CN102531587A - Yttrium-doped barium zirconate-cerate/inorganic salt complex phase-structured proton conductor material and preparation method thereof - Google Patents
Yttrium-doped barium zirconate-cerate/inorganic salt complex phase-structured proton conductor material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a yttrium-doped barium zirconate-cerate/inorganic salt complex phase-structured proton conductor material and a preparation method thereof. BaCO3, ZrO2 plus CeO2 and Y2O3 are batched according to the molar ratio of 1:1:(0.05-0.30), ball-milled to be mixed and calcined under 1100 DEG C to 1500 DEG C, so that matrix material is produced; the matrix material is then added with 1 to 10 mole percent of ZnO and 5 to 30 mole percent of NaOH or Na2CO3, ball-milled to be uniformly mixed, dry-pressed to be shaped under 50MPa to 120MPa and then isostatically pressed under 150MPa to 350MPa; and the mixture is sintered for 1 to 10 hours in the air atmosphere under 1200 DEG C to 1600 DEG C, so that the yttrium-doped barium zirconate-cerate/inorganic salt complex phase-structured proton conductor material is prepared. The invention solves the problems of barium zirconate, i.e. low grain boundary conductivity and poor sinterability, the conductivity of the material can reach more than 10<-2>S/cm under medium and low temperatures, and thereby the invention lays a foundation for the development of electrolytic materials for hydrogen and vapor sensors, solid oxide fuel cells and concentration cells.
Description
Technical field
The present invention is that to belong to the composition be the ceramic composition of characteristic, particularly a kind of Y doping zirconium cerium acid barium/inorganic salt multiphase structure proton conductor material and preparation method thereof.
Background technology
Perovskite structural material is as novel proton conductor material; Except the electrolyte that can be widely used in protonic ceramic fuel cell (PCFC); Or the important component part of proton device, the main application comprises [Iwahara H, et al.Solid State Ionics such as Hydrogen Separation, Preparation of Hydrogen, hydrogen gas sensor, hydrogen concentration cell and organism hydrogenation dehydrogenation reaction; 2004,168 (3-4): 299～310; Yamazaki Y, et al.Chemistry of Materials, 2009,21 (13): 2755～2762; StuartP A, et al.Journal of the European Ceramic Society, 2009,29 (4), 697～702].People such as Japan scholar Iwahara have reported doped perovskite type cerate and zirconate proton conductive and mechanism research [Iwahara H in 1981; Etal.Solid State Ionics; 1981; 3-4:359～363], the research of calcium titanium ore structure proton conductor material at present mainly concentrates on barium zirconate and cerium acid barium.Barium zirconate has higher chemicalstability and crystal grain specific conductivity, but it is difficult to coking property and lower crystal boundary specific conductivity becomes the major obstacle that is applied to SOFC and other components and parts, and bibliographical information barium zirconate material total conductivity is generally 10
-5～10
-3The scope of siemens/cm.Cerium acid barium has higher specific conductivity and coking property preferably, but poor chemical stability is prone at CO
2And H
2The S decomposition (Katahira K, Kohchi Y, Shimura T, Iwahara H.Solid State Ionics, 2000,138:91-98).Ryu (Ryu KH, Haile SM.Solid State Ionics, 1999,125:355-367) be reported in the Ce/Zr proportional range than broad, can realize that the two homogeneous phase of barium zirconate and cerium acid barium is compound, this equal phase composite materials is called zirconium cerium acid barium.Compound through homogeneous phase, can improve the original coking property of barium zirconate and improve its specific conductivity.People such as Guo Ruisong (Guo RS, Deng YP, Gao YY, Zhang LX.J.Alloys Compd., 2011,509:8894-8900) studied the Ce modification Ba (Zr of different content
0.9-xCe
x)
0.9Y
0.1O
2.95Conductivity of electrolyte materials and chemicalstability, and sum up BaZr
0.63Ce
0.27Y
0.1O
2.95Keeping the higher chemically stable crystal boundary specific conductivity that improved simultaneously.But; This method improvement degree is not very satisfactory; How to continue to improve the crystal boundary electricity and lead the total conductivity that improves material then and become key of problem, this normal out-phase compound approach that adopts is solved [Peng ZZ, et al.Journal of the American Ceramic Society; 2008,91 (5): 1534-1538].Chinese invention patent [patent No.: 200710057254.7] has been reported employing multiphase structure design, obtains high conductivity barium zirconate proton conductor material, and out-phase compound substance wherein is that oxyhydroxide or vitriol are (like NaOH or K
2SO
4Or Na
2SO
4Or Li
2SO
4).
