CN103647097B - Sc2o3stablize ZrO2base electrolyte powder body, its preparation method and Sc2o3stablize ZrO2electrolyte ceramics sheet - Google Patents
Sc2o3stablize ZrO2base electrolyte powder body, its preparation method and Sc2o3stablize ZrO2electrolyte ceramics sheet Download PDFInfo
- Publication number
- CN103647097B CN103647097B CN201310712469.3A CN201310712469A CN103647097B CN 103647097 B CN103647097 B CN 103647097B CN 201310712469 A CN201310712469 A CN 201310712469A CN 103647097 B CN103647097 B CN 103647097B
- Authority
- CN
- China
- Prior art keywords
- solution
- powder body
- electrolyte powder
- stablize zro
- raw material
- 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
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
Abstract
The invention discloses a kind of Sc2O3Stablize ZrO2Base electrolyte powder body and preparation method thereof and Sc2O3Stablize ZrO2Electrolyte ceramics sheet.Wherein Sc2O3Stablize ZrO2Base electrolyte powder body is with zirconyl nitrate, Sc2O3, optional CeO2, nitric acid and optional adjuvant be raw material, with ammonium hydrogen carbonate ammonia buffer system as precipitant, the main body formed through co-precipitation spraying heat treating process is the powder body of Emission in Cubic mutually.This Sc2O3Stablize ZrO2Base electrolyte powder material is cheap, nontoxic, can be prepared as the dense electrolyte potsherd with high intensity, and prepared ionic conductivity stability etc. is preferably.Meanwhile, this Sc2O3Stablize ZrO2Base electrolyte powder preparation method avoids in coprecipitation and filters, washs, the follow-up loaded down with trivial details technique such as is dried, and makes reunion reduce, it is ensured that the purity of product, and operation is simple, and the continuous efficiency of process is high, the biggest industrialized production.
Description
Technical field
The invention belongs to solid-oxide fuel battery electrolyte preparation field, relate to a kind of Sc2O3Stablize ZrO2Base electrolyte powder body, its preparation method and Sc2O3Stablize ZrO2Electrolyte ceramics sheet.
Background technology
SOFC (being called for short SOFC) has the most wide application prospect as the new forms of energy of high-efficiency cleaning.External its SOFC product that disclosed in 2010 such as U.S. risk enterprise B loom Energy, and at home, due to starting evening and foreign technology block, the research of SOFC is still in developmental stage.SOFC includes electrolyte, anode, negative electrode, metallic interconnection materials and encapsulant, wherein electrolyte is most crucial parts, its performance (electrical conductivity, stability, thermal expansion, densification temperature etc.) directly affects operating temperature and the energy conversion efficiency of SOFC, so following condition must be had: 1) ionic conductivity height, electronic conductance is negligible；2) high chemical stability；3) thermal coefficient of expansion etc. mate with electrode material, compatible；4) dense film of high intensity, and low cost can be prepared as, nontoxic etc..
The most normally used is the zirconia material (YSZ) of stabilized with yttrium oxide, but owing to it uses temperature the highest, cause electrolyte, electrode and metallic interconnection materials chemical stability at high temperature inadequate, thus restrict development and the use of SOFC (SOFC), intermediate temperature solid oxide fuel cell to be developed, it is necessary to develop the electrolyte that ionic conductivity under low temperature is high.In order to improve the performance of the zirconia material (YSZ) of stabilized with yttrium oxide, research worker proposes a lot of evolutionary approach, such as:
(1) peace triumph et al. is with zirconium-n-propylate (C12H28O4And Sc Zr)2O3For raw material, use coprecipitation method synthesis scandium oxide-stabilizing zirconia (9mol%Sc2O3；ScSZ) powder, but its zirconium expensive raw material price used, inapplicable and industrialized production.
(2) its patent CN201010151728.6 of Jiangxi FanMeiYa Materials Co., Ltd. describes employing ordinary-pressure hydrolysis reaction and low pressure hydro-thermal reaction prepares scandium oxide-stabilizing zirconia powder, but its technique is more complicated, technique is high to used equipment requirements, and difficulty realizes industrialized production.
Although proposing the modification method of many zirconia materials (YSZ) for stabilized with yttrium oxide in the prior art, but existing ScSZ raw powder's production technology, as sol-gel process needed raw material is expensive, hydrolysis-hydro-thermal method is higher to equipment requirements, coprecipitation easily produces hard aggregation etc., it is difficulty with industrialized great production, this seriously inhibits the development of SOFC industry.
Summary of the invention
It is contemplated that overcome the deficiencies in the prior art, it is provided that a kind of Sc2O3Stablize ZrO2Base electrolyte powder body and preparation method thereof and Sc2O3Stablize ZrO2Electrolyte ceramics sheet, to reduce Sc2O3Stablize ZrO2The cost of material of base electrolyte material.
To achieve these goals, according to an aspect of the invention, it is provided a kind of Sc2O3Stablize ZrO2Base electrolyte powder body, this Sc2O3Stablize ZrO2Base electrolyte powder body is with zirconyl nitrate, Sc2O3, optional CeO2, nitric acid and optional adjuvant be raw material, with ammonium hydrogen carbonate-ammonia buffer system as precipitant, be the powder body of Emission in Cubic mutually through the main body of co-precipitation-spraying-heat treating process formation.
Further, above-mentioned Sc2O3Stablize ZrO2Base electrolyte powder body is with ZrO2For substrate, Sc2O3Doping be 8～10mol%, CeO2Doping be 0～3wt.%；In the mixed system of preferred feedstock mixing gained, total metal ion molar concentration is 0.3～1mol/L；The most described Sc2O3Stablize ZrO2Electrolyte powder body neutrality side phase content > 95%, the most described Sc2O3Stablize ZrO2Base electrolyte powder body crystalline size is 20-50nm, aggregated particle size size D50<0.5μm。
Further, in above-mentioned ammonium hydrogen carbonate-ammonia buffer system the mole of ammonium hydrogen carbonate be described raw material mixing gained mixed system in 4～10 times of total metal ion mole, it is preferable that the pH value of described ammonium hydrogen carbonate-ammonia buffer system is 7～10.
