CN105241934A - Power plant and implementation method thereof - Google Patents
Power plant and implementation method thereof Download PDFInfo
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- CN105241934A CN105241934A CN201510712253.6A CN201510712253A CN105241934A CN 105241934 A CN105241934 A CN 105241934A CN 201510712253 A CN201510712253 A CN 201510712253A CN 105241934 A CN105241934 A CN 105241934A
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Abstract
The invention discloses a power plant and an implementation method thereof. A gas alarm is arranged outside of the power generation equipment of the power plant; the gas alarm consists of an alarm device and a detecting device; the detecting device is a solid electrolyte type gas sensor, and has unexpected sensitivity and super fast response speed for hazardous gas detection, can timely find inflammable and explosive dangerous conditions in power plant environment, and has a great market prospect.
Description
Technical field
The present invention relates to electricity field, be specifically related to a kind of generating plant and implementation method thereof.
Background technology
Generating plant refers to that various primary energy nature can contained are converted to the factory of electric energy, has fuel-burning power plant, water generating factory, nuclear plant etc. at present.Traditional power plants and fuel-burning power plant are chemical energy electrogenesis in the next life energy utilizing coal, oil, rock gas or other dyestuffs.
Generating plant can produce various dusty gas in process of production in a large number, generally has oxides of nitrogen, carbon monoxide, sulfide etc., easily causes a hidden trouble to personal security.
Summary of the invention
The present invention is directed to background technology Problems existing, a kind of generating plant and implementation method thereof are provided.
The invention provides following technical scheme:
A kind of generating plant, in the generating set external position of generating plant, gas alarm is set, this gas alarm is made up of warning device and pick-up unit, pick-up unit is based on solid electrolyte type gas sensor, solid electrolyte type gas sensor comprises heating plate, layout yttrium stable zirconium oxide (YSZ) substrate (1) on hot plate and platinum (Pt) reference electrode (4) be arranged on YSZ substrate, sensitive electrode A (3) and sensitive electrode B (5), wherein sensitive electrode A and sensitive electrode B is arranged in the both sides of Pt reference electrode, the material of sensitive electrode A is tungsten oxide nanoparticles dopen Nano nickel oxide powder, the material of sensitive electrode B is nano SnO
2powder.
Preferably, described YSZ substrate is doping 8mol%Y
2o
3, its physics size is 6mm*4mm*0.2mm, adopts electrochemical method to erode away the nano-porous structure in two 1*2mm regions, and this structure is used for placing sensitive electrode A and sensitive electrode B respectively; The platinum round dot that the nanoporous region of YSZ substrate makes diameter 0.1-0.3mm is as the link of YSZ substrate and electrode; The thickness of sensitive electrode A and sensitive electrode B is 0.5mm, SnO in sensitive electrode B
2the particle diameter of nano powder is 15-22nm.
A kind of implementation method of generating plant, in the generating set external position of generating plant, gas alarm is set, this gas alarm is made up of warning device and pick-up unit, pick-up unit is based on solid electrolyte type gas sensor, solid electrolyte type gas sensor comprises porous yttrium stable zirconium oxide (YSZ) substrate, with the platinum be arranged on YSZ substrate (Pt) reference electrode, sensitive electrode A and sensitive electrode B, wherein sensitive electrode A and sensitive electrode B is arranged in the both sides of Pt reference electrode; Wherein,
A. YSZ substrate priority water and the cleaning of absolute ethyl alcohol repeated ultrasonic is got, stand-by after drying;
B. get platinum slurry, the fine strip shape platinum slurry band of the intermediate fabrication 1*2mm size of the YSZ substrate after cleaned, make a little platinum slurry round dot in the porous zone of YSZ respectively, during production in enormous quantities, can silk-screen printing technique be adopted;
C. get the region just coating platinum slurry that three sections of platinum filaments are bonded at YSZ slice, thin piece respectively, under then YSZ substrate being placed on infrared lamp, toast a few hours;
D. appropriate sensitive electrode materials A, B is got, put into respectively after agate mortar fully grinds and add a small amount of deionized water, be deployed into thick slurry A, B, respectively slurry A, B are coated two sensitive electrodes A, B forming sensor in substrate porous structure place, thickness is 0.5mm;
E. the substrate that upper step obtains is put into muffle furnace high temperature 800 DEG C sintering two hours;
F. the one side being printed on Pt electrode at " several " shape Pt heating plate is evenly coated with last layer inorganic glue, is then sticked together by the substrate obtained in heating plate and upper step, puts into muffle furnace 200 DEG C sintering 20 minutes, takes out, obtain sensor prototype device.
Preferably,
(1) porous yttrium stable zirconium oxide (YSZ) (2) preparation:
Double-cell electrochemical etching is adopted to prepare porous structure YSZ;
A. YSZ flat board (8mol%Y is got
2o
3doping, 6mm*4mm*0.2mm), successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, dry;
B. preprocessing solution is prepared: according to mass fraction, 1-1.8% Tea Saponin, 2% malic acid, all the other are pure water, are then dropped into wherein by YSZ flat board, complete submergence, under 50-58 DEG C of condition, process 20-28min, use microwave treatment 2min subsequently, clean natural drying for subsequent use;
The parameter of described microwave treatment is: 2450MHz, 65W, irradiation 2-5s, interval 10min, concurrent irradiation 3-5 time;
C. etchant solution is prepared, get HF (volume parts 40%) and deionized water 1:5 by volume, appropriate interpolation potassium permanganate mixing, put into two electric groove electrochemical appliance, etching tank and fixture are corrosion resistant polytetrafluoroethylmaterial material, electrode is cylindrical metal Pt, and etching tank is divided into two mutual not connected regions by fixture, and fixture central authorities have the hole of two 1*2mm given shapes;
D. corrosion process is carried out under dark condition, and device power supply used is constant current source, and applying corrosion electric current density is 40mA/cm
2, through 30min, YSZ flat board is formed the porous structure (2) in two 1*2mm regions, is kept at after making complete cleaning in absolute ethyl alcohol;
(2) sensitive electrode materials A preparation:
A. synthesize tungsten oxide nanoparticles: take 1.5gNa2WO4 and be dissolved in 45mL deionized water, under agitation, dropping concentration is that the HCl solution of 3mol/L is complete to wolframic acid precipitation; Then centrifuging, puts into small beaker by sediment, adds 30mL deionized water, then adds 75gKNO3, vigorous stirring, and form starchiness thing, hydro-thermal reaction 12h at 180 DEG C, naturally cools to room temperature; Reactant (precipitation) is fully washed with deionized water, then with ethanol washing, filters, dehydrate at 80 DEG C, obtain product and tungsten oxide nanoparticles;
B. tungsten oxide nanoparticles Y-oxides doping: get tungsten oxide nanoparticles that mass ratio is 3:1 and nano-nickel powder puts into stirrer, makes it fully mix; Then composite material is put into vacuum tube furnace, be heated to 300 DEG C, insulation 4h, make nickel powder fully oxidized, last Temperature fall is to room temperature;
(3) sensitive electrode material B preparation:
A. be first the SnO of 15-22nm by particle diameter
2nano powder in 80 DEG C of vacuum drying chambers dry 12 hours;
B. dry SnO is taken
2nano powder 2.0g, then adds 4.0ml platinum acid chloride solution wherein, and concentration is 10mmol/L, by its ultrasonic 15min after dipping is complete, makes it mix;
C. potpourri is left standstill 6h, then put into vacuum drying chamber at 80 DEG C of dry 12h, after drying, potpourri is sintered 12h at 500 DEG C, be naturally down to room temperature, obtain sensitive electrode B.