People such as Zhu (Zhu B, Mellander B-E.Solid State Ionics, 1995,97:244-249) research Al
2O
3-Li
2SO
4Proton conductor material, and β → α phase transformation appears when being reported in 577 ℃, specific conductivity reaches 1 siemens/cm in the time of 600 ℃, has higher proton conductivity.Lunden (Lund é n A, Mellander B-E, Zhu B.Acta Chem.Scand., 1991,45:981-982) think, at Li through research
2SO
4Cube phase structure in, tetrahedral SO
4 2-Produced unusually and rotatablely moved fast, promoted the motion of positively charged ion and proton.(Electrochem.Solid-State Letters such as Schober; 2005; 8 (4): A199-255), also obtained certain effect, because the interface superionic phase changes having carried out some research work aspect the out-phase doping of the sour barium of Y doping decorations; Cause ln (σ T)-1/T curve to occur jumping, their result of study is confirmed middle warm area high conductivity and the HCD experimental result of having explained Zhu well.
The present invention introduces NaOH or Na in Y doping zirconium cerium acid barium on early stage serial working foundation
2CO
3Be distributed in crystal boundary, produce proton conductor material, reduce the activation energy and the crystal boundary potential barrier of material, make material under medium and low temperature, have higher specific conductivity with multiphase structure characteristic.
Though zirconate and cerate carry out compound existing bibliographical information [Wang H, et al.J.Am.Ceram.Soc., J AmerCeram Soc, 2009,92 (11): 2623-2629], continue to take that crystal boundary out-phase is compound does not but see any report.The present invention proposes to prepare zirconate and cerate is compound, adds the multiphase structure proton conductor material new approaches and the new technology of yellow soda ash again, through microstructure design and control; Its preparation is studied, made the out-phase mixture be evenly distributed on crystal boundary, form multiphase structure; Solve the restriction of crystal boundary for material electric conductivity; Realize the performance hop,, make this material get into the practicability stage in the hope of improving the specific conductivity of multiphase structure proton conductor.Relevant report is not also seen in research work in this respect so far
Summary of the invention
It is matrix that the present invention has selected adulterated barium zirconate of Y and cerium acid barium compound proton conductor, is called the adulterated zirconium cerium acid of Y barium, further reduces sintering temperature through adding the ZnO sintering aid, adds inorganic salt NaOH or Na again
2CO
3, be evenly distributed on crystal boundary, form multiphase structure, strengthen the interface proton conduction, its preparation is studied, to improve the specific conductivity of multiphase structure proton conductor.
The present invention is achieved through following technical scheme.
A kind of Y doping zirconium cerium acid barium/inorganic salt multiphase structure proton conductor material, its raw material composition and molar content are following:
Barium zirconate and cerium acid barium mol ratio are 7～9: 1～3, on zirconium cerium acid barium basis, again with 5～30% moles of Y
2O
3As hotchpotch, obtain the acid of Y doping zirconium cerium barium, i.e. body material; On this basis, add 1～10% mole of ZnO and 5～30% moles of NaOH or Na
2CO
3
The described ZnO of adding is a sintering aid, NaOH or Na
2CO
3For having the inorganic salt of proton conductive, be evenly distributed on the crystal boundary place, play and improve the effect that the crystal boundary electricity is led.
