CN105322246A - Storage battery module and fabrication method thereof - Google Patents
Storage battery module and fabrication method thereof Download PDFInfo
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- CN105322246A CN105322246A CN201510712104.XA CN201510712104A CN105322246A CN 105322246 A CN105322246 A CN 105322246A CN 201510712104 A CN201510712104 A CN 201510712104A CN 105322246 A CN105322246 A CN 105322246A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000003860 storage Methods 0.000 title claims abstract description 36
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 147
- 239000000758 substrate Substances 0.000 claims description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 229910052697 platinum Inorganic materials 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 42
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 38
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 38
- 239000007772 electrode material Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 239000002105 nanoparticle Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 21
- 230000007797 corrosion Effects 0.000 claims description 21
- 238000005260 corrosion Methods 0.000 claims description 21
- 238000005530 etching Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- 239000011858 nanopowder Substances 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 18
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 229910052727 yttrium Inorganic materials 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 12
- 238000006056 electrooxidation reaction Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 10
- 230000002093 peripheral effect Effects 0.000 claims description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000008213 purified water Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 238000007650 screen-printing Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 7
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 6
- 241001122767 Theaceae Species 0.000 claims description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 239000001630 malic acid Substances 0.000 claims description 6
- 235000011090 malic acid Nutrition 0.000 claims description 6
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims description 6
- 229930182490 saponin Natural products 0.000 claims description 6
- 150000007949 saponins Chemical class 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000002848 electrochemical method Methods 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 23
- 230000004044 response Effects 0.000 abstract description 19
- 238000011084 recovery Methods 0.000 abstract description 14
- 231100001261 hazardous Toxicity 0.000 abstract description 5
- 239000002360 explosive Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 66
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 18
- 238000001514 detection method Methods 0.000 description 10
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 2
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- 239000004020 conductor Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a storage battery module and a fabrication method thereof. By arranging a solid electrolyte type gas sensor around a storage battery, hazardous gas around the storage battery can be rapidly and accurately detected, moreover, the unexpected sensitivity and the ultrafast response recovery rate are achieved, flammable and explosive dangerous cases during the usage of the storage battery can be timely found, and the storage battery module has great market prospects.
Description
Technical Field
The invention relates to the field of batteries, in particular to a storage battery module and a manufacturing method thereof.
Background
The storage battery is a device for directly converting chemical energy into electric energy, and after discharging, internal active substances can be regenerated in a charging mode, namely, the electric energy is stored into the chemical energy, and the chemical energy is converted into the electric energy again when discharging is needed.
The storage battery is subjected to chemical reaction during operation, which is generally accompanied by generation of gas and the like, and the storage battery is sometimes placed in an environment filled with dangerous gas, so that detection of gas is highly necessary.
Disclosure of Invention
The invention provides a storage battery module and a manufacturing method thereof, aiming at the problems in the background technology.
The invention provides the following technical scheme:
a storage battery module is provided with a solid electrolyte type gas sensor arranged at the periphery of a storage battery, the solid electrolyte type gas sensor comprises a heating plate, a Yttrium Stabilized Zirconia (YSZ) substrate (1) arranged on the heating plate, a platinum (Pt) reference electrode (4) arranged on the YSZ substrate, a sensitive electrode A (3) and a sensitive electrode B (5), wherein the sensitive electrode A and the sensitive electrode B are respectively arranged at two sides of the Pt reference electrode, the sensitive electrode A is made of tungsten oxide nanoparticles doped with nano nickel oxide powder, and the sensitive electrode B is made of nano SnO2And (3) pulverizing.
Preferably, the YSZ substrate is doped with 8 mol% of Y2O3The physical size is 6mm 4mm 0.2mm, and two nano porous structures with 1 x 2mm areas are corroded by an electrochemical method and are respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on the nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and the electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
A manufacturing method of a storage battery module is characterized in that a solid electrolyte type gas sensor is arranged at the peripheral position of a storage battery, the solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged at two sides of the Pt reference electrode; wherein,
a. ultrasonically cleaning a YSZ substrate with water and absolute ethyl alcohol successively for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a 1-by-2 mm thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, sintering in a muffle furnace at 200 ℃ for 20 minutes, and taking out to obtain the prototype device of the sensor.
