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CN102081067A - Carbon nanotube film ionized nitrogen dioxide sensor and its concentration measurement method - Google Patents

Carbon nanotube film ionized nitrogen dioxide sensor and its concentration measurement method Download PDF

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CN102081067A
CN102081067A CN2011100384883A CN201110038488A CN102081067A CN 102081067 A CN102081067 A CN 102081067A CN 2011100384883 A CN2011100384883 A CN 2011100384883A CN 201110038488 A CN201110038488 A CN 201110038488A CN 102081067 A CN102081067 A CN 102081067A
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electrode
nitrogen dioxide
sensor
carbon nanotube
dioxide gas
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CN102081067B (en
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张勇
方静
王进
张晶园
姜为华
宋晓慧
王影花
张建业
牛国平
王晓冰
李昕
唐建文
刘君华
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Xian Jiaotong University
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Xian Jiaotong University
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Abstract

The invention discloses a carbon nanotube film ionization type nitrogen dioxide sensor and a concentration measurement method thereof, wherein the sensor comprises a first electrode, a second electrode and a third electrode which are sequentially distributed, the first electrode is provided with air holes, and the inner surface of the first electrode is attached with a metal film substrate distributed with a carbon nanotube film; the center of the second electrode is provided with a lead-out hole; a blind hole is formed in the surface of the third electrode; the three electrodes are isolated from each other. The method comprises the following steps: 1) placing three sensors with different inter-polar distances; 2) applying a voltage across the electrodes; 3) measuring ion flow values of the sensors; 4) the measured value and the calibration values of the concentration, the temperature and the humidity of the nitrogen dioxide gas form a sample, and the sample and an interpolation sample construct a gas concentration measurement database; 5) constructing a data fusion instrument and establishing an accurate measurement model of the concentration of the nitrogen dioxide gas; 6) and inputting the actual measurement value of the sensor into the measurement model to obtain the accurate measurement value of the concentration of the nitrogen dioxide gas. The sensor has the advantages of high gas detection sensitivity, good linearity and high accuracy.

Description

Carbon nano-tube film ionization type nitrogen dioxide sensor and concentration measuring method thereof
Technical field
The present invention relates to the gas sensing field, particularly a kind of based on the ionization type nitrogen dioxide sensor of carbon nano-tube film and gas discharge principle and the method for measurement content of nitrogen dioxide thereof.
Background technology
Along with pressing for and the development of nanometer technology of all trades and professions gasmetry, nano-sensor has obtained considerable progress.Especially along with the discovery of carbon nano-tube in latter stage in 20th century, carbon nano-tube shows tempting application prospect in gas, temperature, moisture measurement field.Carbon nano-tube film two electrode ionizing transducers in carbon nano-tube gas-sensitive, temperature sensitive, the moisture sensor, advantage such as, measurement gas wide ranges highly sensitive with its measurement, response are fast becomes the research focus in gas, temperature, moisture measurement field.Carbon nano-tube film two electrode Gas-Sensitive Sensor of Ionized Type have overcome the shortcoming of carbon nano-tube gas-sensitive sensors saturated poisoning in tested gas of other type based on gas discharge principle, and gas concentration measurement scope and tested gaseous species scope are wideer.As air-sensitive, temperature sensitive, moisture sensor that sensitive material constitutes, have the irreplaceable advantage of conventional sensors with carbon nano-tube: the one, the specific surface area of carbon nano-tube is big, under the less situation of sensor overall dimensions, can improve the area of electrode greatly; Two are based on the tip curvature radius of carbon nanotube level, and working sensor voltage is greatly reduced, and obtain extremely strong electric field intensity near the carbon nano-tube tip, make tested gas ionization under low-voltage; The 3rd, the size of having dwindled sensor greatly, dynamic response is fast.Therefore, it has result of extraction at aspects such as biology, chemistry, machinery, aviation, military affairs, anti-terrorisms.