The preparation method of Y doping zirconium cerium acid barium/inorganic salt multiphase structure proton conductor material is following:
With BaCO
3: ((1-x) ZrO
2+ xCeO
2): Y
2O
3By 1: 1: 0.05～0.30 mole batching, wherein x=0.1～0.3; With water is medium ball mill mixing 2～10 hours, through dry, grind, sieve, 1100～1500 ℃ of calcinings 3～12 hours, obtain body material; Be benchmark with the body material then, add 1～10% mole ZnO, ball mill mixing 2～10 hours, again through dry, grind, sieve after, be benchmark again with the body material, add 5～30% moles of NaOH or Na
2CO
3, be ground to uniform mixture; Carry out the compound mould of packing into dry-pressing formed, pressure is 50～120MPa, again through static pressure such as 150～350MPa; At 1200～1600 ℃ of sintering in air atmosphere, temperature rise rate is 2～10 ℃/minute, is incubated 1～10 hour, naturally cools to room temperature then, makes Y doping zirconium cerium acid barium/inorganic salt multiphase structure proton conductor material.
Preparing method provided by the present invention is simple, and is with low cost.The present invention carries out on the compound body material basis at barium zirconate and cerium acid barium; Carry out the new approaches of multiphase structure and doping vario-property simultaneously; Through composition and microstructure design and control,, solved the restriction of crystal boundary for material electric conductivity through suitable recombining process; Realized the hop of specific conductivity performance, can under medium and low temperature, make material electric conductivity reach 10
-2More than the siemens/cm, lay a good foundation for developing hydrogen and water vapor sensor, hydrogen pump and concentration cell electrolyte.
Description of drawings
Fig. 1: multiphase structure Y doping zirconium cerium acid barium proton conductor material microtexture synoptic diagram behind Y doping zirconium cerium acid barium proton conductor material and the interpolation inorganic salt;
Fig. 2: different content NaOH or Na
2CO
3Modification Y doping zirconium cerium acid barium proton conductor material total conductivity graphic representation under different sintering conditions;
Fig. 3: add inorganic salt sample section pattern stereoscan photograph;
Fig. 4: fracture surface of sample can spectrogram.
Embodiment
Through specific embodiment the present invention is further described below.
Get 1 mole of BaCO
3, 0.7 mole of ZrO
2, 0.3 mole of CeO
2, 0.1 mole of Y
2O
3, be medium ball mill mixing 4 hours with water, through dry, grind, sieve, obtained Y in 4 hours 1300 ℃ of calcinings
2O
3Adulterated zirconium cerium acid barium body material.Be benchmark with the body material then, add 0.02 mole of ZnO, ball mill mixing 4 hours, again through dry, grind, sieve after, be benchmark with the body material again, add 0.10 moles of NaOH, grinds 1 hour with the assurance uniformity of mixture.Carry out the compound mould of packing into dry-pressing formed, pressure is 50MPa, passes through static pressure such as 200MPa again; At 1320 ℃ of sintering in air atmosphere, 2 ℃/minute of temperature rise rates are incubated 2 hours, naturally cool to room temperature then, make the Y doping zirconium cerium acid barium multiphase structure proton conductor material with excellent conductive performance, detect specific conductivity in the time of 800 ℃ and reach 0.96 * 10
-2Siemens/cm.
Get 1 mole of BaCO
3, 0.7 mole of ZrO
2, 0.3 mole of CeO
2, 0.1 mole of Y
2O
3, be medium ball mill mixing 10 hours with water, through dry, grind, sieve, obtained Y in 4 hours 1300 ℃ of calcinings
2O
3Adulterated zirconium cerium acid barium body material.Be benchmark with the body material then, add 0.02 mole of ZnO, ball mill mixing 10 hours, again through dry, grind, sieve after, be benchmark with the body material again, add 0.05 moles of NaOH, grinds 1 hour with the assurance uniformity of mixture.Carry out the compound mould of packing into dry-pressing formed, pressure is 120MPa, passes through static pressure such as 200MPa again; At 1320 ℃ of sintering in air atmosphere, 10 ℃/minute of temperature rise rates are incubated 2 hours, naturally cool to room temperature then, make the Y doping zirconium cerium acid barium multiphase structure proton conductor material with excellent conductive performance.Detect specific conductivity in the time of 800 ℃ and reach 0.94 * 10
-2Siemens/cm.
