CN116969758B - Preparation method of high-stability zirconia ceramic material - Google Patents
Preparation method of high-stability zirconia ceramic material Download PDFInfo
- Publication number
- CN116969758B CN116969758B CN202310988995.6A CN202310988995A CN116969758B CN 116969758 B CN116969758 B CN 116969758B CN 202310988995 A CN202310988995 A CN 202310988995A CN 116969758 B CN116969758 B CN 116969758B
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- chitosan
- ceramic material
- deionized water
- zirconia ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 69
- 229920001661 Chitosan Polymers 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000008367 deionised water Substances 0.000 claims abstract description 42
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 22
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 11
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002131 composite material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 4
- 229910009253 Y(NO3)3 Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 4
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/636—Polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/40—Engine management systems
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A preparation method of a high-stability zirconia ceramic material comprises the steps of adding a montmorillonite chitosan compound into yttria stabilized zirconia, ball milling and then calcining in sections, wherein the montmorillonite chitosan compound is prepared by adding montmorillonite powder into deionized water to prepare a montmorillonite suspension, adding dilute hydrochloric acid into chitosan to obtain a chitosan solution, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 90-100 ℃, preserving heat for 10-12h, and centrifugally collecting solids, the section calcining is divided into three sections, the temperature of the first section is 400-450 ℃, the temperature of the second section is 550-650 ℃, and the temperature of the third section is 850-900 ℃. The zirconia ceramic material prepared by the method improves the conductivity of the zirconia ceramic material, and has excellent conductivity stability under high-temperature change.
Description
The invention relates to a divisional application of patent application number 202211553803.0, which is named as a preparation method of a zirconia ceramic material for an automobile exhaust sensor.
Technical Field
The invention relates to the technical field of ceramic material preparation, in particular to a preparation method of a high-stability zirconia ceramic material.
Background
The yttria stabilized zirconia is very commonly applied to an automobile oxygen sensor, and the zirconia sensor is effectively applied to measuring the emission of a gasoline automobile, is the current optimal combustion atmosphere measuring mode, and has the advantages of simple structure, rapidness, easiness in maintenance, convenience in use and the like. However, the service life of the zirconia sensor is shorter, and for yttria-stabilized zirconia, the zirconia cannot adapt to the temperature change and long-time working in a high-temperature environment due to the higher working temperature of the oxygen sensor, and the conductivity of the zirconia can also change along with the temperature change, so that the stability is poor, and the sensitivity and the accuracy of the sensor are affected. In addition, in the course of repeated cycles, as the number of cycles increases, its electrical conductivity decreases, resulting in a decay in its lifetime. Therefore, the zirconia is ensured to be stable and unchanged in conductivity under higher temperature change, and meanwhile, the conductivity is stable and not attenuated under multiple cycle operation, and the maintenance of excellent stability is extremely important for the oxygen sensor.
Disclosure of Invention
The invention aims to provide a high-stability zirconia ceramic material, which is free from attenuation of conductivity along with temperature change and increase of cycle times and has excellent conductivity stability.
The invention aims at realizing the following technical scheme:
A preparation method of a high-stability zirconia ceramic material is characterized by comprising the following steps: adding a montmorillonite chitosan compound into yttria stabilized zirconia, ball milling, and then carrying out sectional calcination, wherein the montmorillonite chitosan compound is prepared by adding deionized water into montmorillonite powder prepared by montmorillonite pretreatment to prepare a montmorillonite suspension, adding dilute hydrochloric acid into chitosan to obtain a chitosan solution, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 90-100 ℃, preserving heat for 10-12h, centrifugally collecting solids, washing and drying, and then crushing and sieving.
Further, in the sectional calcination, the temperature of the first stage is raised to 400-450 ℃ at 5-8 ℃/min, the calcination time is 50-70min, the temperature of the second stage is raised to 550-650 ℃ at 4-6 ℃/min, the calcination time is 30-60min, and the temperature of the third stage is raised to 850-900 ℃ at 5-8 ℃/min, and the calcination time is 5-7h.
In the prior art, the montmorillonite-chitosan composite is usually used as an adsorption material, and the adsorption performance of the montmorillonite-chitosan composite is researched, and the stability of the zirconia ceramic material is effectively improved by adding the montmorillonite-chitosan composite and combining three-stage heating and calcining treatment, so that the stability of the zirconia ceramic material in a high-temperature working environment is enhanced, the deformation is small, and the stability of the conductivity and other performances of the zirconia ceramic material under high-temperature change and the performance stability of repeated recycling are improved.
