锐钛矿型(101)晶面吸附SF_6局部放电分解组分的气敏机理分析
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摘要
气体绝缘组合开关(GIS)内部的局部放电会导致绝缘气体SF_6分解,生成多种特征气体。通过检测特征气体的成分和浓度能够及早发现GIS设备内部潜伏性绝缘缺陷,在设备绝缘状况恶化前提前预警,避免突发性故障发生。作为气敏传感领域的研究热点,TiO_2纳米管在GIS故障气体监测领域应用前景广阔。该文从微观层面上研究TiO_2纳米管气体传感器的气敏机理。利用Materials Studio软件仿真计算了锐钛矿型TiO_2(101)晶面的完美晶面、缺陷晶面以及Pt掺杂晶面对特征气体SO_2、SOF_2、SO_2F_2的吸附参数,理论分析了气体分子与晶面的作用过程,建立起晶面导电性能与气体分子吸附的联系。此外,通过气敏实验研究了本征及Pt掺杂TiO_2纳米管传感器对SO_2、SOF_2、SO_2F_2的气敏响应,并基于仿真结果解释实验现象,完善了TiO_2纳米管的气敏机理,为制备GIS设备局部放电监测的气敏传感器奠定了基础。
Partial discharge in gas-insulated switchgears( GIS) would lead to decomposition of insulating gas SF_6,with several kinds of characteristic gases produced. By detecting species and concentrations of these gases,insulating defects in gas-insulated switchgears can be discovered in time,which is essential in avoiding sudden faults of power system. TiO_2 nanotubes gas sensors as possess wide prospect in online monitoring of gasinsulated switchgears has broad application prospects. This paper focuses on the gas-sensing mechanism of TiO_2 nanotubes to SF6 decomposed components from micro level. Materials Studio was adopted to conduct simulation of SO_2,SOF_2,and SO_2F_2 adsorption on anatase( 101) with perfect surface,defect surface and Pt-doped surface.As a result,interaction of gas adsorption and conductive performance of anatase( 101) surface were analyzed.Furthermore,gas-sensing experiment was also conducted to research the gas sensitive response of Pt doped and TiO_2 nanotube sensor to SO_2,SOF_2,and SO_2F_2,of which the results consisted with simulation analysis. Both simulation and experiment provide theoretical and practical basis on detection of SF_6 decomposition using TiO_2 nanotube gas sensors.
Partial discharge in gas-insulated switchgears( GIS) would lead to decomposition of insulating gas SF_6,with several kinds of characteristic gases produced. By detecting species and concentrations of these gases,insulating defects in gas-insulated switchgears can be discovered in time,which is essential in avoiding sudden faults of power system. TiO_2 nanotubes gas sensors as possess wide prospect in online monitoring of gasinsulated switchgears has broad application prospects. This paper focuses on the gas-sensing mechanism of TiO_2 nanotubes to SF6 decomposed components from micro level. Materials Studio was adopted to conduct simulation of SO_2,SOF_2,and SO_2F_2 adsorption on anatase( 101) with perfect surface,defect surface and Pt-doped surface.As a result,interaction of gas adsorption and conductive performance of anatase( 101) surface were analyzed.Furthermore,gas-sensing experiment was also conducted to research the gas sensitive response of Pt doped and TiO_2 nanotube sensor to SO_2,SOF_2,and SO_2F_2,of which the results consisted with simulation analysis. Both simulation and experiment provide theoretical and practical basis on detection of SF_6 decomposition using TiO_2 nanotube gas sensors.
引文
[1]唐炬,陈长杰,张晓星,等.微氧对SF6局部放电分解特征组份的影响[J].高电压技术,2011,37(1):8-14.Tang Ju,Chen Changjie,Zhang Xiaoxing,et al.Influence of trace-level O2on SF6decomposition characteristics under partial discharge[J].High Voltage Engineering,2011,37(1):8-14.
[2]颜湘莲,王承玉,季严松,等.气体绝缘设备中SF6气体分解产物与设备故障关系的建模[J].电工技术学报,2015,30(22):231-238.Yan Xianglian,Wang Chengyu,Ji Yansong,et al.Modeling of the relation between SF6decomposition products andinterior faults in gas insulated equipment[J].Transactions of China Electrotechnical Society,2015,30(22):231-238.
