CN106872548B - A kind of current mode NOx sensor pyrochlore solid electrolyte material and preparation method thereof - Google Patents

A kind of current mode NOx sensor pyrochlore solid electrolyte material and preparation method thereof Download PDF

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CN106872548B
CN106872548B CN201710117538.4A CN201710117538A CN106872548B CN 106872548 B CN106872548 B CN 106872548B CN 201710117538 A CN201710117538 A CN 201710117538A CN 106872548 B CN106872548 B CN 106872548B
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oxide
electrolyte material
sensor
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CN106872548A (en
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钟富兰
时兰钱
蔡国辉
郑勇
肖益鸿
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Fuzhou University
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Fuzhou University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen

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Abstract

The present invention relates to a kind of current mode NOxSensor pyrochlore solid electrolyte material and preparation method thereof, the chemical formula of the solid electrolyte material are Pr2Zr2‑yInyO7+δ, preparation method are as follows: synthesis pyrochlore Pr first2Zr2‑yInyO7+δThen solid electrolyte oxide carries out Pr2Zr2‑yInyO7+δThe post-processing of oxide, finally prepares Pr2Zr2‑yInyO7+δSubstrate.The present invention can be realized sensor to NOxHigh response and restorability.

Description

A kind of current mode NOx sensor pyrochlore solid electrolyte material and its preparation Method
Technical field
The present invention relates to the preparation field for belonging to solid electrolyte material, especially a kind of current mode NOxSensor is burnt Green stone solid electrolyte material and preparation method thereof.
Background technique
In recent years, with China's expanding economy, the continuous improvement of traffic infrastructure level, vehicle guaranteeding organic quantity is fast Speed increases, and pollutant while motor vehicle brings life convenient in its tail gas also brings the health of human body and environment Harm.In order to protect the health and ecological environment of the mankind, the discharge of vehicle exhaust is reduced, vehicle fuel utilization rate is improved, adds The monitoring of strong tail gas has become focus concerned by people, therefore the NO of vehicle exhaust monitoringxSensor comes into being.For automobile The NO of tail gas monitoringxWorking sensor condition is more harsh, it is desirable that in temperature (600-900 DEG C), high humidity and interference gas (HC, CO etc.) not only has good sensitivity characteristic, and with good stability and reliability when coexisting.Reported NOx Sensor has conductor oxidate formula, surface acoustic wave type, electric chemical formula, solid electrolyte formula, FET formula, diode-type and optical fiber Formula.In these sensors, solid electrolyte type NOxSensor can more meet vehicle exhaust exacting terms, and its have compared with The advantages that fast response speed, high sensitivity, low-detection lower limit and preferable selectivity.And traditional YSZ material will be 1000 DEG C or so can be only achieved sufficiently high ionic conductivity, the NO prepared using this solid electrolytexSensor is difficult to meet The middle low-temperature working requirement of diesel engine system.Therefore, develop one kind has higher oxygen ionic conductivity in mesophilic range Novel solid electrolyte replace traditional YSZ material to have become urgent task at present.
It is primarily present the related NO of following items in the prior artxThe patent of sensor.
1071508 A of CN has invented a kind of NOx sensor group.The NOxSensor group is for detecting burning waste gas In NOxContent, and generate a kind of and tested NOxContent is related to survey output signal, but measurement accuracy is by certain journey The limitation of degree.
ZL 201510195226.6 discloses a kind of middle low temperature electric flow pattern NOxSensor solid electrolyte material and its Preparation.Sensor performance stabilization, favorable reproducibility, response and recovery time are respectively 18 and 26 seconds, but still are difficult to reach work The requirement of industry quick response and recovery.
1421416 A of CN discloses a kind of cerium oxide base solid electrolyte ceramic material and its manufacturing method.The solid Although electrolyte oxygen ionic conductivity with higher under middle low temperature, the appraising at the current rate of Ce can generate electronics (or hole) and lead Electric behavior, therefore cerium oxide base solid electrolyte is used for NOxSensor is difficult to industrialize so far.