Further, the ball milling speed of the ball milling is 300-400rpm, and the ball milling time is 15-18h.
Further, the drying temperature is 100-110 ℃, and the drying is 15-18 hours.
Further, the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.2-0.4, the mass ratio of the chitosan in the chitosan solution to the diluted hydrochloric acid is 1:120-150, the mixture is stirred and dissolved at 80-100rpm, the mass fraction of the diluted hydrochloric acid is 5%, and the centrifugal speed is 10000-20000rpm.
Further, the mass ratio of the montmorillonite-chitosan complex to the yttria-stabilized zirconia is 3-8:75-85.
Further, the pretreatment is to dry crushed and sieved montmorillonite, then add deionized water in two steps, then add EDTA-2Na and NaHCO 3, stir and stand to obtain suspension, add edible salt, stand and centrifugally collect precipitate, wash and dry the precipitate, then ball-mill, add dilute hydrochloric acid, treat in water bath and dry to obtain montmorillonite powder.
Further, the deionized water is added into montmorillonite, soaked for 36-40h, stirred for 20-30h at 150-200rpm, and then added, wherein the mass ratio of montmorillonite to the deionized water added for two times is 1:20-30:200-250.
Further, the mass ratio of montmorillonite, EDTA-2Na and NaHCO 3 is 1:0.05-0.08:0.12-0.15, and the edible salt accounts for 10-15% of the mass of the suspension.
Further, the montmorillonite after crushing and sieving is dried by crushing the montmorillonite, sieving with a 100-mesh sieve and then drying at 90-100 ℃ for 24-36h.
Further, the mass ratio of the precipitation after ball milling to the dilute hydrochloric acid is 1:30-40, and the mass fraction of the dilute hydrochloric acid is 5%.
Further, the yttria-stabilized zirconia is prepared by mixing zirconium oxychloride (ZrOCl 2.8H2 O) and yttrium nitrate (Y (NO 3)3) and dissolving in deionized water, adding polyethylene glycol 200, heating to 40-50 ℃, adding hydrochloric acid to adjust pH to 2.0-3.5 within 5-8min, then adding sodium hydroxide to adjust pH to 9.5-10.0, standing to form gel, drying, and calcining at 450-500 ℃ for 2-3h.
Further, the mass ratio of ZrOCl 2.8H2O、Y(NO3)3, polyethylene glycol 200 and deionized water is as follows: 2.48:0.054:0.027:7.8.
Further, the volume fraction of the hydrochloric acid is 5-8%, and the concentration of sodium hydroxide is 0.5mol/L.
The invention has the following technical effects:
according to the invention, by adopting the montmorillonite-chitosan composite for adding and combining the zirconia ceramic material prepared by three-stage heating calcination, the conductivity of the zirconia ceramic material is improved, the conductivity stability under high temperature change is excellent, the temperature change is effectively adapted, the conductivity of the zirconia ceramic material is kept at 93.75% of the initial conductivity of 0.033S/cm after the zirconia ceramic material is recycled 20000 times, the zirconia ceramic material has excellent circulating stability, and long-time stable operation under a high-temperature environment can be ensured.
Drawings
Fig. 1: the zirconia ceramic material prepared by the invention has a conductivity change curve graph along with the temperature change.
Fig. 2: the zirconia ceramic material prepared by the invention is circularly used for 20000 times of conductivity change curve graphs.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be to those skilled in the art in light of the foregoing disclosure.
