CN104387059A - Scandium-cerium co-doped zirconium oxide powder and preparation method thereof - Google Patents
Scandium-cerium co-doped zirconium oxide powder and preparation method thereof Download PDFInfo
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Abstract
A disclosed preparation method for a scandium-cerium co-doped zirconium oxide powder comprises the following steps: A, preparing a mixed salt solution; B, preparing a precipitating-agent solution; C, generating a precursor precipitate; D, post-processing the precursor precipitate; and E, post-processing the scandium-cerium co-doped zirconium oxide powder. The scandium-cerium co-doped zirconium oxide powder prepared by using the preparation method has the advantages of relatively simple operation technology, uniform particle size distribution of the prepared powder, relatively good sintering activity, low cost and the like, and therefore the technology is suitable for large-scale production of the scandium-cerium co-doped zirconium oxide powder.
Description
Technical field
The present invention relates to field of solid oxide fuel, particularly a kind of scandium for solid-oxide fuel battery electrolyte and cerium mixing and doping Zirconium powder and preparation method thereof.
Background technology
The ZrO of undoped
2do not have electroconductibility, the rising with temperature is attended by volume change by monoclinic phase to Tetragonal and cubic phase transition.But with divalence or trivalent doping ZrO
2, can at room temperature obtain stable Emission in Cubic or Tetragonal, simultaneously as the ion Sc with lower valency
3+or Y
3+displacement ZrO
2in Zr
4+time, produce superfluous negative charge, for keeping electric neutrality, form Lacking oxygen positively charged accordingly in crystal, the Lacking oxygen formed so just result in the suitable ion conductivity of zirconium white, thus widespread use is SOFC electrolyte.
In doped zirconia base electrolyte, Sc
2o
3doping ZrO
2(ScSZ) have the highest specific conductivity, such as, 800 DEG C time, the specific conductivity of 11ScSZ is 0.12S/cm, far away higher than the specific conductivity 0.03S/cm of 8YSZ, but due to 11ScSZ after pyroprocessing through often there will be the β phase of low conductivity, therefore CeO
2, Gd
2o
3, CaO, Y
2o
3, Al
2o
3deng usually used as phase stabilizer, with Sc
2o
3codoped ZrO
2, the rhombus β phase in version of the cubic structure c contributing to suppressing high conductivity in ScSZ low conductivity in opposite directions, wherein, 10mol%Sc
2o
3with the ZrO of 1mol%CeO2 doping
2(10Sc1CeSZ) the highest ionic conductivity and good stability is shown after the annealing process.
In recent years, scandium and cerium mixing and doping Zirconium powder (hereinafter referred to as 10Sc1CeSZ) ionogen are owing to having higher specific conductivity, and after high temperature sintering, its cubic structure c phase can be stabilized to the excellent specific property of room temperature, is therefore widely used as the electrolyte of intermediate temperature solid oxide fuel cell (SOFC).But, due to scandium, zirconium ion radius too close to and cause 10Sc1CeSZ ionogen sintering activity poor, therefore need to select a kind of suitable powder preparation method.At present; the preparation of domestic 10Sc1CeSZ powder is only in a small amount of synthesis in laboratory; although prepared powder also has cubic fluorite structure and good sintering activity; but the method adopted; complex process, wayward, more time-consuming, to equipment and ingredient requirement higher, preparation cost also improves accordingly; exactly serious pollution is caused to environment, be all not suitable for the industrial production for mass-producing.Ionogen, as the most key material of SOFC, is suitable for the exploitation of the fabricating technology of the production 10Sc1CeSZ powder of mass-producing, inherently powerful technological development and the commercialization thereof promoting SOFC.