Preferably, the first and second liquid crystal materials are,
(1) porous yttria-stabilized zirconia (YSZ) (2) preparation:
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 6mm by 4mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass portion, 1-1.8% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the YSZ flat plates and are completely immersed, the YSZ flat plates are treated for 20-28min at the temperature of 50-58 ℃, then the YSZ flat plates are treated for 2min by microwave, and the YSZ flat plates are cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 2-5s at an interval of 10min for 3-5 times;
c. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, placing the mixture into a double-electric-tank electrochemical device, wherein the etching tank and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching tank into two non-communicated areas, and the center of the clamp is provided with two holes with a specific shape of 1 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures (2) with the area of 1 x 2mm on a YSZ flat plate, and after the preparation is finished and cleaned, storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g of Na2WO4, dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the condition of stirring until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, adding 75g of KNO3, violently stirring to form a paste, carrying out hydrothermal reaction at 180 ℃ for 12h, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly, SnO with the grain diameter of 15-22nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. and standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain the sensitive electrode B.
The invention has the advantages that:
the solid electrolyte type gas sensor is arranged at the peripheral position of the storage battery, so that unexpected sensitivity and ultra-fast response recovery speed are achieved for detection of dangerous gas, flammable and explosive dangerous situations of the storage battery in the using process can be found in time, and the storage battery has a great market prospect.
Drawings
FIG. 1 is a schematic view of a dual cell electrochemical device;
FIG. 2 is a schematic view of the structure of the secondary battery of the present invention;
FIG. 3 is a schematic diagram of the porous structure of a YSZ plate;
fig. 4 is a schematic structural view of the gas sensor of the present invention.
Detailed Description
The technical invention is mainly designed by considering the following points:
gas sensor
The gas sensor is a device or apparatus capable of converting the type, concentration, etc. of a target gas into a detectable signal according to a certain rule in air or an environment with certain characteristics. The detection modes mainly comprise test current, resistance, potential, heat, temperature and the like. The gas sensor is mainly classified into a semiconductor type, a solid electrolyte type, and the like according to its operating characteristics.
Solid electrolyte
Solid electrolyte type gas sensors are generally electrochemical sensors, mainly composed of electrolytes, sensitive electrodes and reference electrodes, and the electrolytes are important components of the sensors. Conductors are classified into electronic conductors and ionic conductors according to the difference of carriers, the latter being electrolytes, and some ionic crystals having high ionic conductivity in addition to general liquid electrolytes, such solid conductors being called solid electrolytes (solid electrolytes) including ceramics, glass, inorganic metal salts and some organic polymer materials.
The conductive ions in the solid electrolyte may be either cations or anions, which are mainly determined by defects of the material itself.
Yttrium Stabilized Zirconia (YSZ)
Stabilized zirconia/Yttria Stabilized Zirconia (YSZ) is one of the most useful solid electrolytes, zirconia (ZrO) at ambient temperatures2) Is a monoclinic crystal, has low ionic conductivity, and can be doped with proper amount of divalent or trivalent cubic symmetric oxide (Y)2O3、MgO、CaO、Sc2O3) It is treated to exhibit ion conductivity, has high oxygen ion conductivity, excellent chemical stability, and thermal and mechanical stability, and has been widely used in the fields of solid oxide fuel cells and gas sensors.
Porous structure YSZ
The porous structure YSZ is still composed of originally interconnected atoms in terms of elemental composition, but has a unique porous and loose structure. The specific surface area is large, gas can react on a three-phase interface (zirconium oxide, electrode and gas) conveniently, and the sensitivity is improved. The porous region of YSZ is prepared by adopting a double-groove electrochemical corrosion method, the preparation process is simple, and the appearance of the porous region is easy to control.
Gas-sensitive properties of tungsten oxide
Tungsten oxide is an n-type metal oxide semiconductor, and is a surface resistance control type gas sensitive material. The atomic property of the surface of the tungsten oxide crystal is active, gas molecules are easy to adsorb, and when the gas molecules are adsorbed on the surface of the crystal, the concentration of carriers in the tungsten oxide crystal is correspondingly changed, which is expressed as the resistance change of the sensor. The mechanism of resistance change generated by gas absorption and desorption of the tungsten oxide gas sensor, namely the gas-sensitive mechanism, is very complex, and researchers have not been uniformly known so far. Research shows that tungsten oxide is coupled with NO2、HS2、SO2And various gases have better gas-sensitive characteristics. However, the sensitivity, selectivity and the like of a pure tungsten oxide film are mostly insufficient, the tungsten oxide nanoparticles prepared by the method can increase the contact area of the material and the gas to be detected, and improve the sensitivity, and in addition, nickel oxide particles with catalytic action or selectivity on gas adsorption are compounded, so that the selectivity of the sensitive electrode on nitrogen oxide gas is improved.