Usefulness of the present invention is:
The present invention is by arranging gas alarm in generating plant generating set external position, the pick-up unit of this alarm is based on solid electrolyte type gas sensor, it reaches unexpected sensitivity and ultrafast response resume speed to the detection for hazardous gas, the inflammable and explosive dangerous situation of generating plant surrounding enviroment can be found in time, there are very large market outlook.
Accompanying drawing explanation
Fig. 1 is two electric groove electrochemical appliance schematic diagram;
Fig. 2 is the structural representation of generating plant of the present invention;
Fig. 3 is the dull and stereotyped porous structure schematic diagram of YSZ;
Fig. 4 is the structural representation of gas sensor of the present invention.
Embodiment
The design of the technology of the present invention invention is mainly for some consideration following:
Gas sensor
Gas sensor mainly refers to and in the environment of air or a certain characteristic, the kind of object gas and concentration etc. can be converted into a kind of device or the device of detectable signal according to certain rule.The mode detected mainly contains measuring current, resistance, current potential, heat, temperature etc.According to the operating characteristic of gas sensor, be mainly divided into semiconductor-type, solid electrolyte formula etc.
Solid electrolyte
Solid electrolyte class gas sensor is all generally galvanochemistry type sensor, and primarily of electrolyte, sensitive electrode and reference electrode composition, electrolyte is its important component part.According to the difference of charge carrier, conductor can be divided into electronic conductor and ion conductor, the latter and electrolyte, except general liquid electrolyte, some ionic crystals are also had also to have high ionic conductivity, this kind of solid conduction body is referred to as solid electrolyte (solidelectrolyte), comprises pottery, glass, inorganic metal salt and some high-molecular organic materials.
In solid electrolyte, conductive ion also can be able to be negative ion for kation, and it is mainly determined by the defect of material itself.
Yttrium stable zirconium oxide (YSZ)
Stabilizing zirconia/yttrium stable zirconium oxide (YSZ) is the most useful a kind of solid electrolyte, under normal temperature, and zirconia (ZrO
2) be a kind of monoclinic crystal, ionic conductivity is very low, when being doped into appropriate divalence or trivalent cubic symmetry oxide (Y
2o
3, MgO, CaO, Sc
2o
3) it is processed, can ionic conductivity be shown, there is high oxide ion conduction rate, excellent chemical stability and thermal stability and mechanicalness, be widely used in Solid Oxide Fuel Cell and gas sensor domain.
Porous structure YSZ
Porous structure YSZ is still made up of originally interconnected atom at element composition, but has unique porous loose structure.Its specific surface area is large, is beneficial to gas and reacts on three phase boundary (zirconia, electrode, gas), improves sensitivity.The present invention adopts double-cell electrochemical etching to prepare the porous zone of YSZ, and manufacturing process is simple, and porous zone pattern is easy to control.
Tungsten oxide air-sensitive character
Tungsten oxide is n-type metal oxide semiconductor, is a kind of surface resistance control type gas sensitive.The atomic property of tungsten oxide plane of crystal is enlivened, easy adsorption gas molecule, and when gas molecule is adsorbed on plane of crystal, can make its inner carrier concentration generation respective change, shows as the resistance variations of sensor.Mechanism and the gas sensing mechanism of tungsten oxide gas sensor gas adsorption desorption generation resistance variations are very complicated, and researchers there is no unified understanding so far.Research shows, tungsten oxide is to NO
2, HS
2, SO
2good gas-sensitive property is all had etc. multiple gases.But, the sensitivity, selectivity etc. of simple tungsten oxide film have deficiency more, the present invention has prepared tungsten oxide nanoparticles, the contact area of material and gas to be measured can be increased, improve sensitivity, in addition, be compounded with, to gas absorption, there is catalytic action or optionally nickel oxide particle, improve the selectivity of sensitive electrode to oxides of nitrogen gas.
SnO
2air-sensitive character
SnO
2belong to n-type semiconductor, due to the existence of Lacking oxygen or tin ion, gas sensitive effect is obvious, it is generally acknowledged that its gas sensing mechanism is adsorption control type mechanism.When being heated to certain temperature in the air of cleaning, O
2can at SnO
2adsorption, form multiple Adsorbed oxygen species, electronics is by SnO
2crystal grain shifts to adsorb oxygen, forms depletion layer at SnO2 grain surface, and the conductance of sensitive material reduces, and is detected atmosphere (H being exposed to reductibility
2, CO, hydrocarbon gas) in time, detected gas and Adsorbed oxygen species react, SnO
2the adsorb oxygen desorption of grain surface or grain boundaries, depletion layer is thinning, thus causes conductance to increase, and detects gas by the change of conductivity of material.The present invention is at SnO
2nano thin-film basis is added Pt to modify, make to it greatly improves the detection sensitivity to CO.