Get 1 mole of BaCO
3, 0.7 mole of ZrO
2, 0.3 mole of CeO
2, 0.1 mole of Y
2O
3, be medium ball mill mixing 6 hours with water, through dry, grind, sieve, obtained Y in 4 hours 1300 ℃ of calcinings
2O
3Adulterated zirconium cerium acid barium body material.Be benchmark with the body material then, add 0.02 mole of ZnO, ball mill mixing 6 hours, again through dry, grind, sieve after, be benchmark with the body material again, add 0.20 moles of NaOH, grinds 1 hour with the assurance uniformity of mixture.Carry out the compound mould of packing into dry-pressing formed, pressure is 120MPa, passes through static pressure such as 200MPa again; At 1320 ℃ of sintering in air atmosphere, 2 ℃/minute of temperature rise rates are incubated 2 hours, naturally cool to room temperature then, make high conductivity Y doping zirconium cerium acid barium multiphase structure proton conductor material.Detect specific conductivity in the time of 800 ℃ and reach 0.81 * 10
-2Siemens/cm.
Embodiment 4
Get 1 mole of BaCO
3, 0.9 mole of ZrO
2, 0.1 mole of CeO
2, 0.05 mole of Y
2O
3, be medium ball mill mixing 4 hours with water, through dry, grind, sieve, obtained Y in 3 hours 1500 ℃ of calcinings
2O
3Adulterated zirconium cerium acid barium body material.Be benchmark with the body material then, add 0.1 mole of ZnO, ball mill mixing 4 hours, again through dry, grind, sieve after, be benchmark with the body material again, add 0.30 moles of NaOH, grinds 1 hour with the assurance uniformity of mixture.Carry out the compound mould of packing into dry-pressing formed, pressure is 50MPa, passes through static pressure such as 150MPa again; At 1600 ℃ of sintering in air atmosphere, 6 ℃/minute of temperature rise rates are incubated 1 hour, naturally cool to room temperature then, make the Y doping zirconium cerium acid barium multiphase structure proton conductor material with excellent conductive performance.
Get 1 mole of BaCO
3, 0.7 mole of ZrO
2, 0.3 mole of CeO
2, 0.1 mole of Y
2O
3, be medium ball mill mixing 10 hours with water, through dry, grind, sieve, obtained Y in 6 hours 1200 ℃ of calcinings
2O
3Adulterated zirconium cerium acid barium body material.Be benchmark with the body material then, add 0.02 mole of ZnO, ball mill mixing 10 hours, again through dry, grind, sieve after, be benchmark with the body material again, add 0.20 mole of Na
2CO
3, grind 1 hour to guarantee uniformity of mixture.Carry out the compound mould of packing into dry-pressing formed, pressure is 120MPa, passes through static pressure such as 300MPa again; At 1350 ℃ of sintering in air atmosphere, 10 ℃/minute of temperature rise rates are incubated 2 hours, naturally cool to room temperature then, make the Y doping zirconium cerium acid barium multiphase structure proton conductor material with excellent conductive performance.Detect specific conductivity in the time of 800 ℃ and reach 0.81 * 10
-2Siemens/cm.