Have a lot about 10Sc1CeSZ raw powder's production technology at present, common method is coprecipitation method, but the presoma of co-precipitation easily produces hard aggregation at dry and calcination stage, therefore supercritical drying, azeotropic distn etc. has been developed again, but need the equipment compared with complex and expensive, add preparation cost, be therefore difficult to be widely used.And hydrothermal method is that directly from the liquid phase of precipitation presoma, crystallization goes out 10Sc1CeSZ nano-powder, can avoid producing hard aggregation in calcination process, synthesized nano-powder has larger specific surface area, sintering temperature can be effectively reduced, this is because particle size reduces, during sintering, the path of material diffusion is short, and mass transfer speed accelerates, thus causes sintering temperature to reduce; The particle size of material is reduced to nano level simultaneously, and nano particle has larger specific surface energy, causes the motivating force sintered to increase, reduces sintering temperature; In addition, nano-grain crystal boundary often has the defects such as many dislocations, fault, lattice distortion, and the existence of defect also can promote the densification of porcelain body in sintering process.But, current casting technique is widely used in the batch preparation of SOFC electrolytic thin-membrane, and the nano-powder that thus prepared by technique has larger specific surface area, be not suitable for for casting technique, therefore need reasonably to optimize this technique, there is suitable specific surface area and the 10Sc1CeSZ powder having better sintering activity to obtain.
In order to explore the mass production processes of 10Sc1CeSZ powder, select and be hopeful to realize industrial production and the good water heat transfer 10Sc1CeSZ powder of powder characteristic, the phase structure, microscopic appearance, size-grade distribution, sintering character, electrical property etc. of powder are studied, by optimizing the processing condition of Hydrothermal Synthesis 10Sc1CeSZ nano-powder, powder is calcined in differing temps, prepare the 10Sc1CeSZ powder of different-grain diameter, investigate the powder characteristic after differing temps calcining.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of scandium and cerium mixing and doping Zirconium powder and preparation method thereof, namely by optimizing the technique of water heat transfer 10Sc1CeSZ powder, to obtain applicable casting technique and there is the 10Sc1CeSZ powder with applicable specific surface area of better sintering activity, and the suitability for industrialized production realizing 10Sc1CeSZ powder with meet market in SOFC to the demand of efficient electrolysis material prepared by 10Sc1CeSZ powder.
For achieving the above object, technical scheme of the present invention is as follows:
The present invention needs scandium and the cerium mixing and doping Zirconium powder (10Sc1CeSZ powder) of preparation, and its chemical constitution is (Sc
2o
3) 0.1 (CeO
2) 0.01 (ZrO
2) 0.89, its grain-size is 3-35nm, and its powder is of a size of 20-120nm and is single cubic fluorite structure c phase.
In order to obtain the 10Sc1CeSZ powder with above-mentioned chemical constitution, crystalline phase and powder size, a kind of 10Sc1CeSZ raw powder's production technology provided by the invention, comprises the steps:
A: the preparation of mixing salt solution, namely takes ZrOCl
28H
2o, Ce (NO
3)
3xH
2o and Sc (NO
3)
3acquisition mixing salt solution soluble in water, ZrO
2+ionic concn is 0.05-0.3mol/L;
B: the preparation of precipitant solution, namely takes strong aqua, adds tensio-active agent ammonium polyacrylate, is uniformly mixed, and by the concentration dilution of ammoniacal liquor to 1.0-4.0%;
C: the generation of presoma precipitation, namely under whipped state, pours in the precipitant solution of step B by the mixing salt solution of steps A, the hydroxide precursor after precipitin reaction terminates, leaves standstill aging;
D: the aftertreatment of presoma precipitation, namely leave standstill aging after presoma throw out after filtration and washing, then precipitation is dispersed in a small amount of deionized water, after dispersion, puts into reactor hydro-thermal reaction, cooling, filtration, washing, namely obtain scandium and cerium mixing and doping nm-class powder of zirconium oxide after drying;
E: the aftertreatment of scandium and cerium mixing and doping nm-class powder of zirconium oxide, namely in 600-1100 DEG C of calcining, grinding, oven dry, obtains scandium and cerium mixing and doping Zirconium powder finished product.
Preferably, in steps A, in mixing salt solution, add nonionic surface active agent, and stirring and dissolving.
Preferably, the nonionic surface active agent joined in steps A is selected from any one or more in polyethylene glycol type tensio-active agent, and its quality is the 0.2-2.0% of the quality of hydroxide precursor described in step C.