Further, above-mentioned adjuvant includes the dispersant of mixed system gross mass 0.5-3wt.% of described raw material mixing gained, and described dispersant is Macrogol 2000 and/or PEG 20000；Preferably, described adjuvant also includes total metal ion molar concentration 0～the additive of 10% in the mixed system of raw material mixing gained, and described additive is (NH4)2SO4。
According to a further aspect in the invention, it is provided that a kind of Sc2O3Stablize ZrO2Base electrolyte raw powder's production technology, comprises the steps: to configure reaction solution: by zirconyl nitrate, Sc2O3, optional CeO2Join in salpeter solution with optional adjuvant, be mixed to get presoma mother solution salpeter solution；Co-precipitation processes: joined by ammonium hydrogen carbonate-ammonia buffer system solution in described presoma mother solution salpeter solution, stirring reaction, and co-precipitation obtains presoma colloid solution；Spraying treatment: described presoma colloid solution is sprayed as spray liquid, to form precursor powder；Heat treatment: be thermally treated to obtain described Sc by described precursor powder2O3Stablize ZrO2Base electrolyte powder body.
Further, the step of above-mentioned configuration reaction solution includes: is dissolved in water by described zirconyl nitrate, obtains zirconyl nitrate solution；By described Sc2O3, optional CeO2Join in salpeter solution and dissolve, heat and stir, form nitric acid mixed solution, it is preferable that described salpeter solution is the hot salpeter solution of temperature 85-95 DEG C；Described nitric acid mixed solution is joined in zirconyl nitrate solution, the most again adjuvant is joined in described zirconyl nitrate solution, be configured to the presoma salpeter solution that total metal ion molar concentration is 0.3～1mol/L.
Further, the step that above-mentioned co-precipitation processes includes: drop in described presoma mother solution salpeter solution with the speed less than 3ml/min by described ammonium hydrogen carbonate-ammonia buffer system solution under the conditions of temperature is 70～90 DEG C, being 7～10 to pH value, co-precipitation obtains presoma colloid solution；Preferably in ammonium hydrogen carbonate-ammonia buffer system solution in the mixed system that mole is described raw material mixing gained of ammonium hydrogen carbonate 4～10 times of total metal ion mole, the more preferably pH value of ammonium hydrogen carbonate-ammonia buffer system is 7～10.
Further, above-mentioned spray process steps includes: using described presoma colloid solution as spray liquid, being 0.3～0.6MPa at jet pressure, fluid flow is 5～20ml/min, vapo(u)rizing temperature is sprayed under conditions of being 100～300 DEG C, to form described precursor powder.
Further, the step of above-mentioned heat treatment includes: by described precursor powder at air atmosphere, under conditions of calcining heat is 700～1000 DEG C, heat treatment 2～4 hours, it is thus achieved that described Sc2O3Stablize ZrO2Base electrolyte powder body.
According to a further aspect in the invention, it is provided that a kind of Sc2O3Stablize ZrO2Electrolyte ceramics sheet, by above-mentioned Sc2O3Stablize ZrO2Electrolyte powder body is through flow casting molding.
Apply Sc of the present invention2O3Stablize ZrO2Base electrolyte powder body and preparation method thereof has the advantage that
Sc provided by the present invention2O3Stablize ZrO2Base electrolyte powder body is with zirconyl nitrate and Sc2O3For raw material, using co-precipitation-spraying-heat treating process, the principal phase made is the Sc of Emission in Cubic2O3Stablize ZrO2Base electrolyte powder body, not only low in raw material price, nontoxic, and it is applicable to follow-up flow casting molding, sintering process, the dense electrolyte potsherd with high intensity can be prepared as, its ionic conductivity stability is preferable.
Meanwhile, at Sc provided by the present invention2O3Stablize ZrO2Base electrolyte powder preparation method uses co-precipitation-spraying-heat treating process, it is to avoid filters in coprecipitation, wash, the follow-up loaded down with trivial details technique such as be dried, makes reunion reduce, ensure that the purity of product, and operation is simple, the continuous efficiency of process is high, the biggest industrialized production.
Accompanying drawing explanation
The Figure of description of the part constituting the application is used for providing a further understanding of the present invention, and the schematic description and description of the present invention is used for explaining the present invention, is not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows Sc in the embodiment of the present invention 12O3Stablize ZrO2The XRD diffracting spectrum of base electrolyte powder body；
Fig. 2 shows Sc in the embodiment of the present invention 12O3Stablize ZrO2The SEM picture of base electrolyte powder body.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can be mutually combined.Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
The present invention is to solve the existing Sc pointed by background section2O3Stablize ZrO2The problem that base electrolyte powder material is expensive, it is provided that a kind of Sc2O3Stablize ZrO2Base electrolyte powder body, this Sc2O3Stablize ZrO2Base electrolyte powder body is with zirconyl nitrate, Sc2O3, optional CeO2, nitric acid and optional adjuvant be raw material, with ammonium hydrogen carbonate-ammonia buffer system as precipitant, be the powder body of Emission in Cubic mutually through the main body of co-precipitation-spraying-heat treating process formation.
Sc provided by the present invention2O3Stablize ZrO2Base electrolyte powder body is with zirconyl nitrate and Sc2O3For raw material, using co-precipitation-spraying-heat treating process, the principal phase made is the Sc of Emission in Cubic2O3Stablize ZrO2Base electrolyte powder body, not only low in raw material price, cleaning, and by the proportioning controlling each raw material and the phase structure generated, through follow-up flow casting molding, sintering process, can prepare the dense electrolyte potsherd of high intensity, its ionic conductivity, chemical stability etc. are preferable.