Embodiment 6
Get 1 mole of BaCO
3, 0.7 mole of ZrO
2, 0.3 mole of CeO
2, 0.1 mole of Y
2O
3, be medium ball mill mixing 6 hours with water, through dry, grind, sieve, obtained Y in 10 hours 1200 ℃ of calcinings
2O
3Adulterated zirconium cerium acid barium body material.Be benchmark with the body material then, add 0.1 mole of ZnO, ball mill mixing 6 hours, again through dry, grind, sieve after, be benchmark with the body material again, add 0.05 mole of Na
2CO
3, grind 1 hour to guarantee uniformity of mixture.Carry out the compound mould of packing into dry-pressing formed, pressure is 100MPa, passes through static pressure such as 200MPa again; At 1350 ℃ of sintering in air atmosphere, 2 ℃/minute of temperature rise rates are incubated 2 hours, naturally cool to room temperature then, make Y doping zirconium cerium acid barium multiphase structure proton conductor material.Detect specific conductivity in the time of 800 ℃ and reach 0.90 * 10
-2Siemens/cm.
Embodiment 7
Get 1 mole of BaCO
3, 0.8 mole of ZrO
2, 0.2 mole of CeO
2, 0.3 mole of Y
2O
3, be medium ball mill mixing 2 hours with water, through dry, grind, sieve, obtained Y in 12 hours in 1100 calcinings
2O
3Adulterated zirconium cerium acid barium body material.Be benchmark with the body material then, add 0.01 mole of ZnO, ball mill mixing 2 hours, again through dry, grind, sieve after, be benchmark with the body material again, add 0.3 mole of Na
2CO
3, grind 1 hour to guarantee uniformity of mixture.Carry out the compound mould of packing into dry-pressing formed, pressure is 100MPa, passes through static pressure such as 350MPa again; At 1200 ℃ of sintering in air atmosphere, 5 ℃/minute of temperature rise rates are incubated 2 hours, naturally cool to room temperature then, make Y doping zirconium cerium acid barium multiphase structure proton conductor material.
This multiphase structure proton conductor material microstructure characteristic is as shown in Figure 1, is uniform-distribution with inorganic salt on the crystal boundary, makes interfacial characteristics change into crystal grain-inorganic salt contact by original crystal grain-crystal grain contact, thereby changes the crystal boundary potential barrier, helps proton conduction.
The present invention has prepared Y doping zirconium cerium acid barium/inorganic salt multiphase structure proton conductor material of excellent conductive capability, lays a good foundation for developing hydrogen and water vapor sensor, hydrogen pump and concentration cell electrolyte.The present invention proposes on Y doping barium zirconate and cerium acid barium compound body material basis, to introduce the inorganic salt Na with proton conductive at crystal boundary simultaneously
2HO or Na
2CO
3, through compound with burn till control, make its uniform distribution to improve the crystal boundary characteristic; The salts substances melting transition is a superionic phase under working temperature; Improve protolysis reaction speed, form space charge on the crystal boundary out-phase interface simultaneously, strengthen the interface proton conduction; Improve the material total conductivity, some proton conductor material specific conductivity graphic representation is as shown in Figure 2.Fig. 3 has provided the proton conductor material section microtexture photo that adds inorganic salt, for the multiphase structure proton conductor material, owing to be distributed with inorganic salt on the crystal boundary, makes fracture smudgy, can't distinguish crystal boundary.Energy spectrum analysis (Fig. 4) is illustrated in and has detected sodium carbonates' presence on the section.
Y doping zirconium cerium acid barium/yellow soda ash multiphase structure proton conductor material that the present invention proposes and preparation method thereof; Be described through 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 and are included in spirit of the present invention, scope and the content.
Claims (3)
1. Y doping zirconium cerium acid barium/inorganic salt multiphase structure proton conductor material, its raw material form and molar content following:
Barium zirconate and cerium acid barium mol ratio are 7～9: 1～3, on zirconium cerium acid barium basis, again with 5～30% moles of Y
2O
3As hotchpotch, obtain the acid of Y doping zirconium cerium barium, i.e. body material; On this basis, add 1～10% mole of ZnO and 5～30% moles of NaOH or Na
2CO
3
2. according to the Y doping zirconium cerium acid barium/inorganic salt multiphase structure proton conductor material of claim 1, it is characterized in that the described ZnO of adding is a sintering aid, NaOH or Na
2CO
3For having the inorganic salt of proton conductive, be evenly distributed on the crystal boundary place, play and improve the effect that the crystal boundary electricity is led.