For the sensitive mechanism of yttrium stable zirconium oxide base NOx sensor, when sensor is placed in detection gaseous environment, series of chemical can be there is in three phase boundary (zirconia, electrode, gas), because sensitive electrode is different from the catalytic rate of reference electrode, so will form an electric potential difference between sensitive electrode and reference electrode, electromotive force extent reflects the concentration of gas to be measured, thus reaches the object detecting gas and concentration thereof.Can know thus, the galvanochemistry of electrode material and chemical catalysis activity, electrode microstructure etc. are the principal elements that sensitive electrode is considered.
Fig. 2 is the structural representation of generating plant of the present invention, at generating plant 10 generating set outer setting gas sensor 1.
Embodiment 1:
A kind of implementation method of generating plant, in the generating set external position of generating plant, gas alarm is set, this gas alarm is made up of warning device and pick-up unit, pick-up unit is based on solid electrolyte type gas sensor, solid electrolyte type gas sensor comprises porous yttrium stable zirconium oxide (YSZ) substrate, with the platinum be arranged on YSZ substrate (Pt) reference electrode, sensitive electrode A and sensitive electrode B, wherein sensitive electrode A and sensitive electrode B is arranged in the both sides of Pt reference electrode;
Wherein, solid electrolyte type gas sensor, it is made by the following method:
(1) porous yttrium stable zirconium oxide (YSZ) preparation:
Double-cell electrochemical etching is adopted to prepare porous structure YSZ;
A. YSZ flat board (8mol%Y is got
2o
3doping, 6mm*4mm*0.2mm), successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, dry;
B. prepare preprocessing solution: according to mass fraction, 1% Tea Saponin, 2% malic acid, all the other are pure water, and then dropped into wherein by YSZ flat board, complete submergence, processes 20min, use microwave treatment 2min subsequently under 58 DEG C of conditions, cleans natural drying for subsequent use;
The parameter of described microwave treatment is: 2450MHz, 65W, irradiation 5s, interval 10min, a concurrent irradiation 3 times;
C. etchant solution is prepared, get HF (volume parts 40%) and deionized water 1:5 by volume, appropriate interpolation potassium permanganate mixing, put into two electric groove electrochemical appliance (as shown in Figure 1), etching tank and fixture are corrosion resistant poly-four not vinyl materials, electrode is cylindrical metal Pt, and etching tank is divided into two mutual not connected regions by fixture, and fixture central authorities have the hole of two 1*2mm given shapes;
D. corrosion process is carried out under dark condition, and device power supply used is constant current source, and applying corrosion electric current density is 40mA/cm
2, through 30min, YSZ flat board is formed the porous structure in two 1*2mm regions, is kept at after making complete cleaning in absolute ethyl alcohol;
(2) sensitive electrode materials A preparation:
A. tungsten oxide nanoparticles is synthesized: take 1.5gNa
2wO
4be dissolved in 45mL deionized water, under agitation, dropping concentration is that the HCl solution of 3mol/L is complete to wolframic acid precipitation; Then centrifuging, puts into small beaker by sediment, adds 30mL deionized water, then adds 75gKNO
3, vigorous stirring, form starchiness thing, hydro-thermal reaction 12h at 180 DEG C, naturally cools to room temperature; Reactant (precipitation) is fully washed with deionized water, then with ethanol washing, filters, dehydrate at 80 DEG C, obtain product and tungsten oxide nanoparticles;
B. tungsten oxide nanoparticles Y-oxides doping: get tungsten oxide nanoparticles that mass ratio is 3:1 and nano-nickel powder puts into stirrer, makes it fully mix; Then composite material is put into vacuum tube furnace, be heated to 300 DEG C, insulation 4h, make nickel powder fully oxidized, last Temperature fall is to room temperature;
(3) sensitive electrode material B preparation:
A. be first the SnO of 22nm by particle diameter
2nano powder in 80 DEG C of vacuum drying chambers dry 12 hours;
B. dry SnO is taken
2nano powder 2.0g, then adds 4.0ml platinum acid chloride solution wherein, and concentration is 10mmol/L, by its ultrasonic 15min after dipping is complete, makes it mix;
C. potpourri is left standstill 6h, then put into vacuum drying chamber at 80 DEG C of dry 12h, after drying, potpourri is sintered 12h at 500 DEG C, be naturally down to room temperature, obtain sensitive electrode B;
(4) gas sensor makes
Nitrogen oxides sensor is formed primarily of two parts: porous YSZ flat board and Pt " several " shape heated by electrodes plate, and device fabrication steps is as follows:
A. the YSZ substrate after step (1) process is got, successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, stand-by after drying;
B. get platinum slurry, the fine strip shape platinum slurry band of the intermediate fabrication 1*2mm size of the YSZ substrate after cleaned, make a little platinum slurry round dot in the porous zone of YSZ respectively, during production in enormous quantities, can silk-screen printing technique be adopted;
C. get the region just coating platinum slurry that three sections of platinum filaments are bonded at YSZ slice, thin piece respectively, under then YSZ substrate being placed on infrared lamp, toast a few hours;
D. appropriate sensitive electrode materials A, B is got, put into respectively after agate mortar fully grinds and add a small amount of deionized water, be deployed into thick slurry A, B, respectively slurry A, B are coated two sensitive electrodes A, B forming sensor in substrate porous structure place, thickness is 0.5mm;
E. the substrate that upper step obtains is put into muffle furnace high temperature 800 DEG C sintering two hours;
F. the one side being printed on Pt electrode at " several " shape Pt heating plate is evenly coated with last layer inorganic glue (with water glass and Al
2o
3mixing is obtained), then the substrate obtained in heating plate and upper step is sticked together, put into muffle furnace 200 DEG C sintering 20 minutes, take out, obtain sensor prototype device.
When this embodiment device operating temperature is 300 DEG C, to the NO of 100ppm
2, sensitivity can reach 21mV/decade, and response resume speed is very fast, is about 18s; To the CO of 200ppm, sensitivity can reach 39mV/decade, and response resume speed is about 5s.
In the present embodiment, YSZ substrate is doping 8mol%Y
2o
3, its physics size is 6mm*4mm*0.2mm, adopts electrochemical method to erode away the nano-porous structure in two 1*2mm regions, and this structure is used for placing sensitive electrode A and sensitive electrode B respectively; The platinum round dot that the nanoporous region of YSZ substrate makes diameter 0.1 ~ 0.3mm is as the link of YSZ substrate and electrode; The thickness of sensitive electrode A and sensitive electrode B is 0.5mm, SnO in sensitive electrode B
2the particle diameter of nano powder is 15-22nm.