At above-mentioned Sc2O3Stablize ZrO2In base electrolyte powder body, preferably with ZrO2For substrate, Sc2O3Doping be 8～10mol% and CeO2Doping be 0～3wt.%.At Sc of the present invention2O3Stablize ZrO2Sc in base electrolyte powder body2O3And CeO2Doping be not limited to above-mentioned scope, but the most above-mentioned scope.By Sc2O3And CeO2Doping control be conducive within the above range improving Sc2O3Stablize ZrO2The content of Emission in Cubic in base electrolyte powder body, and then the ionic conductivity of electrolyte ceramics sheet prepared by improving and chemical stability.
At above-mentioned Sc2O3Stablize ZrO2In base electrolyte powder body, as long as with zirconyl nitrate and Sc2O3For raw material, the Sc prepared for technique with co-precipitation-spraying-heat treating process2O3Stablize ZrO2Base electrolyte powder body just has the above-mentioned effect being previously mentioned.In the preferred embodiment of the present invention, raw material (zirconyl nitrate, Sc2O3, optional CeO2, nitric acid and optional adjuvant) mixing gained mixed system (presoma mother solution salpeter solution pointed in subsequent processes) in total metal ion molar concentration be 0.3～1mol/L.In the most aforementioned mixed system, total metal ion molar concentration is not limited within the range, is controlled in this scope, advantageously forms even particle size distribution, and the Sc that granularity is thinner2O3Stablize ZrO2Base electrolyte powder body.
At above-mentioned Sc2O3Stablize ZrO2Base electrolyte powder body can not contain CeO2.In a kind of preferred version, above-mentioned Sc2O3Stablize ZrO2Containing CeO in base electrolyte powder body2, and CeO2Doping be preferably 1～3wt.%.CeO2Doped be beneficial to improve electrolyte high-temperature stability, and promote its formed Emission in Cubic thus be conducive to improve electrolyte electrical conductivity.
At above-mentioned Sc2O3Stablize ZrO2In base electrolyte powder body, the content of Emission in Cubic will affect the performances such as the conductivity of its prepared electrolyte, chemical stability, thermal coefficient of expansion, and intensity.The content of Emission in Cubic in one embodiment of the invention > 80%, preferably > 90%, more preferably > 95%.
At above-mentioned Sc2O3Stablize ZrO2In base electrolyte powder body in electrolyte raw material, preferably the crystalline size of powder granule is made as 10～100nm, primary particle size size D50<0.5μm.By Sc2O3Stablize ZrO2The crystallite dimension of electrolyte powder body and primary particle size size control to be conducive within the above range the realization of high-compactness when follow-up powder body molding, sintering, and then are conducive to making the dense electrolyte potsherd of high intensity.
At above-mentioned Sc2O3Stablize ZrO2In base electrolyte powder body in ammonium hydrogen carbonate-ammonia buffer system the mole of ammonium hydrogen carbonate be described electrolyte raw material mixing gained mixed system in 4～10 times of total metal ion mole.Under this molar ratio, mixing can make metal ion precipitate completely.Preferably, in this ammonium hydrogen carbonate-ammonia buffer system, pH value is 7～10, can make precipitation by metallic ion evenly, beneficially the uniformity of powder body component.
At above-mentioned Sc2O3Stablize ZrO2In base electrolyte powder body, in electrolyte raw material, adjuvant at least includes the dispersant of the mixed system gross weight 0.5～3wt.% of raw material mixing gained, it is preferable that dispersant is Macrogol 2000 and/or PEG 20000.Also including additive in above-mentioned adjuvant, additive is chosen as (NH4)2SO4, its sulfate ion by being adsorbed onto the position of nucleating surface positively charged, increases Coulomb repulsion, reduces and reunite, thus play scattered effect.Preferably (NH4)2SO4The mixed system that consumption is raw material mixing gained in total metal ion molar concentration 0～10%.
Meanwhile, the present invention is to solve that in background technology, pointed coprecipitation easily produces hard aggregation, the problem being difficulty with industrialized great production, it is provided that a kind of Sc2O3Stablize ZrO2Base electrolyte raw powder's production technology, this preparation method comprises the steps: to configure reaction solution: by zirconyl nitrate, Sc2O3, optional CeO2Join in salpeter solution with optional adjuvant, be mixed to get presoma mother solution salpeter solution.Co-precipitation processes: joined by ammonium hydrogen carbonate-ammonia buffer system solution in described presoma mother solution salpeter solution, stirring reaction, and co-precipitation obtains presoma colloid solution.Spraying treatment: described presoma colloid solution is sprayed as spray liquid, to form precursor powder.Heat treatment process: by described precursor powder heat treatment to obtain described Sc2O3Stablize ZrO2Base electrolyte powder body.
Sc provided by the present invention2O3Stablize ZrO2Base electrolyte powder preparation method includes: the step of configuration reaction solution-co-precipitation process-spraying treatment-heat treatment (calcination processing), it is referred to as co-precipitation-spraying-heat treating process in the present invention, this method avoid in coprecipitation and filter, wash, the follow-up loaded down with trivial details technique such as be dried, reunion is made to reduce, ensure that the purity of product, and operation is simple, the continuous efficiency of process is high, the biggest industrialized production.Apply this Sc provided by the present invention2O3Stablize ZrO2Base electrolyte powder preparation method can prepare the above-mentioned Sc being previously mentioned2O3Stablize ZrO2Base electrolyte powder body.And by Sc provided by the present invention2O3Stablize ZrO2Product diameter of particle prepared by base electrolyte powder preparation method is little, particle size distribution is concentrated, and is suitable for the most popular casting molding processes, and its production technology is simple, easy to operate, more favorably realizes industrialized great production.