Existing carbon nano-tube film two electrode ionizing transducers comprise by people such as Liu Junhua, the Zhang Yong of Xi'an Communications University, Li Xin, professors Zhu Changchun at the disclosed carbon nano-tube film two electrode ionization type gas sensors (shown in Figure 1) of the international vaccum microelectronics international conference of the 14th IVMC of calendar year 2001.This working sensor is afterwards because interpolar discharge rear space electric charge is difficult to diffusion, sensor is difficult to return to original state, and (Fig. 2 Fig. 3), can't measure gas concentration to present multivalued relation between sensor voltage breakdown, breakdown current and the gas concentration.People such as Nikhil Koratkar of U.S. Rensselaer Polytech Inst (Rensselaer Polytechnic Institute) and Pulickel M professor Ajayan have developed carbon nano-tube film anode two-electrode gas sensor.Present nonlinear relationship between this sensor voltage breakdown and the gas concentration, linear error is bigger between disruptive discharge electric current and the gas concentration; Sparking voltage and discharge current are bigger; Can't realize of the measurement of carbon nano-tube film anode to pure gas.The Hui Guohua of Zhejiang University's biomedical engineering and instrumental science institute, Chen Yuquan professor develops carbon nano-tube thin film cathode two-electrode gas sensor under the condition of 120 microns die openings, studied the flash-over characteristic of sensor in three kinds of pure gases, because sensitivity is lower, do not constitute the gas sensor of measuring concentration.
Therefore, at present all kinds of pure gases of sensitivity are comprised the carbon nano-tube film ionizing transducer of nitrogen dioxide and the research of measuring the method for nitrogen dioxide pure gas concentration thereof, become the technical matters that needs to be resolved hurrily.
Summary of the invention
One of purpose of the present invention, provide a kind of carbon nano-tube film ionization type nitrogen dioxide sensor, the output current of conventional carbon nano-tube film two electrode sensors is divided into electron stream and ion flow, set up the single-valued relationship of ion flow that ionization type nitrogen dioxide sensor collector of the present invention collects and nitrogen dioxide gas concentration, temperature, humidity, overcome carbon nano-tube film two electrode sensor gas concentration sensitivity characteristics and the many-valued nonlinear problem of the quick characteristic that wets.This sensor construction is simple, and cost is low, and detected gas is highly sensitive.
Another object of the present invention, provide a kind of method that detects nitrogen dioxide gas concentration based on carbon nano-tube film ionization type nitrogen dioxide sensor, form sensor array by different poles spacing carbon nano-tube film ionizing transducer, measure nitrogen dioxide gas concentration to be measured, gas temperature and humidity respectively; The hardware configuration that this concentration measuring method requires is simple, adopts data anastomosing algorithm, detected gas accuracy height.
The objective of the invention is to realize by following technical proposals.
Carbon nano-tube film ionization type nitrogen dioxide sensor, it is characterized in that: comprise three first electrode, second electrode and third electrodes that distribute successively from top to bottom, the electrode that described first electrode adheres to the metallic film base that the carbon nano-tube film that distributing is arranged by inside surface and is provided with bleeder vent constitutes; Second electrode is made of the extraction pole pole plate that the center is provided with fairlead; Third electrode is made of the collector that the plate face is provided with blind hole; These three electrodes are isolated mutually by insulation column respectively.
Architectural feature of the present invention also is:
Adjacent two interelectrode die openings are 30~250 μ m in described three electrodes;
Described first electrode and second electrode pad are 0.01~170mm over against area 2, second electrode and third electrode pole plate are 0.01~190mm over against area 2
The bleeder vent of the electrode surface of described first electrode is 1~4, and growth or serigraphy have carbon nano-tube film on the metallic film base that the electrode inner surface adheres to;
The described second electrode extraction pole center is provided with 1~4 fairlead;
Described third electrode collector blind hole is corresponding with the fairlead of second electrode, and the quantity of blind hole is 1~4.
