CN1470478A - Rare earth-doped srstrontium cerate nano crystal ceramic preparing method - Google Patents
Rare earth-doped srstrontium cerate nano crystal ceramic preparing method Download PDFInfo
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- CN1470478A CN1470478A CNA031294162A CN03129416A CN1470478A CN 1470478 A CN1470478 A CN 1470478A CN A031294162 A CNA031294162 A CN A031294162A CN 03129416 A CN03129416 A CN 03129416A CN 1470478 A CN1470478 A CN 1470478A
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- strontium
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Abstract
The present invention for ceramics of rare earth doped with strontium cerate nano crystal mainly adopts sol-gel method, to prepare the solution with a certain concentration by using cerous nitrate, strontium nitrate or strontium acetate and rare earth oxide as raw material, the weight ratio of them is dependent on the composition of ceramics to be prepared, the composition of the ceramics is SrCe1-xRExO3, in which the range of x value is 0.02-0.20, the concentraitons of cerous nitrate, strontium nitrate or strontium acetate are 0.2-2 mol/L respectively, using citric acid as complex builder, the added quantity of citric acid is 1.5-2.5 times the said solution, under stirring or ultrasonic vibration, heating in wate bath with 50-80 deg.C, regulating pH value to obtain transparent gel, drying to obtain opaque dried gel.
Description
Technical field
The present invention relates to a kind of preparation method of rear-earth-doped strontium cerate nanocrystalline ceramics, belong to inorganic ceramic material manufacturing technology field.
Background technology
Adulterated perovskite typed SrCeO
3, BaCeO
3, CaZrO
3, SrZrO
3, BaZrO
3Deng compound oxidate ceramic under middle high-temperature hydrogen and steam atmosphere, has good proton conductive, these proton conductors can be used as hydrogen sensor, middle high-temperature fuel cell, hydrogen pump, the electrolytic preparation of hydrogen, separate and purification, the solid electrolyte of the shortening of organic synthesis and dehydrogenation and multiple electrochemical appliance etc., have important application and wide application prospect, especially in the mensuration of metallurgical industry hydrogen is used, have quick, easy, advantages such as low cost have higher ionic conductivity in middle high temperature solid oxide fuel cell SOFC uses, good special advantages such as battery performance.At present, quite active to the research of this class function ceramics both at home and abroad, and rear-earth-doped perovskite typed SrCeO
3Pottery owing to have very high proton conductivity and lower electronics and oxide ion conduction rate, is considered to the more satisfactory selection of this class ceramic material.
The preparation technology of pottery mainly comprises preparation, moulding and the sintering of powder.Wherein the granular size of ceramic powder has determined the microtexture and the macro property of stupalith.The preparation method of existing compound oxidate ceramic powder comprises solid-phase synthesis, coprecipitation method etc.Adopt the ceramic powder particle of solid-phase synthesis preparation bigger, composition homogeneity is poor, and is synthetic higher with sintering temperature.Though coprecipitation method technology is simple, the powder grain growing that produces is too fast, should not control; The ceramic thermostability that makes simultaneously is relatively poor, and crystal grain is grown up easily in sintering process.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts sol-gel processing to prepare rear-earth-doped strontium cerate solid electrolyte nano ceramics.
The preparation method of a kind of rear-earth-doped strontium cerate nanocrystalline ceramics of the present invention, the main sol-gel processing that adopts, present method is characterised in that, with cerous nitrate, strontium nitrate or strontium acetate, rare earth oxide is that preparation of raw material becomes certain density solution, three's amount beguine is formed according to prepared pottery and is decided, and group of ceramics becomes SrCe
1-xRE
xO
3, wherein the scope of x value is 0.02-0.20, the concentration of cerous nitrate, strontium nitrate or strontium acetate is 0.2-2mol/L; With the citric acid is complexing agent, and the add-on of citric acid is 1.5-2.5 a times of aforementioned solution; Under stirring or sonic oscillation, and in the water-bath of 50-80 ℃ of temperature, heat; To 7-8, make this system be subjected to thermal response, with the pH value of ammoniacal liquor regulator solution until changing clear gel into; This wet gel is carried out infrared drying or vacuum-drying under 120-150 ℃ of temperature, be 10-20 hour time of drying, promptly becomes opaque dried glue; This dried glue was carried out under 900-1000 ℃ of temperature building-up reactions 6-8 hour, obtain nano-ceramic powder; This ceramic powder that makes is waited static pressure 20MPa compacted under, 1250-1350 ℃ of following sintering 4 hours, making nanocrystalline ceramics then.
Rare earth elements RE can be among ytterbium Yb, yttrium Y, scandium Sc, neodymium Nd, gadolinium Gd, samarium Sm, europium Eu, dysprosium Dy, the lanthanum La any.