SnO2Gas-sensitive nature
SnO2Belongs to an n-type semiconductor, and has obvious gas-sensitive effect due to the existence of oxygen vacancies or tin ions, and the gas-sensitive mechanism is generally considered to be a surface adsorption control type mechanism. When heated to a certain temperature in clean air, O2Will be in SnO2Surface adsorption to form multiple adsorbed oxygen species, with electrons from SnO2The crystal grains are transferred to adsorbed oxygen, a depletion layer is formed on the surface of SnO2 crystal grains, the conductivity of sensitive materials is reduced, and the sensitive materials are exposed to a reducing detection atmosphere (H)2CO, hydrocarbon gas), the detected gas reacts with the adsorbed oxygen species, SnO2The adsorbed oxygen on the surface of the crystal grains or on the grain boundary is desorbed, the depletion layer becomes thinner, the conductivity is increased, and the gas is detected through the change of the material conductivity. In the present invention at SnO2Pt is added for modification on the basis of the nano film, so that the detection sensitivity of the nano film to CO is greatly improved.
For the sensitive mechanism of the yttrium-stabilized zirconia-based NOx sensor, when the sensor is placed in a gas detection environment, a series of chemical reactions occur on a three-phase interface (zirconia, an electrode and gas), because the catalytic rates of the sensitive electrode and the reference electrode are different, a potential difference is formed between the sensitive electrode and the reference electrode, and the magnitude of the potential difference reflects the concentration of the gas to be detected, so that the purposes of detecting the gas and the concentration of the gas are achieved. Therefore, the electrochemical and chemical catalytic activity of the electrode material, the electrode microstructure and the like are main factors considered by the sensitive electrode.
Fig. 2 is a schematic structural view of a battery module according to the present invention, in which a gas sensor 1 is provided around the battery module 10.
Example 1:
a manufacturing method of a storage battery module is characterized in that a solid electrolyte type gas sensor is arranged at the peripheral position of a storage battery, the solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged at two sides of the Pt reference electrode;
the solid electrolyte type gas sensor is manufactured by the following method:
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 6mm by 4mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass parts, 1% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the pure water, completely immersed, treated for 20min at the temperature of 58 ℃, then treated for 2min by microwave, cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 5s at an interval of 10min for 3 times in total;
c. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, putting the mixture into a double-cell electrochemical device (shown in figure 1), wherein the etching cell and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching cell into two regions which are not communicated with each other, and the center of the clamp is provided with two holes with a specific shape of 1 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures with the area of 1 x 2mm on a YSZ flat plate, and after the preparation is finished and cleaned, storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g Na2WO4Dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the stirring condition until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, and then adding 75g of KNO3Violently stirring to form paste, carrying out hydrothermal reaction for 12h at 180 ℃, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly, SnO with the particle size of 22nm2Drying the nanometer powder in a vacuum drying oven at 80 deg.CDrying for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain a sensitive electrode B;
(4) gas sensor fabrication
The nitrogen oxide sensor is mainly composed of two parts: porous YSZ flat plate and Pt 'ji' shape electrode heating plate, the device preparation steps are as follows:
a. taking the YSZ substrate treated in the step (1), sequentially carrying out ultrasonic cleaning with water and absolute ethyl alcohol for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a 1-by-2 mm thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. uniformly coating a layer of inorganic adhesive (water glass and Al) on the surface of the n-shaped Pt heating plate printed with the Pt electrode2O3Mixed), then the heating plate and the substrate obtained in the previous step are stuck together and put into a muffle furnace for sintering at 200 DEG CAnd (5) knot for 20 minutes, and taking out to obtain the prototype device of the sensor.
The device of this example operates at 300 ℃ for 100ppm NO2The sensitivity can reach 21mV/decade, and the response recovery speed is higher and is about 18 s; for 200ppm CO, the sensitivity can reach 39mV/decade, and the response recovery speed is about 5 s.