The present invention gives a kind of method based on carbon nano-tube film ionization type nitrogen dioxide sensor measurement nitrogen dioxide gas concentration, and this method comprises the steps:
(1) die opening of three adjacent two electrodes of electrode of selection is set at the carbon nano-tube film ionizing transducer of 30~250 μ m;
The carbon nano-tube film ionization type nitrogen dioxide sensor of three different poles spacings (2) will setting respectively, carbon nano-tube film ionization type temperature sensor, carbon nano-tube film ionization type humidity sensor are placed in the atmosphere that contains nitrogen dioxide gas to be measured;
(3) be 0V to the first electrode on-load voltage of three carbon nano-tube film ionization type nitrogen dioxide sensors, temperature sensor and humidity sensors respectively, the second electrode on-load voltage, 2~200V, third electrode on-load voltage 1~180V;
(4) in nitrogen dioxide gas concentration to be measured, temperature and humidity measurement range, corresponding different concentration, temperature and humidity calibration value, the gas discharge ion flow valuve of all the sensors output in the measuring process (2) respectively;
(5) with all the sensors output ion flow valuve that in concentration, temperature and humidity measurement range, records in the step (4), with corresponding nitrogen dioxide gas concentration, temperature and humidity calibration value, form different samples, form different experimental calibration samples, adopt the piecewise interpolation technology that the experimental calibration sample is carried out interpolation then, obtain interpolated data, obtain interpolated sample, and set up the nitrogen dioxide gas concentration measured database according to all samples that comprised experimental calibration sample and interpolated sample;
(6) adopt the data fusion technology, make up the data fusion instrument, set up the measurement model of nitrogen dioxide sensor, temperature sensor and humidity sensor; With input sample and the desired output sample of the data in the nitrogen dioxide gas concentration measured database as the data fusion instrument, and train and check as the training sample and the test samples of data fusion instrument respectively with data different in the range ability, when assay satisfies the measurement error requirement, the accurate measurement model of concentration of data fusion instrument output nitrogen dioxide sensor;
The accurate measurement model of nitrogen dioxide gas concentration that the ion flow valuve input step (6) of output obtains during (7) with carbon nano-tube film ionization type nitrogen dioxide sensor, temperature sensor and humidity sensor actual measurement, the accurate measured value of this model output nitrogen dioxide gas concentration.
The inventive method feature also is:
In the described carbon nano-tube film ionization type nitrogen dioxide sensor, second electrode potential is higher than first electrode potential, and the third electrode current potential is lower than second electrode potential and is higher than first electrode potential.
The described nitrogen dioxide gas concentration measured database of setting up, be that experimental calibration data and interpolated data are formed database, with each sensor output ion flow valuve and interpolated data thereof as the input sample, with nitrogen dioxide gas concentration, temperature and humidity calibration value and interpolated data thereof as the desired output sample.
Based on the nitrogen dioxide gas concentration measuring method of carbon nano-tube film ionization type nitrogen dioxide sensor, form sensor array by different poles spacing carbon nano-tube film ionizing transducer and measure nitrogen dioxide gas concentration to be measured, temperature and humidity respectively; Power by the sensor electrical potential source; Export by pA level current measurement system detecting sensor; Adjust electrode separation, adjust electrode voltage, in nitrogen dioxide gas to be measured, in temperature, humidity environment, carry out the calibration experiment of sensor; Based on the piecewise interpolation technology experimental calibration data are carried out interpolation, obtain interpolated data; All data that will comprise experimental calibration data and interpolated data are formed the nitrogen dioxide gas concentration measured database, obtain monodrome gas-sensitive property, monodrome responsive to temperature characteristic, the monodrome humidity sensitive characteristic of nitrogen dioxide gas to be measured; According to the data in the nitrogen dioxide gas concentration measured database, based on piecewise interpolation technology and data fusion technology, eliminate the influence of temperature, humidity, set up the accurate measurement model of concentration of nitrogen dioxide gas sensor; The nitrogen dioxide gas concentration measurement model is imported in the output of sensor array in real time during with actual measurement, just can obtain the measured result of nitrogen dioxide gas concentration.This nitrogen dioxide gas concentration measuring method has overcome the many-valued nonlinear problem of carbon nano-tube film two electrode sensor gas-sensitive properties and wet quick characteristic, the hardware configuration that requires is simple, the energy measurement nitrogen dioxide gas, adopt data anastomosing algorithm, cost is low, detected gas is highly sensitive, accuracy is high, is suitable for promoting the use of.