At above-mentioned Sc provided by the present invention2O3Stablize ZrO2In base electrolyte powder preparation method, the step of configuration reaction solution uses common process to make each material dissolution.In the preferred embodiment of the present invention, the step of configuration reaction solution includes: is first dissolved in water by zirconyl nitrate, obtains zirconyl nitrate solution.Again by Sc2O3With optional CeO2Join in salpeter solution and dissolve, heat and stir, form nitric acid mixed solution.Then nitric acid mixed solution is joined in zirconyl nitrate solution, the most again adjuvant is joined in zirconyl nitrate solution, it is thus achieved that presoma mother solution salpeter solution.The method using this step-wise dissolution to mix, advantageously allows the relatively uniform of more raw material mixing, and then the compactness of the electrolyte ceramics sheet prepared by raising.
At above-mentioned Sc provided by the present invention2O3Stablize ZrO2In base electrolyte powder preparation method, co-precipitation processes step and is stirred reacting by ammonium hydrogen carbonate-ammonia buffer system solution and presoma mother solution salpeter solution according to common process.In the preferred embodiment of the present invention, this co-precipitation processes step and includes: drop in described presoma mother solution salpeter solution with the speed less than 3ml/min by ammonium hydrogen carbonate-ammonia buffer system solution under the conditions of temperature is 70-90 DEG C, being 7-10 to pH value, co-precipitation obtains presoma colloid solution.Use this method being slowly added dropwise under the low speed, be conducive to the Sc prepared by improving2O3Stablize ZrO2The purity (content) of Emission in Cubic in base electrolyte powder body, and then the intensity of electrolyte ceramics sheet, compactness, ionic conductivity and the chemical stability prepared by raising.
The present invention uses colloid solution directly as spray liquid, in spray-drying process, hydroxide in colloid solution and carbonate deposition are as nucleating germ, relatively evenly it is distributed in the drop surface of ejection, in drop solvent evaporation process, precipitate in ensure that whole drop, generation full particle simultaneously, thus the realization of high-compactness when beneficially powder body subsequent forming sinters.
At above-mentioned Sc provided by the present invention2O3Stablize ZrO2In base electrolyte powder preparation method, presoma colloid solution is sprayed as spray liquid by spray process steps according to common process, forms presoma powder body.In the preferred embodiment of the present invention, this spray process steps includes: using presoma colloid solution as spray liquid, being 0.3～0.6MPa at jet pressure, fluid flow is 5～20ml/min, vapo(u)rizing temperature is sprayed under conditions of being 100～300 DEG C, to form precursor powder.Above-mentioned spray method can use spray pyrolysis equipment to carry out, and is first heated to design temperature, regulates atmospheric pressure, and regulate fluid flow, then carry out spraying before using spray pyrolysis equipment.
At above-mentioned Sc provided by the present invention2O3Stablize ZrO2In base electrolyte powder preparation method, precursor powder is formed Sc by heat treatment according to common process by the step of heat treatment2O3Stablize ZrO2Base electrolyte powder body.In the preferred embodiment of the present invention, this heat treatment step includes: by precursor powder at air atmosphere, under conditions of calcining heat is 700-1000 DEG C, heat treatment 2-4 hour, it is thus achieved that Sc2O3Stablize ZrO2Base electrolyte powder body.
Meanwhile, Sc provided by the present invention2O3Stablize ZrO2Electrolyte powder body can be prepared as Sc through flow casting molding, normal pressure-sintered technique2O3Stablize ZrO2Electrolyte ceramics sheet, intensity, compactness, ionic conductivity and the chemical stability of this electrolyte ceramics sheet.
The Sc prepared by the present invention is further illustrated below with reference to specific embodiment 1 to 72O3Stablize ZrO2Base electrolyte powder body and Sc2O3Stablize ZrO2The beneficial effect of electrolyte ceramics sheet.
Embodiment 1:
Sc2O3Stablize ZrO2Base electrolyte raw powder's production technology:
(1) configuration reaction solution: zirconyl nitrate is dissolved in water, obtains zirconyl nitrate solution；By Sc2O3(inventory is Sc2O3Stablize ZrO2The 9mol% of base electrolyte powder body integral molar quantity), CeO2(inventory is Sc2O3Stablize ZrO2The 1wt.% of base electrolyte powder body gross mass) join in the hot salpeter solution of temperature 90 DEG C and dissolve, heat and stir, forming nitric acid mixed solution；Nitric acid mixed solution is joined in zirconyl nitrate solution, then by Macrogol 2000 and PEG 20000 (both weight ratios are 1:1, and total consumption is the 1wt.% of presoma mother solution salpeter solution gross weight) and (NH4)2SO4(consumption be in presoma mother solution salpeter solution the 2% of total metal ion molar concentration) joins in raw mixture, it is thus achieved that total metal ion molar concentration is the presoma mother solution salpeter solution of 0.3mol/L.
(2) configuration ammonium hydrogen carbonate-ammonia buffer system solution: obtaining pH value is 8, and the ammonium hydrogen carbonate-ammonia buffer system solution of 6 times of total metal ion mole in the mixed system that the mole of ammonium hydrogen carbonate is raw material mixing gained.
(3) co-precipitation processes: drops in presoma mother solution salpeter solution with the speed of 2ml/min by ammonium hydrogen carbonate-ammonia buffer system solution under the conditions of temperature is 80 DEG C, is 8 to pH value, and co-precipitation obtains presoma colloid solution.
(4) spraying treatment: using presoma colloid solution as spray liquid, being 0.4MPa at jet pressure, fluid flow is 10ml/min, and vapo(u)rizing temperature is sprayed under conditions of being 250 DEG C, to form precursor powder.
(5) heat treatment: by precursor powder at air atmosphere, under conditions of calcining heat is 1000 DEG C, heat treatment 2 hours, it is thus achieved that Sc2O3Stablize ZrO2Base electrolyte powder body.