[3]Casanovas A,Casanovas J,Lagarde F,et al.Study of the decomposition of SF6under DC negative polarity corona discharges(point to plane geometry):influence of the metal constituting the plane electrode[J].Journal of Applied Physics,1992,72(8):3344-3354.
[4]Derdouri A,Casanovas J,Hergli R,et al.Study of the decomposition of wet SF6,subjected to 50 Hz AC corona discharges[J].Journal of Applied Physics,1989,65(5):1852-1857.
[5]郑晓光,郑宇,唐念,等.GIS内环氧树脂绝缘沿面放电强度与产气关联规律的模拟实验[J].电工技术学报,2015,30(17):172-179.Zheng Xiaoguang,Zheng Yu,Tang Nian,et al.Analog experiment on the relationship between the intensity ofepoxy solid insulation surface discharge and the increasing law of characteristic gases in GIS[J].Transactions of China Electrotechnical Society,2015,30(17):172-179.
[6]杨志超,范立新,杨成顺,等.基于GK模糊聚类和LS-SVC的GIS局部放电类型识别[J].电力系统保护与控制,2014,42(20):38-45.Yang Zhichao,Fan Lixin,Yang Chengshun,et al.Identification of partial discharge in gas insulated switchgears based on GK fuzzy clustering&LS-SVM[J].Power System Protection and Control,2014,42(20):38-45.
[7]林涛,韩冬,钟海峰,等.工频交流电晕放电下SF6气体分解物形成的影响因素[J].电工技术学报,2014,29(2):219-225.Lin Tao,Han Dong,Zhong Haifeng,et al.Influence factors of formation of decomposition by-products of SF6in 50 Hz AC corona discharge[J].Transactions of China Electrotechnical Society,2014,29(2):219-225.
[8]Yang D,Fuadi M K,Kang K,et al.Multiplexed gas sensor based on heterogeneous metal oxide nanomaterial array enabled by localized liquid-phase reaction[J].Acs Applied Materials&Interfaces,2015,7(19):10152-10161.
[9]Sotter E,Llobet E,Espinosa E H,et al.New Ti O2and Carbon nanotube hybrid microsensors for detecting traces of O2in beverage grade CO2[C]//International Solid-State Sensors,Actuators and Microsystems Conference,Lyon,France,2007:1039-1042.
[10]宣天美,尹桂林,葛美英,等.纳米Zn O气敏传感器研究进展[J].材料导报,2015,29(1):132-136.Xuan Tianmei,Yin Guilin,Ge Meiying,et.al.Research progress on Nano-Zn O gas sensors[J].Materials Review,2015,29(1):132-136.
[11]Zhu Chunling,Yu Hailong,Zhang Yue,et al.Fe2O3/Ti O2tube-like nanostructures:synthesis,structural transformation and the enhanced sensing properties[J].Acs Applied Materials&Interfaces,2012,4(2):665-671.
[12]Yu Yunpeng,Liu W,Wu Shuxiang,et al.Impact of nitrogen doping on electrical conduction in anatase Ti O2thin films[J].Journal of Physical Chemistry C,2012,116(37):19625-19629.
[13]周沙,景亮.基于矩特征与概率神经网络的局部放电模式识别[J].电力系统保护与控制,2016,44(3):98-102.Zhou Sha,Jing Liang.Pattern recognition of partial discharge based on moment features and probabilistic neural network[J].Power System Protection and Control,2016,44(3):98-102.
[14]王涛云,马宏忠,崔杨柳,等.基于可拓分析和熵值法的GIS状态评估[J].电力系统保护与控制,2016,44(8):115-120.Wang Taoyun,Ma Hongzhong,Cui Yangliu,et al.Condition evaluation of gas insulated switchgear based on extension analysis and entropy method[J].Power System Protection and Control,2016,44(8):115-120.
[15]Qiu J,Zhang S,Zhao H.Recent applications of Ti O2nanomaterials in chemical sensing in aqueous media[J].Sensors&Actuators B Chemical,2011,160(1):875-890.
[16]Moon H G,Shim Y S,Dong S,et al.Embossed Ti O2thin films with tailored links between hollow hemispheres:synthesis and gas-sensing properties[J].Journal of Physical Chemistry C,2011,115(20):9993-9999.
[17]Lee J,Dai H K,Hong S H,et al.A hydrogen gas sensor employing vertically aligned Ti O2nanotube arrays prepared by template-assisted method[J].Sensors&Actuators B Chemical,2011,160(1):1494-1498.