Preferably, a certain amount of ZrOCl is taken by the requirement of 10Sc1CeSZ powder to composition in steps A
28H
2o, Ce (NO
3)
3xH
2o and Sc (NO
3)
3be dissolved in appropriate water, make ZrO
2+ionic concn is 0.1mol/L, then adds PEG400 and PEG6000 wherein as tensio-active agent, and its quality is respectively 1% and 0.5% of generated hydroxide precursor quality, stirs and makes it fully dissolve.
Preferably, in step B, the 1-3 of volume ammoniacal liquor stoichiometric ratio needed for precipitin reaction of strong aqua doubly, the 0.5-2.5% that the quality of tensio-active agent ammonium polyacrylate is the quality of hydroxide precursor described in step C.
Preferably, in step B, by ZrOCl
28H
2o, Ce (NO
3)
3xH
2o and Sc (NO
3)
31.5 times of ammoniacal liquor stoichiometric ratio needed for precipitin reaction take strong aqua (25%-28%, the density 0.9g/cm of certain volume
3), add tensio-active agent ammonium polyacrylate (NH by generate hydroxide precursor quality 1%
4pPA), be uniformly mixed, then by about the concentration dilution to 2.5% of ammoniacal liquor.
Preferably, in step C, precipitin reaction terminates rear continuation high-speed stirring 0.2-2h;
Preferably, in step C, under vigorous stirring, slowly poured in precipitant solution by mixing salt solution, continue to increase stirring velocity uneven to prevent solution from mixing, precipitin reaction terminates rear continuation high-speed stirring 0.5h, to ensure to mix, make precipitin reaction more complete, then leave standstill aging.
Preferably, in step D, the hydroxide precursor throw out washed with de-ionized water after standing aging, be added with the tensio-active agent identical with steps A, and surfactant concentration is identical with tensio-active agent used in steps A in deionized water used.
Preferably, in step D, in deionized water used, be also added with the strong aqua with same concentrations in described step B.
Preferably, in step D, leave standstill aging after hydroxide precursor throw out after filtration and washing, removing Cl-wherein, clean in deionized water used and need to add appropriate PEG400 with PEG6000 (its concentration is identical with the concentration of PEG400 with PEG6000 used in mixing salt solution in steps A), this is to prevent deionized water in washing precipitation process from washing away the surfactant molecule on deposit seeds surface, need to add a certain amount of strong aqua simultaneously, the pH value of deionized water is regulated to be about 8-9, metal ion is caused to run off to prevent from precipitating in washing process because of dissolving, then precipitation is dispersed in a small amount of deionized water, reactor hydro-thermal 24h is put into after dispersion, just the 10Sc1CeSZ nano slurry of crystallization can be obtained after cooling, after filtration also by washing with alcohol, namely 10Sc1CeSZ nano-powder is obtained after 80 DEG C of dry 12h.
Preferably, in step e, calcining temperature is 700-1000 DEG C, and calcination time is 5-20h, after wet ball-milling, oven dry, obtains 10Sc1CeSZ powder.
Pass through technique scheme, the preparation that a kind of scandium provided by the invention and cerium mixing and doping zirconia powder preparation are used for 10Sc1CeSZ powder has the following advantages: (1) directly can obtain the oxide powder that crystallization goes out from solution, do not need high-temperature calcination, avoid the hard aggregation that this process produces; (2) technique is comparatively simple, and mild condition is therefore low for equipment requirements; (3) powder purity prepared is high, crystal formation good, the good dispersity of powder, particle diameter are little, narrow distribution range; (4) molding blank density is large, is conducive to sintering.Therefore; the technique of 10Sc1CeSZ powder is prepared by optimizing the hydrothermal method had; have that easier, the prepared powder granularity of operation is evenly distributed, sintering activity better, low cost and other advantages; therefore this technique is suitable for large-scale production, for the popularization using 10Sc1CeSZ powder to prepare electrolytical SOFC provides industrialization basis.