In this embodiment, the YSZ substrate is doped with 8 mol% Y2O3The physical size is 6mm 4mm 0.2mm, and two nano porous structures with 1 x 2mm areas are corroded by an electrochemical method and are respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on a nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and an electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
Example 2:
a manufacturing method of a storage battery module is characterized in that a solid electrolyte type gas sensor is arranged at the peripheral position of a storage battery, the solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged at two sides of the Pt reference electrode;
the solid electrolyte type gas sensor is manufactured by the following method:
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 7mm by 5mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass portion, 1.8% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the YSZ flat plates and are completely immersed, the YSZ flat plates are treated for 28min at the temperature of 50 ℃, then the YSZ flat plates are treated for 2min by microwave, and the YSZ flat plates are cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 2s at an interval of 10min for 5 times;
c. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, putting the mixture into a double-cell electrochemical device (shown in figure 1), wherein the etching cell and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching cell into two regions which are not communicated with each other, and the center of the clamp is provided with two holes with a specific shape of 2 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures with 2 x 2mm areas on the YSZ flat plate, and after the preparation is finished, cleaning and storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g Na2WO4Dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the stirring condition until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, and then adding 75g of KNO3Violently stirring to form paste, carrying out hydrothermal reaction for 12h at 180 ℃, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly SnO with the particle size of 15nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain a sensitive electrode B;
(4) gas sensor fabrication
The nitrogen oxide sensor is mainly composed of two parts: porous YSZ flat plate and Pt 'ji' shape electrode heating plate, the device preparation steps are as follows:
a. taking the YSZ substrate treated in the step (1), sequentially carrying out ultrasonic cleaning with water and absolute ethyl alcohol for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a2 x 2 mm-sized thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive (prepared by mixing water glass and Al2O 3) on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, putting the substrate into a muffle furnace, sintering at 200 ℃ for 20 minutes, and taking out the substrate to obtain the prototype device of the sensor.
The device of this example operates at 300 ℃ for 100ppm NO2The sensitivity can reach 52mV/decade, and the response recovery speed is faster and is about 8 s; for 200ppm CO, the sensitivity can reach 62mV/decade, and the response recovery speed is about 3 s.
In this embodiment, the YSZ substrate is doped with 8 mol% Y2O3The physical size is 7mm x 5mm x 0.2mm, and a nano porous structure with two 2 x 2mm areas is formed by electrochemical corrosion and is respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on a nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and an electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
By adjusting the size of the YSZ substrate and the porous nano structure and experimental parameters, the detection sensitivity of the YSZ substrate to the hazardous gas CO is improved to 62mV/decade, the response time is shortened to 3s, and an unexpected result is obtained.
Example 3:
a manufacturing method of a storage battery module is characterized in that a solid electrolyte type gas sensor is arranged at the peripheral position of a storage battery, the solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged at two sides of the Pt reference electrode;
the solid electrolyte type gas sensor is manufactured by the following method:
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 8mm by 4mm by 0.2mm), sequentially performing multiple ultrasonic cleaning by using water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass parts, 1.3% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the YSZ flat plates and are completely immersed, the YSZ flat plates are treated for 21min at the temperature of 57 ℃, then the YSZ flat plates are treated for 2min by microwave, and the YSZ flat plates are cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz, 65W, 3s irradiation, 10min interval, 4 total irradiation
c. Preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, putting the mixture into a double-cell electrochemical device (shown in figure 1), wherein the etching cell and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching cell into two regions which are not communicated with each other, and the center of the clamp is provided with two holes with a specific shape of 1 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures with the area of 1 x 2mm on a YSZ flat plate, and after the preparation is finished and cleaned, storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g Na2WO4Dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the stirring condition until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, and then adding 75g of KNO3Violently stirring to form paste, carrying out hydrothermal reaction for 12h at 180 ℃, and naturally cooling to room temperature; washing the reactant (precipitate) with deionized water, washing with ethanol, filtering, and dehydrating at 80 deg.C to obtain the final productTo the product, i.e. tungsten oxide nanoparticles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly, SnO with the particle size of 20nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain a sensitive electrode B;
(4) gas sensor fabrication
The nitrogen oxide sensor is mainly composed of two parts: porous YSZ flat plate and Pt 'ji' shape electrode heating plate, the device preparation steps are as follows:
a. taking the YSZ substrate treated in the step (1), sequentially carrying out ultrasonic cleaning with water and absolute ethyl alcohol for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a 1-by-2 mm thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive (prepared by mixing water glass and Al2O 3) on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, putting the substrate into a muffle furnace, sintering at 200 ℃ for 20 minutes, and taking out the substrate to obtain the prototype device of the sensor.
