CN1189423C - 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
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- CN1189423C CN1189423C CNB031002722A CN03100272A CN1189423C CN 1189423 C CN1189423 C CN 1189423C CN B031002722 A CNB031002722 A CN B031002722A CN 03100272 A CN03100272 A CN 03100272A CN 1189423 C CN1189423 C CN 1189423C
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- ceo
- base
- ceramic material
- solid electrolyte
- sintering
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- 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
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- 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
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Abstract
The present invention relates to a cerium dioxide base solid electrolyte ceramic material and a manufacturing method thereof. The formula of the ceramic material comprises 75 to 95 mol% of cerium dioxide and 4.9 to 20 mol% of samarium oxide or/and gadolinium oxide. The present invention is characterized in that the ceramic material also comprises 0.1 to 5 mol% of specific oxide ceramic aluminum oxide or/and zirconium dioxide. The manufacturing method comprises: 1. CeO2 base electrolyte powder preparation: the traditional components are treated by wet grinding, and then the specific oxide ceramic with the proportion is added for wet grinding by a particle ball mill for 4 to 8 hours; 2. blank preparation; 3. ceramic material sintering: the sintering temperature is from 1400 to 1500 DEG C, and the temperature rise rate is from 6 to 10 DEG C / min. The ceramic material of the present invention has the advantages of high mechanical strength, and the method has the advantages of simple technology, low sintering temperature, high finished product rate, suitability for industrial popularization, etc.
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.VanHerle, 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%): CeO
275~95; Sm
2O
3Or/and Gd
2O
34.9~20, it is characterized in that it also comprises oxide compound 0.1~5, described oxide compound is meant Al
2O
3Or/and 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 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 oxide compound 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 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
2The oxide compound that adds described an amount of ratio in the base electrolyte (is Al
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 is or/and ZrO
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, oxide compound aluminum oxide (Al
2O
3) or/and zirconium white (ZrO
2): 1~3, the screening formulation (mol%) that briefly is described stupalith is CeO
2: Sm
2O
3Or/and Gd
2O
3: oxide compound=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 oxide compound 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)
0.01
Its 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%): CeO
275~95; Sm
2O
3Or/and Gd
2O
34.9~20, it is characterized in that it also comprises oxide compound 0.1~5, described oxide compound is meant Al
2O
3Or/and ZrO
2
2. cerium oxide base solid electrolyte ceramic material according to claim 1 is characterized in that described stupalith prescription (mol%) is CeO
2: Sm
2O
3Or/and Gd
2O
3: oxide compound=85-90: 9~12: 1~3.
3. manufacture method according to claim 1 or 2 described cerium oxide base solid electrolyte ceramic materials, 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 dehydrated alcohol, with particle sphere grinding machine wet-milling 4 hours; After the wet-milling, add the oxide compound of described ratio again, with particle sphere grinding machine wet-milling 4-8 hour; 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 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, and sintering temperature is 1400~1500 ℃, and heat-up rate is 6-10 ℃/minute, and sintering time is 4 hours, cools to the furnace after the room temperature to take out promptly.
4. according to the manufacture method of the described cerium oxide base solid electrolyte ceramic of claim 3 material, it is characterized in that
(1) after the wet-milling, add the oxide compound 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.
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CNB031002722A CN1189423C (en) | 2003-01-10 | 2003-01-10 | Cerium oxide-base solid electrolyte ceramic material and its production process |
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CN102544559B (en) * | 2012-02-23 | 2014-08-20 | 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 |
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