Example 1
The preparation method of the zirconia ceramic material with high stability comprises the following steps:
Step one: preparation of yttria-stabilized zirconia
Mixing zirconium oxychloride (ZrOCl 2.8H2 O) and yttrium nitrate (Y (NO 3)3), adding deionized water, stirring for 10min, adding polyethylene glycol 200, heating to 40 ℃, adding hydrochloric acid with the volume fraction of 5% to adjust the pH to 3.5 within 5min, adding sodium hydroxide with the concentration of 0.5mol/L to adjust the pH to 9.5, standing for 8h to form gel, drying at the vacuum degree of-0.05 to-0.08 MPa and the temperature of 60 ℃ for 3h, and calcining at the temperature of 450 ℃ for 3h, wherein the mass ratio of the ZrOCl 2.8H2O、Y(NO3)3, the polyethylene glycol 200 and the deionized water is 2.48:0.054:0.027:7.8;
Step two: preparation of montmorillonite-chitosan composite material
(1) Pretreatment of montmorillonite
Drying montmorillonite which is crushed and sieved by a 100-mesh sieve at 100 ℃ for 24 hours, adding deionized water for soaking for 40 hours, sequentially adding deionized water, EDTA-2Na and NaHCO 3 at 200rpm, continuously stirring for 15-20 hours, wherein the mass ratio of the montmorillonite to the two-time added deionized water is 1:30:250, the mass ratio of the montmorillonite, the EDTA-2Na and the NaHCO 3 is 1:0.08:0.15, stirring and standing to obtain a suspension, adding edible salt, standing for 1 hour, centrifuging at 10000rpm, collecting precipitate, repeatedly washing the precipitate by using deionized water for 5 times, then drying at 90 ℃ until the water content is lower than 0.2%, then ball-milling, adding dilute hydrochloric acid, stirring for 10 hours at 100rpm simultaneously at 90 ℃, filtering and collecting precipitate after cooling, washing by using deionized water, drying at-0.05-0.08 MPa and drying at 80 ℃, and sieving by 200-mesh sieve to obtain montmorillonite powder;
(2) Composite montmorillonite chitosan
Adding montmorillonite powder into deionized water, stirring at 60rpm for 15min to form montmorillonite suspension, wherein the mass ratio of the montmorillonite powder to the deionized water is 1:80, adding 5% of diluted hydrochloric acid into chitosan to obtain chitosan solution, wherein the mass ratio of the chitosan to the diluted hydrochloric acid is 1:150, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 90 ℃, preserving heat for 12h, wherein the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.4, centrifuging at 10000rpm to collect solids, washing with deionized water for 5 times, drying at 100 ℃ for 18h, crushing and sieving with a 200-mesh sieve to obtain a montmorillonite-chitosan compound;
Step three: preparation of zirconia ceramic powder
Adding a montmorillonite chitosan compound into the yttria-stabilized zirconia prepared in the step one, ball milling, and then performing sectional calcination, wherein the sectional calcination is divided into three sections of temperatures which are gradually increased, the first section of temperature is heated to 400 ℃ at 5 ℃/min and is calcined for 70min, the second section of temperature is heated to 550 ℃ at 4 ℃/min and is calcined for 60min, the third section of temperature is heated to 900 ℃ at 5 ℃/min and is calcined for 5h, and the mass ratio of the montmorillonite chitosan compound to the yttria-stabilized zirconia is 3:85.
The conductivity of the zirconia ceramic material prepared by the embodiment is 0.031S/cm, the conductivity stability is excellent at 400-900 ℃, the conductivity is basically unchanged after 20000 times of circulation, the conductivity is still maintained at 93.16% of the initial conductivity, and the circulation stability is excellent.
Example 2
The preparation method of the high-stability zirconia ceramic material comprises the following steps:
Step one: preparation of yttria-stabilized zirconia
Mixing zirconium oxychloride (ZrOCl 2.8H2 O) and yttrium nitrate (Y (NO 3)3), adding deionized water, stirring for 15min, adding polyethylene glycol 200, heating to 50 ℃, adding hydrochloric acid with the volume fraction of 8% to adjust the pH to 2.0 within 8min, adding sodium hydroxide with the concentration of 0.5mol/L to adjust the pH to 10.0, standing for 12h to form gel, drying at the vacuum degree of-0.05 to-0.08 MPa and the temperature of 80 ℃ for 2h, and calcining at 500 ℃ for 2h, wherein the mass ratio of the ZrOCl 2.8H2O、Y(NO3)3, the polyethylene glycol 200 and the deionized water is 2.48:0.054:0.027:7.8;
Step two: preparation of montmorillonite-chitosan composite material
(1) Pretreatment of montmorillonite
Drying montmorillonite which is crushed and sieved by a 100-mesh sieve at 90 ℃ for 36 hours, adding deionized water for soaking for 36 hours, sequentially adding deionized water, EDTA-2Na and NaHCO 3 at 150rpm, continuously stirring for 20 hours, wherein the mass ratio of the montmorillonite to the twice added deionized water is 1:20:200, the mass ratio of the montmorillonite, EDTA-2Na and NaHCO 3 is 1:0.05:0.12, stirring and standing to obtain a suspension, adding edible salt, standing for 2 hours, centrifuging and collecting precipitate at 8000rpm, repeatedly washing the precipitate with deionized water for 3 times, then drying at 100 ℃ until the water content is lower than 0.2%, then ball-milling, adding 5% of diluted hydrochloric acid, the mass ratio of the precipitate to the diluted hydrochloric acid is 1:40, simultaneously stirring for 12 hours at 80rpm, cooling, filtering and collecting precipitate, washing with deionized water, drying at a vacuum degree of-0.05 to-0.08 MPa and a drying temperature of 70 ℃, and sieving with a 200-mesh sieve to obtain montmorillonite powder;