[18]Chaudhari G N,Bambole D R,Bodade A B,et al.Characterization of nanosized Ti O2based H2S gas sensor[J].Journal of Materials Science,2006,41(15):4860-4864.
[19]Zen Wen,Liu Tianmo,Wang Zhongchang,et al.Selective detection of formaldehyde gas using a Cd-doped Ti O2-Sn O2sensor[J].Sensors,2009,9(11):9029-9038.
[20]Mohammadi M R,Fray D J,Cordero-Cabrera M C.Sensor performance of nanostructured Ti O2thin films derived from particulate sol-gel route and polymeric fugitive agents[J].Sensors&Actuators B:Chemical,2007,124(1):74-83.
[21]Traversa E,Vona M L D,Licoccia S,et al.Sol-Gel processed Ti O2-based nano-sized powders for use in thick-film gas sensors for atmospheric pollutant monitoring[J].Journal of Sol-Gel Science and Technology,2001,22(1):167-179.
[22]王道爱,刘盈,王成伟,等.阳极氧化法制备Ti O2纳米管阵列膜及其应用[J].化学进展,2010,22(6):1035-1043.Wang Daoai,Liu Ying,Wang Chengwei,et al.Ti O2nanotube arrays fabricated by anodization[J].Progress in Chemistry,2010,22(6):1035-1043.
[23]Zhang X,Zhang J,Jia Y,Xiao P,et al.Ti O2nanotube array sensor for detecting the SF6decomposition product SO2[J].Sensors,2012,12(3):3302-3313.
[24]张晓星,吴法清,铁静,等.二氧化钛纳米管气体传感器检测SF6的气体分解组分SO2F2的气敏特性[J].高电压技术,2014,40(11):1003-6520.Zhang Xiaoxing,Wu Faqing,Tie Jing,et al.Ti O2nanotube array sensor for detecting SF6decomposition component SO2F2[J].High Voltage Engineering,2014,40(11):1003-6520.
[25]Zhang X,Tie J,Zhang J.A Pt-doped Ti O2nanotube arrays sensor for detecting SF6decomposition products[J].Sensors,2013,12:14764-14776.
[26]Zhang Xiaoxing,Yu Lei,Tie Jing.Gas sensitivity and sensing mechanism studies on Au-doped Ti O2nanotube arrays for detecting SF6decomposed components[J].Sensors,2014,14(10):19517-19532.
[27]Zhang Xiaoxing,Tie Jing,Chen Qinchuan,et al.Ptdoped Ti O2-based sensors for detecting SF6decomposition components[J].IEEE Transactions on Dielectrics and Electrical Insulation,2015,22(3):1559-1566.
[28]Sunyong H,Hyunah K,Sameer C,et al.A near single crystalline Ti O2nanohelix array:enhanced gas sensing performance and its application as a monolithically integrated electronic nose[J].Analyst,2013,138(2):443-450.
[29]Perdew J P,Wang Y.Accurate and simple analytic representation of the electron-gas correlation energy[J].Physical Review B,1992,45(23):13244-13249.
[30]Monkhorst H,Pack J.Special points for Brillouin-zone integrations[J].Physical Review B,1976,13(12):5188-5192.
[31]Cheng Z,Liu T,Yang C,et al.Ab initio atomic thermodynamics investigation on oxygen defects in the anatase Ti O2[J].Journal of Alloys and Compounds,2013,546(5):246-252.
[32]Sheng J X,Yoshida N,Karasawa J,et al.Investigation of platinum-doped Ti O2film lambda-sensor[J].Sens Mater,1997(9):97-106.
[33]Walton R M,Dwyer D J,Schwank J W,et al.Gas sensing based on surface oxidation/reduction of platinumtitania thin films I.Sensing film activation and characterization[J].Applied Surface Science,1998,125(2):187-198.
[34]Zhang Maolin,Yuan Zhanheng,Song Jianping,et al.Improvement and mechanism for the fast response of a Pt/Ti O2gas sensor[J].Sensors&Actuators B Chemical,2010,148(1):87-92.
[2]颜湘莲,王承玉,季严松,等.气体绝缘设备中SF6气体分解产物与设备故障关系的建模[J].电工技术学报,2015,30(22):231-238.Yan Xianglian,Wang Chengyu,Ji Yansong,et al.Modeling of the relation between SF6decomposition products andinterior faults in gas insulated equipment[J].Transactions of China Electrotechnical Society,2015,30(22):231-238.