Nitrogen dioxide gas concentration detection method of the present invention can realize the measurement of concetration of nitrogen dioxide gas, and accuracy is 1%.The gas concentration detection method of tradition three electrode probes that use in this new gas concentration detection method and the existing ionization detector chromatograph is compared, because adopt carbon nano-tube film to do electrode, sensor has the measurement of concetration accuracy of high sensitivity and 1% to nitrogen dioxide gas.And the carbon nano-tube film ionizing transducer can be realized working sensor voltage with the tip curvature radius of carbon nanotube level, from the safe and practical scope below 600 volts of high pressure drop to 200 volts of ionization detector.Novel nitrogen dioxide gas concentration measuring method of the present invention integrates sensor array technology, pA level current measurement techniques, piecewise interpolation technology and the data fusion technology of different poles spacing, the influence of temperature, humidity can be eliminated, the accurate measurement of nitrogen dioxide gas concentration can be realized.
Description of drawings
Fig. 1 is prior art carbon nano-tube thin film cathode two electrode sensor structural representations.
Fig. 2 is the voltage breakdown of prior art carbon nano-tube film two-electrode gas sensor and the many-valued non-linear gas-sensitive property of gas concentration.
Fig. 3 is the breakdown current of prior art carbon nano-tube film two-electrode gas sensor and the non-linear many-valued gas-sensitive property of gas concentration.
Fig. 4 is a carbon nano-tube film ionization type nitrogen dioxide sensor structural representation of the present invention;
Fig. 5 is a carbon nano-tube film ionization type nitrogen dioxide sensor spatial structure side view of the present invention.
Fig. 6 is the gas discharge ion flow of carbon nano-tube film ionization type nitrogen dioxide sensor output of the present invention and the single valued relation of nitrogen dioxide gas concentration;
Among the figure: 1, first electrode; 2, second electrode; 3, third electrode; 4, be provided with the electrode of bleeder vent; 5, metallic film base; 6, carbon nano-tube film; 7, insulation column.
Embodiment
The present invention will be further described below in conjunction with drawings and the specific embodiments.
Embodiment 1
As Fig. 4, shown in Figure 5, this carbon nano-tube film ionization type nitrogen dioxide sensor, comprise by three successively from top to bottom the electrode of mutual superposition constitute, these three mutual superposition electrodes are respectively equipped with first electrode 1, second electrode 2 and third electrode 3, and described first electrode adheres to the metallic film base 5 that the carbon nano-tube film that distributing is arranged by inside surface and the electrode 4 that is provided with bleeder vent constitutes; Second electrode 2 is made of the extraction pole pole plate that the center is provided with fairlead; Third electrode 3 is made of the collector that the battery lead plate face is provided with blind hole; These three electrodes are isolated mutually by insulation column 7 respectively.
Among the carbon nano-tube film ionization type nitrogen dioxide sensor embodiment shown in Figure 4, the bleeder vent of the electrode surface of first electrode 1 has 2, and bleeder vent is circular; Side surface at this bleeder vent is attached with metallic film base 5, is distributed with carbon nano-tube film 6 on it, and this carbon nano-tube mouth of pipe is downward.Second electrode, 2 centers are provided with 1~4 fairlead, have provided among Fig. 4, Fig. 5 a fairlead and fairlead are set are circular embodiment.Third electrode 3 collector blind holes are corresponding with the fairlead of second electrode, and the quantity of blind hole is 1~4, provided among Fig. 4, Fig. 5 a blind hole to be set and blind hole is the embodiment of cylindrical structure.Insulation column 7 is separately positioned between the metallic film base 5 and second electrode 2 of the carbon nano-tube film that distributing, between second electrode 2 and the third electrode 3, promptly insulation column 7 is distributed in second electrode 2 over against the surperficial both sides of first electrode 1 and the both sides on the inboard golden film surface of third electrode 3.