The device of this example operates at 300 ℃ for 100ppm NO2The sensitivity can reach 30mV/decade, and the response recovery speed is faster and is about 17 s; for 200ppm CO, the sensitivity can reach 45mV/decade, and the response recovery speed is about 4 s.
The YSZ substrate is doped with 8 mol% of Y2O3The physical size is 8mm x 4mm x 0.2mm, and a nano porous structure with two 1 x 2mm areas is formed by electrochemical corrosion and is respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on the nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and the electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
By adjusting the size and experimental parameters of the YSZ substrate and the porous nano structure, the hazardous gas NO is treated2The detection sensitivity of the method is improved to 30mV/decade, and the response time to CO is shortened to 4s, thereby obtaining an unexpected result.
Example 4:
a manufacturing method of a storage battery module is characterized in that a solid electrolyte type gas sensor is arranged at the peripheral position of a storage battery and comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged at two sides of the Pt reference electrode;
the solid electrolyte type gas sensor is manufactured by the following method:
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 9mm by 5mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass parts, 1.7% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the YSZ flat plates and are completely immersed, the YSZ flat plates are treated for 27min at the temperature of 51 ℃, then the YSZ flat plates are treated for 2min by microwave, and the YSZ flat plates are cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 4s at an interval of 10min for 3 times in total;
c. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, putting the mixture into a double-cell electrochemical device (shown in figure 1), wherein the etching cell and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching cell into two regions which are not communicated with each other, and the center of the clamp is provided with two holes with a specific shape of 3 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures with the area of 3 x 2mm on a YSZ flat plate, and after the preparation is finished and cleaned, storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g Na2WO4Dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the stirring condition until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, and then adding 75g of KNO3Violently stirring to form paste, carrying out hydrothermal reaction for 12h at 180 ℃, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly SnO with the particle size of 16nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain a sensitive electrode B;
(4) gas sensor fabrication
The nitrogen oxide sensor is mainly composed of two parts: porous YSZ flat plate and Pt 'ji' shape electrode heating plate, the device preparation steps are as follows:
a. taking the YSZ substrate treated in the step (1), sequentially carrying out ultrasonic cleaning with water and absolute ethyl alcohol for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a thin strip-shaped platinum paste belt with the size of 3 x 2mm in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive (prepared by mixing water glass and Al2O 3) on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, putting the substrate into a muffle furnace, sintering at 200 ℃ for 20 minutes, and taking out the substrate to obtain the prototype device of the sensor.
The device of this example operates at 300 ℃ for 100ppm NO2The sensitivity can reach 40mV/decade, and the response recovery speed is higher and is about 10 s; for 200ppm CO, the sensitivity can reach 53mV/decade, and the response recovery speed is about 5 s.
In this embodiment, the YSZ substrate is doped with 8 mol% Y2O3The physical size is 9mm x 5mm x 0.2mm, and a nano porous structure with two 3 x 2mm areas is formed by electrochemical corrosion and is respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on a nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and an electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
By adjusting the size of the YSZ substrate and the porous nano structure and experimental parameters, the detection sensitivity of the YSZ substrate to the hazardous gas CO is improved to 53mV/decade, and the response time is shortened to 5s, so that an unexpected result is obtained.
