CN114018987A - Solid electrolyte type hydrogen sensor and manufacturing method thereof - Google Patents
Solid electrolyte type hydrogen sensor and manufacturing method thereof Download PDFInfo
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- CN114018987A CN114018987A CN202111073603.0A CN202111073603A CN114018987A CN 114018987 A CN114018987 A CN 114018987A CN 202111073603 A CN202111073603 A CN 202111073603A CN 114018987 A CN114018987 A CN 114018987A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 48
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims abstract 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000005245 sintering Methods 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 239000007772 electrode material Substances 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 6
- 239000010970 precious metal Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 42
- 229910052697 platinum Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 229910013716 LiNi Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 6
- 239000010416 ion conductor Substances 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- -1 lithium nickel copper zinc oxide Chemical compound 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910002582 La0.3Sr0.7TiO3 Inorganic materials 0.000 claims description 3
- 229910010710 LiFePO Inorganic materials 0.000 claims description 3
- 229910002810 Sm0.5Sr0.5CoO3−δ Inorganic materials 0.000 claims description 3
- 229910009866 Ti5O12 Inorganic materials 0.000 claims description 3
- 229910010252 TiO3 Inorganic materials 0.000 claims description 3
- PACGUUNWTMTWCF-UHFFFAOYSA-N [Sr].[La] Chemical compound [Sr].[La] PACGUUNWTMTWCF-UHFFFAOYSA-N 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910012675 LiTiO2 Inorganic materials 0.000 claims description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 2
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical group [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000007581 slurry coating method Methods 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910015645 LiMn Inorganic materials 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 150000002431 hydrogen Chemical class 0.000 description 14
- 229910021526 gadolinium-doped ceria Inorganic materials 0.000 description 10
- 238000000227 grinding Methods 0.000 description 8
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910002430 Ce0.8Gd0.2O2-δ Inorganic materials 0.000 description 2
- 229910002436 Ce0.8Gd0.2O2−δ Inorganic materials 0.000 description 2
- 229910002437 Ce0.8Sm0.2O2−δ Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 1
- 229910020784 Co0.2O2 Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 241000968352 Scandia <hydrozoan> Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
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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
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/36—Embedding or analogous mounting of samples
-
- 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
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/36—Embedding or analogous mounting of samples
- G01N2001/366—Moulds; Demoulding
Abstract
The invention provides a solid electrolyte type hydrogen sensor and a manufacturing method thereof, wherein the structure of the solid electrolyte type hydrogen sensor is a sensitive electrode layer, a solid electrolyte layer and a reference electrode layer which are sequentially and closely contacted; the sensitive electrode layer is made of lithium-containing transition metal oxide materials or titanate materials; the solid electrolyte layer is a solid substance having ion conductivity at high temperature; the reference electrode layer is made of a noble metal material. The manufacturing steps are as follows: pressing solid electrolyte powder into a tablet, sintering at high temperature, coating precious metal slurry on one side of the tablet, leading out a platinum wire to be used as a current collector, and sintering and curing at high temperature to be used as a reference electrode; and coating a small amount of noble metal slurry on the other side, sintering and curing at high temperature, uniformly coating a sensitive electrode material with a certain thickness on the noble metal slurry, and sintering and curing at high temperature again to prepare the sensitive electrode. The hydrogen sensor has the advantages of high sensitivity to hydrogen, strong anti-interference capability, quick response and recovery characteristic, high temperature resistance, simple structure, easy manufacture, low cost and good stability.
Description
Technical Field
The invention belongs to the field of gas sensors, and particularly relates to a solid electrolyte type hydrogen sensor and a manufacturing method thereof.
Background
Hydrogen, a clean and new energy source, has high reducibility and no pollution, and therefore occupies an extremely important position in fields including fuel cell automobiles, metal metallurgy, the electronic industry, medical chemistry, aerospace, military and the like, and is favored by various industries.