Accompanying drawing explanation
Fig. 1 is 10Sc1CeSZ grain-size change comparison diagram under different calcining temperature;
Fig. 2 is 10Sc1CeSZ powder dimensional change comparison diagram under different calcining temperature;
Fig. 3 is 10Sc1CeSZ powder specific-surface area detection change comparison diagram under different calcining temperature;
Fig. 4 is 10Sc1CeSZ powder conductivity variations comparison diagram under different calcining temperature;
The sintering shrinkage comparison diagram of Fig. 5 porcelain body prepared by the powder that obtains under different calcining temperature;
The densification temperature comparison diagram of Fig. 6 porcelain body prepared by the powder that obtains under different calcining temperature;
The relative density comparison diagram of Fig. 7 porcelain body prepared by the powder that obtains under different calcining temperature.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below.
Embodiment 1:
The preparation of mixing salt solution: the chemical constitution of synthesized 10Sc1CeSZ powder is (Sc
2o
3) 0.1 (CeO
2) 0.01 (ZrO
2) 0.89, by it, requirement of composition is taken to the ZrOCl of 2290.37g
28H
2ce (the NO of O, 34.68g
3)
3xH
2sc (the NO of O and 369.02g
3)
3be dissolved in 44L water, make ZrO
2+ionic concn is 0.1mol/L, then adds PEG400 and PEG6000 wherein as (non-ionic type) tensio-active agent, its quality by generation hydroxide precursor quality 1% and 0.5%, stir make it fully dissolve.
Embodiment 2:
Precipitant solution is prepared: by ZrOCl
28H
2o, Ce (NO
3)
3xH
2o and Sc (NO
3)
31.5 times of ammoniacal liquor stoichiometric ratio needed for precipitin reaction take 2.2L strong aqua (25%-28%, density 0.9g/cm
3), add tensio-active agent ammonium polyacrylate (NH by generate hydroxide precursor amount 1%
4pPA), be uniformly mixed, then by about the concentration dilution to 2.5% of ammoniacal liquor.
Embodiment 3:
The generation of presoma precipitation: under vigorous stirring, the mixing salt solution obtained by embodiment 1 is slowly poured in the precipitant solution obtained by embodiment 2, continue to increase stirring velocity uneven to prevent solution from mixing, precipitin reaction terminates rear continuation high-speed stirring 0.5h, to ensure to mix, make precipitin reaction more complete, then leave standstill aging.
Embodiment 4:
Presoma precipitation aftertreatment: in embodiment 3 leave standstill aging after presoma throw out after filtration and washing, removing Cl-wherein, clean in deionized water used and need to add appropriate PEG400 with PEG6000 (its concentration is identical with the concentration in mixing salt solution), this is to prevent deionized water in washing precipitation process from washing away the surfactant molecule on deposit seeds surface, need to add a certain amount of strong aqua simultaneously, the pH value of deionized water is regulated to be about 8-9, metal ion is caused to run off to prevent from precipitating in washing process because of dissolving, then precipitation is dispersed in a small amount of deionized water, reactor hydro-thermal 24h is put into after dispersion, just the 10Sc1CeSZ nano slurry of crystallization can be obtained after cooling, after filtration also by washing with alcohol, namely 10Sc1CeSZ nano-powder is obtained after 80 DEG C of dry 12h.