(2) Composite montmorillonite chitosan
Adding montmorillonite powder into deionized water, stirring for 10min at 80rpm to form montmorillonite suspension, wherein the mass ratio of the montmorillonite powder to the deionized water is 1:100, adding 5% of diluted hydrochloric acid into chitosan to obtain chitosan solution, wherein the mass ratio of the chitosan to the diluted hydrochloric acid is 1:150, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 100 ℃, preserving heat for 10h, wherein the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.2, centrifuging at 12000rpm to collect solids, washing for 3 times with deionized water, drying at 110 ℃ for 15h, and crushing and sieving with a 200-mesh sieve to obtain a montmorillonite-chitosan compound;
Step three: preparation of zirconia ceramic powder
Adding a montmorillonite chitosan compound into the yttria-stabilized zirconia prepared in the step one, ball milling, and then performing sectional calcination, wherein the sectional calcination is divided into three sections of temperatures which are gradually increased, the first section of temperature is heated to 450 ℃ at 8 ℃/min, the calcination is performed for 50min, the second section of temperature is heated to 650 ℃ at 6 ℃/min, the calcination is performed for 30min, the third section of temperature is heated to 850 ℃ at 8 ℃/min, and the calcination is performed for 5h, wherein the mass ratio of the montmorillonite chitosan compound to the yttria-stabilized zirconia is 8:75.
The zirconia ceramic material prepared by the embodiment has the conductivity of 0.032S/cm, excellent stability at 400-900 ℃, basically unchanged conductivity after 20000 times of circulation, the conductivity still maintained at 92.49% of the initial conductivity, and excellent circulation stability.
Example 3
The preparation method of the high-stability zirconia ceramic material comprises the following steps:
Step one: preparation of yttria-stabilized zirconia
Mixing zirconium oxychloride (ZrOCl 2.8H2 O) and yttrium nitrate (Y (NO 3)3), adding deionized water, stirring for 12min, adding polyethylene glycol 200, heating to 45 ℃, adding hydrochloric acid with the volume fraction of 6% to adjust the pH to 3.0 within 5-8min, adding sodium hydroxide with the concentration of 0.5mol/L to adjust the pH to 9.8, standing for 10h to form gel, drying at the vacuum degree of-0.05 to-0.08 MPa and the temperature of 70 ℃ for 2.5h, and calcining at the temperature of 480 ℃ for 2.5h, wherein the mass ratio of the ZrOCl 2.8H2O、Y(NO3)3, the polyethylene glycol 200 and the deionized water is 2.48:0.054:0.027:7.8;
Step two: preparation of montmorillonite-chitosan composite material
(1) Pretreatment of montmorillonite
Drying montmorillonite which is crushed and sieved by a 100-mesh sieve at 95 ℃ for 28 hours, adding deionized water for soaking for 38 hours, sequentially adding deionized water, EDTA-2Na and NaHCO 3 at 180rpm, continuously stirring for 18 hours, wherein the mass ratio of the montmorillonite to the two-time added deionized water is 1:25:230, the mass ratio of the montmorillonite, EDTA-2Na and NaHCO 3 is 1:0.06:0.14, stirring and standing to obtain a suspension, adding edible salt, standing for 1.5 hours, centrifuging and collecting precipitate at 9000rpm, repeatedly washing the precipitate by using deionized water for 4 times, then drying at 95 ℃ until the water content is lower than 0.2%, then ball-milling, adding 5% of diluted hydrochloric acid, the mass ratio of the precipitate to the diluted hydrochloric acid is 1:35, stirring for 11 hours at 90rpm, washing by using deionized water, drying at a vacuum degree of-0.05 to-0.08 MPa, drying at a drying temperature of 75 ℃, and sieving by 200-mesh sieve to obtain montmorillonite powder;
(2) Composite montmorillonite chitosan
Adding montmorillonite powder into deionized water, stirring at 70rpm for 12min to form montmorillonite suspension, wherein the mass ratio of the montmorillonite powder to the deionized water is 1:90, adding 5% of diluted hydrochloric acid into chitosan to obtain chitosan solution, wherein the mass ratio of the chitosan to the diluted hydrochloric acid is 1:130, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 95 ℃, preserving heat for 11h, wherein the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.3, centrifuging at 11000rpm to collect solids, washing with deionized water for 4 times, drying at 105 ℃ for 16h, and crushing and sieving with a 200-mesh sieve to obtain a montmorillonite-chitosan compound;
Step three: preparation of zirconia ceramic powder
Adding a montmorillonite chitosan compound into the yttria-stabilized zirconia prepared in the step one, ball milling, and then performing sectional calcination, wherein the sectional calcination is divided into three sections of temperatures which are gradually increased, the first section of temperature is heated to 420 ℃ at 6 ℃/min, the second section of temperature is heated to 600 ℃ at 5 ℃/min, the calcination is performed for 50min, the third section of temperature is heated to 880 ℃ at 6 ℃/min, and the calcination is performed for 6h, wherein the mass ratio of the montmorillonite chitosan compound to the yttria-stabilized zirconia is 5:80.