Embodiment 2:
A kind of implementation method of generating plant, in the generating set external position of generating plant, gas alarm is set, this gas alarm is made up of warning device and pick-up unit, pick-up unit is based on solid electrolyte type gas sensor, solid electrolyte type gas sensor comprises porous yttrium stable zirconium oxide (YSZ) substrate, with the platinum be arranged on YSZ substrate (Pt) reference electrode, sensitive electrode A and sensitive electrode B, wherein sensitive electrode A and sensitive electrode B is arranged in the both sides of Pt reference electrode;
Wherein, solid electrolyte type gas sensor, it is made by the following method:
(1) porous yttrium stable zirconium oxide (YSZ) preparation:
Double-cell electrochemical etching is adopted to prepare porous structure YSZ;
A. YSZ flat board (8mol%Y is got
2o
3doping, 7mm*5mm*0.2mm), successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, dry;
B. prepare preprocessing solution: according to mass fraction, 1.8% Tea Saponin, 2% malic acid, all the other are pure water, and then dropped into wherein by YSZ flat board, complete submergence, processes 28min, use microwave treatment 2min subsequently under 50 DEG C of conditions, cleans natural drying for subsequent use;
The parameter of described microwave treatment is: 2450MHz, 65W, irradiation 2s, interval 10min, a concurrent irradiation 5 times;
C. etchant solution is prepared, get HF (volume parts 40%) and deionized water 1:5 by volume, appropriate interpolation potassium permanganate mixing, put into two electric groove electrochemical appliance (as shown in Figure 1), etching tank and fixture are corrosion resistant poly-four not vinyl materials, electrode is cylindrical metal Pt, and etching tank is divided into two mutual not connected regions by fixture, and fixture central authorities have the hole of two 2*2mm given shapes;
D. corrosion process is carried out under dark condition, and device power supply used is constant current source, and applying corrosion electric current density is 40mA/cm
2, through 30min, YSZ flat board is formed the porous structure in two 2*2mm regions, is kept at after making complete cleaning in absolute ethyl alcohol;
(2) sensitive electrode materials A preparation:
A. tungsten oxide nanoparticles is synthesized: take 1.5gNa
2wO
4be dissolved in 45mL deionized water, under agitation, dropping concentration is that the HCl solution of 3mol/L is complete to wolframic acid precipitation; Then centrifuging, puts into small beaker by sediment, adds 30mL deionized water, then adds 75gKNO
3, vigorous stirring, form starchiness thing, hydro-thermal reaction 12h at 180 DEG C, naturally cools to room temperature; Reactant (precipitation) is fully washed with deionized water, then with ethanol washing, filters, dehydrate at 80 DEG C, obtain product and tungsten oxide nanoparticles;
B. tungsten oxide nanoparticles Y-oxides doping: get tungsten oxide nanoparticles that mass ratio is 3:1 and nano-nickel powder puts into stirrer, makes it fully mix; Then composite material is put into vacuum tube furnace, be heated to 300 DEG C, insulation 4h, make nickel powder fully oxidized, last Temperature fall is to room temperature;
(3) sensitive electrode material B preparation:
A. be first the SnO of 15nm by particle diameter
2nano powder in 80 DEG C of vacuum drying chambers dry 12 hours;
B. dry SnO is taken
2nano powder 2.0g, then adds 4.0ml platinum acid chloride solution wherein, and concentration is 10mmol/L, by its ultrasonic 15min after dipping is complete, makes it mix;
C. potpourri is left standstill 6h, then put into vacuum drying chamber at 80 DEG C of dry 12h, after drying, potpourri is sintered 12h at 500 DEG C, be naturally down to room temperature, obtain sensitive electrode B;
(4) gas sensor makes
Nitrogen oxides sensor is formed primarily of two parts: porous YSZ flat board and Pt " several " shape heated by electrodes plate, and device fabrication steps is as follows:
A. the YSZ substrate after step (1) process is got, successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, stand-by after drying;
B. get platinum slurry, the fine strip shape platinum slurry band of the intermediate fabrication 2*2mm size of the YSZ substrate after cleaned, make a little platinum slurry round dot in the porous zone of YSZ respectively, during production in enormous quantities, can silk-screen printing technique be adopted;
C. get the region just coating platinum slurry that three sections of platinum filaments are bonded at YSZ slice, thin piece respectively, under then YSZ substrate being placed on infrared lamp, toast a few hours;
D. appropriate sensitive electrode materials A, B is got, put into respectively after agate mortar fully grinds and add a small amount of deionized water, be deployed into thick slurry A, B, respectively slurry A, B are coated two sensitive electrodes A, B forming sensor in substrate porous structure place, thickness is 0.5mm;
E. the substrate that upper step obtains is put into muffle furnace high temperature 800 DEG C sintering two hours;
F. the one side being printed on Pt electrode at " several " shape Pt heating plate be evenly coated with last layer inorganic glue (with water glass and Al2O3 mixing obtained), then the substrate obtained in heating plate and upper step is sticked together, put into muffle furnace 200 DEG C sintering 20 minutes, take out, obtain sensor prototype device.
When this embodiment device operating temperature is 300 DEG C, to the NO of 100ppm
2, sensitivity can reach 52mV/decade, and response resume speed is very fast, is about 8s; To the CO of 200ppm, sensitivity can reach 62mV/decade, and response resume speed is about 3s.
In the present embodiment, YSZ substrate is doping 8mol%Y
2o
3, its physics size is 7mm*5mm*0.2mm, adopts electrochemical method to erode away the nano-porous structure in two 2*2mm regions, and this structure is used for placing sensitive electrode A and sensitive electrode B respectively; The platinum round dot that the nanoporous region of YSZ substrate makes diameter 0.1 ~ 0.3mm is as the link of YSZ substrate and electrode; The thickness of sensitive electrode A and sensitive electrode B is 0.5mm, SnO in sensitive electrode B
2the particle diameter of nano powder is 15-22nm.
By the adjustment to YSZ substrate, porous nanometer structure size and experiment parameter, it brings up to 62mV/decade to the detection sensitivity of hazardous gas CO, and the response time shortens to 3s, obtains beyond thought result.
