CN1421416A - Cerium oxide-base solid electrolyte ceramic material and its production process - Google Patents
Cerium oxide-base solid electrolyte ceramic material and its production process Download PDFInfo
- Publication number
- CN1421416A CN1421416A CN03100272A CN03100272A CN1421416A CN 1421416 A CN1421416 A CN 1421416A CN 03100272 A CN03100272 A CN 03100272A CN 03100272 A CN03100272 A CN 03100272A CN 1421416 A CN1421416 A CN 1421416A
- Authority
- CN
- China
- Prior art keywords
- ceo
- base
- sintering
- cerium oxide
- milling
- 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.)
- Granted
Links
Classifications
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Compositions Of Oxide Ceramics (AREA)
- Fuel Cell (AREA)
Abstract
The present invention relates to one kind of cerium oxide-base soild electrolyte ceramic material and its production process. The material includes in mol% cerium oxide 75-95, samarium oxide and/or gadolinium oxide 4.9-20 and characterized specific oxide ceramic alumina and/or zirconia 0.1-5. The production process includes wet milling traditional components, adding the specific oxide ceramic and wet milling in particle ball mill for 4-8 hr to prepare CeO2 base electrolyte powder; preparing blank sheet; and sintering at 1400-1500 deg.c and 6-10 deg.c/min temperature raising rate to produce the ceramic material. The ceramic material of the present invention has high mechanical strength, low sintering temperature and simple production process suitable for industrial production.
Description
Technical field
The present invention relates to a kind of stupalith and manufacture method thereof, be specially a kind of cerium oxide (CeO
2) based solid electrolyte stupalith and manufacture method technology thereof, international Patent classificating number intends being Int.C1
7.C04B35/00.
Background technology
Solid Oxide Fuel Cell (SOFC) both can have been done not have or away from electrical network area or unit, locate the power supply of electrical equipment as island, border, communication station, offshore drilling platform etc., can make some regional area or unit again, the special-procurement power supply power supply of locating as hospital, machine room, down-hole, mine etc.Because it has the generating efficiency height, fuel source is extensive, does not need precious metal to make catalyzer, can realize advantages such as cogeneration, has shown good prospects for application and huge market potential.
Core among the SOFC is the solid electrolyte material with oxygen conduction.Yttrium oxide (Y
2O
3) stabilizing zirconia (ZrO
2), be called for short YSZ, be to use a kind of solid electrolyte the most general, that research is the most deep among the present SOFC.ZrO in recent years
2The subject matter that base SOFC exposes is: in order to reduce electrolytic resistance, SOFC has in high temperature (850-1000 ℃) operation down.If service temperature can be reduced to mesophilic range (650-800 ℃), then can effectively prevent performance degradation, improve SOFC operation life, reduce the cost cost.At present, reducing the SOFC operating temperature has two approach: the one, and the membranization of YSZ electrolyte thin; The 2nd, select other electrolytes for use, for example in warm ionogen (promptly having high conductance) material in mesophilic range.But the membranization of YSZ electrolyte thin is subjected to technical restriction, because the electrolyte thin film thickness is more little on the one hand, the difficulty of preparation is just big more, and technology is just complicated more; From powder technology and seal request, can not infinitely reduce film thickness on the other hand.Therefore, the research of middle temperature electrolyte is subjected to increasing attention.
In warm electrolyte mainly comprise CeO
2Base, bismuth oxide (Bi
2O
3) base and other compound ionogen.That research is maximum at present is CeO
2The based solid electrolyte material.Adulterated CeO
2Based solid electrolyte is at 800 ℃ of about 0.1S.cm of specific conductivity, and is suitable 1000 ℃ of specific conductivity with the YSZ material.But CeO
2Main drawback of based solid electrolyte is that intensity is low behind the sintering, is difficult for densification, according to contriver's test, CeO
2The flexural strength of sill only is 60-70MPa, very easily fracture in manufacturing, use, and for example, when curtain coating prepared ceramic membrane, yield rate was extremely low.For addressing this problem, just need higher sintering temperature (about 1600 ℃).Samarium trioxide (the Sm that the analytical pure powder is made for example
2O
3) stablize cerium oxide (CeO
2)
0.9(Sm
2O
3)
0.1System, sintering temperature must be more than 1580 ℃, and this has just brought another main drawback: energy consumption cost significantly increases.Under high temperature like this, also hindered CeO
2The possibility of other materials such as based solid electrolyte and electrode co-sintering.And will be when lower sintering temperature, then conductivity of electrolyte materials reduces, bad stability.For example, Rui Si people such as (Reiss) research 1700 ℃ of sintering Ce in air
0.82Gd
0.18O
1.82, only can obtain 95% sintered density (referring to I.Reiss, D.Braunshtein, D.S.Tannhauser, U.S.'s pottery can will (J. Am.Ceram.Soc.), 1981; 64:479); Hull people such as (Herle) discovers general CeO
2Diameter of particle is greater than 0.5 μ m during the based solid electrolyte wet-milling, must be could sintering more than 1650 ℃, and sintered density lower (95-96%) is (referring to J.Van Herle, T.Horita, T.Kawada et al, solid state ionics (Solid StateIonics), 1996; 86-88:1255); Human sol-gel methodes such as Huang are made the even spherical Ce that mean diameter is 250nm
0.9Gd
0.1O
1.95, obtained 99% sintered density at 1585 ℃, grain-size is 1-10 μ m, but its complex process, energy consumption and cost all than higher (referring to K.Huang, M.Feng, J.B.Goodenough, U.S.'s pottery can will (J.Am.Ceram.Soc.), 1998; 81:357), so middle temperature ionogen does not obtain general promotion and application yet.