Example 5 comparative example:
a manufacturing method of a storage battery module is characterized in that a solid electrolyte type gas sensor is arranged at the peripheral position of a storage battery, the solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged at two sides of the Pt reference electrode;
the solid electrolyte type gas sensor is manufactured by the following method:
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 10mm by 5mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: soaking in purified water for 10min, cleaning, and naturally drying;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 2s at an interval of 10min for 5 times;
b. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, putting the mixture into a double-cell electrochemical device (shown in figure 1), wherein the etching cell and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching cell into two regions which are not communicated with each other, and the center of the clamp is provided with two holes with a specific shape of 2 x 4 mm;
c. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, two porous structures with 2 x 4mm areas are formed on the YSZ flat plate,after the preparation is finished, cleaning and storing in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g Na2WO4Dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the stirring condition until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, and then adding 75g of KNO3Violently stirring to form paste, carrying out hydrothermal reaction for 12h at 180 ℃, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly SnO with the particle size of 5nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain a sensitive electrode B;
(4) gas sensor fabrication
The nitrogen oxide sensor is mainly composed of two parts: porous YSZ flat plate and Pt 'ji' shape electrode heating plate, the device preparation steps are as follows:
a. taking the YSZ substrate treated in the step (1), sequentially carrying out ultrasonic cleaning with water and absolute ethyl alcohol for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a2 x 4 mm-sized thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive (prepared by mixing water glass and Al2O 3) on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, putting the substrate into a muffle furnace, sintering at 200 ℃ for 20 minutes, and taking out the substrate to obtain the prototype device of the sensor.
The device of this example operates at 300 ℃ for 100ppm NO2The sensitivity can reach 50mV/decade, and the response recovery speed is faster and is about 15 s; for 200ppm CO, the sensitivity can reach 60mV/decade, and the response recovery speed is about 3 s.
At the working temperature of 300 ℃, the device is used for 100ppm of NO2The sensitivity can reach 79mV/decade, and the response recovery speed is faster and is about 20 s; for 200ppm CO, the sensitivity can reach 125mV/decade, and the response recovery speed is about 9 s.
In this embodiment, the YSZ substrate is doped with 8 mol% Y2O3The physical size is 10mm x 5mm x 0.2mm, and two 2 x 4mm regions of nanometer are formed by electrochemical etchingA porous structure, which is used for placing a sensitive electrode A and a sensitive electrode B respectively; manufacturing platinum dots with the diameter of 0.1-0.3mm on a nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and an electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
Through adjustment of YSZ substrate, size of porous nanostructure and experimental parameters, the composite material can be used for treating CO and NO in hazardous gases2The detection sensitivity is respectively improved to 125mV/decade and 79mV/decade, and the response time is respectively shortened to 9s and 20s, thereby obtaining unexpected results.
Therefore, the solid electrolyte type gas sensor is arranged at the periphery of the storage battery, and the performances of the sensor are compared under different experimental process parameters, so that the optimal sensitivity and response time are obtained, unexpected effects are obtained, the flammable and explosive dangerous situations of the storage battery in the using process can be found in time, and the storage battery has a great market prospect.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical invention and the inventive concept thereof are equivalent to or changed within the technical scope of the present invention.
Claims (4)
1. A storage battery module is characterized in that a solid electrolyte type gas sensor is arranged at the peripheral position of a storage battery and comprises a heating plate, a Yttrium Stabilized Zirconia (YSZ) substrate arranged on the heating plate, a platinum (Pt) reference electrode arranged on the YSZ substrate, a sensitive electrode A and a sensitive electrode B, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged at two sides of the Pt reference electrode, the sensitive electrode A is made of tungsten oxide nanoparticles doped with nano nickel oxide powder, and the sensitive electrode B is made of nano SnO2And (3) pulverizing.
2. The battery module of claim 1, wherein the YSZ substrate is doped with 8 mol% Y2O3The physical size is 6mm 4mm 0.2mm, and two nano porous structures with 1 x 2mm areas are corroded by an electrochemical method and are respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on a nano porous area of the YSZ substrate, and connecting the YSZ substrate and the electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
3. A method for realizing a storage battery module is characterized in that a solid electrolyte type gas sensor is arranged at the peripheral position of the storage battery module, the solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged at two sides of the Pt reference electrode; wherein,
a. ultrasonically cleaning a YSZ substrate with water and absolute ethyl alcohol successively for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a 1-2 mm-sized thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a platinum paste round point with the diameter of 0.1-0.3mm in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, sintering in a muffle furnace at 200 ℃ for 20 minutes, and taking out to obtain the prototype device of the sensor.