However, hydrogen gas is a colorless and odorless gas, has a very small molecular weight, risks of leakage during storage, transportation and use, and is difficult to find, and the relevant information shows that the explosion limit of hydrogen gas is 4% -75% (40000 ppm-750000 ppm), namely hydrogen gas is exposed to air, and the content of hydrogen gas is in the range, and explosion is extremely easy to occur when exposed to open fire. Therefore, how to safely and efficiently use and monitor and detect hydrogen in the process of using hydrogen also becomes a research hotspot, and strict requirements are put on a hydrogen sensor for detecting hydrogen in use.
The hydrogen sensor is a device capable of converting the concentration of hydrogen in the air into an electric signal and rapidly acquiring relevant information of the hydrogen. Among them, the electrochemical hydrogen sensor can be divided into two categories based on the selected electrolyte material: liquid electrolyte type hydrogen sensors and solid electrolyte type hydrogen sensors. The former has the defects of difficult packaging, easy corrosion, easy leakage, fast aging, short service life, no high temperature resistance and the like, and the latter is developed for solving the problem. Further, another great advantage of the solid electrolyte type gas sensor is that it can operate in a high-temperature and severe environment.
The structure of the solid electrolyte type gas sensor is a three-layer structure of a sensitive electrode, a solid electrolyte and a reference electrode. Commonly used reference electrodes are noble metal electrodes, such as Pt electrodes; the sensitive electrode material is a material having catalytic activity for hydrogen. Solid state electrolytes are materials that have a high oxygen ion or proton conductivity at high temperatures. Improving the catalytic activity of the sensitive electrode on hydrogen is a key technology for improving the response of the sensor on the gas to be detected. The current commonly used sensitive electrode materials in the prior art are noble metals, metal oxides and other materials. Noble metal materials are expensive, and in the case of Pt, a hydrogen sensor using Pt as a sensitive electrode has a small response at an operating temperature higher than 500 ℃ and a poor selectivity at a temperature lower than 400 ℃. The price of the metal oxide is cheaper, and Lu and the like report that a hydrogen sensor taking ZnO as a sensitive electrode has higher response potential to 200ppm of hydrogen at 600 ℃, but the response and recovery time is relatively longer (5-10 seconds). In addition, the expansion of the three-phase reaction interface by regulating and controlling the sensitive electrode microstructure is also an important method for improving the sensitive electrode performance, however, the methods have the problems of high cost, complex process, difficulty in repetition and the like. The solid electrolyte-based gas sensor uses the lithium-containing transition metal oxide or the doped titanate material as the sensitive electrode material, has higher selectivity and responsivity to hydrogen in a larger temperature range, and has the advantages of simple device structure, simple manufacturing process, low cost and good stability.
Disclosure of Invention
Based on the defects of the prior art, the technical problem to be solved by the invention is to provide a solid electrolyte type hydrogen sensor with a good response effect on hydrogen and a manufacturing method thereof.
The invention adopts the following technical scheme:
a solid electrolyte type hydrogen sensor comprises a sensitive electrode material layer (1), a solid electrolyte layer (2) and a reference electrode layer (3) which are in close contact with each other in sequence,
the sensitive electrode layer (1) is made of lithium-containing transition metal oxide or titanate material;
the material of the solid electrolyte layer (2) is an oxygen ion conductor, or a proton conductor, or a compound of the oxygen ion conductor and a semiconductor material, or a compound of the proton conductor and the semiconductor material;
the reference electrode layer (3) is made of one of a noble metal electrode material, silver Ag and platinum Pt.