Summary of the invention
At the deficiencies in the prior art, the technical problem that the present invention mainly solves provides a kind of CeO
2Based solid electrolyte stupalith and manufacture method thereof, this stupalith has higher mechanical strength; To have technology simple for this manufacture method simultaneously, and sintering temperature is low, the yield rate height, can the industry popularization etc. advantage.
The technical scheme that the present invention solves described material technology problem is: design a kind of cerium oxide base solid electrolyte ceramic material, prescription comprises (mol%): cerium oxide (CeO
2): 75～95; Samarium trioxide (Sm
2O
3) or/and gadolinium sesquioxide (Gd
2O
3): 4.9～20, it is characterized in that it also comprises the particular oxides pottery: 0.1～5, described particular oxides pottery is meant aluminum oxide (Al
2O
3) or/and zirconium white (ZrO
2).
The technical scheme that the present invention solves described manufacture method technical problem is: it comprises:
1. prepare CeO
2Base electrolyte powder: earlier with CeO
2, Sm
2O
3Or/and Gd
2O
3Raw material adds an amount of dehydrated alcohol after mixing according to described prescription, uses the wet-milling of particle sphere grinding machine after 4 hours, and 40 mesh sieves are crossed 700 ℃ of calcinings 0.5 hour in the oven dry back, get CeO
2The base electrolyte powder, it is characterized in that wet-milling after, add the particular oxides pottery (Al of described ratio again
2O
3Or/and Zr
2O
3), with particle sphere grinding machine wet-milling 4-8 hour;
2. prepare the base sheet: with the CeO that makes
2The base electrolyte powder is by rolling a kind of base sheet of making the shape and the size of design in embrane method, casting method or the compression molding;
3. firing ceramics material: the base sheet that makes is put into Si-Mo rod stove sintering: sintering time is 4 hours, takes out promptly after cooling to room temperature with the furnace, it is characterized in that sintering temperature is 1400～1500 ℃, and heat-up rate is 6-10 ℃/minute.
For rolling embrane method and casting method process materials, also need binder removal technology before the sintering routinely.
The present invention utilizes composite mixed technology, by a small amount of multi-element doping, promptly at CeO
2Add an amount of particular oxides pottery (Al in the base electrolyte
2O
3Or/and ZrO
2), improved CeO
2Electrolyte strength (can increase more than 1 times) has been improved the mechanical property of stupalith; And on manufacture method, also reduced sintering temperature (can reduce to 1400～1500 ℃).Accelerated heat-up rate (bringing up to 6-10 ℃/minute by 5 ℃/minute), saved the energy, raised the efficiency, technology is simple, with low cost simultaneously, has also improved yield rate, is suitable for industrial mass production.
Studies show that prior art is doped with Al not
2O
3Or/and ZrO
2Ceramic material sample, required sintering temperature is about 1600 ℃.Its shrinking percentage is slightly larger than 10%.If continue to improve sintering temperature, though the sintering degree of sample can continue to improve, energy consumption is huge, and is unreasonable economically.And at 1500 ℃, particularly when 1450 ℃ and following temperature sintering, material can not become porcelain at all.This explanation, the doped cerium oxide base electrolyte material is not difficult to sintering at a lower temperature.