[3]Casanovas A,Casanovas J,Lagarde F,et al.Study of the decomposition of SF6under DC negative polarity corona discharges(point to plane geometry):influence of the metal constituting the plane electrode[J].Journal of Applied Physics,1992,72(8):3344-3354.
[4]Derdouri A,Casanovas J,Hergli R,et al.Study of the decomposition of wet SF6,subjected to 50 Hz AC corona discharges[J].Journal of Applied Physics,1989,65(5):1852-1857.
[5]郑晓光,郑宇,唐念,等.GIS内环氧树脂绝缘沿面放电强度与产气关联规律的模拟实验[J].电工技术学报,2015,30(17):172-179.Zheng Xiaoguang,Zheng Yu,Tang Nian,et al.Analog experiment on the relationship between the intensity ofepoxy solid insulation surface discharge and the increasing law of characteristic gases in GIS[J].Transactions of China Electrotechnical Society,2015,30(17):172-179.
[6]杨志超,范立新,杨成顺,等.基于GK模糊聚类和LS-SVC的GIS局部放电类型识别[J].电力系统保护与控制,2014,42(20):38-45.Yang Zhichao,Fan Lixin,Yang Chengshun,et al.Identification of partial discharge in gas insulated switchgears based on GK fuzzy clustering&LS-SVM[J].Power System Protection and Control,2014,42(20):38-45.
[7]林涛,韩冬,钟海峰,等.工频交流电晕放电下SF6气体分解物形成的影响因素[J].电工技术学报,2014,29(2):219-225.Lin Tao,Han Dong,Zhong Haifeng,et al.Influence factors of formation of decomposition by-products of SF6in 50 Hz AC corona discharge[J].Transactions of China Electrotechnical Society,2014,29(2):219-225.
[8]Yang D,Fuadi M K,Kang K,et al.Multiplexed gas sensor based on heterogeneous metal oxide nanomaterial array enabled by localized liquid-phase reaction[J].Acs Applied Materials&Interfaces,2015,7(19):10152-10161.
[9]Sotter E,Llobet E,Espinosa E H,et al.New Ti O2and Carbon nanotube hybrid microsensors for detecting traces of O2in beverage grade CO2[C]//International Solid-State Sensors,Actuators and Microsystems Conference,Lyon,France,2007:1039-1042.
[10]宣天美,尹桂林,葛美英,等.纳米Zn O气敏传感器研究进展[J].材料导报,2015,29(1):132-136.Xuan Tianmei,Yin Guilin,Ge Meiying,et.al.Research progress on Nano-Zn O gas sensors[J].Materials Review,2015,29(1):132-136.
[11]Zhu Chunling,Yu Hailong,Zhang Yue,et al.Fe2O3/Ti O2tube-like nanostructures:synthesis,structural transformation and the enhanced sensing properties[J].Acs Applied Materials&Interfaces,2012,4(2):665-671.
[12]Yu Yunpeng,Liu W,Wu Shuxiang,et al.Impact of nitrogen doping on electrical conduction in anatase Ti O2thin films[J].Journal of Physical Chemistry C,2012,116(37):19625-19629.
[13]周沙,景亮.基于矩特征与概率神经网络的局部放电模式识别[J].电力系统保护与控制,2016,44(3):98-102.Zhou Sha,Jing Liang.Pattern recognition of partial discharge based on moment features and probabilistic neural network[J].Power System Protection and Control,2016,44(3):98-102.
[14]王涛云,马宏忠,崔杨柳,等.基于可拓分析和熵值法的GIS状态评估[J].电力系统保护与控制,2016,44(8):115-120.Wang Taoyun,Ma Hongzhong,Cui Yangliu,et al.Condition evaluation of gas insulated switchgear based on extension analysis and entropy method[J].Power System Protection and Control,2016,44(8):115-120.
[15]Qiu J,Zhang S,Zhao H.Recent applications of Ti O2nanomaterials in chemical sensing in aqueous media[J].Sensors&Actuators B Chemical,2011,160(1):875-890.
[16]Moon H G,Shim Y S,Dong S,et al.Embossed Ti O2thin films with tailored links between hollow hemispheres:synthesis and gas-sensing properties[J].Journal of Physical Chemistry C,2011,115(20):9993-9999.