Sc prepared by said method2O3Stablize ZrO2The Phase Structure Analysis of base electrolyte powder body is as depicted in figs. 1 and 2.It is Sc by Fig. 12O3Stablize ZrO2(in its XRD figure spectrum, lattice constant is the XRD diffracting spectrum of base electrolyte powder body ) and Fig. 2 be Sc2O3Stablize ZrO2The SEM picture of base electrolyte powder body.By Fig. 1 and Fig. 2 it can be seen that the Zr that electrolyte powder body is cubic prepared by the embodiment of the present invention 10.89Sc0.10Ce0.01O1.92, and aggregated particle size is below 0.1 μm.
Sc2O3Stablize ZrO2The preparation of electrolyte ceramics sheet: by through the Sc prepared by said method2O3Stablize ZrO2Base electrolyte powder body uses flow casting molding, and wherein molded blank carries out normal pressure-sintered to obtain potsherd at 1200 DEG C.
Embodiment 2:
Sc2O3Stablize ZrO2Base electrolyte raw powder's production technology: with embodiment 1, wherein, does not add CeO2。
Embodiment 3:
Sc2O3Stablize ZrO2Base electrolyte raw powder's production technology:
(1) configuration reaction solution: zirconyl nitrate is dissolved in water, obtains zirconyl nitrate solution；By Sc2O3(inventory is Sc2O3Stablize ZrO2The 8mol% of base electrolyte powder body integral molar quantity) and CeO2(inventory is Sc2O3Stablize ZrO2The 3wt.% of base electrolyte powder body gross mass) join in the hot salpeter solution of temperature 85 DEG C and dissolve, heat and stir, forming nitric acid mixed solution；Nitric acid mixed solution is joined in zirconyl nitrate solution, again the Macrogol 2000 3wt.% of presoma mother solution salpeter solution gross weight (consumption be) is joined in raw mixture, it is thus achieved that total metal ion molar concentration is the presoma mother solution salpeter solution of 1mol/L.
(2) configuration ammonium hydrogen carbonate-ammonia buffer system solution: obtaining pH value is 7, and the ammonium hydrogen carbonate-ammonia buffer system solution of 10 times of total metal ion mole in the mixed system that the mole of ammonium hydrogen carbonate is raw material mixing gained.
(3) co-precipitation processes: drops in presoma mother solution salpeter solution with the speed less than 3ml/min by ammonium hydrogen carbonate-ammonia buffer system solution under the conditions of temperature is 70 DEG C, is 10 to pH value, and co-precipitation obtains presoma colloid solution.
(4) spraying treatment: using presoma colloid solution as spray liquid, being 0.3MPa at jet pressure, fluid flow is 20ml/min, and vapo(u)rizing temperature is sprayed under conditions of being 300 DEG C, to form precursor powder.
(5) heat treatment: by precursor powder at air atmosphere, under conditions of calcining heat is 700 DEG C, heat treatment 4 hours, it is thus achieved that Sc2O3Stablize ZrO2Base electrolyte powder body.
Sc2O3Stablize ZrO2The preparation of electrolyte ceramics sheet: by through the Sc prepared by said method2O3Stablize ZrO2Base electrolyte powder body uses flow casting molding, and wherein molded blank carries out normal pressure-sintered to obtain potsherd at 1000 DEG C.
Embodiment 4:
Sc2O3Stablize ZrO2Base electrolyte raw powder's production technology:
(1) configuration reaction solution: zirconyl nitrate is dissolved in water, obtains zirconyl nitrate solution；By Sc2O3(inventory is by being intended to Sc2O3Stablize ZrO2The 10mol% of base electrolyte powder body integral molar quantity) and CeO2(inventory is by being intended to Sc2O3Stablize ZrO2The 2wt.% of base electrolyte powder body gross mass) join in the hot salpeter solution of temperature 85～95 DEG C and dissolve, heat and stir, forming nitric acid mixed solution；Nitric acid mixed solution is joined in zirconyl nitrate solution, then by the PEG 20000 1wt.% of presoma mother solution salpeter solution (consumption be) and (NH4)2SO4(consumption is the % of total metal ion molar concentration in presoma mother solution salpeter solution) joins in raw mixture, it is thus achieved that total metal ion molar concentration is the presoma mother solution salpeter solution of 1.1mol/L.
(2) configuration ammonium hydrogen carbonate-ammonia buffer system solution: obtaining pH value is 10, and the ammonium hydrogen carbonate-ammonia buffer system solution of 4 times of total metal ion mole in the mixed system that the mole of ammonium hydrogen carbonate is raw material mixing gained.
(3) co-precipitation processes: drops in presoma mother solution salpeter solution with the speed of 2.9ml/min by ammonium hydrogen carbonate-ammonia buffer system solution under the conditions of temperature is 90 DEG C, is 10 to pH value, and co-precipitation obtains presoma colloid solution
(4) spraying treatment: using presoma colloid solution as spray liquid, being 0.6MPa at jet pressure, fluid flow is 5ml/min, and vapo(u)rizing temperature is sprayed under conditions of being 100 DEG C, to form precursor powder.
(5) heat treatment: by precursor powder at air atmosphere, under conditions of calcining heat is 800 DEG C, heat treatment 3.2 hours, it is thus achieved that Sc2O3Stablize ZrO2Base electrolyte powder body.
Sc2O3Stablize ZrO2The preparation of electrolyte ceramics sheet: by through the Sc prepared by said method2O3Stablize ZrO2Base electrolyte powder body uses flow casting molding, and wherein molded blank carries out normal pressure-sintered to obtain potsherd at 1000 DEG C.