The present invention has that raw material is easy to get, technology is simple, reaction process is easy to advantages such as control, temperature of reaction and sintering temperature are low.Preparation-obtained rear-earth-doped strontium cerate solid electrolyte nano ceramics, nanocrystalline grain size is between 20-70nm, have the even purity height of composition, characteristics such as any surface finish defective is few, specific conductivity is high, Heat stability is good, be the ideal proton conductor, have potential using value in fields such as senser element and fuel cell solid ionogen.
Embodiment
Now specific embodiments of the invention are described in detail in after.
Embodiment one: preparation SrCe
0.95Yb
0.05O
3Nanocrystalline ceramics
With Yb
2O
30.233g be dissolved in the 20ml concentrated nitric acid, as the A raw material, with Sr (NO
3)
25.00g with deionized water 20ml wiring solution-forming, as the B raw material, with Ce (NO
3)
36H
2O 9.75g as the C raw material, after A, B, C raw material stirring being mixed, adds 2.0 times of ionic weights (19.9g) citric acid, the about 250ml of wiring solution-forming with deionized water 20ml wiring solution-forming again.Under stirring or sonic oscillation, solution transfers to pH=7～8 with strong aqua, at 60 ℃ of heating in water bath, until changing clear gel into.This wet gel 120 ℃ of infrared dryings or vacuum-drying 15 hours, is promptly become opaque dried glue, carried out building-up reactions in 6 hours 1000 ℃ of calcinings again, can obtain pure iris nano-ceramic powder at last.To be pressed into diameter under the static pressure 20MPa be that 20 millimeters, thickness are 1 millimeter disk to wait with the ceramic powder that makes, 1300 ℃ of temperature lower calcinations 4 hours, makes SrCe then
0.95Yb
0.05O
3Nanocrystalline ceramics.
Prepared sample, relative density big (＞97%); Any surface finish, thermal stability is good, specific conductivity height (～10
-1S/cm).
Embodiment two: preparation SrCe
0.90Y
0.10O
3Nanocrystalline ceramics
With Y
2O
30.535g be dissolved in the 20ml concentrated nitric acid, as the A raw material, with Sr (NO
3)
25.00g with deionized water 20ml wiring solution-forming, as the B raw material, with Ce (NO
3)
36H
2O 9.26g is with deionized water 20ml wiring solution-forming, as the C raw material.After again A, B, C raw material stirring being mixed, add the citric acid of 2.0 times of ionic weights (19.9g), the about 250ml of wiring solution-forming.Transfer pH=4～5,70 ℃ heating in water bath with ammoniacal liquor, until changing clear gel into.This wet gel under 130 ℃ of temperature, is carried out infrared drying or vacuum-drying 10 hours, promptly become opaque dried glue.1000 ℃ of calcinings 8 hours, carrying out building-up reactions again, obtain nano-ceramic powder at last, is that 20 millimeters, thickness are 1 millimeter disk with being pressed into diameter under the static pressure 20MPa such as ceramic powder that make, and makes SrCe in 4 hours at 1300 ℃ of sintering
0.90Y
0.10O
3Nanocrystalline ceramics.
This sample also has the performance close with embodiment one.
Embodiment three: preparation SrCe
0.85Yb
0.15O
3Nanocrystalline ceramics
With Yb
2O
30.699g be dissolved in the 20ml concentrated nitric acid, as the A raw material, with Sr (NO
3)
25.00g with deionized water 20ml wiring solution-forming, as the B raw material, with Ce (NO
3)
36H
2O 8.72g is with deionized water 20ml wiring solution-forming, as the C raw material.After again A, B, C raw material stirring being mixed, add the citric acid of 2.0 times of ionic weights (19.9g), the about 250ml of wiring solution-forming.Transfer pH=7～8,60 ℃ heating in water bath with ammoniacal liquor, until changing clear gel into.With dry 150 seconds of this wet gel (power 800W) in microwave oven, promptly become opaque dried glue, calcined 6 hours down at 1000 ℃ again, carry out building-up reactions, obtain nano-ceramic powder at last, to be pressed into diameter under the static pressure 20MPa moulding be that 20 millimeters, thickness are 1 millimeter disk to wait with the ceramic powder that makes, made SrCe in 4 hours at 1300 ℃ of sintering temperatures then
0.85Yb
0.15O
3Nanocrystalline ceramics.
This sample also has the performance close with embodiment one.
Claims (4)
1. the preparation method of a rear-earth-doped strontium cerate nanocrystalline ceramics, the main sol-gel processing that adopts, present method is characterised in that, with cerous nitrate, strontium nitrate or strontium acetate, rare earth oxide is that preparation of raw material becomes certain density solution, three's amount beguine is formed according to prepared pottery and is decided, and group of ceramics becomes SrCe
1-xRE
xO
3, wherein the scope of x value is 0.02-0.20, the concentration of cerous nitrate, strontium nitrate or strontium acetate is 0.2-2mol/L; With the citric acid is complexing agent, and the add-on of citric acid is 1.5-2.5 a times of aforementioned solution; Under stirring or sonic oscillation, and in the water-bath of 50-80 ℃ of temperature, heat; To 7-8, make this system be subjected to thermal response, with the pH value of ammoniacal liquor regulator solution until changing clear gel into; This wet gel is carried out infrared drying or vacuum-drying under 120-150 ℃ of temperature, be 10-20 hour time of drying, promptly becomes opaque dried glue; This dried glue was carried out under 900-1000 ℃ of temperature building-up reactions 6-8 hour, obtain nano-ceramic powder; This ceramic powder that makes is waited static pressure 20MPa compacted under, 1250-1350 ℃ of following sintering 4 hours, making nanocrystalline ceramics then.