[17]Lee J,Dai H K,Hong S H,et al.A hydrogen gas sensor employing vertically aligned Ti O2nanotube arrays prepared by template-assisted method[J].Sensors&Actuators B Chemical,2011,160(1):1494-1498.
[18]Chaudhari G N,Bambole D R,Bodade A B,et al.Characterization of nanosized Ti O2based H2S gas sensor[J].Journal of Materials Science,2006,41(15):4860-4864.
[19]Zen Wen,Liu Tianmo,Wang Zhongchang,et al.Selective detection of formaldehyde gas using a Cd-doped Ti O2-Sn O2sensor[J].Sensors,2009,9(11):9029-9038.
[20]Mohammadi M R,Fray D J,Cordero-Cabrera M C.Sensor performance of nanostructured Ti O2thin films derived from particulate sol-gel route and polymeric fugitive agents[J].Sensors&Actuators B:Chemical,2007,124(1):74-83.
[21]Traversa E,Vona M L D,Licoccia S,et al.Sol-Gel processed Ti O2-based nano-sized powders for use in thick-film gas sensors for atmospheric pollutant monitoring[J].Journal of Sol-Gel Science and Technology,2001,22(1):167-179.
[22]王道爱,刘盈,王成伟,等.阳极氧化法制备Ti O2纳米管阵列膜及其应用[J].化学进展,2010,22(6):1035-1043.Wang Daoai,Liu Ying,Wang Chengwei,et al.Ti O2nanotube arrays fabricated by anodization[J].Progress in Chemistry,2010,22(6):1035-1043.
[23]Zhang X,Zhang J,Jia Y,Xiao P,et al.Ti O2nanotube array sensor for detecting the SF6decomposition product SO2[J].Sensors,2012,12(3):3302-3313.
[24]张晓星,吴法清,铁静,等.二氧化钛纳米管气体传感器检测SF6的气体分解组分SO2F2的气敏特性[J].高电压技术,2014,40(11):1003-6520.Zhang Xiaoxing,Wu Faqing,Tie Jing,et al.Ti O2nanotube array sensor for detecting SF6decomposition component SO2F2[J].High Voltage Engineering,2014,40(11):1003-6520.
[25]Zhang X,Tie J,Zhang J.A Pt-doped Ti O2nanotube arrays sensor for detecting SF6decomposition products[J].Sensors,2013,12:14764-14776.
[26]Zhang Xiaoxing,Yu Lei,Tie Jing.Gas sensitivity and sensing mechanism studies on Au-doped Ti O2nanotube arrays for detecting SF6decomposed components[J].Sensors,2014,14(10):19517-19532.
[27]Zhang Xiaoxing,Tie Jing,Chen Qinchuan,et al.Ptdoped Ti O2-based sensors for detecting SF6decomposition components[J].IEEE Transactions on Dielectrics and Electrical Insulation,2015,22(3):1559-1566.
[28]Sunyong H,Hyunah K,Sameer C,et al.A near single crystalline Ti O2nanohelix array:enhanced gas sensing performance and its application as a monolithically integrated electronic nose[J].Analyst,2013,138(2):443-450.
[29]Perdew J P,Wang Y.Accurate and simple analytic representation of the electron-gas correlation energy[J].Physical Review B,1992,45(23):13244-13249.
[30]Monkhorst H,Pack J.Special points for Brillouin-zone integrations[J].Physical Review B,1976,13(12):5188-5192.
[31]Cheng Z,Liu T,Yang C,et al.Ab initio atomic thermodynamics investigation on oxygen defects in the anatase Ti O2[J].Journal of Alloys and Compounds,2013,546(5):246-252.
[32]Sheng J X,Yoshida N,Karasawa J,et al.Investigation of platinum-doped Ti O2film lambda-sensor[J].Sens Mater,1997(9):97-106.
[33]Walton R M,Dwyer D J,Schwank J W,et al.Gas sensing based on surface oxidation/reduction of platinumtitania thin films I.Sensing film activation and characterization[J].Applied Surface Science,1998,125(2):187-198.
[34]Zhang Maolin,Yuan Zhanheng,Song Jianping,et al.Improvement and mechanism for the fast response of a Pt/Ti O2gas sensor[J].Sensors&Actuators B Chemical,2010,148(1):87-92.