The specific method of the technical scheme is as follows: the sensitive electrode layer (1) is made of lithium-containing transition metal oxide lithium nickel cobalt aluminum oxide (LiNi)xCo1-x-yAlyO2-δX is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, x + y is more than or equal to 0 and less than or equal to 1) and lithium nickel cobalt manganese oxide (LiNi)xCoyMn1-x-yO2-δX is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, x + y is more than or equal to 0 and less than or equal to 1) and lithium nickel copper zinc oxide (LiNi)1-x-yCuxZnyO2-δX is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, x + y is more than or equal to 0 and less than or equal to 1), lithium iron phosphate (LiFePO)4) Lithium manganate (LiMn)2O4) Lithium titanate (Li)4Ti5O12Or LiTiO2) One of (1); the titanate material is lanthanum strontium titanate (La)1-xSrxTiO3X is more than or equal to 0 and less than or equal to 1) lanthanum strontium calcium titanium oxide (La0.3Sr0.7CayTi1-yO3Y is more than or equal to 0 and less than or equal to 1).
The material of the solid electrolyte layer (2) is oxygen ion conductor zirconia-based electrolyte or doped ceria-based electrolyte; the proton conductor is a barium zirconate-based electrolyte or a barium cerate-based electrolyte; the semiconductor material is solid oxide fuel cell electrode material, or ZnO, TiO2、CeO2、WO3、SrTiO3One kind of (1). Wherein the electrode material of the solid oxide fuel cell is La0.3Sr0.7TiO3，Sm0.5Sr0.5CoO3-δ，La1-xSrxMnO3-δ、La1-xSrxCoyFe1-yO3-δ、Ba1-xSrxCoyFe1- yO3-δ、La1-xSrxCayTi1-yO3-δ、La1-xSrxCryMn1-yO3-δ、Sr0.97Ti1-xFexO3-δ、La1-xSrxFeyTi1-yO3-δOne kind of (1).
According to the components, the invention provides a preparation method of a solid electrolyte type hydrogen sensor, which comprises the following manufacturing steps:
(a) pressing the powdery solid electrolyte material into tablets, and sintering at high temperature;
(b) uniformly coating precious metal slurry on one side surface of the sintered substrate, leading out a platinum wire as a current collector, and sintering and curing at high temperature to prepare a reference electrode;
(c) coating a small amount of noble metal slurry on the other side of the substrate with the prepared reference electrode, leading out a platinum wire as a current collector, sintering and curing at high temperature, uniformly coating a sensitive electrode material on the other side, sintering and curing at high temperature again to prepare the sensitive electrode, wherein the coating thickness of the sensitive electrode material is based on covering the noble metal and the electrolyte and meeting the use requirement, and then the product of the invention is obtained.
The coating method in the above steps is one of a slurry coating method, a screen printing method, a casting method, or a sputtering method.
Or in the step (b), one end of one side surface of the sintered substrate is uniformly coated with noble metal slurry, and a platinum wire is led out to be used as a current collector and to be sintered and solidified at high temperature to be used as a reference electrode; and (c) coating a small amount of precious metal slurry on the other end of the same side, leading out a platinum wire serving as a current collector, sintering and curing at high temperature, uniformly coating a sensitive electrode material on the end, and sintering and curing at high temperature again to prepare the sensitive electrode.
Because the invention adopts the novel sensitive electrode material, compared with the prior art, the invention has the following beneficial effects: the solid electrolyte type hydrogen sensor and the manufacturing method thereof have the characteristics of high sensitivity to hydrogen gas, good anti-interference performance and fast response recovery characteristic in a wider temperature range, and the device is simple in manufacturing process, low in cost, and good in repeatability and stability.
Drawings
FIGS. 1 and 2 are schematic views showing two types of flat plate structures of a solid electrolyte type gas sensor;
FIG. 3 is a schematic representation of the use of LiNi0.8Co0.15Al0.05O2As a sensitive electrode, Ce0.8Sm0.2O2-δGas sensor using (SDC, samarium-doped cerium oxide) as solid electrolyte material and Ag as reference electrode is used for detecting H at 400 DEG C2The response curve of (c). The response voltage rose from-19.8 mV to 1.3mV after the addition of 50ppm of hydrogen.