Embodiment 3:
A kind of implementation method of generating plant, in the generating set external position of generating plant, gas alarm is set, this gas alarm is made up of warning device and pick-up unit, pick-up unit is based on solid electrolyte type gas sensor, solid electrolyte type gas sensor comprises porous yttrium stable zirconium oxide (YSZ) substrate, with the platinum be arranged on YSZ substrate (Pt) reference electrode, sensitive electrode A and sensitive electrode B, wherein sensitive electrode A and sensitive electrode B is arranged in the both sides of Pt reference electrode;
Wherein, solid electrolyte type gas sensor, it is made by the following method:
(1) porous yttrium stable zirconium oxide (YSZ) preparation:
Double-cell electrochemical etching is adopted to prepare porous structure YSZ;
A. YSZ flat board (8mol%Y is got
2o
3doping, 8mm*4mm*0.2mm), successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, dry;
B. prepare preprocessing solution: according to mass fraction, 1.3% Tea Saponin, 2% malic acid, all the other are pure water, and then dropped into wherein by YSZ flat board, complete submergence, processes 21min, use microwave treatment 2min subsequently under 57 DEG C of conditions, cleans natural drying for subsequent use;
The parameter of described microwave treatment is: 2450MHz, 65W, irradiation 3s, interval 10min, a concurrent irradiation 4
C. etchant solution is prepared, get HF (volume parts 40%) and deionized water 1:5 by volume, appropriate interpolation potassium permanganate mixing, put into two electric groove electrochemical appliance (as shown in Figure 1), etching tank and fixture are corrosion resistant poly-four not vinyl materials, electrode is cylindrical metal Pt, and etching tank is divided into two mutual not connected regions by fixture, and fixture central authorities have the hole of two 1*2mm given shapes;
D. corrosion process is carried out under dark condition, and device power supply used is constant current source, and applying corrosion electric current density is 40mA/cm
2, through 30min, YSZ flat board is formed the porous structure in two 1*2mm regions, is kept at after making complete cleaning in absolute ethyl alcohol;
(2) sensitive electrode materials A preparation:
A. tungsten oxide nanoparticles is synthesized: take 1.5gNa
2wO
4be dissolved in 45mL deionized water, under agitation, dropping concentration is that the HCl solution of 3mol/L is complete to wolframic acid precipitation; Then centrifuging, puts into small beaker by sediment, adds 30mL deionized water, then adds 75gKNO
3, vigorous stirring, form starchiness thing, hydro-thermal reaction 12h at 180 DEG C, naturally cools to room temperature; Reactant (precipitation) is fully washed with deionized water, then with ethanol washing, filters, dehydrate at 80 DEG C, obtain product and tungsten oxide nanoparticles;
B. tungsten oxide nanoparticles Y-oxides doping: get tungsten oxide nanoparticles that mass ratio is 3:1 and nano-nickel powder puts into stirrer, makes it fully mix; Then composite material is put into vacuum tube furnace, be heated to 300 DEG C, insulation 4h, make nickel powder fully oxidized, last Temperature fall is to room temperature;
(3) sensitive electrode material B preparation:
A. be first the SnO of 20nm by particle diameter
2nano powder in 80 DEG C of vacuum drying chambers dry 12 hours;
B. dry SnO is taken
2nano powder 2.0g, then adds 4.0ml platinum acid chloride solution wherein, and concentration is 10mmol/L, by its ultrasonic 15min after dipping is complete, makes it mix;
C. potpourri is left standstill 6h, then put into vacuum drying chamber at 80 DEG C of dry 12h, after drying, potpourri is sintered 12h at 500 DEG C, be naturally down to room temperature, obtain sensitive electrode B;
(4) gas sensor makes
Nitrogen oxides sensor is formed primarily of two parts: porous YSZ flat board and Pt " several " shape heated by electrodes plate, and device fabrication steps is as follows:
A. the YSZ substrate after step (1) process is got, successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, stand-by after drying;
B. get platinum slurry, the fine strip shape platinum slurry band of the intermediate fabrication 1*2mm size of the YSZ substrate after cleaned, make a little platinum slurry round dot in the porous zone of YSZ respectively, during production in enormous quantities, can silk-screen printing technique be adopted;
C. get the region just coating platinum slurry that three sections of platinum filaments are bonded at YSZ slice, thin piece respectively, under then YSZ substrate being placed on infrared lamp, toast a few hours;
D. appropriate sensitive electrode materials A, B is got, put into respectively after agate mortar fully grinds and add a small amount of deionized water, be deployed into thick slurry A, B, respectively slurry A, B are coated two sensitive electrodes A, B forming sensor in substrate porous structure place, thickness is 0.5mm;
E. the substrate that upper step obtains is put into muffle furnace high temperature 800 DEG C sintering two hours;
F. the one side being printed on Pt electrode at " several " shape Pt heating plate be evenly coated with last layer inorganic glue (with water glass and Al2O3 mixing obtained), then the substrate obtained in heating plate and upper step is sticked together, put into muffle furnace 200 DEG C sintering 20 minutes, take out, obtain sensor prototype device.
When this embodiment device operating temperature is 300 DEG C, to the NO of 100ppm
2, sensitivity can reach 30mV/decade, and response resume speed is very fast, is about 17s; To the CO of 200ppm, sensitivity can reach 45mV/decade, and response resume speed is about 4s.
Described YSZ substrate is doping 8mol%Y
2o
3, its physics size is 8mm*4mm*0.2mm, adopts electrochemical method to erode away the nano-porous structure in two 1*2mm regions, and this structure is used for placing sensitive electrode A and sensitive electrode B respectively; The platinum round dot that the nanoporous region of YSZ substrate makes diameter 0.1-0.3mm is as the link of YSZ substrate and electrode; The thickness of sensitive electrode A and sensitive electrode B is 0.5mm, SnO in sensitive electrode B
2the particle diameter of nano powder is 15-22nm.
By the adjustment to YSZ substrate, porous nanometer structure size and experiment parameter, it is to hazardous gas NO
2detection sensitivity bring up to 30mV/decade, 4s is shortened to the response time of CO, obtains beyond thought result.