CN201594086U discloses a kind of all-solid mixed-potential type NOxSensor.The sensor can detect NOxConcentration Range is 1-75 %, and the response time was less than 2 minutes.
That there are sensor detectable limits is high for the above patent, the service life is short, at high cost, structure is complicated, preparation process is cumbersome etc. urgently Problem to be solved.
Summary of the invention
In view of this, the purpose of the present invention is to propose to a kind of current mode NOxSensor pyrochlore solid electrolyte material And preparation method thereof, realize sensor to NOxHigh response and restorability.
The present invention is realized using following scheme: a kind of current mode NOxSensor pyrochlore solid electrolyte material, it is described The chemical formula of solid electrolyte material is Pr2Zr2-yInyO7+δ。
Further, the range of the y is 0≤y≤0.3.
Further, the range of the δ is 0 < δ < 1.
Current mode NO described above is prepared the present invention also provides a kind ofxSensor pyrochlore solid electrolyte material Method, specifically includes the following steps:
Step S1: synthesis pyrochlore Pr2Zr2-yInyO7+δSolid electrolyte oxide:
26.10 grams of praseodymium nitrates, 0-2.71 grams of indium nitrate, 16.43-19.34 grams of basic zirconium chloride are weighed according to stoichiometric ratio And 5-10 grams of urea is added 300 ml deionized waters, dissolution is sufficiently stirred, is denoted as solution A in 500 milliliters of beakers；It weighs Acclimatization agent is placed in 1000 milliliters of conical flask, and 150 milliliters of deionized water dissolving is added, is stirred using electric mixer 10-30 minutes, it is denoted as B solution；Then the revolving speed of electric mixer is increased to 700-1000 r/min, rapidly falls solution A Enter into B solution, after persistently stirring 1-5 hours, obtained sediment is averagely poured into five 100 milliliters together with solution together Reaction kettle is placed in baking oven, 120-200 DEG C after heating 10-24 hours, cooling, its presoma is filtered, washed, is dried With Pr is obtained after roasting2Zr2-yInyO7+δOxide;
Step S2:Pr2Zr2-yInyO7+δThe post-processing of oxide:
Weigh the Pr that step S1 is obtained2Zr2-yInyO7+δ4-18 grams of oxide, 10-20 milliliters of ethanol-water solution is added, Using ball mill to above-mentioned Pr2Zr2-yInyO7+δOxide carries out wet ball grinding, obtains Pr after drying and roasting2Zr2- yInyO7+δOxide powder；
Step S3: preparation Pr2Zr2-yInyO7+δSubstrate:
Weigh the Pr that step S2 is obtained2Zr2-yInyO7+δAfter 5-12 grams of oxide powder is fully ground in agate jar, Powder is formed using tablet press machine, is subsequently placed in cold isostatic press under 280 MPa pressure pressure maintaining 5-10 minutes, and fine and close oxygen is obtained Compound substrate, and fine and close oxide substrate is put in Muffle furnace after progress low temperature procedure calcining and carries out high-temperature calcination again, it obtains To Pr2Zr2-yInyO7+δSubstrate.
Further, precipitating reagent described in step S1 is ammonium hydroxide, in sodium carbonate, ammonium carbonate, sodium bicarbonate, ammonium hydrogen carbonate It is one or more.
Further, Pr is obtained after its presoma being filtered, washed, dry and roasted described in step S12Zr2- yInyO7+δOxide specifically: by its presoma through filtering, deionized water washing three times, in 90-130 DEG C of drying 5-20 hours, 500-800 DEG C obtains Pr after roasting 4-10 hours2Zr2-yInyO7+δOxide.
Further, use ball mill to above-mentioned Pr described in step S22Zr2-yInyO7+δOxide carries out wet process ball Pr is obtained after mill, drying and roasting2Zr2-yInyO7+δOxide powder, wherein the wet ball grinding time is 0.5-12 hours, is turned Speed is 300-800 revs/min；Drying temperature is 90-130 DEG C, and drying time is 4-20 hours；Maturing temperature is 700-1000 DEG C, heating rate is 1-10 DEG C/min, and calcining time is 4-10 hours.