The present invention's first electrode 1 adopts silicon sheet material to make, and a side surface of first electrode 1 is attached with metallic film base 5; Described carbon nano-tube film 6 can adopt FePC as catalyzer, and adopts carbon source, and carbon nano-tube film 6 is made in growth on metallic film base 5, and perhaps the serigraphy carbon nano-tube film 6.Second electrode 2 and third electrode 3 all adopt silicon wafer to manufacture.The two sides of first electrode 1 and third electrode 3 medial surfaces, second electrode 2 are equipped with metal film.
On the electrode in the present invention's first electrode 12 bleeder vents are arranged, be convenient to gas to be detected and enter electrode gap; Metallic film base 5 is attached to first electrode, 1 one side surfaces; On second electrode 2 fairlead is arranged; Third electrode 3 collectors can be collected the positive ion stream that gas ionization produces.Between first electrode 1 and second electrode 2, isolate mutually by insulation column 7 between second electrode 2 and the third electrode 3; Tested gas enters in the gap of adjacent two electrodes of sensor by the gap between the sensor peripheral electrode.
The present invention takes the carbon nano-tube film ionization type nitrogen dioxide sensor of said structure when measuring nitrogen dioxide gas concentration, and second electrode potential is higher than first electrode potential, and the third electrode current potential is lower than second electrode potential and is higher than first electrode potential.Second electrode and first electrode form the electron stream loop, and the third electrode and first electrode form the ion flow loop, realize electron stream is separated with ion flow.Between the ion flow and nitrogen dioxide gas concentration, gas temperature and humidity of the output of carbon nano-tube film ionizing transducer, apply at second electrode on the basis of certain voltage, present monodrome gas concentration sensitive relations (Fig. 6), monodrome responsive to temperature relation, monodrome humidity sensitive relation.By piecewise interpolation and data fusion, realized the accuracy of measurement of nitrogen dioxide gas concentration 1%.The carbon nano-tube film ionizing transducer array technique of different poles spacing, pA level current measurement techniques, piecewise interpolation technology and data fusion technology are the features of concentration measuring method of the present invention.
Below by an instantiation, the method that carbon nano-tube film ionization type nitrogen dioxide sensor of the present invention is detected nitrogen dioxide gas concentration is described further.
Adopt the fixing carbon nano-tube film ionization type nitrogen dioxide sensor of die opening, experiment has obtained the monodrome gas-sensitive property (shown in Figure 6) of pure gas nitrogen dioxide, content of nitrogen dioxide measurement model that the ion flow input data fusion of sensor output is set up has obtained accuracy less than 1% pure gas nitrogen dioxide gas concentration measured value.
Carbon nano-tube film ionization type nitrogen dioxide sensor shown in Figure 6 detects among the embodiment of nitrogen dioxide gas concentration, and the experimental situation condition is 40.7 ℃ of temperature, relative humidity 18.5%RH, atmospheric pressure 93.5KPa.Adjacent two the interelectrode die openings of three electrodes of carbon nano-tube film ionization type nitrogen dioxide sensor are 200 μ m; The die opening of the carbon nano-tube film ionizing transducer adjacent electrode that monitor temperature is used is 170 μ m; The die opening of the carbon nano-tube film ionizing transducer adjacent electrode that monitoring humidity is used is respectively 200 μ m, 100 μ m.First electrode 1 of above-mentioned three carbon nano-tube film ionizing transducers and second electrode, 2 pole plates are 170mm over against area 2, second electrode 2 is 190mm with third electrode 3 pole plates over against area 2Nitrogen dioxide sensor first electrode 1 cathode voltage is 0V, second electrode, 2 extraction pole on-load voltage 130V, third electrode 3 collector on-load voltage 10V.Temperature sensor first, second, third electrode voltage is respectively 0V, 70V, 10V; Humidity sensor first, second, third electrode voltage is respectively 0V, 90V, 10V.Along with the rising of nitrogen dioxide gas concentration, the ion flow that collector is collected reduces, and ion flow presents the relation that monodrome descends with the content of nitrogen dioxide increase; Temperature, humidity sensor sensing characteristic and nitrogen dioxide sensor are similar.In 0~734.795ppm content of nitrogen dioxide scope, 10 groups of experimental calibration data have been obtained.Three sensor ion flow valuves are as the input sample, and pure gas content of nitrogen dioxide calibration value is as the desired output sample data.Adopt linear interpolation to 10 groups of experimental calibration sample data interpolation, in 0~734.795ppm concentration range, be that spacing is carried out equidistant interpolation with 5ppm, and near demand value (being the gas concentration critical value), carry out intensive interpolation, obtain 266 groups of interpolated datas altogether, and form database with 10 groups of experimental datas; Totally 267 groups of data are as training sample to select 266 groups of interpolated datas and 1 group of experimental calibration data for use, and 9 groups of experimental datas adopt the data fusion technology as test samples, obtain the nitrogen dioxide gas concentration measurement model.The linearity of content of nitrogen dioxide measurement model is that the assay fiducial error maximal value of 0.185%, 9 group of test samples is 0.187%, has reached 1% content of nitrogen dioxide accuracy of measurement.