Embodiment 4:
A kind of implementation method of generating plant, in the generating set external position of generating plant, gas alarm is set, this gas alarm is made up of warning device and pick-up unit, pick-up unit is based on solid electrolyte type gas sensor, solid electrolyte type gas sensor comprises porous yttrium stable zirconium oxide (YSZ) substrate, with the platinum be arranged on YSZ substrate (Pt) reference electrode, sensitive electrode A and sensitive electrode B, wherein sensitive electrode A and sensitive electrode B is arranged in the both sides of Pt reference electrode;
Wherein, solid electrolyte type gas sensor, it is made by the following method:
(1) porous yttrium stable zirconium oxide (YSZ) preparation:
Double-cell electrochemical etching is adopted to prepare porous structure YSZ;
A. YSZ flat board (8mol%Y is got
2o
3doping, 9mm*5mm*0.2mm), successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, dry;
B. prepare preprocessing solution: according to mass fraction, 1.7% Tea Saponin, 2% malic acid, all the other are pure water, and then dropped into wherein by YSZ flat board, complete submergence, processes 27min, use microwave treatment 2min subsequently under 51 DEG C of conditions, cleans natural drying for subsequent use;
The parameter of described microwave treatment is: 2450MHz, 65W, irradiation 4s, interval 10min, a concurrent irradiation 3 times;
C. etchant solution is prepared, get HF (volume parts 40%) and deionized water 1:5 by volume, appropriate interpolation potassium permanganate mixing, put into two electric groove electrochemical appliance (as shown in Figure 1), etching tank and fixture are corrosion resistant poly-four not vinyl materials, electrode is cylindrical metal Pt, and etching tank is divided into two mutual not connected regions by fixture, and fixture central authorities have the hole of two 3*2mm given shapes;
D. corrosion process is carried out under dark condition, and device power supply used is constant current source, and applying corrosion electric current density is 40mA/cm
2, through 30min, YSZ flat board is formed the porous structure in two 3*2mm regions, is kept at after making complete cleaning in absolute ethyl alcohol;
(2) sensitive electrode materials A preparation:
A. tungsten oxide nanoparticles is synthesized: take 1.5gNa
2wO
4be dissolved in 45mL deionized water, under agitation, dropping concentration is that the HCl solution of 3mol/L is complete to wolframic acid precipitation; Then centrifuging, puts into small beaker by sediment, adds 30mL deionized water, then adds 75gKNO
3, vigorous stirring, form starchiness thing, hydro-thermal reaction 12h at 180 DEG C, naturally cools to room temperature; Reactant (precipitation) is fully washed with deionized water, then with ethanol washing, filters, dehydrate at 80 DEG C, obtain product and tungsten oxide nanoparticles;
B. tungsten oxide nanoparticles Y-oxides doping: get tungsten oxide nanoparticles that mass ratio is 3:1 and nano-nickel powder puts into stirrer, makes it fully mix; Then composite material is put into vacuum tube furnace, be heated to 300 DEG C, insulation 4h, make nickel powder fully oxidized, last Temperature fall is to room temperature;
(3) sensitive electrode material B preparation:
A. be first the SnO of 16nm by particle diameter
2nano powder in 80 DEG C of vacuum drying chambers dry 12 hours;
B. dry SnO is taken
2nano powder 2.0g, then adds 4.0ml platinum acid chloride solution wherein, and concentration is 10mmol/L, by its ultrasonic 15min after dipping is complete, makes it mix;
C. potpourri is left standstill 6h, then put into vacuum drying chamber at 80 DEG C of dry 12h, after drying, potpourri is sintered 12h at 500 DEG C, be naturally down to room temperature, obtain sensitive electrode B;
(4) gas sensor makes
Nitrogen oxides sensor is formed primarily of two parts: porous YSZ flat board and Pt " several " shape heated by electrodes plate, and device fabrication steps is as follows:
A. the YSZ substrate after step (1) process is got, successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, stand-by after drying;
B. get platinum slurry, the fine strip shape platinum slurry band of the intermediate fabrication 3*2mm size of the YSZ substrate after cleaned, make a little platinum slurry round dot in the porous zone of YSZ respectively, during production in enormous quantities, can silk-screen printing technique be adopted;
C. get the region just coating platinum slurry that three sections of platinum filaments are bonded at YSZ slice, thin piece respectively, under then YSZ substrate being placed on infrared lamp, toast a few hours;
D. appropriate sensitive electrode materials A, B is got, put into respectively after agate mortar fully grinds and add a small amount of deionized water, be deployed into thick slurry A, B, respectively slurry A, B are coated two sensitive electrodes A, B forming sensor in substrate porous structure place, thickness is 0.5mm;
E. the substrate that upper step obtains is put into muffle furnace high temperature 800 DEG C sintering two hours;
F. the one side being printed on Pt electrode at " several " shape Pt heating plate be evenly coated with last layer inorganic glue (with water glass and Al2O3 mixing obtained), then the substrate obtained in heating plate and upper step is sticked together, put into muffle furnace 200 DEG C sintering 20 minutes, take out, obtain sensor prototype device.
When this embodiment device operating temperature is 300 DEG C, to the NO of 100ppm
2, sensitivity can reach 40mV/decade, and response resume speed is very fast, is about 10s; To the CO of 200ppm, sensitivity can reach 53mV/decade, and response resume speed is about 5s.
In the present embodiment, YSZ substrate is doping 8mol%Y
2o
3, its physics size is 9mm*5mm*0.2mm, adopts electrochemical method to erode away the nano-porous structure in two 3*2mm regions, and this structure is used for placing sensitive electrode A and sensitive electrode B respectively; The platinum round dot that the nanoporous region of YSZ substrate makes diameter 0.1 ~ 0.3mm is as the link of YSZ substrate and electrode; The thickness of sensitive electrode A and sensitive electrode B is 0.5mm, SnO in sensitive electrode B
2the particle diameter of nano powder is 15-22nm.
By the adjustment to YSZ substrate, porous nanometer structure size and experiment parameter, it brings up to 53mV/decade to the detection sensitivity of hazardous gas CO, and the response time shortens to 5s, obtains beyond thought result.