Further, the volume ratio of the ethanol-water solution in step S2 is 20:1-5.
Further, the diameter of substrate described in step S3 is 10-20 millimeters, with a thickness of 2-6 millimeters.
Further, in the step S3, low temperature procedure calcining is small for 300 DEG C of roastings 1-2 hours, 500 DEG C of roasting 1-2 When, 600 DEG C roasting 2-4 hours；High-temperature calcination temperature is 1300-1700 DEG C, and heating and rate of temperature fall are 0.5-10 DEG C/min, Calcination time is 2-20 hours.
Compared with prior art, the invention has the following beneficial effects:
1, the present invention provides a kind of novel Pr with pyrochlore constitution2Zr2-yInyO7+δSolid electrolyte material, from knot It is seen on structure, which can be write as general formula: A2B2O7□.In seven oxygen sites, six of them oxygen position always accounts for completely According to, and the 7th oxygen position can accommodate an additional oxygen atom.Therefore, the minimal amount of Lacking oxygen is 12.5 %, is one The oxygen ion conductor of kind high concentration defect, and this Open architecture can be by other ion dopings come the migration for oxonium ion More multi-hole is provided, to further increase ion conductivity；
2, compared with traditional YSZ material, under middle low temperature, with higher oxygen ionic conductivity and it is lower from Sub- activation energy；
3, the NO made of the solid electrolytexSensor, under the conditions of simulated automotive tail gas, response and recovery time The advantages such as short, high sensitivity, performance stabilization, favorable reproducibility, Monitoring lower-cut be low, are a kind of NO suitable for large-scale promotion applicationx Detection method.
Detailed description of the invention
Fig. 1 is Pr in the embodiment of the present invention2Zr2-yInyO7+δ(0≤y≤0.3,0 < δ < 1) solid electrolyte material exists Sample XRD spectrogram after being roasted 5 hours at 1500 DEG C.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and embodiments.
Embodiment 1.
In the present embodiment, Pr is carried out first2Zr1.95In0.05O7.025The preparation of solid electrolyte oxide powder:
(1) 26.10 grams of praseodymium nitrates, 0.45 gram of indium nitrate, 18.85 basic zirconium chlorides and 5 grams of urea are weighed respectively, are made into 300 This solution, is poured into the ammonium carbonate-ammonia spirit for 0.5 mol/L being stirred continuously, and the pH of solution is made to be about 9 by milliliter solution, Solution mean transferred is set in five 100 milliliters of reaction kettles after being sufficiently stirred 2 hours, is subsequently placed in 160 DEG C of heating 20 in baking oven Hour, it is cooling, presoma is filtered, washed, 120 DEG C dry 20 hours, 600 DEG C obtain after roasting 4 hours Pr2Zr1.95In0.05O7.025Oxide.
(2) 10 grams of above-mentioned oxide is weighed in agate jar, 15 milliliters of ethanol-water solutions are added, and is turned in ball mill Speed for 500 revs/min lower wet ball grinding 2 hours, 100 DEG C drying 10 hours after 800 DEG C calcine 4 hours, heating rate 10 DEG C/min, obtain Pr2Zr1.95In0.05O7.025Oxide powder.
In the present embodiment, followed by Pr2Zr1.95In0.05O7.025The preparation of ceramic substrate:
Weigh above-mentioned Pr2Zr1.95In0.05O7.025After 10 grams of oxide powder are fully ground in agate jar, powder is adopted It is placed in cold isostatic press under 280 MPa pressure pressure maintaining 5-10 minutes with tablet press machine molding, obtains fine and close oxide substrate, Substrate diameter is 10 millimeters, with a thickness of 2.5 millimeters.Then low temperature procedure is carried out in Muffle furnace by the heating rate of 5 DEG C/min Calcining: 300 DEG C roast 1 hour, and 500 DEG C roast 1 hour, and 600 DEG C roast 3 hours；After 1500 DEG C of high temperature are calcined 5 hours Naturally it is down to room temperature, the XRD spectra of obtained sample is as shown in Figure 1.