Detailed Description
Example 1:
0.5g of powdered solid electrolyte Ce0.8Sm0.2O2-δAnd (SDC, samarium-doped cerium oxide) is put into a grinding tool and pressed into an SDC substrate, and the SDC substrate is sintered at high temperature to ensure that the SDC substrate has certain rigidity. Uniformly coating silver paste on one side of the SDC substrate, leading out a platinum wire, sintering and curing at high temperature in a tube furnace, and preparing the reference electrode. Coating a small amount of silver dots on the other side, leading out a platinum wire, and performing high-temperature sintering treatment as above. A reference electrode is made. Coating a small amount of silver dots on the other side, leading out a platinum wire, and performing high-temperature sintering treatment as above. Sensitive electrode material LiNi by using brush coating method0.8Co0.15Al0.05O2(Here Nix,x＝0.8、AlyY-0.05, NCAL) is uniformly coated on one side of the SDC substrate with a small amount of silver dots to ensure that the silver dots are completely covered by the material, and the sensitive electrode is obtained by high-temperature sintering. The resulting device was a solid electrolyte type gas sensor. The response data of the sensor to hydrogen at 400 degrees celsius is shown in fig. 3.
Example 2:
0.4g of powdered solid electrolyte Ce0.8Gd0.2O2-δ(GDC, gadolinium doped cerium oxide) is put into a grinding tool and pressed into a GDC substrate, and the GDC substrate is sintered at high temperature to have certain rigidity. And uniformly coating platinum slurry on one side of the GDC substrate, leading out a platinum wire, and sintering at high temperature to solidify the platinum slurry to prepare the reference electrode. Coating a small amount of platinum dots on the other side, leading out a platinum wire, and performing high-temperature sintering treatment as above. Sensitive electrode material LiNi by using brush coating method0.8Co0.2O2(Here Nix,x＝0.8、MnyY is 0, LNCO for short) is uniformly coated on one side of the GDC substrate having a small number of platinum dots to ensure that the platinum dots are completely covered by the material, thereby forming the sensing electrode. The resulting device was a solid electrolyte type gas sensor.
Example 3: 0.5g of powdered solid electrolyte Ce0.8Sm0.2O2-δ-Ce0.8Gd0.2O2-δ(SDC-GDC) is put into a grinding tool and pressed into an SDC-GDC substrate, and the SDC-GDC substrate is sintered at high temperature to have certain rigidity. Uniformly coating silver paste on one side of the SDC-GDC substrate, leading out a platinum wire, sintering and curing at high temperature in a tube furnace, and preparing the reference electrode. Coating a small amount of silver dots on the other side, leading out a platinum wire, and performing high-temperature sintering treatment as above. Sensitive electrode material LiNi is prepared by using spin coating method1/3Co1/3Mn1/3O2(Here Nix,x＝1/3、Mny1/3 LNCM below) is coated on the side of SDC substrate with a small amount of silver dots to ensure that the silver dots are covered by the material completely, and then the sensitive electrode is obtained by high-temperature sintering. The resulting device was a solid electrolyte type gas sensor.
Example 4: 0.6g of powdered solid electrolyte YSZ (yttria stabilized zirconia) is put into a grinding tool and pressed into a YSZ substrate, and the YSZ substrate is sintered at high temperature to ensure that the YSZ substrate has certain rigidity. And uniformly coating platinum slurry on one side of the YSZ substrate, leading out a platinum wire, sintering and curing at high temperature in a tube furnace, and preparing the reference electrode. Coating a small amount of platinum dots on the other side, leading out a platinum wire, and performing high-temperature sintering treatment as above. Sensitive electrode material lithium titanate (Li) by screen printing method4Ti5O12LTO) is uniformly coated on one side of the SDC substrate with a small number of platinum points to ensure that the platinum points are completely covered by the material, and the sensitive electrode is obtained by high-temperature sintering. The resulting device was a solid electrolyte type gas sensor.