What the present invention proposed considers in cerium oxide base electrolyte prescription or a small amount of doped with Al
2O
3Or/and ZrO
2Technical scheme, can obviously improve the sintering character of stupalith.Studies show that, along with Al
2O
3Or/and ZrO
2The increase of add-on, the material contracts rate significantly rises.To the Al that mixed
2O
3Or/and ZrO
2Sample, can under 1400-1500 ℃, burn till.When sample doping during at 5mol%, when 1450 ℃ of sintering, material just can reach maximum contraction rate 20%.This illustrates that an amount of doped ceramics oxide compound can make material densified sintering product at a lower temperature, also has significant acceleration of sintering effect.Moreover, on manufacture method, can also improve heat-up rate (bringing up to 6-10 ℃/minute), thereby save energy consumption cost, shorten the process time, enhance productivity by 5 ℃/minute.
No matter further studies show that, be to 1450 ℃ or to 1600 ℃ of agglomerating samples, the Strength Changes of gained material all presents same rule: along with Al
2O
3Or/and ZrO
2The raising of doping content, intensity increases gradually; Work as Al
2O
3Or/and ZrO
2When doping content reached the 3mol% left and right sides, it is maximum that intensity reaches, with doped with Al not
2O
3Or/and ZrO
2Sample compare, the strength of materials is enhanced about more than once.Along with the further increase of dopant dose, intensity begins to descend.When doping during less than 3mol%, 1450 ℃ of agglomerating sample strengths are a little more than 1600 ℃ of agglomerating samples.And doping is during greater than 3mol%, and intersecting appears in doping-intensity curve, and sintering temperature weakens the influence of intensity.Work as Al
2O or/and
3ZrO
2When doping content was 3mol%, 800 ℃ of specific conductivity descended more.To 1450 ℃ of agglomerating samples, the good comprehensive properties doping content is about 2mol%, and this moment, specific conductivity was about 0.06S.cm
-1, intensity is about 105MPa.Though specific conductivity slightly descends, the intensity of material improves about 2/3.To 1600 ℃ of agglomerating samples, reach better comprehensive performance, doping content is also about 2mol%.
Crystalline structure research to material also shows: the fracture of material of the present invention is mainly transgranular fracture, and section is coarse, and the cleavage striped is darker, and corresponding sample intensity is bigger.And not the fracture of doped samples be transcrystalline, along brilliant blended fracture mode.The brilliant composition in edge wherein is bigger, and section is smooth, and the river pattern that the cleavage striped causes is more shallow, and corresponding intensity is lower.Research also shows, in the process of cooling behind sintering, because thermal expansivity does not match, can produce compressive stress in crystal grain, can hinder further expanding of crackle; In addition, Al
2O
3Or/and ZrO
2Be distributed in the crystal boundary place, will make crack deflection, in deflection, can consume portion of energy, crack the deflection toughening mechanisms, improve the strength of materials.More than the influence of two aspect factors, can make CeO of the present invention
2Based solid electrolyte stupalith intensity increases.
After deliberation, the screening formulation of stupalith of the present invention is (mol%): cerium oxide (CeO
2): 85-90; Samarium trioxide (Sm
2O
3) or/and gadolinium sesquioxide (Gd
2O
3): 9～12, particular oxides ceramic alumina (Al
2O
3) or/and zirconium white (ZrO
2).: 1～3, the formula rate that briefly is described stupalith component is 85-90: 9～12: 1～3.
The selection process of stupalith manufacture method of the present invention is:
1 at preparation CeO
2In the base electrolyte powder technology, after the wet-milling, add the particular oxides pottery of described ratio again, with particle sphere grinding machine wet-milling 6 hours;
3. in the firing ceramics material technology, sintering temperature is 1450 ℃, and heat-up rate is 10 ℃/minute.
Embodiment
Embodiment 1
Stupalith prescription of the present invention is (mol%): (CeO
2)
0.89(Sm
2O
3)
0.09(Al
2O
3)
0.02Its manufacture method is:
1 preparation CeO
2Base electrolyte powder: earlier with described formula material component: CeO
2, Sm
2O
3Mix, add an amount of dehydrated alcohol, after 4 hours, continue to add Al with the wet-milling of particle sphere grinding machine
2O
3Grind and put into oven for drying after 6 hours, take out after 0.5 hour 700 ℃ of calcinings.Cross 40 mesh sieves after the granulation, can get CeO
2The base electrolyte powder;
2 preparation base sheets: the powder after the granulation is made the base bar of 5mm * 4mm * 50mm with compression molding, handle through the static pressure that waits of 2000M;
3 firing ceramics materials: the base bar that makes is put into Si-Mo rod kiln roasting strip.Its technology is 10 ℃/minute of heat-up rates, reach 1450 ℃ of sintering temperatures after, sintering time 4 hours takes out promptly after cooling to room temperature with the furnace.