3. the preparation method of the Y doping zirconium cerium of claim 1 acid barium/inorganic salt multiphase structure proton conductor material is following:
With BaCO
3: ((1-x) ZrO
2+ x CeO
2): Y
2O
3By 1: 1: 0.05～0.30 mole batching, wherein x=0.1～0.3; With water is medium ball mill mixing 2～10 hours, through dry, grind, sieve, 1100～1500 ℃ of calcinings 3～12 hours, obtain body material; Be benchmark with the body material then, add 1～10% mole ZnO, ball mill mixing 2～10 hours, again through dry, grind, sieve after, be benchmark again with the body material, add 5～30% moles of NaOH or Na
2CO
3, be ground to uniform mixture; Carry out the compound mould of packing into dry-pressing formed, pressure is 50～120MPa, again through static pressure such as 150～350MPa; At 1200～1600 ℃ of sintering in air atmosphere, temperature rise rate is 2～10 ℃/minute, is incubated 1～10 hour, naturally cools to room temperature then, makes Y doping zirconium cerium acid barium/inorganic salt multiphase structure proton conductor material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942364A (en) * | 2012-11-02 | 2013-02-27 | 天津大学 | Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof |
| CN103165930A (en) * | 2013-03-25 | 2013-06-19 | 南京工业大学 | Method for improving sintering performance of electrolyte of proton conductor solid oxide fuel cell (SOFC) |
| CN103224394A (en) * | 2013-04-19 | 2013-07-31 | 天津大学 | Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof |
| CN103586014A (en) * | 2013-11-28 | 2014-02-19 | 南京工程学院 | Membrane capable of performing electrocatalysis degradation of tail gas nitrogen oxide with high selectivity under low temperature and its preparation method |
| CN105552415A (en) * | 2015-12-28 | 2016-05-04 | 哈尔滨工业大学 | Preparation method for rear-earth zirconate/carbonate composite electrolyte powder |
| CN110600777A (en) * | 2018-06-12 | 2019-12-20 | 阜阳师范学院 | Double-doped zirconium dioxide and alkali metal salt compound and preparation method thereof |
-
2012
- 2012-01-06 CN CN2012100034136A patent/CN102531587A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| RUISONG GUO ET.AL: "Fabrication and properties of Ba(Zr1−xCex)0.9Y0.1O2.95/NaCl composite electrolyte materials", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| RUISONG GUO ET.AL: "Fabrication and properties of Ba(Zr1−xCex)0.9Y0.1O2.95/NaCl composite electrolyte materials", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 509, 25 June 2011 (2011-06-25), pages 8894 - 8900 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942364A (en) * | 2012-11-02 | 2013-02-27 | 天津大学 | Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof |
| CN103165930A (en) * | 2013-03-25 | 2013-06-19 | 南京工业大学 | Method for improving sintering performance of electrolyte of proton conductor solid oxide fuel cell (SOFC) |
| CN103224394A (en) * | 2013-04-19 | 2013-07-31 | 天津大学 | Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof |
| CN103586014A (en) * | 2013-11-28 | 2014-02-19 | 南京工程学院 | Membrane capable of performing electrocatalysis degradation of tail gas nitrogen oxide with high selectivity under low temperature and its preparation method |
| CN103586014B (en) * | 2013-11-28 | 2015-10-07 | 南京工程学院 | Film of low temperature high selectivity Electrocatalysis Degradation tail gas nitrogen oxide and preparation method thereof |
| CN105552415A (en) * | 2015-12-28 | 2016-05-04 | 哈尔滨工业大学 | Preparation method for rear-earth zirconate/carbonate composite electrolyte powder |
| CN110600777A (en) * | 2018-06-12 | 2019-12-20 | 阜阳师范学院 | Double-doped zirconium dioxide and alkali metal salt compound and preparation method thereof |
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Application publication date: 20120704 |