基于Na3Zr2Si2PO12固体电解质的非平衡态SO2传感器

doi:10.15541/jim20170312

摘要/Abstract

摘要：

基于Na₃Zr₂Si₂PO₁₂(NASICON)固体电解质, 分别以Na₂SO₄-BaSO₄混合盐和NaRe(SO₄)₂复盐为敏感电极材料制备了片式SO₂非平衡态气体传感器。结果表明, 该类型传感器的输出电动势与SO₂气体浓度的对数呈良好的线性关系, 在低温260℃具有最佳性能, 灵敏度分别达到了160 mV/decade和136 mV/decade。传感器在不同浓度的SO₂气体中的交流阻抗谱测试结果显示, 气体在敏感电极的三相界面处电化学反应的活性随着气体浓度的增大而增强, 结合敏感电极结构, 对该类敏感电极的机理进行了分析。由于NASICON具有良好的低温钠离子导电性, 可以大幅降低传感器的工作温度; 由于Na₂SO₄-BaSO₄混合盐和NaRe(SO₄)₂敏感材料具有更好的化学稳定性, 制备的传感器具有良好的可重复性和稳定性。基于非平衡态设计的传感器, 具有结构简单和成本低的优点。以上特性为该传感器在SO₂气体在环境监测方面的应用提供了可能。

关键词: 非平衡态, SO2传感器, NASICON, 复阻抗谱, 稀土硫酸复盐

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

中图分类号:

TQ174

李强, 史王艳, 张骋, 蒋丹宇. 基于Na₃Zr₂Si₂PO₁₂固体电解质的非平衡态SO₂传感器[J]. 无机材料学报, 2018, 33(2): 229-236.

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.

图/表 14

图1 传感器的结构示意图

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

图2 基于Na2SO4-BaSO4混合盐传感器(a)对不同浓度SO2气体的响应恢复曲线和(b)阶梯响应曲线

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

图3 不同温度下基于Na2SO4-BaSO4混合盐传感器的输出电势与SO2气体浓度关系

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

表1 不同温度下基于Na2SO4-BaSO4混合盐传感器的线性拟合度(R)和灵敏度(S) (mV/decade)

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

图4 基于Na2SO4-BaSO4混合盐传感器的输出电动势的重复性测试

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)

图5 基于Na2SO4-BaSO4混合盐传感器模型示意图

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

图6 基于Na2SO4-BaSO4混合盐传感器在不同浓度的SO2气氛中的(a)交流阻抗谱图和(b)根据等效电路拟合的Nyquist谱图

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

表2 260℃时基于Na2SO4-BaSO4混合盐传感器的电解质电阻和电极电阻

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

图7 基于Na2SO4-BaSO4混合盐传感器电极电阻与SO2浓度对数的关系图

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

图8 硫酸钠复盐作电极材料的传感器(a)NaLa(SO4)2和(b) NaCe(SO4)2的输出电动势与SO2浓度关系图

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

图9 基于硫酸钠复盐传感器的灵敏度与温度的关系

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

图10 硫酸镧钠为电极材料的传感器(a)交流阻抗谱图和(b)等效电路拟合图

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

表3 260℃时基于NaLa(SO4)2传感器的电解质电阻和电极电阻

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

图11 基于NaLa(SO4)2混合盐传感器电极电阻与SO2浓度对数的关系图

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

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基于Na₃Zr₂Si₂PO₁₂固体电解质的非平衡态SO₂传感器

SO₂ Non-equilibrium Gas Sensor Based on Na₃Zr₂Si₂PO₁₂ Solid Electrolyte

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