改性石墨烯基传感器对SF<sub>6</sub>分解组分H<sub>2</sub>S的吸附机理及检测特性研究

doi:10.19595/j.cnki.1000-6753.tces.220842

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摘要作为SF₆的重要分解组分,H₂S能够有效反映SF₆气体绝缘电气设备内部绝缘故障类型及程度。本文以H₂S为目标检测气体,探究了改性石墨烯基传感器对H₂S的吸附机理及检测特性。基于第一性原理建立了环氧基化石墨烯(G-O)、钯掺杂石墨烯(Pd-G)和环氧基与钯共掺杂石墨烯(Pd-G-O)改性模型和H₂S吸附模型,从吸附能、态密度、轨道、脱吸附时间等多方面计算分析了G-O、Pd-G、Pd-G-O的改性机理与吸附机理,结果表明Pd-G-O对H₂S表现出优异的吸附性能,吸附能达到-1.015 eV,为较强的化学吸附,且对应着强烈的电荷转移值0.281 e;制备了G-O、Pd-G、Pd-G-O传感材料及器件,基于微量气敏测试平台测试了改性石墨烯基传感器检测H₂S的温度、浓度、响应恢复及稳定特性,其中Pd-G-O传感器对H₂S表现出低工作温度(175℃)及快速响应优势。本文的仿真计算与气敏测试分析为研制检测SF₆分解组分的低功耗、高灵敏度及快速响应传感器提供了理论基础与实验支撑。

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	高新
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关键词 ：改性石墨烯, SF₆分解组分, H₂S检测吸附机理, 检测特性

Abstract：H₂S is one of the important decomposition products of SF₆. It is the characteristic component in the event of high energy partial discharge or strong overheating fault, and can reflect the severity of the fault.The gas sensor method is a method using gas sensitive materials to detect the gas composition and concentration, and is often used to detect SF₆ decomposed components.The gas sensing materials based on intrinsic graphene only show weak physical adsorption for most gases. Therefore, the sensing performance of graphene gas sensing materials and graphene gas sensors can be improved through various optimization methods such as doping, functionalization of functional groups, and composite.However, there are few studies on the properties of metal and functional group functionalized co-modified graphene in gas sensing detection at present.Based on this, three different modification methods including metal doping, functional group functionalization, doping and functional group functionalization co-modification were selected to improve the gas sensitivity of intrinsic graphene to H₂S.
Firstly, the modification models of epoxy graphene (G-O), palladium doped graphene (Pd-G) and epoxy and palladium Co-doped graphene (Pd-G-O) are established, and the modification mechanism is analyzed. Secondly, the adsorption models of modified graphene for H₂S are built, and the adsorption effect of H₂S is analyzed from adsorption energy, density of state, orbitand desorption time.Thirdly, G-O, Pd-G and Pd-G-O sensing materials and planar gas sensors are prepared based on the oxidation-reduction method and drop coating method. The gas sensing performance for H₂S are tested based on the micro gas sensing test platform.Finally, the response ability of the modified graphene sensors to H₂S is evaluated from temperature characteristics, concentration characteristics, response-recovery characteristics and stability.
The simulation results of the modified models show that, the epoxy group effectively increases the energy gap of intrinsic graphene, from 0.049 eV to 0.218 eV. The doping of Pd introduces a new impurity level at the Fermi level, which effectively improves the charge transfer of intrinsic graphene. Through the co-doping of epoxy group and Pd, the energy gap reaches 0.214 eV, and the graphene system is more stable and the charge transfer ability is enhanced. In G-O adsorbing H₂S system, the adsorption energy and charge transfer are -1.326 eV and 0.003 e, respectively. The adsorption energy is the largest, but the charge transfer capacity is extremely weak.In the system of H₂S adsorbed on Pd-G, the charge transfer is 0.254 e, and the minimum adsorption energy is -0.897 eV. In Pd-G-O adsorbing H₂S system, the co-modified graphene system shows the best adsorption performance, with the adsorption energy of -1.015 eV, which corresponds to a strong charge transfer value of 0.281 e. The results of gas sensitivity test show that, the optimum working temperature of G-O, Pd-G and Pd-G-O sensors is 225, 175 and 175 ℃ respectively. The lower detection limits for H₂S are 6.9, 2.3, 0.5 μL/L. The response recovery time of Pd-G-O to 50 μL/L of H₂S is 23/18 s. The response value is 10.02, which is the 1.818 and 1.538 times of that of G-O and Pd-G.
The following conclusions can be drawn from the analysis: 1) The stability and charge transfer ability of Pd-G-O system have been improved. The energy gap of intrinsic graphene is increased and metal energy level appears at Fermi energy level through the co-doping of epoxy group and Pd. 2) G-O, Pd-G, Pd-G-O improved the adsorption performance of intrinsic graphene for H₂S. The Absolute value of adsorption energy is G-O>Pd-G-O>Pd-G; The charge transfer value is Pd-G-O>Pd-G>G-O. Among them, Pd-G-O shows great adsorption effect and charge transfer ability, attributing to the strong hybridization between the S 3p orbital and the Pd 4d orbital. 3) Pd-G-O sensor shows excellent gas sensing performance, and can be used as a promising gas sensor material for detecting H₂S. Pd-G-O gas sensor shows the advantages of low operating temperature, low detection limit and high response value, suitable for the detection of trace H₂S.

Key words： Modified graphene SF₆ decomposed component H₂S detection adsorption mechanism detection characteristics

收稿日期: 2022-05-17

PACS:

TM855

基金资助:国家自然科学基金资助项目（52077177）

通讯作者: 周渠男,1983年生,教授,博士生导师,研究方向为电力设备在线监测与故障诊断。E-mail：zhouqu@swu.edu.cn

作者简介: 高新女,1998年生,硕士研究生,研究方向为电力设备在线监测与故障诊断。E-mail：1289547142@qq.com.

引用本文:

高新, 李志慧, 刘宇鹏, 陈伟根, 周渠. 改性石墨烯基传感器对SF₆分解组分H₂S的吸附机理及检测特性研究[J]. 电工技术学报, 0, (): 19-19. Gao Xin, Li Zhihui, Liu Yupeng, Chen Weigen, Zhou Qu. Study on Adsorption Mechanism and Detection Characteristics of Modified Graphene Sensors for SF₆ Decomposed Component H₂S. Transactions of China Electrotechnical Society, 0, (): 19-19.

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