In the present embodiment, current mode NO can also be carried outxThe preparation of sensor:
Above-mentioned calcined substrate is cleaned up with ethyl alcohol and acetone respectively, using screen printing technique on substrate two sides Upper NiO and Pt slurry is printed respectively, and draws Pt conducting wires respectively, and NO is madexSensor, 1000 DEG C of roastings 1 in high temperature furnace After hour, it is placed in tube furnace.
This implementation additionally provides properties of product test:
0.18 % CO, 350 ppm C is passed through in laboratory simulation vehicle exhaust3H6, 4.7% CO2, 5% H2O, 600 ppm NO2, 14 % O2, balanced gas N2, connect measurement route.Its conductivity and its right is tested using IM6 electrochemical analyser NO2Response and recovery time.
Embodiment 2.
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that by substrate calcination time from 4 Hour is changed to 15 hours.
Embodiment 3.
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that by wet oxide ball milling Time was changed to 12 hours from 1 hour.
Embodiment 4.
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that by substrate calcination temperature from 1500 DEG C are changed to 1300 DEG C.
Embodiment 5.
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that by substrate calcination temperature from 1500 DEG C are changed to 1650 DEG C.
Embodiment 6.
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that the heating that substrate is calcined Rate is changed to 0.5 DEG C/min from 5 DEG C/min, calcines 12 hours.
Embodiment 7.
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that the heating that substrate is calcined It is adjusted to 0.5 DEG C/min with rate of temperature fall, calcines 12 hours.
Embodiment 8.
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that using Pr2Zr1.7In0.3O7.15Solid electrolyte.
Embodiment 9.
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that using pure Pr2Zr2O7Solid Electrolyte.
Embodiment 10.
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that will Pr2Zr1.95In0.05O7.05Solid electrolyte material is substituted for 8%Y2O3-ZrO2 (YSZ)。
Following table is using Pr2Zr2-xInxO7+δThe sensor of (0≤x≤0.3,0 < δ < 1) solid electrolyte preparation is 700 DEG C when conductivity and its to NO2Response and recovery time.
Serial number Solid electrolyte Conductivity (Scm-1) Response time (S) Recovery time (S)
1 Pr2Zr1.95In0.05O7.025 0.010 68 95
2 Pr2Zr1.95In0.05O7.025 0.012 60 90
3 Pr2Zr1.95In0.05O7.025 0.020 58 75
4 Pr2Zr1.95In0.05O7.025 0.008 110 115
5 Pr2Zr1.95In0.05O7.025 0.030 39 59
6 Pr2Zr1.95In0.05O7.025 0.040 8 22
7 Pr2Zr1.95In0.05O7.025 0.060 3 18
8 Pr2Zr1.7In0.3O7.15 0.005 96 107
9 Pr2Zr2O7 0.003 109 117
10 YSZ 0.020 10 25
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (7)

1. a kind of current mode NOxSensor pyrochlore solid electrolyte material, it is characterised in that: the solid electrolyte material Chemical formula be Pr2Zr2-yInyO7+δ；
Wherein, the range of the y is 0≤y≤0.3；
Wherein, the range of the δ is 0 < δ < 1.