Embodiment 5:
Sc2O3Stablize ZrO2Base electrolyte raw powder's production technology: with embodiment 1, difference is:
Step (1) configuration reaction solution: zirconyl nitrate is dissolved in water, obtains zirconyl nitrate solution；By Sc2O3(inventory is Sc2O3Stablize ZrO2The 12mol% of base electrolyte powder body integral molar quantity), CeO2(inventory is Sc2O3Stablize ZrO2The 3.5wt.% of base electrolyte powder body gross mass) join in the hot salpeter solution of temperature 90 DEG C and dissolve.
Sc2O3Stablize ZrO2The preparation of electrolyte ceramics sheet: with embodiment 1.
Embodiment 6:
Sc2O3Stablize ZrO2Base electrolyte raw powder's production technology: with embodiment 1, difference is:
Step (1) configuration reaction solution: by zirconyl nitrate, Sc2O3(inventory is by being intended to Sc2O3Stablize ZrO2The 8～10mol% of base electrolyte powder body integral molar quantity) and CeO2(inventory is by being intended to Sc2O3Stablize ZrO2The 2wt.% of base electrolyte powder body gross mass), the PEG 20000 2wt.% of presoma mother solution salpeter solution gross weight (consumption be) and (NH4)2SO4(consumption is the 2.5% of presoma mother solution salpeter solution total metal ion molar concentration) joins in salpeter solution and dissolves, it is thus achieved that total metal ion molar concentration is the presoma mother solution salpeter solution of 0.8mol/L.
Sc2O3Stablize ZrO2The preparation of electrolyte ceramics sheet: with embodiment 1.
Embodiment 7:
Sc2O3Stablize ZrO2Base electrolyte raw powder's production technology: with embodiment 1, difference is:
Step (2) configuration ammonium hydrogen carbonate-ammonia buffer system solution: obtaining pH value is 11, and the ammonium hydrogen carbonate-ammonia buffer system solution of 3.5 times of total metal ion mole in the mixed system that the mole of ammonium hydrogen carbonate is raw material mixing gained.
Step (3) co-precipitation processes: drops in presoma mother solution salpeter solution with the speed less than 3.5ml/min by ammonium hydrogen carbonate-ammonia buffer system solution under the conditions of temperature is 100 DEG C, is 11 to pH value, and co-precipitation obtains presoma colloid solution
Step (4) spraying treatment: using presoma colloid solution as spray liquid, being 0.8MPa at jet pressure, fluid flow is 4ml/min, and vapo(u)rizing temperature is sprayed under conditions of being 100 DEG C, to form precursor powder.
Step (5) heat treatment: by precursor powder at air atmosphere, under conditions of calcining heat is 600 DEG C, heat treatment 8 hours, it is thus achieved that Sc2O3Stablize ZrO2Base electrolyte powder body.
Sc2O3Stablize ZrO2The preparation of electrolyte ceramics sheet: with embodiment 1.
Test:
By the Sc prepared by embodiment 1 to 72O3Stablize ZrO2Base electrolyte powder body and Sc2O3Stablize ZrO2Electrolyte ceramics sheet carries out following test, to further illustrate beneficial effects of the present invention.
Sc2O3Stablize ZrO2Base electrolyte powder body test event and method:
The phase structure of powder: use X-ray diffraction analysis.
Powder surface pattern: use scanning electron microscope analysis.
The crystallite dimension of powder: use X-ray diffraction analysis.
Aggregated particle size size D of powder50: use laser particle analyzer.
Sc2O3Stablize ZrO2The measure the item of electrolyte ceramics sheet and method:
The bending strength of potsherd: use anti-reflecting bending strength test machine.
The consistency of potsherd: use solid density/bulk density to characterize.Solid density can use XRD test to obtain, and bulk density can record with Archimedes's drainage.
The ionic conductivity of potsherd: use AC impedence method.
Measurement result is as shown in table 1.
Table 1.
By data in table 1 it can be seen that the Sc prepared by method provided by the present invention2O3Stablize ZrO2Base electrolyte powder body is Emission in Cubic mutually, and the content of Emission in Cubic can reach more than 95%, and crystallite dimension is relatively thin, and less than 50nm, agglomeration is less, and aggregated particle size is also respectively less than 0.5 μm.And by this Sc2O3Stablize ZrO2The bending strength of the potsherd prepared by base electrolyte powder body can reach more than 480MPa, and consistency can reach more than 95%, and electrochemical stability is preferable, in the range of remaining able to maintain 0.2 to 0.25S/cm at 700～800 DEG C.
Meanwhile, Sc provided by the present invention2O3Stablize ZrO2Base electrolyte powder body is with zirconyl nitrate and Sc2O3For raw material, using co-precipitation-spraying-heat treating process, the principal phase made is the Sc of Emission in Cubic2O3Stablize ZrO2Base electrolyte powder body, not only low in raw material price, nontoxic, and it is applicable to follow-up flow casting molding, sintering process, the dense electrolyte potsherd with high intensity can be prepared as, its ionic conductivity, chemical stability etc. are preferable.Additionally at Sc provided by the present invention2O3Stablize ZrO2Base electrolyte powder preparation method uses co-precipitation-spraying-heat treating process, it is to avoid filters in coprecipitation, wash, the follow-up loaded down with trivial details technique such as be dried, makes reunion reduce, ensure that the purity of product, and operation is simple, the continuous efficiency of process is high, the biggest industrialized production.
These are only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (14)
1. a Sc2O3Stablize ZrO2Base electrolyte powder body, it is characterised in that described Sc2O3Stablize ZrO2Base electrolyte powder body with
Zirconyl nitrate, Sc2O3, nitric acid and adjuvant be raw material or with zirconyl nitrate, Sc2O3、CeO2, nitric acid and adjuvant be raw material；
Described Sc2O3Stablize ZrO2Base electrolyte powder body with ammonium hydrogen carbonate-ammonia buffer system as precipitant, through co-precipitation-
The main body that spraying-heat treating process is formed is the powder body of Emission in Cubic mutually；The pH value of described ammonium hydrogen carbonate-ammonia buffer system be 7～
10；
Described adjuvant includes the dispersant of mixed system gross mass 0.5-3wt.% of described raw material mixing gained, described dispersant
For Macrogol 2000 and/or PEG 20000；Described adjuvant also includes total gold in the mixed system of raw material mixing gained
Belonging to ion molar concentration 2～the additive of 10%, described additive is (NH4)2SO4。
Electrolyte powder body the most according to claim 1, it is characterised in that total gold in the mixed system of described raw material mixing gained
Belonging to ion molar concentration is 0.3～1mol/L.
