CN102557591A - CO2 gas-sensitive material and preparation method and application thereof - Google Patents

CO2 gas-sensitive material and preparation method and application thereof Download PDF

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Publication number
CN102557591A
CN102557591A CN2012100524544A CN201210052454A CN102557591A CN 102557591 A CN102557591 A CN 102557591A CN 2012100524544 A CN2012100524544 A CN 2012100524544A CN 201210052454 A CN201210052454 A CN 201210052454A CN 102557591 A CN102557591 A CN 102557591A
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gas
gas sensitive
sensitive
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hours
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胡季帆
王小风
秦宏伟
范楷
鞠林
时长民
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Shandong University
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Shandong University
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Abstract

The invention relates to a CO2 gas-sensitive material and a preparation method and application thereof. The CO2 gas-sensitive material can be expressed as La1-xCaxMn1-yCuyO3, wherein x is more than or equal to 0 and less than or equal to 0.4, and y is more than or equal to 0 and less than or equal to 0.05. The preparation method comprises the following steps of: synthesizing a precursor by using lanthanum nitrate, calcium nitrate, manganese nitrate, copper nitrate and citric acid as raw materials through a sol-gel method, drying, annealing, grinding, and annealing to obtain a La1-xCaxMn1-yCuyO3 powder material. The material can be used as a thick-film CO2 gas-sensitive element and a ceramic tube filled CO2 gas-sensitive element. The CO2 gas-sensitive material has high gas sensitivity to CO2 gas and is widely applied, the preparation process is simple, and preparation conditions are easy to control.

Description

A kind of CO 2Gas sensitive
Technical field
The present invention relates to the sensing material technical field, particularly a kind of CO 2The air-sensitive sensing material.
Background technology
Human a large amount of fossil energy that uses makes CO2 emissions rise to annual more than 60 hundred million tons, as a kind of greenhouse gases, is considered to cause the principal element of Global warming.Reduce with the carbonic acid gas at present is that main greenhouse gas emission has been classified as the society and economy problem of extraordinarily paying close attention to both at home and abroad.Because people give off carbon dioxide, and monitor the gas concentration lwevel in the enclosed environment, hold ventilation ventilation condition automatically, particularly important for the automatic air exchangeable conditioner equipment of the high-performance of a new generation, need develop convenient, small-sized, sensitive CO 2Detector or monitor.
The infrared absorption type transmitter is arranged at present, and this method measuring accuracy is high, but install huge, price is high, popularize practical difficulty.Also has CO 2Electrochemistry Severinghaus electrode sensor, but be subject to EMI, be mainly used in the carbonic acid gas of surveying in the blood at present.People have have also researched and developed NASICON solid electrolyte type CO 2Transmitter, the requirement of this transmitter counter electrode are very harsh, have strengthened actual manufacturing complexity and cost, also need further perfect.Lead based on electricity at present or resistive type CO 2Gas sensitive mainly concentrates on p-n junction type composite oxide material, for example CuO-BaTiO 3Matrix material, but this sensing member generally is operated in more than 400 ℃, and two kinds of phases of material internal, a kind of p N-type semiconductorN, a kind of n type is produced and is had complicacy, and cost is higher.And performance is also not very high.
Summary of the invention
The object of the invention is exactly for shortcomings such as the complicated process of preparation that solves the prior art existence, working temperature height, and designs a kind of La 1-xCa xMn 1-yCu yO 3Nanocrystalline CO 2Gas sensitive, and provided preparation method and application.
The present invention is realized by following technical scheme: this CO 2The general formula of gas sensitive is La 1-xCa xMn 1-yCu yO 3, wherein, 0≤x≤0.4,0≤y≤0.05.