Comparative example 1:
unlike example 3, after the yttria-stabilized zirconia was prepared in step one, the three-stage temperature-rising calcination treatment in step three was directly performed, i.e., without adding the montmorillonite-chitosan composite. The remaining steps and parameters remain the same as in example 3.
Comparative example 2:
Compared with the embodiment 3, the third step adopts a one-stage temperature calcination treatment, specifically, calcination is carried out at 900 ℃ for 10 hours, and the zirconia ceramic powder is obtained after cooling.
Performance test:
The zirconia ceramic powders prepared in example 3, comparative example 1 and comparative example 2 were processed to prepare electrodes, and performance test was performed. The method comprises the following steps:
Adding 25% PVA solution into zirconia ceramic powder to prepare granules, and sieving the granules with a 200-mesh sieve, wherein the mass ratio of the zirconia powder to the PVA is 1:0.2; pressing into a blank sheet under 25MPa, wherein the pressing density is 3.6g/cm < 2 >; sintering the blank, and printing the blank into an electrode by using a screen.
(1) The electrodes prepared from the zirconia ceramic powders prepared in example 3, comparative example 1 and comparative example 2 were respectively subjected to conductivity test at 300 to 900 c, and the record of the change in conductivity was made every 100 c, and the experimental results are shown in table 1.
Table 1: conductivity change at different temperatures
From the above results and fig. 1, it can be seen that the zirconia ceramic materials prepared in the present invention have higher conductivity and excellent stability at different temperatures, whereas the zirconia ceramic materials prepared in comparative examples 1 and 2 have lower initial conductivity, and have a larger conductivity, a sharp rising trend and a poor temperature stability with increasing temperature.
(2) The electrodes prepared by the zirconia ceramic materials prepared in the example 3, the comparative example 1 and the comparative example 2 are recycled 20000 times at 800 ℃, the conductivity change of the electrodes is shown in figure 2, and it can be seen that the conductivity of the zirconia ceramic material prepared in the invention is basically unchanged after being recycled 20000 times, the conductivity is still maintained at 93.75% of the original conductivity, and the electrodes have excellent recycling stability; the zirconia ceramic materials prepared in comparative examples 1 and 2 showed significant attenuation during the circulation process, and after 20000 times of circulation, the conductivities were 26.7% and 26.3% of the initial period, respectively, and the circulation stability was poor.
Claims (5)
1. A preparation method of a high-stability zirconia ceramic material is characterized by comprising the following steps: adding a montmorillonite chitosan compound into yttria stabilized zirconia, ball milling, and then performing sectional calcination, wherein the montmorillonite chitosan compound is prepared by adding deionized water into montmorillonite powder prepared by montmorillonite pretreatment to prepare a montmorillonite suspension, adding dilute hydrochloric acid into chitosan to obtain a chitosan solution, adding the montmorillonite suspension into the chitosan solution, stirring and heating to 90-100 ℃, preserving heat for 10-12 hours, centrifugally collecting solids, washing and drying, and then crushing and sieving to obtain the yttrium oxide stabilized zirconia; the pretreatment comprises the steps of drying crushed and sieved montmorillonite, adding deionized water in two steps, adding EDTA-2Na and NaHCO 3, stirring and standing to obtain suspension, adding edible salt, standing, centrifugally collecting precipitate, washing and drying the precipitate, ball-milling, adding dilute hydrochloric acid, water-bath treatment and drying to obtain montmorillonite powder, wherein the deionized water is added into the montmorillonite, soaking for 36-40h, stirring for 20-30h at 150-200rpm, and adding deionized water, wherein the mass ratio of the montmorillonite to the deionized water added in two times is 1:20-30:200-25.