Embodiment 2
Stupalith prescription of the present invention is (mol%): (CeO
2)
0.90(Gd
2O
3)
0.05(ZrO
2)
0.05Its manufacture method is:
1. prepare CeO
2Base electrolyte powder: earlier with described formula material component: CeO
2, Gd
2O
3Mix, add an amount of dehydrated alcohol, after 4 hours, continue to add ZrO with the wet-milling of particle sphere grinding machine
2Grind and put into oven for drying after 4 hours, take out after 0.5 hour 700 ℃ of calcinings.Cross 40 mesh sieves after the granulation, can get CeO
2The base electrolyte powder;
2. prepare the base sheet: the powder after the granulation is added the polyethylene alcohol and water, mix.Roll into the thick base sheet of 0.3mm with roll forming machine.The base sheet that rolls into heats binder removal;
3. firing ceramics material: the base bar that makes is put into Si-Mo rod kiln roasting ceramic membrane.Its technology is 8 ℃/minute of heat-up rates, reach 1400 ℃ of sintering temperatures after, sintering time 4 hours takes out promptly after cooling to room temperature with the furnace.
Embodiment 3
Stupalith prescription of the present invention is (mol%): (CeO
2)
0.92(Sm
2O
3)
0.03(Gd
2O
3)
0.03(Al
2O
3)
0.01(ZrO
2)
0.01Its manufacture method is:
1. prepare CeO
2Base electrolyte powder: earlier with described formula material component: CeO
2, Gd
2O
3, Sm
2O
3Mix, add an amount of dehydrated alcohol, after 4 hours, continue to add Al with the wet-milling of particle sphere grinding machine
2O
3, ZrO
2Grind and put into oven for drying after 4 hours, take out after 0.5 hour 700 ℃ of calcinings.Cross 40 mesh sieves after the granulation;
2. preparation base sheet: the powder after the granulation is added cakingagent, make the base sheet of 1mm, binder removal after heating with casting machine;
3. firing ceramics material: the base bar that makes is put into Si-Mo rod kiln roasting ceramic membrane.Its technology is 6 ℃/minute of heat-up rates, reach 1500 ℃ of sintering temperatures after, sintering time 4 hours takes out promptly after cooling to room temperature with the furnace.
Embodiment 4
Stupalith prescription of the present invention is (mol%): (CeO
2)
0.75(Sm
2O
3)
0.1(Gd
2O
3)
0.1(Al
2O
3)
0.025(ZrO
2)
0.025Sintering temperature in its manufacture method is 1450 ℃, and heat-up rate is 10 ℃/minute, and is surplus with embodiment 3.
Embodiment 5
Stupalith prescription of the present invention is (mol%): (CeO
2)
0.95(Sm
2O
3)
0.02(Gd
2O
3)
0.029(Al
2O
3)
0.001Its manufacture method is with embodiment 4.
Claims (4)
1. cerium oxide base solid electrolyte ceramic material, prescription comprises (mol%): cerium oxide (CeO
2): 75～95; Samarium trioxide (Sm
2O
3) or/and gadolinium sesquioxide (Gd
2O
3): 4.9～20, it is characterized in that it also comprises the particular oxides pottery: 0.1～5, described particular oxides pottery is meant aluminum oxide (Al
2O
3) or/and zirconium white (ZrO
2).
2. stupalith according to claim 1, the formula rate that it is characterized in that described stupalith component is 85-90: 9～12: 1～3.
3. manufacture method according to claim 1,2 described stupaliths, it comprises:
(1) preparation cerium oxide base ionogen powder: earlier with described formula material CeO
2, Sm
2O
3Or/and Gd
2O
3After the mixing, add an amount of dehydrated alcohol, with particle sphere grinding machine wet-milling 4 hours; Calcined 0.5 hour down at 700 ℃ the oven dry back, crosses 40 mesh sieves, can get CeO
2The base electrolyte powder;
(2) preparation base sheet: with the CeO that makes
2The base electrolyte powder is by rolling a kind of base sheet of making the shape and the size of design in embrane method, casting method or the compression molding;
(3) firing ceramics material: the ceramic green sheet that makes is put into Si-Mo rod stove sintering: sintering time is 4 hours, cools to the furnace after the room temperature to take out promptly, it is characterized in that
(1) after the wet-milling, adds the particular oxides pottery of described ratio again, with particle sphere grinding machine wet-milling 4-8 hour;
(3) sintering temperature is 1400～1500 ℃, and heat-up rate is 6-10 ℃/minute.