Embodiment 5 comparative example:
A kind of implementation method of generating plant, in the generating set external position of generating plant, gas alarm is set, this gas alarm is made up of warning device and pick-up unit, pick-up unit is based on solid electrolyte type gas sensor, solid electrolyte type gas sensor comprises porous yttrium stable zirconium oxide (YSZ) substrate, with the platinum be arranged on YSZ substrate (Pt) reference electrode, sensitive electrode A and sensitive electrode B, wherein sensitive electrode A and sensitive electrode B is arranged in the both sides of Pt reference electrode;
Wherein, solid electrolyte type gas sensor, it is made by the following method:
(1) porous yttrium stable zirconium oxide (YSZ) preparation:
Double-cell electrochemical etching is adopted to prepare porous structure YSZ;
A. YSZ flat board (8mol%Y is got
2o
3doping, 10mm*5mm*0.2mm), successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, dry;
B. prepare preprocessing solution: pure water soaks 10min, clean natural drying for subsequent use;
The parameter of described microwave treatment is: 2450MHz, 65W, irradiation 2s, interval 10min, a concurrent irradiation 5 times;
B. etchant solution is prepared, get HF (volume parts 40%) and deionized water 1:5 by volume, appropriate interpolation potassium permanganate mixing, put into two electric groove electrochemical appliance (as shown in Figure 1), etching tank and fixture are corrosion resistant poly-four not vinyl materials, electrode is cylindrical metal Pt, and etching tank is divided into two mutual not connected regions by fixture, and fixture central authorities have the hole of two 2*4mm given shapes;
C. corrosion process is carried out under dark condition, and device power supply used is constant current source, and applying corrosion electric current density is 40mA/cm
2, through 30min, YSZ flat board is formed the porous structure in two 2*4mm regions, is kept at after making complete cleaning in absolute ethyl alcohol;
(2) sensitive electrode materials A preparation:
A. tungsten oxide nanoparticles is synthesized: take 1.5gNa
2wO
4be dissolved in 45mL deionized water, under agitation, dropping concentration is that the HCl solution of 3mol/L is complete to wolframic acid precipitation; Then centrifuging, puts into small beaker by sediment, adds 30mL deionized water, then adds 75gKNO
3, vigorous stirring, form starchiness thing, hydro-thermal reaction 12h at 180 DEG C, naturally cools to room temperature; Reactant (precipitation) is fully washed with deionized water, then with ethanol washing, filters, dehydrate at 80 DEG C, obtain product and tungsten oxide nanoparticles;
B. tungsten oxide nanoparticles Y-oxides doping: get tungsten oxide nanoparticles that mass ratio is 3:1 and nano-nickel powder puts into stirrer, makes it fully mix; Then composite material is put into vacuum tube furnace, be heated to 300 DEG C, insulation 4h, make nickel powder fully oxidized, last Temperature fall is to room temperature;
(3) sensitive electrode material B preparation:
A. be first the SnO of 5nm by particle diameter
2nano powder in 80 DEG C of vacuum drying chambers dry 12 hours;
B. dry SnO is taken
2nano powder 2.0g, then adds 4.0ml platinum acid chloride solution wherein, and concentration is 10mmol/L, by its ultrasonic 15min after dipping is complete, makes it mix;
C. potpourri is left standstill 6h, then put into vacuum drying chamber at 80 DEG C of dry 12h, after drying, potpourri is sintered 12h at 500 DEG C, be naturally down to room temperature, obtain sensitive electrode B;
(4) gas sensor makes
Nitrogen oxides sensor is formed primarily of two parts: porous YSZ flat board and Pt " several " shape heated by electrodes plate, and device fabrication steps is as follows:
A. the YSZ substrate after step (1) process is got, successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, stand-by after drying;
B. get platinum slurry, the fine strip shape platinum slurry band of the intermediate fabrication 2*4mm size of the YSZ substrate after cleaned, make a little platinum slurry round dot in the porous zone of YSZ respectively, during production in enormous quantities, can silk-screen printing technique be adopted;
C. get the region just coating platinum slurry that three sections of platinum filaments are bonded at YSZ slice, thin piece respectively, under then YSZ substrate being placed on infrared lamp, toast a few hours;
D. appropriate sensitive electrode materials A, B is got, put into respectively after agate mortar fully grinds and add a small amount of deionized water, be deployed into thick slurry A, B, respectively slurry A, B are coated two sensitive electrodes A, B forming sensor in substrate porous structure place, thickness is 0.5mm;
E. the substrate that upper step obtains is put into muffle furnace high temperature 800 DEG C sintering two hours;
F. the one side being printed on Pt electrode at " several " shape Pt heating plate be evenly coated with last layer inorganic glue (with water glass and Al2O3 mixing obtained), then the substrate obtained in heating plate and upper step is sticked together, put into muffle furnace 200 DEG C sintering 20 minutes, take out, obtain sensor prototype device.
When this embodiment device operating temperature is 300 DEG C, to the NO of 100ppm
2, sensitivity can reach 50mV/decade, and response resume speed is very fast, is about 15s; To the CO of 200ppm, sensitivity can reach 60mV/decade, and response resume speed is about 3s.
When device operating temperature is 300 DEG C, to the NO of 100ppm
2, sensitivity can reach 79mV/decade, and response resume speed is very fast, is about 20s; To the CO of 200ppm, sensitivity can reach 125mV/decade, and response resume speed is about 9s.
In the present embodiment, YSZ substrate is doping 8mol%Y
2o
3, its physics size is 10mm*5mm*0.2mm, adopts electrochemical method to erode away the nano-porous structure in two 2*4mm regions, and this structure is used for placing sensitive electrode A and sensitive electrode B respectively; The platinum round dot that the nanoporous region of YSZ substrate makes diameter 0.1 ~ 0.3mm is as the link of YSZ substrate and electrode; The thickness of sensitive electrode A and sensitive electrode B is 0.5mm, SnO in sensitive electrode B
2the particle diameter of nano powder is 15-22nm.
By the adjustment to YSZ substrate, porous nanometer structure size and experiment parameter, it is to hazardous gas CO and NO
2detection sensitivity bring up to 125mV/decade and 79mV/decade respectively, the response time shortens to 9s, 20s respectively, obtains beyond thought result.