2. the preparation method of rear-earth-doped strontium cerate nanocrystalline ceramics according to claim 1 is characterized in that, described rare earth elements RE can be among ytterbium Yb, yttrium Y, scandium Sc, neodymium Nd, gadolinium Gd, samarium Sm, europium Eu, dysprosium Dy, the lanthanum La any.
3. the preparation method of rear-earth-doped strontium cerate nanocrystalline ceramics according to claim 1 is characterized in that, the concentration of described cerous nitrate, strontium nitrate or the strontium acetate aqueous solution, its optimum concn are 1.0mol/L.The add-on of citric acid, the best are 2.0 times of aforementioned solution.
4. the preparation method of rear-earth-doped strontium cerate nanocrystalline ceramics according to claim 1 is characterized in that, described synthesis temperature, and the best is 1000 ℃; Described sintering temperature the best is 1300 ℃.
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|---|---|---|---|
| CN 03129416 CN1203025C (en) | 2003-06-20 | 2003-06-20 | Rare earth-doped srstrontium cerate nano crystal ceramic preparing method |
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| CN1203025C CN1203025C (en) | 2005-05-25 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011156960A1 (en) * | 2010-06-17 | 2011-12-22 | 海洋王照明科技股份有限公司 | Strontium cerate luminous materials, preparation methods and use thereof |
| CN104386748A (en) * | 2014-10-31 | 2015-03-04 | 渤海大学 | Method for preparing strontium scandium tantalate powder |
| CN105664987A (en) * | 2014-11-21 | 2016-06-15 | 中国科学院大连化学物理研究所 | Synthetic method of nano ceramic and nano carbide composite material |
| CN108695532A (en) * | 2017-04-11 | 2018-10-23 | 阜阳师范学院 | High stability adulterates strontium cerate/cerium acid zirconium-alkali metal salt composite electrolyte and preparation method thereof |
| CN111635230A (en) * | 2020-05-28 | 2020-09-08 | 浙江大学 | High-quality-factor strontium cerate microwave dielectric ceramic material and preparation method thereof |
| US20220363559A1 (en) * | 2021-05-17 | 2022-11-17 | Phillips 66 Company | Enhanced proton conduction and steam tolerance of a donor doped electrolyte for solid oxide electrolysis cells |
-
2003
- 2003-06-20 CN CN 03129416 patent/CN1203025C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011156960A1 (en) * | 2010-06-17 | 2011-12-22 | 海洋王照明科技股份有限公司 | Strontium cerate luminous materials, preparation methods and use thereof |
| CN104386748A (en) * | 2014-10-31 | 2015-03-04 | 渤海大学 | Method for preparing strontium scandium tantalate powder |
| CN104386748B (en) * | 2014-10-31 | 2016-04-20 | 渤海大学 | A kind of scandium tantalic acid strontium raw powder's production technology |
| CN105664987A (en) * | 2014-11-21 | 2016-06-15 | 中国科学院大连化学物理研究所 | Synthetic method of nano ceramic and nano carbide composite material |
| CN105664987B (en) * | 2014-11-21 | 2018-04-03 | 中国科学院大连化学物理研究所 | A kind of synthetic method of nano ceramics and nano-carbide composite |
| CN108695532A (en) * | 2017-04-11 | 2018-10-23 | 阜阳师范学院 | High stability adulterates strontium cerate/cerium acid zirconium-alkali metal salt composite electrolyte and preparation method thereof |
| CN108695532B (en) * | 2017-04-11 | 2021-01-15 | 阜阳师范学院 | High-stability doped strontium cerate/zirconium cerate-alkali metal salt composite electrolyte and preparation method thereof |
| CN111635230A (en) * | 2020-05-28 | 2020-09-08 | 浙江大学 | High-quality-factor strontium cerate microwave dielectric ceramic material and preparation method thereof |
| CN111635230B (en) * | 2020-05-28 | 2021-07-09 | 浙江大学 | High-quality-factor strontium cerate microwave dielectric ceramic material and preparation method thereof |
| US20220363559A1 (en) * | 2021-05-17 | 2022-11-17 | Phillips 66 Company | Enhanced proton conduction and steam tolerance of a donor doped electrolyte for solid oxide electrolysis cells |
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| Publication number | Publication date |
|---|---|
| CN1203025C (en) | 2005-05-25 |
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