SO2 Non-equilibrium Gas Sensor Based on Na3Zr2Si2PO12 Solid Electrolyte

doi:10.15541/jim20170312

Abstract

Abstract:

This paper reported fabrication and sensing properties of solid-state gas electrochemical sensors for sulfur dioxide based on a non-equilibrium working mechanism. Based on Na₃Zr₂Si₂PO₁₂(NASICON) solid electrolyte, SO₂ non-equilibrium gas sensors were fabricated by using Na₂SO₄-BaSO₄ mixture and NaRe(SO₄)₂as sensing electrodes. The results showed that there was a good linear relationship between the logarithm of SO₂ gas concentration and the sensor output electric potential value. Working at low temperature of 260℃, the sensors display best performances, with sensitivity up to 160 mV/decade and 136 mV/decade. Furthermore, the devices has good repeatability and stability. AC impedance of the sensors in different concentrations of SO₂ gas reveals that the electrochemical activity at three phase boundary (TPB) rised with the increased SO₂ concentration. Working temperature of the prepared sensor is obviously decreased which is benefited from the high Na⁺ conductivity of NASICON at low temperature. The sensor possesses good stability and repeatability due to its high chemical stability of Na₂SO₄-BaSO₄ mixture and NaRe(SO₄)₂ as sensing materials. The sensor based on non-equilibrium mechanism has many advantages, such as low-cost and simple structure. Owing to the above features, the sensor can be possibly applied in the environment monitoring of SO₂.

Key words: non-equilibrium, SO2 gas sensor, NASICON, AC impedance spectroscopy, rare earth sodium sulfate complex salts

CLC Number:

TQ174

LI Qiang, SHI Wan-Yan, ZHANG Chen, JIANG Dan-Yu. SO₂ Non-equilibrium Gas Sensor Based on Na₃Zr₂Si₂PO₁₂ Solid Electrolyte[J]. Journal of Inorganic Materials, 2018, 33(2): 229-236.

Figures/Tables 14

Fig. 1 Schematic diagram of the sensor (a) Top and bottom view; (b) Cross-section view

Fig. 2 (a) Response/recovery transients and (b) step response transients to SO2 concentration for the sensor based on Na2SO4- BaSO4 mixture

Fig. 3 Relationship between EMF and the logarithmic SO2 concentration of the sensor based on Na2SO4-BaSO4 mixtures at different temperatures

Table 1 Linearity (R) and sensitivity (S) of the sensors based on Na2SO4-BaSO4 mixtures at different temperatures

260℃		300℃		400℃		500℃		600℃
R	S	R	S	R	S	R	S	R	S
0.99	160	0.99	59	0.99	37	0.99	106	0.99	101

Fig. 4 Repeatability of the output electric potential for the sensor based on Na2SO4-BaSO4 mixtures (a) Different temperature; (b)Different preservation time(black-as prepared; red-preserved for two weeks)

Fig. 5 Schematic diagram of the SO2 sensing model for the sensor based on Na2SO4-BaSO4 mixtures

Fig. 6 (a) Impedance spectra and (b) equivalent circuit fitting curves of the sensor based on Na2SO4-BaSO4 mixtures under the atmophere with different concentrations of SO2

Table 2 Electrolyte resistance (Rs) and electrode resistance (Rp) of the sensor based on Na2SO4-BaSO4 mixtures at 260℃

SO₂	R_s/Ω	R_p/kΩ
0 ppm	43.02	248.90
20 ppm	43.02	96.91
40 ppm	44.12	67.15
60 ppm	44.37	49.72
80 ppm	44.05	37.81
100 ppm	45.01	23.14

Fig. 7 Relationship between logarithmic SO2 concentration and electrode resistance of the sensor based on Na2SO4- BaSO4 mixtures

Fig. 8 Relationship between EMF and the logarithmic SO2 concentration of the sensor (a) NaLa(SO4)2 and (b) NaCe(SO4)2

Fig. 9 Relationship between sensitivity and temperature of the sensors based on rare earth sodium sulfate complex salts

Fig. 10 (a) Impedance spectra and (b) equivalent circuit fitting curves of the sensor based on NaLa (SO4)2

Table 3 Electrolyte resistance (Rs) and electrode resistance (Rp) of the sensor based on NaLa(SO4)2 at 260℃

SO₂ conc.	R_s/Ω	R_p/kΩ
21% O₂	77.02	172.9
20 ppm	74.55	97.21
40 ppm	73.85	66.76
60 ppm	72.11	48.89
80 ppm	70.06	34.75
100 ppm	66.89	22.55

Fig. 11 Relationship between logarithmic SO2 concentration and electrode resistance of the sensor based on NaLa(SO4)2

References 17

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SO₂ Non-equilibrium Gas Sensor Based on Na₃Zr₂Si₂PO₁₂ Solid Electrolyte

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