The present invention gives La1 -xCa xMn 1-yCu yO 3The preparation method, concrete steps are following:
(1) works as x=0, during y=0, press LaMnO 3Stoichiometric ratio takes by weighing Lanthanum trinitrate respectively, and iron nitrate is dissolved in the deionized water, is mixed with the solution of 0.5～1mol/L; When 0＜x≤0.4, during y=0, press La 1-xCa xMn 1-yCu yO 3Stoichiometric ratio takes by weighing Lanthanum trinitrate respectively, nitrocalcite, and manganous nitrate is dissolved in the deionized water, is mixed with the solution of 0.5～1mol/L; Work as x=0, LaMn is pressed in 0＜y≤0.05 o'clock 1-yCu yO 3Stoichiometric ratio takes by weighing Lanthanum trinitrate respectively, and manganous nitrate, cupric nitrate are dissolved in the deionized water, is mixed with the solution of 0.5～1mol/L; Press La 1-xCa xMn 1-yCu yO 3Stoichiometric ratio takes by weighing Lanthanum trinitrate, nitrocalcite, manganous nitrate, cupric nitrate respectively, is dissolved in the deionized water, is mixed with the solution of 0.5～1mol/L;
(2) taking by weighing mol ratio with gas sensitive is 1～3 Hydrocerol A, is dissolved in the deionized water, after the solution that is mixed with 0.5～1mol/L is treated to dissolve fully, will more than various solution mix;
(3) under 40～95 ℃ of conditions, heated while stirring 8～48 hours, make colloidal sol;
(4) colloidal sol is put into baking oven, drying is 2～20 hours under 60～150 ℃, obtains gel;
(5) gel is placed 300～500 ℃ of lehres, annealed 0.5～10 hour, naturally cooling grinds cooled material 10～30 minutes, obtains powder;
(6) the material powder after will grinding was annealed 1～10 hour in 600～1200 ℃ of air, and naturally cooling obtains material La 1-xCa xMn 1-yCu yO 3
The La that obtains according to the inventive method 1-xCa xMn 1-yCu yO 3Material is the calcium titanium ore structure phase, and this phase thermal stability is good.Gas sensitive is not only relevant with prescription, and relevant with the powder annealing after grinding, and is lower than 600 ℃, and the crystallization of uhligite phase is bad, and temperature is higher than 1200 ℃, and crystal grain is too big, and is unfavorable to air-sensitive performance.Optimizing temperature is between 800-1050 ℃.
The invention provides a kind of CO 2The application of gas sensitive is with CO of the present invention 2Gas sensitive is as thick-film type CO 2Gas sensor.Thick-film type CO 2The preparation of gas sensor mark ratio by weight is by 32～44 parts of CO 2Gas sensitive, 1～3 part of glass powder and 55～65 parts of Terpineol 350s mix sizes mixing, and is printed on the Al for preparing electrode 2O 3On the substrate, and under 90～110 ℃, dried 15～35 minutes, annealed 1～3 hour down at 650～850 ℃ at last, make CO 2The thick film gas-sensitive device.
The invention provides another kind of CO 2Gas sensitive La 1-xA xFeO 3Application, with CO of the present invention 2Gas sensitive is as vitrified pipe filled CO 2Gas sensor.Vitrified pipe filled CO 2The preparation of gas sensor mark ratio by weight is by 85～90 parts of CO 2Gas sensitive, 10～15 parts of Terpineol 350s mix, and are filled in the vitrified pipe for preparing electrode, anneal 1.5～4.5 hours down at 600～700 ℃.
The invention has the beneficial effects as follows CO of the present invention 2Gas sensitive and prior art CO 2Gas sensitive is compared, and technology is simple, and preparation condition is easy to control, and to CO 2The air-sensitive of gas is highly sensitive.
Embodiment
Embodiment 1:
Take by weighing the Hydrocerol A of 0.06mol Lanthanum trinitrate, 0.04mol nitrocalcite, 0.1mol manganous nitrate and 0.2mol; Be dissolved in respectively in the deionized water, after the solution that is mixed with 0.5mol/L is treated to dissolve fully, several solns mixed; Under 60 ℃ of conditions, stirred 15 hours the colloidal sol of system; Colloidal sol is put into baking oven, and drying is 5 hours under 90 ℃, obtains gel; Gel is placed 400 ℃ of lehres, annealed 4 hours, ground 20 minutes in agate mortar the cooling back, obtains powder; Material powder after grinding is put into 900 ℃ of lehres once more, annealed 5 hours, obtain powder material La 0.6Ca 0.4MnO 3
La with gained 0.6Ca 0.4MnO 3Material, frit, Terpineol 350 are pressed mass ratio and are mixed at 49: 1: 50, and sizing mixing is printed on the Al for preparing electrode 2O 3On the substrate, and under 110 ℃, dried 15 minutes, annealed 3 hours down at 650 ℃ at last, make CO 2The thick film gas-sensitive device.Prepared CO 2The gas sensitive element is under 320 ℃, to the CO of 2000ppm and 4000ppm 2Sensitivity S=the R of gas g/ R aBe respectively 1.42 and 1.73.