Embodiment 2
Present embodiment basic structure is with embodiment 1, different is: adjacent two the interelectrode die openings of three electrodes of carbon nano-tube film ionization type nitrogen dioxide sensor are respectively 250 μ m, 30 μ m, and first electrode 1 and second electrode, 2 pole plates are 0.01mm over against area 2, second electrode 2 is 0.01mm with third electrode 3 pole plates over against area 2
The bleeder vent of the electrode surface of first electrode 1 has 1, and bleeder vent is quadrilateral, pentagon or hexagon; Second electrode, 2 center fairleads are 4, and fairlead is quadrilateral, pentagon or hexagon; The quantity of third electrode 3 blind holes is 4, and blind hole is 3~6 prisms or pyramid.
The detection method of present embodiment is substantially the same manner as Example 1, and different is:
The first electrode cathode voltage of carbon nano-tube film ionization type nitrogen dioxide sensor is 0V, the second electrode extraction pole on-load voltage 2V, third electrode collector on-load voltage 1V.
Embodiment 3
Present embodiment basic structure is with embodiment 1, different is: adjacent two interelectrode die openings are respectively 250 μ m, 30 μ m in three electrodes of carbon nano-tube film ionization type nitrogen dioxide sensor, and first electrode 1 and second electrode, 2 pole plates are 10mm over against area 2, second electrode 2 is 100mm with third electrode 3 pole plates over against area 2
The bleeder vent of the electrode surface of first electrode 1 has 4, and bleeder vent is quadrilateral, pentagon or hexagon; Second electrode, 2 center fairleads are 2, and fairlead is quadrilateral, pentagon or hexagon; The quantity of third electrode 3 blind holes is 2, and blind hole is 3~6 prisms or pyramid.
The detection method of present embodiment is substantially the same manner as Example 1, and different is:
The first electrode cathode voltage of carbon nano-tube film ionization type nitrogen dioxide sensor is 0V, the second electrode extraction pole on-load voltage 200V, third electrode collector on-load voltage 180V.
The present invention forms sensor array, the output of pA level current measurement system detecting sensor, piecewise interpolation and data fusion method by different poles spacing carbon nano-tube film ionizing transducer, form a kind of novel, can measure nitrogen dioxide gas, antijamming capability is strong, accuracy is high nitrogen dioxide gas concentration measuring method.The sensor of different poles spacing in the sensor array, the disturbing effect of detected temperatures, humidity directly detects nitrogen dioxide gas concentration in real time; PA level current measurement system can detect the pA level electric current of each sensor output of corresponding nitrogen dioxide gas concentration, temperature and humidity simultaneously; Piecewise interpolation and data fusion method can be eliminated temperature, humidity interference, the high nitrogen dioxide gas concentration measured value of output accuracy.
Though the present invention has made detailed description with above-mentioned preferred embodiment to the present invention, the foregoing description also is not used in qualification the present invention.Under the situation that does not break away from given technical characterictic of technical solution of the present invention and range of structures, the increase that technical characterictic is done, distortion or with the replacement of the same content in this area all should belong to protection scope of the present invention.

