参比氢分压对固体电解质浓差电池氢传感器测试准确性的影响

doi:10.15541/jim20170027

摘要/Abstract

摘要：

采用固相反应法合成了CaZr_0.9In_0.1O_3-_α高温质子导体材料并制备了固体电解质管。通过组装两类浓差电池氢传感器研究了不同参比氢分压对电动势测量误差和待测端氢分压计算误差的影响。结果表明, 在873~1073 K, 且待测端氢分压在0.005~0.1 atm (1 atm=1.013×10⁵Pa)范围内, 参比端氢分压与测试端氢分压相差越大, 所测电动势相对误差越大, 尤其在873 K低温下更明显。根据Nernst定律计算待测端氢分压的计算误差极大依赖于参比端与待测端氢分压的比值。该误差可通过用电动势为零时的参比氢分压代替测试端氢分压的方法加以消除。利用该方法测定出在873~1073 K, 氢化锆在β-ZrH_x和δ-ZrH_x两相共存区的平台氢分压以及两相转变过程中的生成焓和生成熵。

关键词: 固体电解质, 高温质子导体, Nernst定律, 氢分压, CaZr_0.9In_0.1O_3-_α;

Abstract:

High temperature proton conductor CaZr_0.9In_0.1O_3-_α powders were prepared. By using the prepared powders, solid state electrolyte tubes were prepared. After assembling two types of concentration cell type hydrogen sensors, the effects of reference hydrogen partial pressures on electromotive force errors and hydrogen partial pressure calculation errors were investigated. At temperatures ranging from 873-1073 K and in the hydrogen partial pressure range of 0.005-0.1 atm (1 atm=1.013×10⁵Pa), the relative errors of electromotive forces increase when the hydrogen partial pressure difference between reference and measurement sides enlarged. This phenomenon is more obvious at low temperature of 873 K. The calculation error of the hydrogen partial-pressure according to the Nernst law is greatly dependent on hydrogen pressure ratio of the two sides of the cell. This error can be eliminated through reference hydrogen partial pressure at electromotive force of zero instead of hydrogen partial pressure. Hydrogen pressures platforms of β-ZrH_x and δ-ZrH_x coexistence zone were calculated by this method, as well as the formation enthalpy and formation entropy in the phases conversion process.

Key words: solid state electrolyte, high temperature proton conductor, Nernst law, hydrogen partial pressure, CaZr_0.9In_0.1O_3-_α;

中图分类号:

TB321

陈建勋, 吴树森, 张亚楠, 毛有武, 吕书林. 参比氢分压对固体电解质浓差电池氢传感器测试准确性的影响[J]. 无机材料学报, 2017, 32(11): 1195-1201.

CHEN Jian-Xun, WU Shu-Sen, ZHANG Ya-Nan, MAO You-Wu, LÜ Shu-Lin. Reference Hydrogen Partial Pressure on Accurancy of Hydrogen Determination Utilizing Concentration Cell Type Sensor Based on Solid State Electrolyte[J]. Journal of Inorganic Materials, 2017, 32(11): 1195-1201.

图/表 12

图1 氢浓差电池原理图

Fig. 1 Schematic drawing of hydrogen concentration cell

图2 A型传感器原理图(a)及其实物照片(b); B型传感器原理图(c)及其装配后照片(d)

Fig. 2 Schematic (a) and corresponding photo (b) of type A sensor, schematic (c) of type B sensor and assembly photo (d)

图3 传感器测氢实验装置图

Fig. 3 Schematic layout of experimental apparatus for hydrogen determination

图4 固体电解质粉末XRD物相分析图谱(a)及全谱拟合结果(b)

Fig. 4 XRD phases analysis (a) and rietveld fitted (b) patterns of solid state electrolyte powders

图5 CaZr0.9In0.1O3-α电解质管断面形貌

Fig. 5 Fracture surface image of a CaZr0.9In0.1O3-α electrolyte tube showing an average grain size of no more than 3 μm

图6 A型传感器对不同氢分压的响应曲线(a)以及参比氢分压分别为104 Pa (b)和5×104 Pa (b)时的稳定电动势值

Fig. 6 Sensing results of type A sensor: (a) response curves, (b, c) stable electromotive forces vs reference hydrogen partial pressure of 104 Pa and 5×104 Pa, respectively (The solid straight lines represent the electromotive forces calculated according to function (6))

图7 873 K (a)、973 K (b)及1073 K (c), 不同参比氢分压选择对A型传感器实测电动势与理论电动势比值的影响

Fig. 7 Electromotive force ratios of measurement values to theory Nernst values for type A sensor with variable reference hydrogen partial pressure at temperatures of 873 K (a), 973 K (b) and 1073 K (c)

图8 不同外部参比氢分压气氛下B型传感器电动势响应曲线(a)和稳定电动势值(b)

Fig. 8 Electromotive force response curves (a) and stable electromotive forces (b) of type B sensor towards variable reference hydrogen partial pressures

图9 由图8(b)中电动势数据根据式(8)计算得到的873 K到1073 K不同温度下(β+δ) ZrHx平衡氢压值

Fig. 9 Hydrogen pressures of (β+δ) ZrHx at temperatures ranging from 873 K to 1073 K calculated according to Equation (8) utilizing electromotive forces values in Fig. 8(b)

图10 不同氢分压比值和电动势误差下测氢计算误差

Fig. 10 Hydrogen calculation errors obtained from different hydrogen pressures ratios and electromotive force errors

表1 采用不同研究方法得到的(β+δ)ZrHx氢分压、氢化物生成焓和生成熵

Table 1 Comparisons of (β+δ) ZrHx hydrogen partial pressures, formation enthalpy and formation entropy obtained from different research methods

In(P_eq/ Pa)	ΔH^f/(kJ·mol^-1)	ΔS^f/(kJ·K^-1·mol^-1)	Temperature/K	Method	Reference
-26119/T+34.1	-217.2	-0.284	823-1123	Exp.	Ref. [20]
-28160/T+37	-234.1	-0.305	823-873	Calc.	Ref. [21]
-25078/T+32.9	-208.5	-0.274	873-1073	Exp.	This work

图11 通过图8(b)中数据拟合求零点得到的(β+δ)ZrHx氢压值

Fig. 11 Hydrogen pressures of (β+δ)ZrHx calculated from null points after data fitting of data in Fig. 8(b) at different tempeartures

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