Embodiment 2:
Take by weighing the Hydrocerol A of 0.06mol Lanthanum trinitrate, 0.04mol nitrocalcite, 0.095mol manganous nitrate, 0.005mol cupric nitrate and 0.3mol; Be dissolved in respectively in the deionized water, be mixed with the solution of 1mol/L, after treating to dissolve fully, several solns is mixed; Under 60 ℃ of conditions, stirred 17 hours the colloidal sol of system; Colloidal sol is put into baking oven, and drying is 5 hours under 100 ℃, obtains gel; Gel is placed 350 ℃ of lehres, annealed 3 hours, ground 25 minutes in agate mortar the cooling back, obtains powder; Material powder after grinding is put into 950 ℃ of lehres once more, annealed 3 hours, obtain powder material La 0.6Ca 0.4Mn 0.95Cu 0.05O 3
La with gained 0.6Ca 0.4Mn 0.95Cu 0.05O 3Material, frit, Terpineol 350 are pressed mass ratio and are mixed at 38: 2: 60, and sizing mixing is printed on the Al for preparing electrode 2O 3On the substrate, and under 90 ℃, dried 35 minutes, annealed 1 hour down at 850 ℃ at last, make CO 2The thick film gas-sensitive device.Prepared CO 2The gas sensitive element is under 320 ℃, to the CO of 2000ppm and 4000ppm 2Sensitivity S=the R of gas g/ R aBe respectively 1.35 and 1.61.
Embodiment 3:
Take by weighing the Hydrocerol A of 0.07mol Lanthanum trinitrate, 0.03mol nitrocalcite, 0.1mol manganous nitrate and 0.2mol; Be dissolved in respectively in the deionized water, be mixed with the solution of 0.8mol/L, after treating to dissolve fully, several solns is mixed; Under 80 ℃ of conditions, stirred 17 hours the colloidal sol of system; Colloidal sol is put into baking oven, and drying is 6 hours under 95 ℃, obtains gel; Gel is placed 450 ℃ of lehres, annealed 3 hours, ground 25 minutes in agate mortar the cooling back, obtains powder; Material powder after grinding is put into 1050 ℃ of lehres once more, annealed 4 hours, obtain powder material La 0.7Ca 0.3MnO 3
La with gained 0.7Ca 0.3MnO 3Material mixes by mass ratio with Terpineol 350 at 15: 1, and Al packs into 2O 3Vitrified pipe, and under 600 ℃, annealed 4.5 hours, make CO 2The gas sensitive device.Prepared CO 2The gas sensitive element is under 320 ℃, to the CO of 2000ppm and 4000ppm 2Sensitivity S=the R of gas g/ R aBe respectively 1.5 and 1.7.
Embodiment 4:
Take by weighing the Hydrocerol A of 0.09mol Lanthanum trinitrate, 0.01mol nitrocalcite, 0.1mol manganous nitrate and 0.2mol; Be dissolved in respectively in the deionized water, be mixed with the solution of 0.8mol/L, after treating to dissolve fully, several solns is mixed; Under 75 ℃ of conditions, stirred 24 hours the colloidal sol of system; Colloidal sol is put into baking oven, and drying is 20 hours under 100 ℃, obtains gel; Gel is placed 400 ℃ of lehres, annealed 3 hours, ground 30 minutes in agate mortar the cooling back, obtains powder; Material powder after grinding is put into 960 ℃ of lehres once more, annealed 2 hours, obtain powder material La 0.9Ca 0.1MnO 3
La with gained 0.9Ca 0.1MnO 3Material mixes by mass ratio with Terpineol 350 at 17: 1, and Al packs into 2O 3Vitrified pipe, and under 700 ℃, annealed 1.5 hours, make CO 2The gas sensitive device.Prepared CO 2The gas sensitive element is under 320 ℃, to the CO of 2000ppm and 4000ppm 2Sensitivity S=the R of gas g/ R aBe respectively 1.98 and 2.54.