4. The implementation method of claim 3,
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 6mm by 4mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass portion, 1-1.8% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the YSZ flat plates and are completely immersed, the YSZ flat plates are treated for 20-28min at the temperature of 50-58 ℃, then the YSZ flat plates are treated for 2min by microwave, and the YSZ flat plates are cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 2-5s at an interval of 10min for 3-5 times;
c. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, placing the mixture into a double-electric-tank electrochemical device, wherein the etching tank and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching tank into two non-communicated areas, and the center of the clamp is provided with two holes with a specific shape of 1 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures with the area of 1 x 2mm on a YSZ flat plate, and after the preparation is finished and cleaned, storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g of Na2WO4, dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the condition of stirring until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, adding 75g of KNO3, violently stirring to form a paste, carrying out hydrothermal reaction at 180 ℃ for 12h, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly, SnO with the grain diameter of 15-22nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. and standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain the sensitive electrode B.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109216815A (en) * | 2017-06-29 | 2019-01-15 | 北京小米移动软件有限公司 | Battery, electronic equipment, corrosion method for early warning and device, readable storage medium storing program for executing |
| CN110352533A (en) * | 2017-05-25 | 2019-10-18 | 株式会社东芝 | Electricity accumulating unit and accumulating system |
| CN111525205A (en) * | 2020-04-28 | 2020-08-11 | 山东宏匀纳米科技有限公司 | Lithium ion battery containing lithium lanthanum zirconium oxygen three electrodes and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201141848Y (en) * | 2008-01-14 | 2008-10-29 | 吉林大学 | Integrated dual-function NASICON solid electrolyte gas sensor |
| CN101318703A (en) * | 2008-07-08 | 2008-12-10 | 清华大学 | Tungstic oxide nano-wire and method for preparing tungstic oxide nano-wire ammonia sensitive sensor |
| CN103424435A (en) * | 2013-08-20 | 2013-12-04 | 天津大学 | Preparation method of porous silicon-based tungsten trioxide nanorod composite-structure gas sensor element |
| CN103900767A (en) * | 2012-12-26 | 2014-07-02 | 汽车能源供应公司 | Leak detection method of battery module and the battery module |
| CN103954670A (en) * | 2014-05-08 | 2014-07-30 | 吉林大学 | YSZ (Yttria Stabilization Zirconia)-based mixed potential type NO2 sensor with high-efficiency three-phase boundary and preparation method thereof |
| CN104820068A (en) * | 2015-04-22 | 2015-08-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin oxide alumina-based low-concentration acetone gas sensor and preparation method thereof |
-
2015
- 2015-10-28 CN CN201510712104.XA patent/CN105322246A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201141848Y (en) * | 2008-01-14 | 2008-10-29 | 吉林大学 | Integrated dual-function NASICON solid electrolyte gas sensor |
| CN101318703A (en) * | 2008-07-08 | 2008-12-10 | 清华大学 | Tungstic oxide nano-wire and method for preparing tungstic oxide nano-wire ammonia sensitive sensor |
| CN103900767A (en) * | 2012-12-26 | 2014-07-02 | 汽车能源供应公司 | Leak detection method of battery module and the battery module |
| CN103424435A (en) * | 2013-08-20 | 2013-12-04 | 天津大学 | Preparation method of porous silicon-based tungsten trioxide nanorod composite-structure gas sensor element |
| CN103954670A (en) * | 2014-05-08 | 2014-07-30 | 吉林大学 | YSZ (Yttria Stabilization Zirconia)-based mixed potential type NO2 sensor with high-efficiency three-phase boundary and preparation method thereof |
| CN104820068A (en) * | 2015-04-22 | 2015-08-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin oxide alumina-based low-concentration acetone gas sensor and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110352533A (en) * | 2017-05-25 | 2019-10-18 | 株式会社东芝 | Electricity accumulating unit and accumulating system |
| CN110352533B (en) * | 2017-05-25 | 2022-07-19 | 株式会社东芝 | Power storage unit and power storage system |
| CN109216815A (en) * | 2017-06-29 | 2019-01-15 | 北京小米移动软件有限公司 | Battery, electronic equipment, corrosion method for early warning and device, readable storage medium storing program for executing |
| CN111525205A (en) * | 2020-04-28 | 2020-08-11 | 山东宏匀纳米科技有限公司 | Lithium ion battery containing lithium lanthanum zirconium oxygen three electrodes and preparation method thereof |
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