Embodiment 5-9:
The aftertreatment of 10Sc1CeSZ nano-powder: the nano-powder synthesized through embodiment 4 is incubated 10h at 700-1000 DEG C, through wet ball-milling, dry, can obtain the 10Sc1CeSZ powder of the different specific surfaces of grain growth, its comparing result is as shown in table 1:
Table 1: powder characteristic contrast after calcining under differing temps
According to above-mentioned table 1, adopt hydro-thermal reaction method to synthesize 10Sc1CeSZ powder, investigated hydro-thermal 10Sc1CeSZ (normal temperature 20 DEG C does not sinter) and the performance of powder after 700-1000 DEG C of calcining, research shows:
1. hydro-thermal 10Sc1CeSZ and through 700-1000 DEG C calcining powder all in single cubic fluorite structure c phase, do not have the β phase of low conductivity to occur, along with the rising of calcining temperature, its average grain size is grown up gradually, grows 25nm from 6nm, as shown in Figure 1;
2. hydro-thermal 10Sc1CeSZ (normal temperature 20 DEG C is not calcined) and the powder after 700-1000 DEG C of calcining thereof are along with the rising of calcining temperature, powder granule is grown up gradually, can grow up to 100nm (as shown in Figure 2) from 30nm, wherein hydro-thermal 10Sc1CeSZ and through 700,800,900 DEG C calcining powder dispersities better, present weakly agglomerated, and comparatively serious through the 10Sc1CeSZ powder reuniting of 1000 DEG C of calcinings, its specific surface area successively decreases (as shown in Figure 3) successively; Wherein, through 900 DEG C of powders calcined, because it has suitable specific surface area, particle, comparatively being evenly suitable for curtain coating prepares film and other purposes;
3. hydro-thermal 10Sc1CeSZ powder shows good low-temperature sintering activity, and along with powder calcination temperature raises, prepared by it, the sintering shrinkage of porcelain body reduces gradually, and sintering activity also reduces gradually, as shown in Figure 5; Prepared by hydro-thermal 10Sc1CeSZ powder there are three maximum value in the sintering shrinkage rate curve of porcelain body, show multistage Sintering mode, and through 700,800,900,1000 DEG C of calcinings 10Sc1CeSZ powders prepared by the sintering shrinkage rate curve of porcelain body all only have a maximum value, temperature corresponding to its maximum value is respectively 930,980,1030,1060,1140 DEG C, shows that the densification temperature of porcelain body also increases gradually along with the rising of calcining temperature;
4. along with powder calcination temperature raises, hydro-thermal 10Sc1CeSZ (normal temperature 20 DEG C does not sinter) and through 700,800,900,1000 DEG C of calcinings powders prepared by the densification temperature of porcelain body also present rising trend, sintering densification is realized respectively at 1000,1100,1100,1100,1400 DEG C, its relative density is respectively 97.4%, 97.1%, 97.3%, 96.7%, 96.1%, as shown in figs. 6 and 7;
5. hydro-thermal 10Sc1CeSZ and through the powders of 700,800,900,1000 DEG C of calcinings through the green compact of dry-pressing formed preparation after 1000-1400 DEG C of high temperature sintering 10h, still in single cubic fluorite structure, there is not the β phase of low conductivity, show that CeO2 really enters in ZrO2 lattice, show that this hydro-thermal reaction method can well for the preparation of the different 10Sc1CeSZ powder of particle diameter further;
6. hydro-thermal 10Sc1CeSZ and after 700,800,900 DEG C of calcinings the specific conductivity of powder increase along with the rising of air themperature, as shown in Figure 4, the specific conductivity of the powder wherein at 1000 DEG C is not surveyed.
To be apparent for those skilled in the art to the multiple amendment of above-described embodiment, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. scandium and a cerium mixing and doping Zirconium powder, is characterized in that, its chemical constitution is (Sc
2o
3) 0.1 (CeO
2) 0.01 (ZrO
2) 0.89, its grain-size is 3-35nm, and its powder is of a size of 20-120nm and is single cubic fluorite structure c phase.
2. a preparation method for scandium as claimed in claim 1 and cerium mixing and doping Zirconium powder, is characterized in that, comprise the steps:
A: the preparation of mixing salt solution, namely takes ZrOCl28H
2o, Ce (NO
3)
3xH
2o and Sc (NO
3)
3acquisition mixing salt solution soluble in water, ZrO
2+ionic concn is 0.05-0.3mol/L;
B: the preparation of precipitant solution, namely takes strong aqua, adds tensio-active agent ammonium polyacrylate, is uniformly mixed, and by the concentration dilution of ammoniacal liquor to 1.0-4.0%;
C: the generation of presoma precipitation, namely under whipped state, pours in the precipitant solution of step B by the mixing salt solution of steps A, the hydroxide precursor after precipitin reaction terminates, leaves standstill aging;
D: the aftertreatment of presoma precipitation, namely leave standstill aging after presoma throw out after filtration and washing, then precipitation is dispersed in a small amount of deionized water, after dispersion, puts into reactor hydro-thermal reaction, cooling, filtration, washing, namely obtain scandium and cerium mixing and doping nm-class powder of zirconium oxide after drying;
E: the aftertreatment of scandium and cerium mixing and doping nm-class powder of zirconium oxide, namely in 600-1100 DEG C of calcining, grinding, oven dry, obtains scandium and cerium mixing and doping Zirconium powder finished product.