Embodiment 5:
Take by weighing the Hydrocerol A of 0.075mol Lanthanum trinitrate, 0.025mol nitrocalcite, 0.097mol manganous nitrate, 0.003mol cupric nitrate and 0.3mol; Be dissolved in respectively in the deionized water, be mixed with the solution of 1mol/L, after treating to dissolve fully, several solns is mixed; Under 60 ℃ of conditions, stirred 10 hours the colloidal sol of system; Colloidal sol is put into baking oven, and drying is 5 hours under 120 ℃, obtains gel; Gel is placed 300 ℃ of lehres, annealed 4 hours, ground 20 minutes in agate mortar the cooling back, obtains powder; Material powder after grinding is put into 1000 ℃ of lehres once more, annealed 2 hours, obtain powder material La 0.75Ca 0.25Mn 0.97Cu 0.03O 3
La with gained 0.75Ca 0.25Mn 0.97Cu 0.03O 3Material, frit, Terpineol 350 are pressed mass ratio and are mixed at 49: 1: 50, and sizing mixing is printed on the Al for preparing electrode 2O 3On the substrate, and under 100 ℃, dried 20 minutes, annealed 2 hours down at 700 ℃ at last, make CO 2The thick film gas-sensitive device.Prepared CO 2The gas sensitive element is under 320 ℃, to the CO of 2000ppm and 4000ppm 2Sensitivity S=the R of gas g/ R aBe respectively 1.35 and 1.62.
Embodiment 6:
Take by weighing the Hydrocerol A of 0.085mol Lanthanum trinitrate, 0.015mol nitrocalcite, 0.098mol manganous nitrate, 0.002mol cupric nitrate and 0.1mol; Be dissolved in respectively in the deionized water, be mixed with the solution of 1mol/L, after treating to dissolve fully, several solns is mixed; Under 80 ℃ of conditions, stirred 40 hours the colloidal sol of system; Colloidal sol is put into baking oven, and drying is 15 hours under 90 ℃, obtains gel; Gel is placed 450 ℃ of lehres, annealed 5 hours, ground 30 minutes in agate mortar the cooling back, obtains powder; Material powder after grinding is put into 900 ℃ of lehres once more, annealed 4 hours, obtain powder material La 0.85Ca 0.15Mn 0.98Cu 0.02O 3
La with gained 0.85Ca 0.15Mn 0.98Cu 0.02O 3Material, frit, Terpineol 350 are pressed mass ratio and are mixed at 38: 2: 60, and sizing mixing is printed on the Al for preparing electrode 2O 3On the substrate, and under 110 ℃, dried 30 minutes, annealed 2 hours down at 800 ℃ at last, make CO 2The thick film gas-sensitive device.Prepared CO 2The gas sensitive element is under 320 ℃, to the CO of 2000ppm and 4000ppm 2Sensitivity S=the R of gas g/ R aBe respectively 1.41 and 1.78.
Embodiment 7:
Take by weighing the Hydrocerol A of 0.08mol Lanthanum trinitrate, 0.02mol nitrocalcite, 0.1mol manganous nitrate and 0.3mol; Be dissolved in respectively in the deionized water, be mixed with the solution of 1mol/L, after treating to dissolve fully, several solns is mixed; Under 80 ℃ of conditions, stirred 35 hours the colloidal sol of system; Colloidal sol is put into baking oven, and drying is 10 hours under 110 ℃, obtains gel; Gel is placed 400 ℃ of lehres, annealed 3 hours, ground 20 minutes in agate mortar the cooling back, obtains powder; Material powder after grinding is put into 1050 ℃ of lehres once more, annealed 2 hours, obtain powder material La 0.8Ca 0.2MnO 3
La with gained 0.8Ca 0.2MnO 3Material mixes by mass ratio with Terpineol 350 at 19: 1, and Al packs into 2O 3Vitrified pipe, and under 600 ℃, annealed 2 hours, make CO 2The gas sensitive device.Prepared CO 2The gas sensitive element is under 320 ℃, to the CO of 2000ppm and 4000ppm 2Sensitivity S=the R of gas g/ R aBe respectively 2.1 and 3.15.