Example 5: 0.35g of powdered solid electrolyte SSZ (scandia stabilized zirconia) was placed in a grinding tool and pressed into an SSZ substrate, which was sintered at high temperature to give it a certain rigidity. And uniformly coating platinum slurry on one side of the SSZ substrate, leading out a platinum wire, sintering and curing at high temperature in a tube furnace, and preparing the reference electrode. Coating a small amount on the other sidePlatinum points are formed, a platinum wire is led out, and the high-temperature sintering treatment is the same as the above. Using magnetron sputtering method to make sensitive electrode material lanthanum strontium titanate (La)0.3Sr0.7TiO3LST for short) is uniformly prepared on one side of the SSZ substrate with a small amount of platinum points to ensure that the material is completely covered, and the sensitive electrode is obtained by high-temperature sintering. The resulting device was a solid electrolyte type gas sensor.
Example 6: 0.5g of powdered solid electrolyte Ce0.8Sm0.2O2-δ-Sm0.5Sr0.5CoO3-δ(SDC-SSC) is put into a grinding tool and pressed into an SDC-SSC substrate, and the substrate is sintered at high temperature to ensure that the substrate has certain rigidity. And uniformly coating platinum slurry on one side of the SDC-SSC substrate, leading out a platinum wire, sintering and curing at high temperature in a tubular furnace, and preparing the reference electrode. Coating a small amount of platinum dots on the other side, leading out a platinum wire, and performing high-temperature sintering treatment as above. The sensitive electrode material lithium iron phosphate (LiFePO) is prepared by a tape casting method4LFP for short) is uniformly prepared on one side of the SDC-SSC substrate with a small number of platinum points to ensure that the material is completely covered, and the sensitive electrode is obtained by high-temperature sintering. The resulting device was a solid electrolyte type gas sensor.
Example 7: 0.5g of powdered solid electrolyte Ce0.8Sm0.05Ca0.15O2-δ-La0.3Sr0.7TiO3(SCDC-LST) is put into a grinding tool and pressed into an SCDC-LST substrate, and the SCDC-LST substrate is sintered at high temperature to ensure that the SCDC-LST substrate has certain rigidity. And uniformly coating platinum slurry on one side of the SCDC-LST substrate, leading out a platinum wire, sintering and curing at high temperature in a tubular furnace, and preparing the reference electrode. Coating a small amount of platinum dots on the other side, leading out a platinum wire, and performing high-temperature sintering treatment as above. The sensitive electrode material lithium manganate (LiMn) is sprayed2O4LMO for short) is uniformly prepared on one side of the SCDC-LST substrate with a small amount of platinum points to ensure that the material is completely covered, and the sensitive electrode is obtained by high-temperature sintering. The resulting device was a solid electrolyte type gas sensor.
Example 8: 0.5g of powdery solid electrolyte powder BaZr0.9Y0.1O3(BZY) is put into a grinding tool and pressed into a BZY substrate, and the BZY substrate is sintered at high temperature to ensure that the BZY substrate has certain rigidity.And uniformly coating platinum slurry on one side of the BZY substrate, leading out a platinum wire, sintering and curing at high temperature in a tubular furnace, and preparing the reference electrode. Coating a small amount of platinum dots on the other side, leading out a platinum wire, and performing high-temperature sintering treatment as above. Sensitive electrode material LiNi by using brush coating method0.8Cu0.15Zn0.05O2-δ(Here Cu)x,x＝0.15、ZnyY 0.05, hereinafter LNCZ) is uniformly prepared on one side of the SCDC-LST substrate with a small number of platinum dots to ensure that the material is completely covered, and the sensitive electrode is obtained by high-temperature sintering. The resulting device was a solid electrolyte type gas sensor.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. A solid electrolyte type hydrogen sensor comprises a sensitive electrode material layer (1), a solid electrolyte layer (2) and a reference electrode layer (3) which are sequentially and closely contacted; the sensitive electrode layer (1) is made of lithium-containing transition metal oxide or titanate material; the material of the solid electrolyte layer (2) is an oxygen ion conductor, or a proton conductor, or a compound of the oxygen ion conductor and a semiconductor material, or a compound of the proton conductor and the semiconductor material; the reference electrode layer (3) is made of a noble metal electrode material, and is made of one of silver Ag and platinum Pt;