Claims (6)

1.碳纳米管薄膜电离式二氧化氮传感器,其特征在于:包括三个自上而下依次分布的第一电极、第二电极和第三电极,所述第一电极由内表面附着有分布着碳纳米管薄膜的金属膜基底以及设有透气孔的电极构成;第二电极由中心设有引出孔的引出极极板构成;第三电极由板面设有盲孔的收集极构成;该三个电极分别通过绝缘支柱相互隔离。1. The carbon nanotube thin film ionized nitrogen dioxide sensor is characterized in that: it includes three first electrodes, second electrodes and third electrodes distributed sequentially from top to bottom, and the first electrodes are attached with distributed The metal film substrate with carbon nanotube thin film and the electrode with vent holes; the second electrode is composed of the lead-out electrode plate with the lead-out hole in the center; the third electrode is composed of the collector electrode with the blind hole on the plate surface; The three electrodes are separated from each other by insulating pillars. 2.根据权利要求1所述的碳纳米管薄膜电离式二氧化氮传感器,其特征在于:所述三个电极中相邻两个电极间的极间距为30~250μm;所述第一电极与第二电极极板正对面积为0.01~170mm2,第二电极与第三电极极板正对面积为0.01~190mm22. The carbon nanotube film ionized nitrogen dioxide sensor according to claim 1, characterized in that: the pole spacing between two adjacent electrodes among the three electrodes is 30-250 μm; The facing area of the second electrode plate is 0.01-170 mm 2 , and the facing area of the second electrode and the third electrode plate is 0.01-190 mm 2 . 3.根据权利要求1所述的碳纳米管薄膜电离式二氧化氮传感器,其特征在于:所述第一电极的电极表面的透气孔为1~4个,在电极内侧表面附着的金属膜基底上生长或者丝网印刷有碳纳米管薄膜;3. The carbon nanotube thin film ionized nitrogen dioxide sensor according to claim 1, characterized in that: the air holes on the electrode surface of the first electrode are 1 to 4, and the metal film substrate attached to the inner surface of the electrode Growth or screen printing of carbon nanotube films; 所述第二电极引出极中心设有1~4个引出孔;The center of the second electrode lead-out pole is provided with 1 to 4 lead-out holes; 所述第三电极收集极盲孔与第二电极的引出孔相对应,盲孔的数量为1~4个。The collector blind hole of the third electrode corresponds to the lead-out hole of the second electrode, and the number of blind holes is 1-4. 4.基于碳纳米管薄膜电离式二氧化氮传感器的二氧化氮气体浓度测量方法,其特征在于,该方法包括下述步骤:4. The nitrogen dioxide gas concentration measurement method based on carbon nanotube film ionization nitrogen dioxide sensor, it is characterized in that, the method comprises the following steps: (1)选择三个电极相邻两个电极的极间距设定为30~250μm的碳纳米管薄膜电离式传感器;(1) Select a carbon nanotube thin film ionization sensor with three electrodes whose electrode spacing between two adjacent electrodes is set to 30-250 μm; (2)分别将设定的三个不同极间距的碳纳米管薄膜电离式二氧化氮传感器、碳纳米管薄膜电离式温度传感器和碳纳米管薄膜电离式湿度传感器,放置在含有待测二氧化氮气体的气氛中;(2) Place the carbon nanotube thin film ionization nitrogen dioxide sensor, carbon nanotube thin film ionization temperature sensor and carbon nanotube thin film ionization humidity sensor with three different pole spacings that are set, respectively, in a place containing the measured carbon dioxide In an atmosphere of nitrogen gas; (3)分别对三个碳纳米管薄膜电离式二氧化氮传感器、温度传感器和湿度传感器的第一电极加载电压为0V,第二电极加载电压2~200V,第三电极加载电压1~180V;(3) The first electrodes of the three carbon nanotube film ionized nitrogen dioxide sensors, the temperature sensor and the humidity sensor are loaded with a voltage of 0V, the second electrode is loaded with a voltage of 2-200V, and the third electrode is loaded with a voltage of 1-180V; (4)在待测二氧化氮气体浓度、温度和湿度测量范围内,对应不同的浓度、温度和湿度标定值,分别测量步骤(2)中所有传感器输出的气体放电离子流值;(4) within the measurement range of nitrogen dioxide gas concentration, temperature and humidity to be measured, corresponding to different concentration, temperature and humidity calibration values, respectively measure the gas discharge ion current values