Electrolyte powder body the most according to claim 1 and 2, it is characterised in that carbon in described ammonium hydrogen carbonate-ammonia buffer system
In the mixed system that mole is described raw material mixing gained of acid hydrogen ammonium 4～10 times of total metal ion mole.
Electrolyte powder body the most according to claim 2, it is characterised in that described Sc2O3Stablize ZrO2Base electrolyte powder body with
ZrO2For substrate, Sc2O3Doping be 8～10mol%, CeO2Doping be 0～3wt.%.
Electrolyte powder body the most according to claim 2, it is characterised in that described Sc2O3Stablize ZrO2Electrolyte powder body is neutral
Side's phase content > 95%.
Electrolyte powder body the most according to claim 2, it is characterised in that described Sc2O3Stablize ZrO2Base electrolyte powder body is brilliant
Body a size of 20-50nm, aggregated particle size size D50<0.5μm。
7. the Sc according to any one of a claim 1 to 62O3Stablize ZrO2Base electrolyte raw powder's production technology, its feature
It is, comprises the steps:
Configuration reaction solution: described raw material is zirconyl nitrate, Sc2O3, nitric acid and adjuvant, or described raw material be zirconyl nitrate,
Sc2O3、CeO2, nitric acid and adjuvant, other component in described raw material is joined in described nitric acid, is mixed to get forerunner
Body mother solution salpeter solution；
Co-precipitation processes: is joined in described presoma mother solution salpeter solution by ammonium hydrogen carbonate-ammonia buffer system solution, stirs
Mixing reaction, co-precipitation obtains presoma colloid solution；
Spraying treatment: described presoma colloid solution is sprayed as spray liquid, to form precursor powder；
Heat treatment: be thermally treated to obtain described Sc by described precursor powder2O3Stablize ZrO2Base electrolyte powder body；Institute
The pH value stating ammonium hydrogen carbonate-ammonia buffer system is 7～10；
Described adjuvant includes the dispersant of mixed system gross mass 0.5-3wt.% of described raw material mixing gained, described dispersant
For Macrogol 2000 and/or PEG 20000；Described adjuvant also includes total gold in the mixed system of raw material mixing gained
Belonging to ion molar concentration 2～the additive of 10%, described additive is (NH4)2SO4。
Preparation method the most according to claim 7, it is characterised in that described raw material is zirconyl nitrate, Sc2O3、CeO2, nitre
Acid and adjuvant, the step of described configuration reaction solution includes:
Described zirconyl nitrate is dissolved in water, obtains zirconyl nitrate solution；
By described Sc2O3、CeO2Join in salpeter solution and dissolve, heat and stir, form nitric acid mixed solution；
Described nitric acid mixed solution is joined in zirconyl nitrate solution, then adjuvant is joined in described zirconyl nitrate solution,
It is configured to the presoma salpeter solution that total metal ion molar concentration is 0.3～1mol/L.
Preparation method the most according to claim 7, it is characterised in that the step that described co-precipitation processes includes:
By described ammonium hydrogen carbonate-ammonia buffer system solution under the conditions of temperature is 70～90 DEG C with the speed less than 3ml/min
Dropping in described presoma mother solution salpeter solution, be 7～10 to pH value, co-precipitation obtains presoma colloid solution.
Preparation method the most according to claim 7, it is characterised in that described spray process steps includes: by described presoma
Colloid solution, as spray liquid, is 0.3～0.6MPa at jet pressure, and fluid flow is 5～20ml/min, vapo(u)rizing temperature
Spray under conditions of being 100～300 DEG C, to form described precursor powder.
11. preparation methoies according to claim 7, it is characterised in that the step of described heat treatment includes: by described presoma
Powder is at air atmosphere, under conditions of calcining heat is 700～1000 DEG C, and heat treatment 2～4 hours, it is thus achieved that described Sc2O3
Stablize ZrO2Base electrolyte powder body.
12. preparation methoies according to claim 8, it is characterised in that described salpeter solution is that the hot nitric acid of temperature 85-95 DEG C is molten
Liquid.
13. preparation methoies according to claim 9, it is characterised in that carbonic acid in described ammonium hydrogen carbonate-ammonia buffer system solution
The mole of hydrogen ammonium be described raw material mixing gained mixed system in 4～10 times of total metal ion mole.