Embodiment 8:
Take by weighing the Hydrocerol A of 0.085mol Lanthanum trinitrate, 0.015mol nitrocalcite, 0.099mol manganous nitrate, 0.001mol cupric nitrate and 0.1mol; Be dissolved in respectively in the deionized water, be mixed with the solution of 1mol/L, after treating to dissolve fully, several solns is mixed; Under 95 ℃ of conditions, stirred 9 hours the colloidal sol of system; Colloidal sol is put into baking oven, and drying is 8 hours under 120 ℃, obtains gel; Gel is placed 500 ℃ of lehres, annealed 2 hours, ground 30 minutes in agate mortar the cooling back, obtains powder; Material powder after grinding is put into 950 ℃ of lehres once more, annealed 4 hours, obtain powder material La 0.85Ca 0.15Mn 0.99Cu 0.01O 3
La with gained 0.85Ca 0.15Mn 0.99Cu 0.01O 3Material, frit, Terpineol 350 are pressed mass ratio and are mixed at 38: 2: 60, and sizing mixing is printed on the Al for preparing electrode 2O 3On the substrate, and under 110 ℃, dried 15 minutes, annealed 3 hours down at 700 ℃ at last, make CO 2The thick film gas-sensitive device.Prepared CO 2The gas sensitive element is under 320 ℃, to the CO of 2000ppm and 4000ppm 2Sensitivity S=the R of gas g/ R aBe respectively 1.46 and 1.75.
Embodiment 9:
Take by weighing the Hydrocerol A of 0.1mol Lanthanum trinitrate, 0.1mol manganous nitrate and 0.1mol; Be dissolved in respectively in the deionized water, be mixed with the solution of 1mol/L, after treating to dissolve fully, several solns is mixed; Under 40 ℃ of conditions, stirred 48 hours the colloidal sol of system; Colloidal sol is put into baking oven, and drying is 20 hours under 60 ℃, obtains gel; Gel is placed 300 ℃ of lehres, annealed 10 hours, ground 10 minutes in agate mortar the cooling back, obtains powder; Material powder after grinding is put into 600 ℃ of lehres once more, annealed 10 hours, obtain powder material LaMnO 3
LaMnO with gained 3Material mixes by mass ratio with Terpineol 350 at 9: 1, and Al packs into 2O 3Vitrified pipe, and under 600 ℃, annealed 2 hours, make CO 2The gas sensitive device.Prepared CO 2The gas sensitive element is under 320 ℃, to the CO of 2000ppm and 4000ppm 2Sensitivity S=the R of gas g/ R aBe respectively 1.06 and 1.13.
Embodiment 10:
Take by weighing the Hydrocerol A of 0.1mol Lanthanum trinitrate, 0.095mol manganous nitrate, 0.005mol cupric nitrate and 0.3mol; Be dissolved in respectively in the deionized water, be mixed with the solution of 1mol/L, after treating to dissolve fully, several solns is mixed; Under 95 ℃ of conditions, stirred 8 hours the colloidal sol of system; Colloidal sol is put into baking oven, and drying is 2 hours under 150 ℃, obtains gel; Gel is placed 500 ℃ of lehres, annealed 0.5 hour, ground 30 minutes in agate mortar the cooling back, obtains powder; Material powder after grinding is put into 1200 ℃ of lehres once more, annealed 1 hour, obtain powder material LaMn 0.95Cu 0.05O 3
LaMn with gained 0.95Cu 0.05O 3Material, frit, Terpineol 350 are pressed mass ratio and are mixed at 38: 2: 60, and sizing mixing is printed on the Al for preparing electrode 2O 3On the substrate, and under 110 ℃, dried 25 minutes, annealed 3 hours down at 750 ℃ at last, make CO 2The thick film gas-sensitive device.Prepared CO 2The gas sensitive element is under 320 ℃, to the CO of 2000ppm and 4000ppm 2Sensitivity S=the R of gas g/ R aBe respectively 1.08 and 1.15.
Though above-mentioned specific embodiments of the invention is described; But be not restriction to protection domain of the present invention; One of ordinary skill in the art should be understood that; On the basis of technical scheme of the present invention, those skilled in the art need not pay various modifications that creative work can make or distortion still in protection scope of the present invention.

Claims (9)

1. CO 2Gas sensitive is characterized in that, CO 2The general formula of gas sensitive is La 1-xCa xMn 1-yCu yO 3, wherein, 0≤x≤0.4,0≤y≤0.05.