output by all sensors in step (2); (5)将步骤(4)中在浓度、温度和湿度测量范围内测得的所有传感器输出离子流值,与相应的二氧化氮气体浓度、温度和湿度标定值,组成不同的样本,组成不同的实验标定样本,然后采用分段插值技术对实验标定样本进行插值,获得插值数据,得到插值样本,并根据包含了实验标定样本及插值样本的所有样本组建二氧化氮气体浓度测量数据库;(5) All the sensor output ion current values measured in the concentration, temperature and humidity measurement ranges in step (4) are combined with the corresponding nitrogen dioxide gas concentration, temperature and humidity calibration values to form different samples, and the composition is different The experimental calibration samples, and then use the segmental interpolation technology to interpolate the experimental calibration samples to obtain the interpolation data, get the interpolation samples, and build the nitrogen dioxide gas concentration measurement database according to all samples including the experimental calibration samples and interpolation samples; (6)采用数据融合技术,构建数据融合仪,建立二氧化氮传感器、温度传感器及湿度传感器的测量模型;以二氧化氮气体浓度测量数据库中的数据作为数据融合仪的输入样本和期望输出样本,并以量程范围内不同的数据分别作为数据融合仪的训练样本和检验样本进行训练和检验,检验结果满足实测误差要求时,数据融合仪输出二氧化氮传感器的浓度准确测量模型;(6) Using data fusion technology, build a data fusion instrument, and establish measurement models for nitrogen dioxide sensors, temperature sensors and humidity sensors; use the data in the nitrogen dioxide gas concentration measurement database as the input samples and expected output samples of the data fusion instrument , and use different data within the range as the training samples and inspection samples of the data fusion instrument for training and inspection. When the inspection results meet the actual measurement error requirements, the data fusion instrument outputs an accurate measurement model for the concentration of the nitrogen dioxide sensor; (7)将碳纳米管薄膜电离式二氧化氮传感器、温度传感器和湿度传感器实测时输出的离子流值输入步骤(6)获得的二氧化氮气体浓度准确测量模型,该模型输出二氧化氮气体浓度的准确测量值。(7) The ion current value output during the actual measurement of carbon nanotube film ionized nitrogen dioxide sensor, temperature sensor and humidity sensor is input into the accurate measurement model of nitrogen dioxide gas concentration obtained in step (6), and the model outputs nitrogen dioxide gas Accurate measurement of concentration. 5.根据权利要求4所述的基于碳纳米管薄膜电离式二氧化氮传感器的二氧化氮气体浓度测量方法,其特征在于:所述碳纳米管薄膜电离式二氧化氮传感器中,第二电极电位高于第一电极电位,第三电极电位低于第二电极电位且高于第一电极电位。5. the nitrogen dioxide gas concentration measuring method based on the carbon nanotube thin film ionization nitrogen dioxide sensor according to claim 4, is characterized in that: in the described carbon nanotube thin film ionization nitrogen dioxide sensor, the second electrode The potential is higher than the potential of the first electrode, the potential of the third electrode is lower than the potential of the second electrode and higher than the potential of the first electrode. 6.根据权利要求4所述的基于碳纳米管薄膜电离式二氧化氮传感器的二氧化氮气体浓度测量方法,其特征在于:所述建立二氧化氮气体浓度测量数据库,是将实验标定数据与插值数据组成数据库,将各传感器输出离子流值及其插值数据作为输入样本,将二氧化氮气体浓度、温度和湿度标定值及其插值数据作为期望输出样本。6. the nitrogen dioxide gas concentration measuring method based on carbon nanotube thin film ionization nitrogen dioxide sensor according to claim 4, is characterized in that: described establishment nitrogen dioxide gas concentration measurement database is the experiment calibration data and The interpolation data forms a database, the ion current value output by each sensor and its interpolation data are used as input samples, and the nitrogen dioxide gas concentration, temperature and humidity calibration values and their interpolation data are used as expected output samples.
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