14. 1 kinds of Sc2O3Stablize ZrO2Electrolyte ceramics sheet, it is characterised in that by the Sc according to any one of claim 1 to 62O3
Stablize ZrO2Electrolyte powder body is through flow casting molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310712469.3A CN103647097B (en) | 2013-12-20 | 2013-12-20 | Sc2o3stablize ZrO2base electrolyte powder body, its preparation method and Sc2o3stablize ZrO2electrolyte ceramics sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310712469.3A CN103647097B (en) | 2013-12-20 | 2013-12-20 | Sc2o3stablize ZrO2base electrolyte powder body, its preparation method and Sc2o3stablize ZrO2electrolyte ceramics sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103647097A CN103647097A (en) | 2014-03-19 |
| CN103647097B true CN103647097B (en) | 2016-08-17 |
Family
ID=50252288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310712469.3A Active CN103647097B (en) | 2013-12-20 | 2013-12-20 | Sc2o3stablize ZrO2base electrolyte powder body, its preparation method and Sc2o3stablize ZrO2electrolyte ceramics sheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103647097B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106025349B (en) * | 2016-07-28 | 2018-10-30 | 上海应用技术学院 | A kind of LiBaLaZrREAlO method for preparing solid electrolyte |
| CN111244514A (en) * | 2020-01-17 | 2020-06-05 | 中国恩菲工程技术有限公司 | Method for preparing scandium-zirconium powder by coprecipitation coupling spray pyrolysis and scandium-zirconium powder prepared by method |
| CN111205095A (en) * | 2020-01-17 | 2020-05-29 | 中国恩菲工程技术有限公司 | Method for preparing scandium-zirconium powder by spray pyrolysis and scandium-zirconium powder prepared by method |
| CN111115683A (en) * | 2020-01-17 | 2020-05-08 | 中国恩菲工程技术有限公司 | Device for preparing scandium-zirconium powder by coprecipitation coupling spray pyrolysis |
| CN112679206B (en) * | 2020-12-30 | 2022-07-19 | 南京瑞洋新材料科技有限公司 | High-structural-strength permanent magnetic ferrite magnetic shoe and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710742A (en) * | 2004-06-18 | 2005-12-21 | 中国科学院过程工程研究所 | Method for low-temp. preparing nano-crystal zirconium-oxide base solid electrolyte |
| CN1794486A (en) * | 2005-12-26 | 2006-06-28 | 潮州三环（集团）股份有限公司 | Preparation method of solid oxide fuel battery electrolyte diaphram |
| CN101500943A (en) * | 2006-08-17 | 2009-08-05 | H.C.施塔克有限公司 | Zirconium oxide and method for the production thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104159665B (en) * | 2012-03-09 | 2016-08-24 | 国立大学法人大分大学 | Catalyst, the manufacture method of catalyst and employ the manufacture method of hydrogen-containing gas of this catalyst, apparatus for forming hydrogen, fuel cell system and load silicon CeZr system oxide |
-
2013
- 2013-12-20 CN CN201310712469.3A patent/CN103647097B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710742A (en) * | 2004-06-18 | 2005-12-21 | 中国科学院过程工程研究所 | Method for low-temp. preparing nano-crystal zirconium-oxide base solid electrolyte |
| CN1794486A (en) * | 2005-12-26 | 2006-06-28 | 潮州三环（集团）股份有限公司 | Preparation method of solid oxide fuel battery electrolyte diaphram |
| CN101500943A (en) * | 2006-08-17 | 2009-08-05 | H.C.施塔克有限公司 | Zirconium oxide and method for the production thereof |
Non-Patent Citations (1)
| Title |
|---|
| Electrical conductivity of the ZrO2-Ln2O3 (Ln=lanthanides) system;Y. Arachi，H. Sakai，O. Yamamoto等;《Solid State Ionics》;19990630;第121卷(第1-4期);第135页表1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103647097A (en) | 2014-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103647097B (en) | Sc2o3stablize ZrO2base electrolyte powder body, its preparation method and Sc2o3stablize ZrO2electrolyte ceramics sheet | |
| Xu et al. | Electrochemical synthesis of ammonia using a cell with a Nafion membrane and SmFe 0.7 Cu 0.3− x Ni x O 3 (x= 0− 0.3) cathode at atmospheric pressure and lower temperature | |
| CN106498435B (en) | A kind of cathode of electrolytic tank of solid oxide material and preparation method thereof | |
| US8546284B2 (en) | Process for the production of plasma sprayable yttria stabilized zirconia (YSZ) and plasma sprayable YSZ powder produced thereby | |
| CN101475377B (en) | Preparation of solid oxide electrolytic cell anode barrier layer nano powder and barrier layer | |
| TW201940416A (en) | Multi-stage process for producing a material of a battery cell | |
| CN102617139A (en) | Preparation method for strontium titanate lanthanum based powder material | |
| CN110875472A (en) | Preparation method of micro-nano positive electrode material of lithium battery | |
| CN101100379B (en) | Method for preparing nano-crystalline and amorphous composite structure yttrium oxide stabilization zirconium oxide spherical powder | |
| CN103474645A (en) | Preparation method for lithium titanate | |
| CN101186287A (en) | Method for preparing apatite type oxide electrolyte powder | |
| CN112062567A (en) | Method for preparing zirconium-yttrium-doped barium cerate powder by using molten salt and powder obtained by method | |
| CN101967057A (en) | Zirconium oxide-based solid electrolyte powder for automobile oxygen sensor and preparation method thereof | |
| CN101585558A (en) | The preparation method of nano-powder of cathode of solid oxide fuel cell | |
| Li et al. | Comparative study of yttria-stabilized zirconia synthesis by Co-precipitation and solvothermal methods | |
| CN101830505A (en) | Scandium oxide-stabilizing zirconia powder and preparation method thereof | |
| CN111205095A (en) | Method for preparing scandium-zirconium powder by spray pyrolysis and scandium-zirconium powder prepared by method | |
| CN100423346C (en) | Method for low-temp. preparing nano-crystal zirconium-oxide base solid electrolyte | |
| JP5969632B2 (en) | Method for synthesizing air electrode powder for medium- and low-temperature solid oxide fuel cells by sol-gel method | |
| Lim et al. | Ceramic nanocomposites for solid oxide fuel cells | |
| CN105428677B (en) | A kind of barium stannate base complex phase electrolyte and preparation method thereof | |
| CN111205088A (en) | Method for preparing scandia-stabilized zirconia powder by hydrothermal method and scandia-stabilized zirconia powder prepared by method | |
| CN101257120A (en) | Process for synthesizing biphase nanometer fuel battery cathode material | |
| TWI794987B (en) | Materials and methods of producing lithium cobalt oxide materials of a battery cell | |
| CN102167403A (en) | Preparation method of composite metallic oxide powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 |