2. The method for preparing the high-stability zirconia ceramic material according to claim 1, wherein the method comprises the following steps: the first stage temperature is heated to 400-450 ℃ at 5-8 ℃/min, the second stage temperature is heated to 550-650 ℃ at 4-6 ℃/min, and the third stage temperature is heated to 850-900 ℃ at 5-8 ℃/min.
3. A method for preparing a high stability zirconia ceramic material according to claim 1 or 2, wherein: the ball milling speed of the ball milling is 300-400rpm, and the ball milling time is 15-18h.
4. A method for preparing a high stability zirconia ceramic material as defined in claim 3, wherein: the mass ratio of the montmorillonite suspension to the chitosan solution is 1:0.2-0.4, the mass ratio of the chitosan in the chitosan solution to the diluted hydrochloric acid is 1:120-150, the mixture is stirred and dissolved at 80-100rpm, the mass fraction of the diluted hydrochloric acid is 5%, and the centrifugal speed is 10000-20000rpm.
5. The method for preparing the high-stability zirconia ceramic material according to claim 4, wherein the method comprises the following steps: the mass ratio of the montmorillonite-chitosan complex to the yttria-stabilized zirconia is 3-8:75-85.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310988995.6A CN116969758B (en) | 2022-12-06 | 2022-12-06 | Preparation method of high-stability zirconia ceramic material |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211553803.0A CN116003125B (en) | 2022-12-06 | 2022-12-06 | Preparation method of zirconia ceramic material for automobile exhaust sensor |
| CN202310988995.6A CN116969758B (en) | 2022-12-06 | 2022-12-06 | Preparation method of high-stability zirconia ceramic material |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211553803.0A Division CN116003125B (en) | 2022-12-06 | 2022-12-06 | Preparation method of zirconia ceramic material for automobile exhaust sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116969758A CN116969758A (en) | 2023-10-31 |
| CN116969758B true CN116969758B (en) | 2024-06-04 |
Family
ID=86032549
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211553803.0A Active CN116003125B (en) | 2022-12-06 | 2022-12-06 | Preparation method of zirconia ceramic material for automobile exhaust sensor |
| CN202310988995.6A Active CN116969758B (en) | 2022-12-06 | 2022-12-06 | Preparation method of high-stability zirconia ceramic material |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211553803.0A Active CN116003125B (en) | 2022-12-06 | 2022-12-06 | Preparation method of zirconia ceramic material for automobile exhaust sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN116003125B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110550952A (en) * | 2019-09-24 | 2019-12-10 | 华南理工大学 | zirconia ceramic powder and preparation method thereof |
| CN113512299A (en) * | 2021-05-19 | 2021-10-19 | 广西荣昇新材料有限公司 | Preparation method of lignin/chitosan/montmorillonite composite material |
| WO2022170652A1 (en) * | 2021-02-09 | 2022-08-18 | 广东海洋大学深圳研究院 | Chitosan and copper-loaded montmorillonite intercalation composite material, and preparation method therefor and use thereof |
| CN115138339A (en) * | 2022-07-25 | 2022-10-04 | 贵州省地质矿产勘查开发局一0五地质大队 | Montmorillonite-chitosan-hydroxyl iron composite material and preparation method thereof |
Family Cites Families (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2852638C2 (en) * | 1978-12-06 | 1986-01-16 | Robert Bosch Gmbh, 7000 Stuttgart | Gas sensor with cermet electrodes |
| JPS60112620A (en) * | 1983-11-22 | 1985-06-19 | Nok Corp | Mixed electrically-conductive zirconia and its nanufacture |
| JP2879965B2 (en) * | 1990-10-30 | 1999-04-05 | 日本碍子株式会社 | Method for manufacturing oxygen sensor element |
| JP5172076B2 (en) * | 2005-03-18 | 2013-03-27 | 株式会社ニッカトー | Highly conductive zirconia sintered body |
| US9829463B2 (en) * | 2010-03-31 | 2017-11-28 | Toyota Jidosha Kabushiki Kaisha | Method for producing oxygen sensor |