As can be seen here, the present invention passes through in generating plant generating set outer setting based on solid electrolyte type gas alarm, by the contrast to different experiments technological parameter condition lower sensor performance, obtain optimum sensitivity and response time, obtain unexpected effect, the inflammable and explosive dangerous situation of generating plant surrounding enviroment can be found in time, there are very large market outlook.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technological invention of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (4)
1. a generating plant, it is characterized in that, at generating plant generating set outer setting gas alarm, this gas alarm is made up of warning device and pick-up unit, pick-up unit is based on solid electrolyte type gas sensor, solid electrolyte type gas sensor comprises heating plate, arrange yttrium stable zirconium oxide (YSZ) substrate on hot plate and platinum (Pt) reference electrode be arranged on YSZ substrate, sensitive electrode A and sensitive electrode B, wherein sensitive electrode A and sensitive electrode B is arranged in the both sides of Pt reference electrode, the material of sensitive electrode A is tungsten oxide nanoparticles dopen Nano nickel oxide powder, the material of sensitive electrode B is nano SnO
2powder.
2. according to the generating plant described in claim 1, it is characterized in that, described YSZ substrate is doping 8mol%Y
2o
3, its physics size is 6mm*4mm*0.2mm, adopts electrochemical method to erode away the nano-porous structure in two 1*2mm regions, and this structure is used for placing sensitive electrode A and sensitive electrode B respectively; The nanoporous region of YSZ substrate makes the platinum round dot of diameter 0.1 ~ 0.3mm, as the link of YSZ substrate and electrode; The thickness of sensitive electrode A and sensitive electrode B is 0.5mm, SnO in sensitive electrode B
2the particle diameter of nano powder is 15-22nm.
3. the implementation method of a generating plant, it is characterized in that at generating plant generating set outer setting gas alarm, this gas alarm is made up of warning device and pick-up unit, pick-up unit is based on solid electrolyte type gas sensor, solid electrolyte type gas sensor comprises porous yttrium stable zirconium oxide (YSZ) substrate, with the platinum be arranged on YSZ substrate (Pt) reference electrode, sensitive electrode A and sensitive electrode B, wherein sensitive electrode A and sensitive electrode B is arranged in the both sides of Pt reference electrode; Wherein,
A. YSZ substrate priority water and the cleaning of absolute ethyl alcohol repeated ultrasonic is got, stand-by after drying;
B. get platinum slurry, the fine strip shape platinum slurry band of the intermediate fabrication 1*2mm size of the YSZ substrate after cleaned, make the platinum slurry round dot of a diameter 0.1 ~ 0.3mm in the porous zone of YSZ respectively, during production in enormous quantities, can silk-screen printing technique be adopted;
C. get the region just coating platinum slurry that three sections of platinum filaments are bonded at YSZ slice, thin piece respectively, under then YSZ substrate being placed on infrared lamp, toast a few hours;
D. appropriate sensitive electrode materials A, B is got, put into respectively after agate mortar fully grinds and add a small amount of deionized water, be deployed into thick slurry A, B, respectively slurry A, B are coated two sensitive electrodes A, B forming sensor in substrate porous structure place, thickness is 0.5mm;
E. the substrate that upper step obtains is put into muffle furnace high temperature 800 DEG C sintering two hours;
F. the one side being printed on Pt electrode at " several " shape Pt heating plate is evenly coated with last layer inorganic glue, is then sticked together by the substrate obtained in heating plate and upper step, puts into muffle furnace 200 DEG C sintering 20 minutes, takes out, obtain sensor prototype device.
4. implementation method according to claim 3, is characterized in that,
(1) porous yttrium stable zirconium oxide (YSZ) preparation:
Double-cell electrochemical etching is adopted to prepare porous structure YSZ;
A. YSZ flat board (8mol%Y is got
2o
3doping, 6mm*4mm*0.2mm), successively with water and the cleaning of absolute ethyl alcohol repeated ultrasonic, dry;
B. preprocessing solution is prepared: according to mass fraction, 1-1.8% Tea Saponin, 2% malic acid, all the other are pure water, are then dropped into wherein by YSZ flat board, complete submergence, under 50-58 DEG C of condition, process 20-28min, use microwave treatment 2min subsequently, clean natural drying for subsequent use;
The parameter of described microwave treatment is: 2450MHz, 65W, irradiation 2-5s, interval 10min, concurrent irradiation 3-5 time;
C. etchant solution is prepared, get HF (volume parts 40%) and deionized water 1:5 by volume, appropriate interpolation potassium permanganate mixing, put into two electric groove electrochemical appliance, etching tank and fixture are corrosion resistant polytetrafluoroethylmaterial material, electrode is cylindrical metal Pt, and etching tank is divided into two mutual not connected regions by fixture, and fixture central authorities have the hole of two 1*2mm given shapes;
D. corrosion process is carried out under dark condition, and device power supply used is constant current source, and applying corrosion electric current density is 40mA/cm
2, through 30min, YSZ flat board is formed the porous structure in two 1*2mm regions, is kept at after making complete cleaning in absolute ethyl alcohol;
(2) sensitive electrode materials A preparation:
A. synthesize tungsten oxide nanoparticles: take 1.5gNa2WO4 and be dissolved in 45mL deionized water, under agitation, dropping concentration is that the HCl solution of 3mol/L is complete to wolframic acid precipitation; Then centrifuging, puts into small beaker by sediment, adds 30mL deionized water, then adds 75gKNO3, vigorous stirring, and form starchiness thing, hydro-thermal reaction 12h at 180 DEG C, naturally cools to room temperature; Reactant (precipitation) is fully washed with deionized water, then with ethanol washing, filters, dehydrate at 80 DEG C, obtain product and tungsten oxide nanoparticles;
B. tungsten oxide nanoparticles Y-oxides doping: get tungsten oxide nanoparticles that mass ratio is 3:1 and nano-nickel powder puts into stirrer, makes it fully mix; Then composite material is put into vacuum tube furnace, be heated to 300 DEG C, insulation 4h, make nickel powder fully oxidized, last Temperature fall is to room temperature;
(3) sensitive electrode material B preparation:
A. be first the SnO of 15-22nm by particle diameter
2nano powder in 80 DEG C of vacuum drying chambers dry 12 hours;
B. dry SnO is taken
2nano powder 2.0g, then adds 4.0ml platinum acid chloride solution wherein, and concentration is 10mmol/L, by its ultrasonic 15min after dipping is complete, makes it mix;
C. potpourri is left standstill 6h, then put into vacuum drying chamber at 80 DEG C of dry 12h, after drying, potpourri is sintered 12h at 500 DEG C, be naturally down to room temperature, obtain sensitive electrode B.
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