2. CO as claimed in claim 1 2The preparation method of gas sensitive comprises the steps:
(1) works as x=0, during y=0, press LaMnO 3Stoichiometric ratio takes by weighing Lanthanum trinitrate respectively, and iron nitrate is dissolved in the deionized water, is mixed with the solution of 0.5～1mol/L; When 0＜x≤0.4, during y=0, press La 1-xCa xMn 1-yCu yO 3Stoichiometric ratio takes by weighing Lanthanum trinitrate respectively, nitrocalcite, and manganous nitrate is dissolved in the deionized water, is mixed with the solution of 0.5～1mol/L; Work as x=0, LaMn is pressed in 0＜y≤0.05 o'clock 1-yCu yO 3Stoichiometric ratio takes by weighing Lanthanum trinitrate respectively, and manganous nitrate, cupric nitrate are dissolved in the deionized water, is mixed with the solution of 0.5～1mol/L; Press La 1-xCa xMn 1-yCu yO 3Stoichiometric ratio takes by weighing Lanthanum trinitrate, nitrocalcite, manganous nitrate, cupric nitrate respectively, is dissolved in the deionized water, is mixed with the solution of 0.5～1mol/L;
(2) taking by weighing mol ratio with gas sensitive is 1～3 Hydrocerol A, is dissolved in the deionized water, after the solution that is mixed with 0.5～1mol/L is treated to dissolve fully, will more than various solution mix;
(3) under 40～95 ℃ of conditions, heated while stirring 8～48 hours, make colloidal sol;
(4) colloidal sol is put into baking oven, drying is 2～20 hours under 60～150 ℃, obtains gel;
(5) gel is placed 300～500 ℃ of lehres, annealed 0.5～10 hour, naturally cooling grinds cooled material 10～30 minutes, obtains powder;
(6) the material powder after will grinding was annealed 1～10 hour in 600～1200 ℃ of air, and naturally cooling obtains material La 1-xCa xMn 1-yCu yO 3
3. CO as claimed in claim 2 2The preparation method of gas sensitive is characterized in that, the annealing temperature in the said step (5) is 800-1050 ℃.
4. CO as claimed in claim 1 2Gas sensitive is made thick-film type CO 2The application of gas sensor.
5. CO as claimed in claim 4 2Gas sensitive is made thick-film type CO 2The application of gas sensor is characterized in that, thick-film type CO 2The preparation of gas sensor mark ratio by weight is by 32～44 parts of CO 2Gas sensitive, 1～3 part of glass powder and 55～65 parts of Terpineol 350s mix sizes mixing, and is printed on the Al for preparing electrode 2O 3On the substrate, and under 90～110 ℃, dried 15～35 minutes, annealed 1～3 hour down at 650～850 ℃ at last, make CO 2The thick film gas-sensitive device.
6. one kind by CO as claimed in claim 1 2The thick-film type CO that gas sensitive is processed 2Gas sensor.
7. CO as claimed in claim 1 2Gas sensitive is made vitrified pipe filled CO 2The application of gas sensor.
8. CO as claimed in claim 7 2Gas sensitive is made vitrified pipe filled CO 2The application of gas sensor is characterized in that, vitrified pipe filled CO 2The preparation of gas sensor mark ratio by weight is by 85～90 parts of CO 2Gas sensitive, 10～15 parts of Terpineol 350s mix, and are filled in the vitrified pipe for preparing electrode, anneal 1.5～4.5 hours down at 600～700 ℃.
9. one kind by CO as claimed in claim 1 2The vitrified pipe filled CO that gas sensitive is processed 2Gas sensor.
CN2012100524544A 2012-03-02 2012-03-02 CO2 gas-sensitive material and preparation method and application thereof Pending CN102557591A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106501448A (en) * 2016-10-17 2017-03-15 中国石油大学(华东) A kind of carbonic acid gas lanthanum nano-particular film sensitive to carbon dioxide
CN114813880A (en) * 2022-04-28 2022-07-29 安徽大学 Integrated electrochemical gas sensor and preparation process thereof

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Title
《JETP LETTERS》 19990610 S. A. Sergeenkov et al A sharp decrease of resistivity in La0.7Ca0.3Mn0.96Cu0.04O3: Evidence for Cu-assisted coherent tunneling of spin polarons 858-862 1、2、4-9 第69卷, 第11期 *
《Sensors and Actuators B》 20000610 Youichi Shimizu et al Solid electrolyte CO2 sensor using NASICON and perovskite-type oxide electrode 102-106 1、2、4-9 第64卷, 第1-3期 *
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106501448A (en) * 2016-10-17 2017-03-15 中国石油大学(华东) A kind of carbonic acid gas lanthanum nano-particular film sensitive to carbon dioxide
CN114813880A (en) * 2022-04-28 2022-07-29 安徽大学 Integrated electrochemical gas sensor and preparation process thereof

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Application publication date: 20120711