| US9647275B2 (en) * | 2012-06-13 | 2017-05-09 | Stc.Unm | Bi-functional catalysts for oxygen reduction and oxygen evolution |
| JP5716008B2 (en) * | 2012-12-27 | 2015-05-13 | 株式会社デンソー | Method for producing partially stabilized zirconia porcelain |
| CN103151526A (en) * | 2013-04-08 | 2013-06-12 | 严百坤 | Preparation method of carbon-coated cerium-modified lithium iron phosphate composite anode material |
| KR102236436B1 (en) * | 2013-04-29 | 2021-04-06 | 옵토도트 코포레이션 | Nanoporous composite separators with increased thermal conductivity |
| WO2016110810A1 (en) * | 2015-01-07 | 2016-07-14 | Director General, Centre For Materials For Electronics Technology | Glass ceramic composite electrolyte for low temperature solid oxide fuel cell |
| CN104876613A (en) * | 2015-04-13 | 2015-09-02 | 安徽省含山瓷业股份有限公司 | High-strength carbon-fiber-reinforced zirconia-ceramic-base composite material and preparation method thereof |
| CN104803680B (en) * | 2015-04-23 | 2016-10-05 | 福州大学 | Low temp. electric flow pattern NO in onexsensor solid electrolyte material and preparation thereof |
| WO2016172824A1 (en) * | 2015-04-27 | 2016-11-03 | 深圳市商德先进陶瓷有限公司 | Zirconium oxide composite ceramic and preparation method therefor |
| CN105214624B (en) * | 2015-11-02 | 2017-08-04 | 李建中 | A kind of dialyzate adsorption stuffing, its preparation method and application |
| CN106116569A (en) * | 2016-06-28 | 2016-11-16 | 郭舒洋 | A kind of preparation method of green antistatic zirconia ceramics |
| CN107383405B (en) * | 2017-08-02 | 2020-06-30 | 湖北工程学院 | Composite proton exchange membrane and preparation method thereof |
| CN107759218B (en) * | 2017-12-11 | 2020-06-16 | 内蒙古科技大学 | Yttria-stabilized zirconia ceramic and preparation method thereof |
| CN108467264A (en) * | 2018-03-06 | 2018-08-31 | 三祥新材股份有限公司 | A kind of combined oxidation zirconium powder for lambda sensor |
| CN108516807B (en) * | 2018-04-20 | 2020-11-06 | 湖南省美程陶瓷科技有限公司 | Preparation method of alumina ceramic for automobile pressure sensor |
| CN109244534B (en) * | 2018-10-22 | 2020-08-11 | 北京科技大学 | Montmorillonite-based composite solid electrolyte and solid lithium battery |
| CN109818023B (en) * | 2019-01-17 | 2020-12-01 | 湖北工程学院 | Flower-like hydrotalcite composite alkaline polyelectrolyte membrane and preparation method and application thereof |
| CN109904501B (en) * | 2019-01-17 | 2021-03-23 | 湖北工程学院 | Composite alkaline polyelectrolyte membrane and preparation method and application thereof |
| CN109627046A (en) * | 2019-01-23 | 2019-04-16 | 江西省千陶新型材料有限公司 | A kind of preparation method of thermostabilization high tenacity ceramic glaze |
| CN109678500A (en) * | 2019-01-30 | 2019-04-26 | 广州德隆宝环保科技有限公司 | Yttrium stable zirconium oxide ceramic powders and its preparation method and application |
| CN110256041A (en) * | 2019-07-17 | 2019-09-20 | 福建省德化县鹏欣陶瓷有限公司 | A kind of photocatalysis antibacterial ceramics easy to clean and preparation method thereof |
| CN110862092B (en) * | 2019-12-05 | 2021-03-16 | 长沙理工大学 | Method for preparing polydopamine modified montmorillonite nano material by mechanical ball milling method |
| CN111161960B (en) * | 2019-12-31 | 2021-08-10 | 华北水利水电大学 | Spinel type CuCo grown on carbon cloth substrate2O4Method for synthesizing high-performance electrode material |
| CN111495371A (en) * | 2020-05-28 | 2020-08-07 | 太原理工大学 | Rapid preparation method of cobalt spinel catalyst |
| CN111848162A (en) * | 2020-07-30 | 2020-10-30 | 山东东大新材料研究院有限公司 | Preparation method of porous zirconia ceramic with adjustable resistivity and porosity |
| CN112979346B (en) * | 2021-02-08 | 2023-04-18 | 东莞信柏结构陶瓷股份有限公司 | Zirconia ceramic surface conduction method |
| CN112903779A (en) * | 2021-03-10 | 2021-06-04 | 东北电力大学 | Foam nickel loaded CuCo2O4Non-enzymatic glucose electrochemical sensor |
| CN114031376B (en) * | 2021-12-24 | 2023-03-17 | 武汉理工大学 | Preparation method of high-hardness fine-grain ZTA system complex phase ceramic material |
