CN102617147A - Perovskite structure aluminate-based mixing conductive ceramics and preparation method thereof - Google Patents
Perovskite structure aluminate-based mixing conductive ceramics and preparation method thereof Download PDFInfo
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- CN102617147A CN102617147A CN2012101124017A CN201210112401A CN102617147A CN 102617147 A CN102617147 A CN 102617147A CN 2012101124017 A CN2012101124017 A CN 2012101124017A CN 201210112401 A CN201210112401 A CN 201210112401A CN 102617147 A CN102617147 A CN 102617147A
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Abstract
The invention provides perovskite structure aluminate-based mixing conductive ceramics and a preparation method thereof. The material has the general formula as follow: Ln0.9Sr0.1Al1-xBxO3-Delta, wherein x is greater than or equal to 0.1 and is less than or equal to 0.5, Ln is any one of rare-earth metal elements: Pr and Nd, and B is any one of transition metal elements: Mn, Fe and Co. The preparation method comprises the following steps of: adopting citric acid as complexing agent; taking corresponding metallic oxides and inorganic salt as main raw materials according to proportion of each element in the general formula of Ln0.9Sr0.1Al1-xBxO3-Delta; preparing a one-phase ceramics nano-powder body by adopting an organogel method; and preparing the perovskite structure aluminate-based mixing conductive ceramics through pelleting, forming, rubber removing and sintering. The obtained material has higher conductivity, and conduction characteristic of mixed oxygen ion-electron, and p-type electronic conduction is dominated.
Description
Technical field
The present invention relates to a kind of perovskite typed hybrid conductive pottery and preparation method thereof, belong to the inorganic non-metallic field of functional materials.
Background technology
Ion-electron mixing conductor (MIEC) all has the potential purposes at aspects such as SOFC, oxygen separation membrane, film catalysis and membrane reactors.The anode material that MIEC is used for SOFC can expand to entire electrode-gas interface by electrode ︱ ionogen ︱ gas three phase boundary (TPB) with effective electrochemical reaction zone of electrode; Effectively increase the electrochemical reaction zone; Reduce activation resistance, thereby improved the overall performance of battery; When using MIEC,, need not external circuits and can accomplish oxygen by the transmission of high keto sectional pressure to low oxygen partial pressure because material itself has the ion-electron mixed conductivity as the oxygen separation membrane material; Oxygen separation membrane still can be used for the oxidative coupling reaction (OCM) of petroleum chemistry field such as methane in addition; The membrane reactor critical material of reaction such as methane portion oxidation (POM); Pure oxygen preparation and these reaction integration are used to prepare synthetic gas, can practice thrift the cost of preparation pure oxygen.The ion-electron mixing conductor material mainly comprises perovskite typed (ABO
3), fluorite type (MO
2), pyrochlore-type (A
2B
2O
7) oxide compound etc., wherein perovskite material is because chemicalstability and structural stability are higher, and 90% metallic element can get into calcium titanium ore structure, thereby obtained more attention and research.
Simple perofskite type oxide can be expressed as ABO
3, wherein the A position is the bigger basic metal of ionic radius, earth alkali metal or REE, the B position is the less metal of ionic radius, is transition metal mostly.Because of there is openr space its inside, for oxonium ion portion's conduction within it provides bigger passage, wherein the equivalent position of oxygen is maximum in the cubic structure, helps the migration of oxonium ion, so the oxygen ionic conductivity of perovskite material is very big in the calcium titanium ore structure.And mostly metals ion can mix and gets into ABO
3Structure can be regulated the electrical property of material, catalytic performance etc. through selecting doping doping elements kind and content.In the calcium titanium ore structure hybrid conductive investigation of materials more be LnMO
3Series material (Ln is a REE, and M is transient metal Mn, Fe, Co etc.), this series material has outstanding specific conductivity and advantages of high catalytic activity, but its relatively poor stability limit under low oxygen partial pressure the use of these materials.LaGaO with high oxygen ionic conductivity
3Series material is new research focus, but its Ga when having high temperature sintering
2The evaporation of O and anode-chemical stability problems such as electrolyte interface Ga ionic reduction.With adulterated CeO
2, LaGaO
3Series material is compared, LnAlO
3The based perovskite material has advantages such as cheap, that thermal expansivity is moderate, has therefore just obtained certain concern and research since the seventies in 20th century.The LnAlO of acceptor doping
3Conductivity of electrolyte materials is main with ionic conductance, study as electrolyte mostly, but the specific conductivity of this series material is generally lower, and 800 ℃ specific conductivity is about 10
-2Magnitude.Because Nd
3+, Pr
3+Ratio of ionic radii Sm
3+Greatly, bigger ionic radius can improve the free volume of structure cell, thereby helps the migration in oxygen room, improves specific conductivity, so the NdAlO of alkaline earth metal doping
3And PrAlO
3The specific conductivity of base pottery is than corresponding SmAlO
3Base pottery big.To LaAlO
3, SmAlO
3Deng discovering of series material material;, the A position introduces certain being prone to appraise at the current rate transition metal such as Mn, Fe, Co etc. when carrying out acceptor doping again in the B position; In order to keep the electroneutral of material; Material will appraise at the current rate through the transition metal that forms oxygen room and B position and form the little polaron of p type and carry out charge compensation, make material have ion-electron mixing conductance property, can be used for aspects such as solid oxide fuel cell electrode material, oxygen separation membrane material.
The method for preparing perovskite typed hybrid conductive material mainly contains solid reaction process, sol-gel method, chemical coprecipitation etc.Wherein the sample of organic gel method preparation has following advantage: the technological process temperature is low, and reaction conditions is gentle, can make the particle diameter materials with smaller; The sample granularity narrowly distributing, good uniformity; Sample purity is high.
Summary of the invention
The objective of the invention is to be to provide a kind of perovskite structure aluminate-base hybrid conductive pottery and preparation method thereof, in order to the low and lower shortcoming of aluminate material density of aluminate material electric conductivity that solves A position acceptor doping.
Main technical schemes of the present invention is following: a kind of perovskite structure aluminate-base hybrid conductive pottery, said hybrid conductive stupalith has general formula Ln
0.9Sr
0.1Al
1-
x B
x O
3-
δ , wherein 0.1≤
x≤0.5,
δBe oxygen nonstoichiometry value, Ln is any of thulium Pr and Nd, and B is any among transition metal Mn, Fe and the Co.
A kind of method for preparing described perovskite structure aluminate-base hybrid conductive pottery is a complexing agent with the Hydrocerol A, presses general formula Ln
0.9Sr
0.1Al
1-
x B
x O
3-
δ In each element ratio be main raw material with corresponding metal oxide and inorganic salt; Adopt organic gel method to prepare the one-component ceramic nano-powder earlier, make described calcium titanium ore structure aluminate-base hybrid conductive pottery through granulation, moulding, binder removal and sintering process then.
Described general formula Ln
0.9Sr
0.1Al
1-
x B
x O
3-
δ In Ln provide by corresponding rare earth oxide, dissolve earlier during use with rare nitric acid, it is raw material that other metallic element adopts corresponding inorganic salt.
Described inorganic salt are nitrate salt or acetate.
The consumption of Hydrocerol A is 1.2 ~ 2 times of amount of total metal ion species in the solution, and the pH value of regulator solution is 2 ~ 5.
Described one-component ceramic nano-powder carries out after the granulation pressing down at 400Mpa pressure with Z 150PH processes disk shape blank forming.
The temperature of binder removal is 400 ~ 600 ℃, soaking time 1 ~ 2 h; The agglomerating temperature is 1250 ~ 1500 ℃, soaking time 5 ~ 10 h; The temperature rise rate of binder removal process is 0.5 ℃/min, and the temperature rate of sintering process is 1 ℃/min.
Beneficial effect:
1, introduces p type electronic conductance through the codoped of alkaline earth and transition metal and make parent LnAlO
3Electrical property improved Ln greatly
0.9Sr
0.1Al
1-
x B
x O
3-
δ The LnAlO of the simple alkaline earth metal doping of the specific conductivity of pottery
3Material improves more than about 2 ~ 3 one magnitude, and transition metal Co, Fe and the Mn of the introducing of mixing simultaneously also can improve the catalytic activity of material.This series material has good potential using value in high-temperature electrochemistry devices such as SOFC, oxygen separation membrane, membrane reactor.
2, because Nd
3+And Pr
3+Ionic radius relatively large, help improving structure cell free volume and mobility of charge carrier, so NdAlO involved in the present invention
3And PrAlO
3The specific conductivity of system is than the corresponding alkaline earth of our former report and transient metal doped SmAlO
3The specific conductivity of system is higher.
3, prepared stupalith purity of the present invention and density are higher, and raw materials cost is cheap relatively, and process is simple and easy to control.
Description of drawings
Fig. 1 is Pr
0.9Sr
0.1Al
0.5M
0.5O
3-
δ The powder X-ray RD spectrum of (M=Co, Fe, Mn) ceramic block.
Fig. 2 is Pr
0.9Sr
0.1Al
0.5M
0.5O
3-
δ The specific conductivity of (M=Co, Fe, Mn) concerns with variation of temperature.
Fig. 3 is Nd
0.9Sr
0.1Al
1-
x Co
x O
3-
δ (
x=0.15,0.3,0.5) the powder X-ray RD of ceramic block spectrum.
Fig. 4 is Nd
0.9Sr
0.1Al
1-
x Co
x O
3-
δ (
x=0.15,0.3,0.5) specific conductivity concerns with variation of temperature.
Embodiment
The material that the present invention relates to comprises but is not limited to the material of following examples.
A kind of perovskite structure aluminate hybrid conductive stupalith, the chemical general formula of this hybrid conductive stupalith is Ln
0.
9Sr
0.1Al
1-
x B
x O
3-
δ , wherein 0.1≤
x≤0.5, Ln is any of REE Pr, Nd, and B is any among transient metal Mn, Fe, the Co.
A kind of preparation method of perovskite structure aluminate hybrid conductive pottery is a complexing agent with the Hydrocerol A, presses general formula Ln
0.9Sr
0.1Al
1-
x B
x O
3-
δ In each element ratio be main raw material with corresponding metal oxide and inorganic salt; Adopt organic gel method to prepare the one-component ceramic nano-powder earlier, make described calcium titanium ore structure aluminate-base hybrid conductive pottery through granulation, moulding, binder removal and sintering process then.Step is following more specifically:
A. according to title product Ln
0.
9Sr
0.1Al
1-
x B
x O
3-
δ Stoichiometric ratio be ratio Ln ︰ Sr ︰ Al ︰ B=0.9 ︰, the 0.1 ︰ 1-of amount of substance
x︰
xRatio take by weighing a certain amount of rare earth oxide and metal inorganic salt, MOX need be dissolved in rare nitric acid in advance, simultaneously takes by weighing an amount of complexing agent Hydrocerol A again to be dissolved in jointly in the deionized water, Hydrocerol A is 1.2 ~ 2 ︰ 1 with the ratio of the amount of total metal ion species; Metal inorganic salt can be corresponding acetate or nitrate salt.
B. using the pH value of ammoniacal liquor regulator solution after treating to dissolve fully is 2 ~ 5, continues about 20 ~ 24 h of magnetic agitation;
C. use the rotary evaporation in vacuo appearance that the water-bath under 50 ~ 75 ℃ temperature of step b gained solution is flashed to comparatively heavy-gravity gel;
D. the gel that obtains among the step c is put into vacuum drying oven and under 100 ℃, smoke into xerogel, and then make the pure phase nanometer ceramic powder at 900 ℃ of roasting 5 h;
E. after the gained powder carries out granulation with PVAC polyvinylalcohol; Press down at the pressure of 400 Mpa and to process disk shape base substrate; Base substrate is put into program control high-temperature electric resistance furnace carry out binder removal prior to (400 ~ 600 ℃) insulation 1 ~ 2 h under the low temperature; Further be warmed up to 1200 ~ 1600 ℃ of sintering 5 ~ 10 h then, make fine and close ceramic body.The temperature rise rate of binder removal process is 0.5 ℃/min, and the temperature rate of sintering densification process is 1 ℃/min subsequently.
Embodiment 1:Pr
0.9
Sr
0.1
Al
0.5
Co
0.5
O
3-
δ
The preparation of pottery
Get the Pr of 7.6608 g earlier
6O
11Pour in the 200 mL deionized waters, under 60 ℃ of water bath condition, slowly splash into concentrated nitric acid and make Pr
6O
11Corresponding nitrate soln is processed in dissolving fully; And then get the Sr (NO of 1.0582g
3)
2, the Al (NO of 9.3783g
3)
39H
2O, the Co (NO of 7.2758 g
3)
26H
2O and 31.5210 g Hydrocerol As add in the above-mentioned solution in the lump, treat that solution all dissolves the back and uses ammoniacal liquor that the pH value of solution is adjusted to about 3, continue magnetic agitation 24 h.Use Rotary Evaporators the vacuum hydro-extraction under 65 ℃ bath temperature of above-mentioned solution to be processed the wet gel of certain viscosity; Wet gel is processed xerogel at 100 ℃ of following vacuum dryings, then xerogel is synthesized well-crystallized's superfine ceramic powder at 900 ℃ of roasting temperature 5 h.Use Z 150PH that powder is carried out granulation; Press down at the pressure of 400 Mpa then that to process diameter be that 25 mm, thickness are 2 ~ 3 base substrate; Putting into program control high-temperature electric resistance furnace at last earlier is warmed up to 450 ℃ with 0.5 ℃/min and carries out binder removal; Be incubated behind 1 h again temperature rise rate with 1 ℃/min and be heated to 1250 ℃ and carry out sintering, be incubated that the speed with 1 ℃/min cools to 400 ℃ behind 6 h, naturally cool to room temperature preparation subsequently and go out comparatively fine and close single-phase Pr
0.9Sr
0.1Al
0.5Co
0.5O
3-
δ Ceramic body.Specific conductivity when specific density is 94%, 850 ℃ reaches 137.23 S/cm.
Embodiment 2:Pr
0.9
Sr
0.1
Al
0.5
Fe
0.5
O
3-
δ
The preparation of pottery
Basic preparation process is with embodiment 1, and that different is Co (NO in the raw material
3)
26H
2O changes Fe (NO into
3)
39H
2O, quality is 10.1000 g, sintering temperature becomes 1450 ℃.Prepared Pr
0.9Sr
0.1Al
0.5Fe
0.5O
3-
δ Specific conductivity when the specific density of ceramic body is 94%, 750 ℃ is the highest, is 12.03 S/cm.
Embodiment 3:Pr
0.9
Sr
0.1
Al
0.5
Mn
0.5
O
3-
δ
The preparation of pottery
Basic preparation process is with embodiment 1, and that different is raw material Co (NO
3)
26H
2O changes Mn (CH into
3COO)
24H
2O, quality is 6.1273 g, sintering temperature becomes 1500 ℃.Prepared Pr
0.9Sr
0.1Al
0.5Mn
0.5O
3-
δ The specific density of ceramic body is that 92%, 850 ℃ specific conductivity is 11.80 S/cm.
Embodiment 4:Nd
0.9
Sr
0.1
Al
0.5
Co
0.5
O
3-
δ
The preparation of pottery
Basic preparation process is with embodiment 1, and that different is Pr in the starting material
6O
11Change Nd into
2O
3, quality is 7.5708 g.Prepared Nd
0.9Sr
0.1Al
0.5Co
0.5O
3-
δ The specific density of ceramic body is that 94%, 750 ℃ specific conductivity is 100.77 S/cm.
Embodiment 5:Nd
0.9
Sr
0.1
Al
0.7
Co
0.3
O
3-
δ
The preparation of pottery
Basic preparation process is with embodiment 4, and that different is Al (NO in the material
3)
39H
2O and Co (NO
3)
36H
2The quality of O becomes 13.1296 g and 4.3655 g respectively.Prepared Nd
0.9Sr
0.1Al
0.7Co
0.3O
3-
δ The specific density of pottery is that 89%, 750 ℃ specific conductivity is 25.05 S/cm.
Embodiment 6:Nd
0.9
Sr
0.1
Al
0.85
Co
0.15
O
3-
δ
The preparation of pottery
Basic preparation process is with embodiment 4, and that different is Al (NO in the starting material
3)
39H
2O and Co (NO
3)
36H
2The quality of O becomes 15.9430 g and 2.1828 g respectively.Prepared Nd
0.9Sr
0.1Al
0.85Co
0.15O
3- δ The specific density of ceramic body is that 77%, 750 ℃ specific conductivity is 1.67 S/cm.
Embodiment 7:Nd
0.9
Sr
0.1
Al
0.5
Fe
0.5
O
3-
δ
The preparation of pottery
Basic preparation process is with embodiment 4, and that different is the Co (NO in the starting material
3)
36H
2O changes Fe (NO into
3)
39H
2O, quality is 10.1000 g, sintering temperature becomes 1450 ℃.Prepared Nd
0.9Sr
0.1Al
0.5Fe
0.5O
3-
δ The specific density of ceramic body is that 89%, 850 ℃ specific conductivity is 7.70S/cm.
Embodiment 8:Nd
0.9
Sr
0.1
Al
0.5
Mn
0.5
O
3-
δ
The preparation of pottery
Basic preparation process is with embodiment 4, and that different is raw material Co (NO
3)
26H
2O changes Mn (CH into
3COO)
24H
2O, quality is 6.1273g, sintering temperature becomes 1500 ℃.Prepared Nd
0.9Sr
0.1Al
0.5Mn
0.5O
3-
δ The specific density of ceramic body is that 90%, 850 ℃ specific conductivity is 4.93 S/cm.
Claims (7)
1. a perovskite structure aluminate-base hybrid conductive is ceramic, and it is characterized in that: said hybrid conductive stupalith has general formula Ln
0.9Sr
0.1Al
1-
x B
x O
3-
δ , wherein 0.1≤
x≤0.5,
δBe oxygen nonstoichiometry value, Ln is any among thulium Pr and the Nd, and B is any among transition metal Mn, Fe and the Co.
2. a method for preparing the described perovskite structure aluminate-base of claim 1 hybrid conductive pottery is characterized in that, is complexing agent with the Hydrocerol A, presses general formula Ln
0.9Sr
0.1Al
1-
x B
x O
3-
δ In each element ratio be main raw material with corresponding metal oxide and inorganic salt; Adopt organic gel method to prepare the one-component ceramic nano-powder earlier, make described calcium titanium ore structure aluminate-base hybrid conductive pottery through granulation, moulding, binder removal and sintering process then.
3. the method for preparing perovskite structure aluminate-base hybrid conductive pottery according to claim 2 is characterized in that described general formula Ln
0.9Sr
0.1Al
1-
x B
x O
3-
δ In Ln provide by corresponding rare earth oxide, dissolve earlier during use with nitric acid, it is raw material that other metallic element adopts corresponding inorganic salt.
4. the method for preparing perovskite structure aluminate-base hybrid conductive pottery according to claim 3 is characterized in that described inorganic salt are nitrate salt or acetate.
5. the method for preparing perovskite structure aluminate-base hybrid conductive pottery according to claim 2 is characterized in that, the consumption of Hydrocerol A is 1.2 ~ 2 times of amount of total metal ion species in the solution, and the pH value of regulator solution is 2 ~ 5.
6. the method for preparing perovskite structure aluminate-base hybrid conductive pottery according to claim 2 is characterized in that, described one-component ceramic nano-powder carries out after the granulation pressing down at 400Mpa pressure with Z 150PH processes disk shape blank forming.
7. the method for preparing perovskite structure aluminate-base hybrid conductive pottery according to claim 2 is characterized in that the temperature of binder removal is 400 ~ 600 ℃, soaking time 1 ~ 2 h; The agglomerating temperature is 1250 ~ 1500 ℃, soaking time 5 ~ 10 h; The temperature rise rate of binder removal process is 0.5 ℃/min, and the temperature rate of sintering process is 1 ℃/min.
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| CN108218406A (en) * | 2018-01-19 | 2018-06-29 | 北京元六鸿远电子科技股份有限公司 | Low-temperature co-burning ceramic material of low dielectric constant and low loss and preparation method thereof |
| CN111235589A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | High-temperature electrolytic cell cathode material and preparation and application thereof |
| CN112110740A (en) * | 2020-09-27 | 2020-12-22 | 景德镇陶瓷大学 | Method for preparing aluminum oxide-based composite biological ceramic material through in-situ reaction and product prepared by method |
| CN112919547A (en) * | 2021-01-25 | 2021-06-08 | 合肥学院 | Novel magnetic material and preparation method thereof |
| CN114920559A (en) * | 2022-06-07 | 2022-08-19 | 西北工业大学 | High-entropy oxide powder material for thermal barrier coating and preparation method and application thereof |
| CN116514549A (en) * | 2023-05-05 | 2023-08-01 | 上海大学 | Three-phase mixed conductor oxygen permeable membrane material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108218406A (en) * | 2018-01-19 | 2018-06-29 | 北京元六鸿远电子科技股份有限公司 | Low-temperature co-burning ceramic material of low dielectric constant and low loss and preparation method thereof |
| CN111235589A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | High-temperature electrolytic cell cathode material and preparation and application thereof |
| CN111235589B (en) * | 2018-11-29 | 2021-06-01 | 中国科学院大连化学物理研究所 | High-temperature electrolytic cell cathode material and preparation and application thereof |
| CN112110740A (en) * | 2020-09-27 | 2020-12-22 | 景德镇陶瓷大学 | Method for preparing aluminum oxide-based composite biological ceramic material through in-situ reaction and product prepared by method |
| CN112919547A (en) * | 2021-01-25 | 2021-06-08 | 合肥学院 | Novel magnetic material and preparation method thereof |
| CN114920559A (en) * | 2022-06-07 | 2022-08-19 | 西北工业大学 | High-entropy oxide powder material for thermal barrier coating and preparation method and application thereof |
| CN116514549A (en) * | 2023-05-05 | 2023-08-01 | 上海大学 | Three-phase mixed conductor oxygen permeable membrane material and preparation method thereof |
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Application publication date: 20120801 |