4. according to the manufacture method of the described stupalith of claim 3, it is characterized in that
(1) after the wet-milling, add the particular oxides pottery of described ratio again, with the particle sphere grinding machine wet-milling time be 6 hours;
(3) sintering temperature is 1450 ℃, and heat-up rate is 10 ℃/minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031002722A CN1189423C (en) | 2003-01-10 | 2003-01-10 | Cerium oxide-base solid electrolyte ceramic material and its production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031002722A CN1189423C (en) | 2003-01-10 | 2003-01-10 | Cerium oxide-base solid electrolyte ceramic material and its production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1421416A true CN1421416A (en) | 2003-06-04 |
| CN1189423C CN1189423C (en) | 2005-02-16 |
Family
ID=4789796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031002722A Expired - Fee Related CN1189423C (en) | 2003-01-10 | 2003-01-10 | Cerium oxide-base solid electrolyte ceramic material and its production process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1189423C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544559A (en) * | 2012-02-23 | 2012-07-04 | 郑州大学 | Cerium-oxide-based electrolyte for solid oxide fuel cell and manufacturing method thereof |
| CN114380595A (en) * | 2020-10-16 | 2022-04-22 | 宜兴摩根热陶瓷有限公司 | Oxygen ion conductive ceramic material with low sintering temperature and preparation method thereof |
-
2003
- 2003-01-10 CN CNB031002722A patent/CN1189423C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544559A (en) * | 2012-02-23 | 2012-07-04 | 郑州大学 | Cerium-oxide-based electrolyte for solid oxide fuel cell and manufacturing method thereof |
| CN114380595A (en) * | 2020-10-16 | 2022-04-22 | 宜兴摩根热陶瓷有限公司 | Oxygen ion conductive ceramic material with low sintering temperature and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1189423C (en) | 2005-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sameshima et al. | Thermal and mechanical properties of rare earth-doped ceria ceramics | |
| Ding et al. | High reactive Ce0. 8Sm0. 2O1. 9 powders via a carbonate co-precipitation method as electrolytes for low-temperature solid oxide fuel cells | |
| Van Herle et al. | Oxalate coprecipitation of doped ceria powder for tape casting | |
| Zhang et al. | Sinterability and ionic conductivity of coprecipitated Ce0. 8Gd0. 2O2− δ powders treated via a high-energy ball-milling process | |
| CN110128115A (en) | A kind of method that flash burning prepares oxide eutectic ceramics | |
| CN102659403A (en) | Ceramic material for high-temperature-resistant thermal barrier coating and preparation method thereof | |
| CN110467457A (en) | It is a kind of based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process and its preparation and application | |
| CN101838144B (en) | BaTiO3-based PTC thermal sensitive ceramic material and preparation method thereof | |
| Mori et al. | Effect of alumina on sintering behavior and electrical conductivity of high‐purity yttria‐stabilized zirconia | |
| JP3980927B2 (en) | Solid electrolyte based on ceria | |
| Cheng et al. | A strategy for improving sinterability and electrical properties of gadolinium-doped ceria electrolyte using calcium oxide additive | |
| CN101439969A (en) | Rare-earth oxide and manganese oxide co-stable zirconia ceramics and preparation thereof | |
| CN113173787B (en) | Gadolinium zirconate/gadolinium tantalate composite ceramic and preparation method thereof | |
| CN116666670B (en) | Lanthanum-niobium co-doped intermediate-temperature SOFC cathode material and preparation method and application thereof | |
| CN100416904C (en) | Technique for preparing perovskite type ionic conductor material composite doped by alkaline earth and transition metal | |
| CN1189423C (en) | Cerium oxide-base solid electrolyte ceramic material and its production process | |
| Hbaieb | Reducing sintering temperature of yttria stabilized zirconia through addition of lithium nitrate and alumina | |
| CN106866137A (en) | A kind of preparation method of electrolyte | |
| CN110391455B (en) | Yttrium-stabilized zirconium dioxide-low-melting-point glass powder compound and preparation method thereof | |
| Li et al. | Increasing the sinterability of tape cast oxalate-derived doped ceria powder by ball milling | |
| CN110600780B (en) | Zinc oxide and yttrium oxide double-doped zirconium dioxide and alkali metal salt compound and preparation method thereof | |
| CN110600778B (en) | MgO and Y 2 O 3 Double-doped ZrO 2 -alkali metal salt complex and process for producing the same | |
| CN108550874B (en) | Cerium oxide-barium cerate-based solid oxide fuel cell electrolyte and preparation method thereof | |
| CN113121227A (en) | Gadolinium-nickel co-doped magnesium-based lanthanum hexaaluminate ceramic and preparation method thereof | |
| Dudek et al. | Synthesis of ceria-based nanopowders suitable for manufacturing solid oxide electrolytes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |