

3.2 Electrochemical properties of the sintered samples

4. Conclusions

Abbreviations

Declarations

Additional information

Author Contribution

Acknowledgments

References

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Version 1