2. a kind of prepare current mode NO described in claim 1xThe method of sensor pyrochlore solid electrolyte material, it is special Sign is: the following steps are included:
Step S1: synthesis pyrochlore Pr2Zr2-yInyO7+δSolid electrolyte oxide:
According to stoichiometric ratio weigh 26.10 grams of praseodymium nitrates, 0-2.71 grams of indium nitrate, 16.43-19.34 grams of basic zirconium chloride and 5-10 grams of urea is added 300 ml deionized waters, dissolution is sufficiently stirred, is denoted as solution A in 500 milliliters of beakers；It weighs appropriate Precipitating reagent is placed in 1000 milliliters of conical flask, and 150 milliliters of deionized water dissolving is added, and stirs 10- using electric mixer 30 minutes, it is denoted as B solution；Then the revolving speed of electric mixer is increased to 700-1000 r/min, is rapidly poured into solution A In B solution, after persistently stirring 1-5 hours, obtained sediment is averagely poured into together with solution to five 100 milliliters of reaction together Kettle is placed in baking oven, 120-200 DEG C after heating 10-24 hours, cooling, its presoma is filtered, washed, dries and is roasted Pr is obtained after burning2Zr2-yInyO7+δOxide;
Step S2:Pr2Zr2-xInxO7+δThe post-processing of oxide:
Weigh the Pr that step S1 is obtained2Zr2-yInyO7+δ4-18 grams of oxide, 10-20 milliliters of ethanol-water solution is added, uses Ball mill is to above-mentioned Pr2Zr2-yInyO7+δOxide carries out wet ball grinding, obtains Pr after drying and roasting2Zr2-yInyO7+δOxygen Compound powder；
Step S3: preparation Pr2Zr2-yInyO7+δSubstrate:
Weigh the Pr that step S2 is obtained2Zr2-yInyO7+δAfter 5-12 grams of oxide powder is fully ground in agate jar, powder It is formed, is subsequently placed in cold isostatic press under 280 MPa pressure pressure maintaining 5-10 minutes using tablet press machine, obtain fine and close oxide Substrate, and fine and close oxide substrate is put in Muffle furnace after progress low temperature procedure calcining and carries out high-temperature calcination again, it obtains Pr2Zr2-yInyO7+δSubstrate；
In the step S3, low temperature procedure calcining roasts for roasting 1-2 hours, 500 DEG C for roasting 1-2 hours, 600 DEG C for 300 DEG C 2-4 hours；High-temperature calcination temperature is 1300-1700 DEG C, and heating and rate of temperature fall are 0.5-10 DEG C/min, calcination time 2-20 Hour.
3. a kind of current mode NO is prepared according to claim 2xThe method of sensor pyrochlore solid electrolyte material, It is characterized by: precipitating reagent described in step S1 be one of ammonium hydroxide, sodium carbonate, ammonium carbonate, sodium bicarbonate, ammonium hydrogen carbonate or It is a variety of.
4. a kind of current mode NO is prepared according to claim 2xThe method of sensor pyrochlore solid electrolyte material, It is characterized by: obtaining Pr after its presoma is filtered, washed, dries and is roasted described in step S12Zr2-yInyO7+δOxidation Object specifically: roast its presoma for drying 5-20 hours, 500-800 DEG C three times, in 90-130 DEG C through filtering, deionized water washing Pr is obtained after burning 4-10 hours2Zr2-yInyO7+δOxide.
5. a kind of current mode NO is prepared according to claim 2xThe method of sensor pyrochlore solid electrolyte material, It is characterized by: using ball mill to above-mentioned Pr described in step S22Zr2-yInyO7+δOxide carries out wet ball grinding, through drying Pr is obtained after dry and roasting2Zr2-yInyO7+δOxide powder, wherein the wet ball grinding time is 0.5-12 hours, revolving speed 300- 800 revs/min；Drying temperature is 90-130 DEG C, and drying time is 4-20 hours；Maturing temperature is 700-1000 DEG C, heating speed Rate is 1-10 DEG C/min, and calcining time is 4-10 hours.
6. a kind of current mode NO is prepared according to claim 2xThe method of sensor pyrochlore solid electrolyte material, It is characterized by: the volume ratio of the ethanol-water solution in step S2 is 20:1-5.
7. a kind of current mode NO is prepared according to claim 2xThe method of sensor pyrochlore solid electrolyte material, It is characterized by: the diameter of substrate described in step S3 is 10-20 millimeters, with a thickness of 2-6 millimeters.
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