| CN114990486B (en) * | 2022-07-28 | 2022-10-18 | 广州市尤特新材料有限公司 | Rotary zirconia target material and preparation method thereof |
-
2022
- 2022-12-06 CN CN202211553803.0A patent/CN116003125B/en active Active
- 2022-12-06 CN CN202310988995.6A patent/CN116969758B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110550952A (en) * | 2019-09-24 | 2019-12-10 | 华南理工大学 | zirconia ceramic powder and preparation method thereof |
| WO2022170652A1 (en) * | 2021-02-09 | 2022-08-18 | 广东海洋大学深圳研究院 | Chitosan and copper-loaded montmorillonite intercalation composite material, and preparation method therefor and use thereof |
| CN113512299A (en) * | 2021-05-19 | 2021-10-19 | 广西荣昇新材料有限公司 | Preparation method of lignin/chitosan/montmorillonite composite material |
| CN115138339A (en) * | 2022-07-25 | 2022-10-04 | 贵州省地质矿产勘查开发局一0五地质大队 | Montmorillonite-chitosan-hydroxyl iron composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116969758A (en) | 2023-10-31 |
| CN116003125A (en) | 2023-04-25 |
| CN116003125B (en) | 2023-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109360983B (en) | Modified high-nickel ternary cathode material and preparation method and application thereof | |
| CN113496825B (en) | Preparation method, product and application of porous carbon dodecahedron electrode material | |
| CN101698609A (en) | Method for preparing spherical, monodisperse and single-size yttrium oxide nano-powder | |
| CN109637827A (en) | A kind of preparation method of nitrogenous porous carbon/manganese dioxide nanowire combination electrode | |
| CN116969758B (en) | Preparation method of high-stability zirconia ceramic material | |
| CN108525637B (en) | Carbon template method modified calcium-based carbon dioxide adsorbent and preparation method thereof | |
| CN104576043A (en) | Inner electrode paste | |
| CN112490428A (en) | Pretreatment method of ternary precursor, product and application thereof | |
| CN115372414A (en) | Ti 3 C 2 T x MXene modified ZnO sensitive material and preparation method and application thereof | |
| WO2023108950A1 (en) | PREPARATION METHOD FOR Z-SCHEME α-FE2O3/ZNIN2S4 COMPOSITE PHOTOCATALYST AND USE THEREOF | |
| CN106381521A (en) | Preparation method of conductive titanium dioxide crystal whisker with surface-coated aluminium-doped zinc oxide | |
| CN108010745A (en) | One kind is based on Ag/PPy/MnO2Stretchable Asymmetric Supercapacitor of composite nano materials and preparation method thereof | |
| CN105244172B (en) | A kind of preparation method and applications of dye-sensitized solar cell anode | |
| CN102637889A (en) | Method of preparing saturation aza-lanthanum silicate solid electrolyte film by adopting microwave plasma | |
| CN103700505B (en) | The method of Fast Sintering large-area dye-sensitized solar battery photo-anode | |
| CN1295189C (en) | Method for preparing double functional ceramics of pressure-sensitive capacitance based on SrTiO3 | |
| CN111420661A (en) | Bimetallic solid alkaline nano-catalyst and preparation method and application thereof | |
| CN112047736A (en) | Preparation and ceramic sintering method of high-conductivity solid electrolyte lithium lanthanum zirconium oxide powder | |
| CN111115708A (en) | Preparation method of zirconium-doped cobalt oxide | |
| CN108389726A (en) | A kind of alpha-ferric oxide nanometer stick array of carbon film coated and its preparation method and application | |
| CN111115709A (en) | Preparation method of titanium-doped cobalt oxide | |
| CN111115701A (en) | Preparation method of vanadium-doped cobalt oxide | |
| CN109439320A (en) | A kind of flower-shaped thulium ytterbium codope C 12 A 7 and preparation method thereof | |
| CN110323433B (en) | Lithium titanate composite material and preparation method thereof, lithium ion battery and preparation method thereof | |
| CN108516822A (en) | A kind of ceramic capacitance material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |