CN100481272C - Compound lanthanum zirconate proton conductor mixed material and preparing method thereof - Google Patents
Compound lanthanum zirconate proton conductor mixed material and preparing method thereof Download PDFInfo
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- CN100481272C CN100481272C CNB2007100566438A CN200710056643A CN100481272C CN 100481272 C CN100481272 C CN 100481272C CN B2007100566438 A CNB2007100566438 A CN B2007100566438A CN 200710056643 A CN200710056643 A CN 200710056643A CN 100481272 C CN100481272 C CN 100481272C
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Abstract
The invention relates to recombination doping zirconic acid lanthanum proton conductor material and its preparation method. Its chemical formula and matching is: La2-yNyZr2-xMxO7-delta;M is that Yb3+,Er3+,Gd3+,Sc3+ are doping in Zr bit, x is 0.01-1;N is Sr2+,Ca2+ are doping in La bit, y is 0.002-0.4;delta is oxygen vacant site, it depends on x and y. Dosage as proportion, water or alcohol is the medium, it is ball grinded and mixed for 4-10 hours and then dried, then synthesized in 1400DEG C, heat preserved for 2-20 hours. The synthesized material is then ball grinded, dried, screened, and loaded into die. The pressure is 50-120MPa, it is isostatic pressing, the pressure is 120-300MPa;it is adglutinated in 1400-1650DEG C, the warming-up rate is 2-10DEG C/ minute, heat preserved for 2-50 hours, then cooled to room temperature, the doping zirconic acid lanthanum material is produced. The invention adopts the recombination doping which is not reported to produce proton conductor material which possesses perfect conductivity; it lays the foundation of developing hydrogen gas and steam sensor, hydrogen pump, accelerant and concentration cell electrolyte material.
Description
Technical field
The invention belongs to technical field of ceramic material, particularly compound lanthanum zirconate proton conductor mixed material and preparation method thereof.
Background technology
Studies show that the pyrochlore-type material has good electric property, have required high ionic conductivity of solid electrolyte and the required high mixed conductivity of electrode material, thereby make its electrolyte that may become fuel cell or electrode material.Zirconic acid lanthanum (La
2Zr
2O
7) be the focus of studying in the pyrochlore, particularly the electric property to it has carried out a large amount of research, its special performance makes it use in a lot of fields and has broad prospects, as: the electrolyte of catalytic combustion activity agent, high temperature thermal insulation coating, Solid Oxide Fuel Cell, actinium family element fixing base etc. in the nuke rubbish.The pyrochlore-type material has chemical general formula A
2B
2O
7(wherein A, B be respectively+3 valencys and+4 valency cations), belong to cubic system, this structure can be considered to the cation (A by two kinds of different radiis
3+, B
4+) and the fluorite type structure formed of 1/8 anion vacancy.
Pyrochlore is used as heat barrier coat material for a long time.Japan Patent (JP7130385), United States Patent (USP) (US6258467), United States Patent (USP) (US6284323), world patent (WO02/081768), European patent (EP1514953), document (MaterialsTransactions, 2004,45 (8): 2634-2637) grade has all been carried out many-sided report to this.Japan Patent (JP6154605) has been reported a kind of La
2Zr
2O
7Preparation methods is used for the catalyst carrier of hydrocarbon combustion, and Pt family metal load is on carrier.
Pyrochlore constitution is a kind of Open architecture, can be by A atom or the B atom in other low price ion (as rare earth or alkaline-earth metal) replacement structure, adjust the relative ionic radius of A and B, increase the randomness that the structure intermediate ion is arranged, improve the vacancy concentration in the structure, finally improve the ionic conduction ability.According to its special architectural characteristic, behind the A atom or B atom in the foreign atom replacement lattice, generation is in two kinds of oxygen rooms of different chemical environment, and the ionic conduction ability that is had can be different, so the ionic conducting property of structure can be adjusted in the controlled doping position.Zr base pyrochlore has some special electrical properties: in the oxygen atmosphere, the ionic conductivity during middle temperature (400～800 ℃) has surpassed the zirconia of stabilized with yttrium oxide; And some oxide is (as La
2Zr
2O
7) under the saturated hydrogen atmosphere of water vapour, show the proton conductive behavior again, after low price ion (as Rare Earth Y or alkaline-earth metal Ca, Sr) replacement rare earth element wherein, conductivity increases, and proton conductivity can be compared with perovskite structure proton conductive oxide, but the conduction temperature is lower.Pyrochlore improves electrical property, and carries out application and development by doping vario-property, is to study focus at present.
More bibliographical information the has been arranged electrical property of pyrochlore materials is in the hope of as hydrogen pump and concentration cell.People such as Yamamura (Solid State Ionics, 2003,158 (3-4): 359-365) system research Ln
2Zr
2O
7The electrical property of (Ln=La, Nd, Sm, Eu, Gd, Y, Yb) system, near 800 ℃, Eu
2Zr
2O
7Conductivity 8.3 * 10 with system maximum
-3S/cm.The Ln that Y mixes
2Zr
2O
7The conductivity of series oxide under the saturated hydrogen atmosphere of water vapour: unadulterated La
2Zr
2O
7Conductivity in the time of 1000 ℃ is approximately 4.5 * 10
-4S/cm, 10%Y reaches 2.1 * 10 with conductivity under the condition after mixing
-3S/cm.La with the Y doping
2Zr
2O
7Be used for hydrogen or water vapour concentration cell as solid electrolyte, shown stable electromotive force; Further with La
2Zr
1.8Y
0.2O
7When being used for the electrochemistry hydrogen pump, anode hydrogen effusion rate and theoretical value meet finely, prove La
2Zr
1.8Y
0.2O
7Proton conductive.People such as Xie Yahong (Chinese Journal of Inorganic Chemistry, 2004,20 (5): 551-554) La that chemical method is synthesized
1.9Ca
0.1Zr
2O
7With codope La
1.9Ca
0.1Zr
1.6Ce
0.4O
6.975Carried out the research work of ordinary-pressure synthesis of ammonia, two kinds of systems all demonstrate stable ammonia productive rate, have fully proved the proton-conductive properties of sample.(Solid State Ionics, 1996,86-88 (Part1): 685-689 such as Shimura, Omata and Labrincha; Solid State Ionics, 1997,104 (3-4): 249-258; Solid State Ionics, 1997,99 (1-2): 33-40) use Ca
2+Doping La
2Zr
2O
7After the system, in wet hydrogen atmosphere, (La
1.95Ca
0.05) Zr
2O
7-δAnd La
2(Zr
1.985Ca
0.025) O
7-δConductivity in the time of 600 ℃ is respectively 6.8 * 10
-4S/cm and 1.0 * 10
-4S/cm, the protolysis number that obtains by the hydrogen concentration cell approaches 1.They have also studied a series of alkaline-earth metal (Mg
2+, Ca
2+, Sr
2+, Ba
2+) La that mixes
2Zr
2O
7System shows that from the gas analysis of separating out water vapour doped samples all has proton-conductive properties.(Solid State Ionics, 1995,80 (1-2): 99-110) studied Gd such as Kutty
2Zr
2O
7The architectural characteristic of series, and measured the crystals resistance and the grain boundary resistance of system with AC impedence method, system has just shown ionic conducting property preferably under the lower temperature in air atmosphere.Gd
2Zr
2O
7Middle r
3+/ r
4+Equal 1.23, only be a bit larger tham 1.22, be in pyrochlore-type and fluorite type border, a certain amount of doping than heavy ion radius element not only can be stablized pyrochlore constitution, can also increase the unordered degree that ion is arranged, and improves ionic conductivity.Gd in the time of 600 ℃
2Zr
2O
7Total conductivity be 1.1 * 10
-4S/cm uses 20%Sr
2+After the replacement, conductivity has improved an order of magnitude.Ga
3+And Sb
3+Average ion radius and Ti
4Much at one.Therefore, (Solid State Ionics, 2000,134 (1-2): such as Takamura 67-73) with Gd
3+And Sb
3+The common Ti that replaces
4+, and with further replacing Gd
3+And Sb
3+Come the ionic conduction ability of improved system.As x=0.4,0.6,0.8 the time, Gd
2(GaSb)
1-xZr
2xO
7Ionic conductivity reaches 2.5 * 10 respectively in the time of 1000 ℃
-6S/cm, 3.6 * 10
-5S/cm, 2.1 * 10
-3S/cm.(Solid State Ionics, 2000,135 (1-4): 675-679) studied Pr such as Holtappels
2Zr
2O
7The system of mixing with Mn or Ce in the Zr position is at 1000 ℃, 1%H
2/ 3%H
2O/96%N
2In the system, Pr
2Zr
1.9Mn
0.1O
7And Pr
2Zr
1.6Ce
0.4O
7Conductivity be respectively 1 * 10
-3S/cm and 3.6 * 10
-3S/cm, in the curve of conductivity and temperature, slope is bigger, has obviously shown high ionic conduction behavior.But in the present bibliographical information, mainly be to have studied the different Ln of Ln
2Zr
2O
7Material, La
2Zr
2O
7Independent doping and minority are in the preparation and the performance of the independent dopant material in Zr position in the La position.Also have many other compositions not have R and D, can not well utilize La
2Zr
2O
7Characteristic.
Summary of the invention
The present invention has selected a large amount of other ions to make up, at La
2Zr
2O
7La position and Zr position carry out composite mixedly, its preparation is studied, according to its architectural characteristic, the difference that changes La position or Zr position is mixed and can be adjusted the characteristic of oxide.
Zirconic acid lanthanum high conductivity proton conductor material and preparation method thereof is used Yb
3+, Er
3+, Gd
3+, Sc
3+Deng trivalent ion monobasic doping Zr position, carry out Sr simultaneously
2+, Ca
2+Composite mixed Deng divalent ion La position.
Material of the present invention and proportioning are as follows:
Compound lanthanum zirconate proton conductor mixed material of the present invention: chemical formula and proportioning are as follows:
La
2-yN
yZr
2-xM
xO
7-δWherein M is Yb
3+, Er
3+, Gd
3+Or Sc
3+, they mix to the Zr position, and doping x is 0.01～1; N is Sr
2+Or Ca
2+, they mix to the La position, and doping y is 0.002～0.4.
δ is the oxygen room that composite mixed back produces, and can determine that according to usual way its value depends on x and y.
Its preparation method of compound lanthanum zirconate proton conductor mixed material of the present invention is: prepare burden in proportion, water or ethanol are that medium carries out ball milling mixing 4～10 hours, synthetic in 1200 ℃～1500 ℃ then, be incubated 2～20 hours, synthesis material again through ball milling, the granulation of drying, sieve, the mould of packing into carries out dry-pressing formed, pressure is 50～120MPa, carry out isostatic compaction again, pressure is 120～300MPa; At 1400～1650 ℃ of sintering in air atmosphere, 2～10 ℃/minute of heating rates are incubated 2～50 hours, naturally cool to room temperature then, make doping zirconic acid lanthanum material.
The present invention adopts common employing solid phase method or liquid phase method also can prepare.
The present invention reports high conductivity proton conductor material and preparation method thereof, and material matrix is La
2Zr
2O
7, its structure is similar to fluorite very much, can think to lack anionic fluorite structure to a certain extent.Unadulterated zirconic acid lanthanum, oxygen ion vacancy is orderly, occupies VOID POSITIONS in case oxonium ion leaves the lattice position of oneself, just produces ionic conduction.It is a kind of Open architecture, can pass through other ion dopings, increases the randomness that the structure intermediate ion is arranged, and for the migration of oxonium ion, proton provides the hole, or increases hole concentration, thereby improves the ionic conduction ability.According to its architectural characteristic, the different doping that changes La position and Zr position can be adjusted the characteristic of oxide.The present invention is by composite mixed to zirconic acid lanthanum La position and Zr position, studied the influence of different elements and doping and sintering process to zirconic acid lanthanum electric property, exploration has obtained better dopant ion, obtains to have the more sub-conductor material of zirconic acid lanthanum matrix of high conductivity.
The present invention has adopted do not reported composite mixed, has prepared the proton conductor material of excellent conductive capability, lays a good foundation for developing hydrogen and water vapor sensor, hydrogen pump, catalyst and concentration cell electrolyte.
Specific embodiments
Embodiment 1
Get lanthana 53.63 grams, zirconia 32.78 grams, ytterbium oxide 13.10 grams, strontium carbonate 0.49 gram, preparation La
1.98Sr
0.02Zr
1.6Yb
0.4O
7-δ(δ=0.21).The employing ball milling mixes, and makes medium with absolute ethyl alcohol, 6 hours ball milling time.Dry back is incubated 8 hours in 1400 ℃ of pre-synthesizing.Dry-pressing formed 100MPa+ isostatic compaction 200MPa moulding sample is adopted in drying, the granulation of sieving behind the ball milling once more, 1600 ℃ of sintering in air, and 3 ℃/minute of heating rates are incubated 10 hours and obtain sintered body.700 ℃ proton conductivity is 6.9 * 10 in wet hydrogen atmosphere
-4S/cm.
Embodiment 2
Get lanthana 53.28 grams, zirconia 32.90 grams, ytterbium oxide 13.15 grams, calcium carbonate 0.67 gram, preparation La
1.96Ca
0.04Zr
1.6Yb
0.4O
7-δ(δ=0.22).The employing ball milling mixes, and makes medium with absolute ethyl alcohol, 6 hours ball milling time.Dry back is incubated 10 hours in 1400 ℃ of pre-synthesizing.Dry-pressing formed 100MPa+ isostatic compaction 200MPa moulding sample is adopted in drying, the granulation of sieving behind the ball milling once more, 1600 ℃ of sintering in air, and 4 ℃/minute of heating rates are incubated 15 hours and obtain sintered body.700 ℃ proton conductivity is 6.07 * 10 in wet hydrogen atmosphere
-4S/cm.
Embodiment 3
Get lanthana 56.82 grams, zirconia 42.81 grams, gadolinium oxide 0.32 gram, strontium carbonate 0.05 gram, preparation La
1.998Sr
0.002Zr
1.99Gd
0.01O
7-δ(δ=0.006).The employing ball milling mixes, and makes medium with absolute ethyl alcohol, 4 hours ball milling time.Dry back is incubated 2 hours in 1400 ℃ of pre-synthesizing.Drying, the granulation of sieving behind the ball milling once more, adopt dry-pressing formed 50MPa+ isostatic compaction 120MPa moulding sample, 1650 ℃ of sintering in air, 10 ℃/minute of heating rates, be incubated 2 hours and obtain sintered body, in wet hydrogen atmosphere, have higher proton conductivity in the time of 700 ℃.
Embodiment 4
Get lanthana 50.92 grams, zirconia 24.07 grams, scandium oxide 13.47 grams, strontium carbonate 11.54 grams, preparation La
1.6Sr
0.4ZrScO
7-δ(δ=0.7).The employing ball milling mixes, and makes medium with absolute ethyl alcohol, 6 hours ball milling time.Dry back is incubated 20 hours in 1400 ℃ of pre-synthesizing.Drying, the granulation of sieving behind the ball milling once more, adopt dry-pressing formed 120MPa+ isostatic compaction 300MPa moulding sample, 1600 ℃ of sintering in air, 8 ℃/minute of heating rates, be incubated 20 hours and obtain sintered body, in wet hydrogen atmosphere, have higher proton conductivity in the time of 700 ℃.
Embodiment 5
Get lanthana 51.87 grams, zirconia 28.31 grams, erbium oxide 18.83 grams, calcium carbonate 0.99 gram, preparation La
1.94Ca
0.06Zr
1.4Er
0.6O
7-δ(δ=0.33).The employing ball milling mixes, and makes medium with absolute ethyl alcohol, 8 hours ball milling time.Dry back is incubated 16 hours in 1500 ℃ of pre-synthesizing.Drying, the granulation of sieving behind the ball milling once more, adopt dry-pressing formed 120MPa+ isostatic compaction 120MPa moulding sample, 1400 ℃ of sintering in air, 2 ℃/minute of heating rates, be incubated 50 hours and obtain sintered body, in wet hydrogen atmosphere, have higher proton conductivity in the time of 700 ℃.
Embodiment 6
Get lanthana 53.11 grams, zirconia 32.79 grams, ytterbium oxide 13.11 grams, strontium carbonate 0.98 gram, preparation La
1.96Sr
0.04Zr
1.6Yb
0.4O
7-δ(δ=0.22).The employing ball milling mixes, and makes medium with absolute ethyl alcohol, 6 hours ball milling time.Dry back is incubated 8 hours in 1200 ℃ of pre-synthesizing.Dry-pressing formed 50MPa+ isostatic compaction 300MPa moulding sample is adopted in drying, the granulation of sieving behind the ball milling once more, 1580 ℃ of sintering in air, and 6 ℃/minute of heating rates are incubated 16 hours and obtain sintered body.700 ℃ proton conductivity is 7.1 * 10 in wet hydrogen atmosphere
-4S/cm.
Compound lanthanum zirconate proton conductor mixed material that the present invention proposes and preparation method thereof, be described by embodiment, person skilled obviously can be changed or suitably change and combination content as herein described in not breaking away from content of the present invention, spirit and scope, realizes the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (2)
1. compound lanthanum zirconate proton conductor mixed material, it is characterized in that: chemical formula and proportioning are as follows:
La
2-yN
yZr
2-xM
x0
7-δWherein M is Yb
3+, Er
3+, Gd
3+Or Sc
3+, they mix to the Zr position, and doping x is 0.01～1; N is Sr
2+Or Ca
2+, they mix to the La position, and doping y is 0.002～0.4; δ is the oxygen room that composite mixed back produces, and can determine that according to usual way its value depends on x and y.
2. its preparation method of the described compound lanthanum zirconate proton conductor mixed material of claim 1, it is characterized in that: prepare burden in proportion, water or ethanol are that medium carries out ball milling mixing 4～10 hours, then in 1200 ℃～1500 ℃ synthetic, be incubated 2～20 hours, synthesis material again through ball milling, the granulation of drying, sieve, the mould of packing into carries out dry-pressing formed, pressure is 50～120MPa, carries out isostatic compaction again, and pressure is 120～300MPa; At 1400～1650 ℃ of sintering in air atmosphere, 2～10 ℃/minute of heating rates are incubated 2～50 hours, naturally cool to room temperature then, make doping zirconic acid lanthanum material.
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|---|---|---|---|---|
| CN101543732B (en) * | 2009-02-25 | 2011-03-16 | 中国科学技术大学 | Metallic oxide proton conduction material and preparation method thereof |
| CN102659403A (en) * | 2012-05-31 | 2012-09-12 | 北京科技大学 | Ceramic material for high-temperature-resistant thermal barrier coating and preparation method thereof |
| CN103319179B (en) * | 2013-05-14 | 2015-04-22 | 内蒙古工业大学 | Zirconium-doped modified La2NiMnO6 ceramic dielectric adjustable material and preparation method thereof |
| CN103693962B (en) * | 2013-12-26 | 2015-03-25 | 浙江大学 | SiO2 doping-modified La2Zr2O7 ceramic and preparation method thereof |
| CN109950616A (en) * | 2019-03-13 | 2019-06-28 | 江西星盈科技有限公司 | Lacking oxygen solid electrolyte and positive electrode and positive plate and lithium ion battery and preparation process |
| CN110272278B (en) * | 2019-05-17 | 2021-11-05 | 东华大学 | High-entropy ceramic powder for thermal barrier coating and preparation method thereof |
| CN111978087B (en) * | 2019-05-22 | 2022-04-15 | 北京理工大学 | Composite material and preparation method and application thereof |
| CN110256075B (en) * | 2019-08-06 | 2021-10-29 | 内蒙古科技大学 | Doped modified Gd2Zr2O7 ceramic material and preparation method thereof |
| CN112125281B (en) * | 2020-10-28 | 2022-02-08 | 中国科学院上海应用物理研究所 | Method for preparing lanthanide oxide material by using coprecipitation combined with molten salt deposition method and application thereof |
| CN115724463A (en) * | 2021-12-13 | 2023-03-03 | 湖州南木纳米科技有限公司 | Precursor material for preparing lithium lanthanum zirconium oxide |
| CN115341174B (en) * | 2022-07-29 | 2024-01-12 | 中国航发北京航空材料研究院 | Lanthanum zirconium praseodymium oxygen thermal barrier coating material and preparation method thereof |
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