3. the preparation method of a kind of scandium according to claim 2 and cerium mixing and doping Zirconium powder, is characterized in that, in steps A, in mixing salt solution, adds nonionic surface active agent, and stirring and dissolving.
4. the preparation method of a kind of scandium according to claim 3 and cerium mixing and doping Zirconium powder, it is characterized in that, the nonionic surface active agent joined in steps A is selected from any one or more in polyethylene glycol type tensio-active agent, and its quality is the 0.2-2.0% of the quality of hydroxide precursor described in step C.
5. the preparation method of a kind of scandium according to claim 1 and cerium mixing and doping Zirconium powder, it is characterized in that, in step B, the 1-3 of volume ammoniacal liquor stoichiometric ratio needed for precipitin reaction of strong aqua doubly, the 0.5-2.5% that the quality of tensio-active agent ammonium polyacrylate is the quality of hydroxide precursor described in step C.
6. the preparation method of a kind of scandium according to claim 1 and cerium mixing and doping Zirconium powder, is characterized in that, in step C, precipitin reaction terminates rear continuation high-speed stirring 0.2-2h.
7. the preparation method of a kind of scandium according to claim 1 and cerium mixing and doping Zirconium powder, it is characterized in that, in step D, hydroxide precursor throw out washed with de-ionized water after standing aging, be added with the tensio-active agent identical with steps A in deionized water used, and surfactant concentration is identical with tensio-active agent used in steps A.
8. the preparation method of a kind of scandium according to claim 7 and cerium mixing and doping Zirconium powder, is characterized in that, in step D, is also added with the strong aqua with same concentrations in described step B in deionized water used.
9. the preparation method of a kind of scandium according to claim 1 and cerium mixing and doping Zirconium powder, is characterized in that, in step e, calcining temperature is 700-1000 DEG C, calcination time is 5-20h, after wet ball-milling, oven dry, obtains scandium and cerium mixing and doping Zirconium powder.
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| CN110342931A (en) * | 2019-07-11 | 2019-10-18 | 河北铭万精细化工有限公司 | A kind of preparation method of ceramic nano zirconium oxide powder |
| CN111138188A (en) * | 2020-01-20 | 2020-05-12 | 中国恩菲工程技术有限公司 | Preparation facilities of scandia stabilized zirconia powder |
| CN111138189A (en) * | 2020-01-20 | 2020-05-12 | 中国恩菲工程技术有限公司 | Method and device for preparing scandium-zirconium powder |
| CN111233467A (en) * | 2020-01-15 | 2020-06-05 | 中国恩菲工程技术有限公司 | Oxide-doped scandium-zirconium powder and preparation method thereof |
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| CN114927733A (en) * | 2022-05-27 | 2022-08-19 | 潮州三环（集团）股份有限公司 | Zirconia-based electrolyte powder and preparation method and application thereof |
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| CN110350225A (en) * | 2019-07-05 | 2019-10-18 | 湖南稀土金属材料研究院 | A kind of scandium zircon ceramic electrolyte sheet and preparation method thereof |
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| CN111233467A (en) * | 2020-01-15 | 2020-06-05 | 中国恩菲工程技术有限公司 | Oxide-doped scandium-zirconium powder and preparation method thereof |
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| CN115893461B (en) * | 2022-12-06 | 2023-11-17 | 山东麦丰新材料科技股份有限公司 | Production process of nano alumina polishing powder |
| CN116864763A (en) * | 2023-09-04 | 2023-10-10 | 中石油深圳新能源研究院有限公司 | ScSZ electrolyte layer, preparation method thereof and battery |
| CN116864763B (en) * | 2023-09-04 | 2023-11-10 | 中石油深圳新能源研究院有限公司 | ScSZ electrolyte layer, preparation method thereof and battery |
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