the method is characterized in that: the sensitive electrode layer (1) is made of lithium-containing transition metal oxide (LiNi-Co-Al-O-Al oxide)xCo1-x-yAlyO2-δX is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, x + y is more than or equal to 0 and less than or equal to 1) and lithium nickel cobalt manganese oxide (LiNi)xCoyMn1-x-yO2-δX is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, x + y is more than or equal to 0 and less than or equal to 1) and lithium nickel copper zinc oxide (LiNi)1-x-yCuxZnyO2-δX is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, x + y is more than or equal to 0 and less than or equal to 1), lithium iron phosphate (LiFePO)4) Lithium manganate (LiMn)2O4) Lithium titanate (Li)4Ti5O12Or LiTiO2) One of (1);
or said sensitive electrode layer (1)The material is titanate material is lanthanum strontium titanate (La)1-xSrxTiO3X is more than or equal to 0 and less than or equal to 1) lanthanum strontium calcium titanium oxide (La0.3Sr0.7CayTi1-yO3Y is more than or equal to 0 and less than or equal to 1).
2. A solid electrolyte type hydrogen sensor according to claim 1, characterized in that the material of the solid electrolyte layer (2) is an oxygen ion conductor zirconia-based electrolyte, or a doped ceria-based electrolyte; the proton conductor is a barium zirconate-based electrolyte or a barium cerate-based electrolyte; the semiconductor material is solid oxide fuel cell electrode material, or ZnO, TiO2、CeO2、WO3、SrTiO3One kind of (1).
3. A solid electrolyte type hydrogen sensor according to claim 1 or 2, characterized in that the electrode material of the solid oxide fuel cell is La0.3Sr0.7TiO3，Sm0.5Sr0.5CoO3-δ，La1-xSrxMnO3-δ、La1-xSrxCoyFe1- yO3-δ、Ba1-xSrxCoyFe1-yO3-δ、La1-xSrxCayTi1-yO3-δ、La1-xSrxCryMn1-yO3-δ、Sr0.97Ti1-xFexO3-δ、La1- xSrxFeyTi1-yO3-δOne kind of (1).
4. A preparation method of a solid electrolyte type hydrogen sensor is characterized by comprising the following specific manufacturing steps:
(a) pressing the powdery solid electrolyte material into tablets, and sintering at high temperature to ensure that the solid electrolyte material has certain rigidity;
(b) uniformly coating precious metal slurry on one side surface of the sintered substrate, leading out a platinum wire as a current collector, and sintering and curing at high temperature to prepare a reference electrode;
(c) coating a small amount of noble metal slurry on the other side of the substrate with the prepared reference electrode, leading out a platinum wire as a current collector, sintering and curing at high temperature, uniformly coating a sensitive electrode material on the other side, sintering and curing at high temperature again to prepare the sensitive electrode, wherein the coating thickness of the sensitive electrode material is based on covering the noble metal and the electrolyte and meeting the use requirement, and then the product of the invention is obtained.
The coating method in the above steps is one of a slurry coating method, a screen printing method, a casting method, or a sputtering method.
5. The method according to claim 4, wherein in the step (b), a noble metal paste is uniformly applied to one end of one side of the sintered substrate, and a platinum wire is led out to serve as a current collector, and is sintered and cured at a high temperature to serve as a reference electrode; and (c) coating a small amount of precious metal slurry on the other end of the same side, leading out a platinum wire serving as a current collector, sintering and curing at high temperature, uniformly coating a sensitive electrode material on the end, and sintering and curing at high temperature again to prepare the sensitive electrode.
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