CN100462329C - Multi-phase structure designed high-conductive electrical zirconate barium proton conductor and preparation method thereof - Google Patents
Multi-phase structure designed high-conductive electrical zirconate barium proton conductor and preparation method thereof Download PDFInfo
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- CN100462329C CN100462329C CNB2007100572547A CN200710057254A CN100462329C CN 100462329 C CN100462329 C CN 100462329C CN B2007100572547 A CNB2007100572547 A CN B2007100572547A CN 200710057254 A CN200710057254 A CN 200710057254A CN 100462329 C CN100462329 C CN 100462329C
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Abstract
The invention relates to a barium zirconate proton conductor designed by complex phase structure with a high electric conductivity and its manufacturing method. The invention is coating a layer of NaOH or sulfate around the crystal grain of the barium zirconate. The manufacturing method is: taking the BaCO3, ZrO2 and Y2O3 as raw material, water as medium, ball milling mixing for 4-10 hours, calcining for 4-12 hours in 1200-1400 DEG C; then adding 1-10% molar ZnO, ball milling mixing for 4-10 hours, adding 5-50% mol NaOH or K2SO4 or Na2SO4 or Li2SO4 in a way of hand lapping to make the mixture uniform; putting the mixing material into the die and dry pressing molding under a pressure of 50-120 MPa, and then isopressing under 200-350 MPa; sintering in the air of 1200-1500 DEG C with a heating rate of 2-10 DEG C/minute and keeping warm for 2-10 hours, then cooling to the room temperature to produce the barium zirconate proton conductor material with a high electric conductivity. The invention adopts the new designing thought of complex phase structure to establish a foundation for exploiting hydrogen gas and vapor sensor, hydrogen pump and concentration cell electrolyte material.
Description
Technical field
The invention belongs to technical field of ceramic material, particularly multi-phase structure designed high-conductive electrical zirconate barium proton conductor and preparation method thereof.
Background technology
The perovskite typed proton conductor is the new conductor material of a class, can be widely used in the electrolyte, hydrogen pump (Hydrogen Separation), sensitive material (wet quick and hydrogen gas sensor) etc. of Solid Oxide Fuel Cell (SOFC).Since people such as Iwahara have reported doped perovskite type cerate and zirconate proton conductive and mechanism research, in the ascendant to the research of various proton conductor materials both at home and abroad, lot of domestic and foreign research institution has successively carried out number of research projects from all angles, all respects.Aspect raising proton conductor specific conductivity, although carried out number of research projects, do not obtain gratifying progress, data in literature is generally 10
-5～10
-3The scope of S/cm, thus its application of marching toward has been caused substantial obstruction.Discover that crystal boundary is the key factor that influences the proton conductor material specific conductivity.Because the crystal grain electricity is led much larger than the crystal boundary electricity and led, the two differs 3 orders of magnitude, therefore how to improve the key that the crystal boundary electricity is led becomes problem.
People such as Gomes (J.Euro.Ceram.Soc., 2006,6 (14): 2991-2997) to mixed conductor material La as fuel cell electrode
0.95Sr
0.05Ga
0.90Mg
0.10O
3-δAdopt the way of crystal boundary engineering, carry out the out-phase structure design, introduce Fe at crystal boundary, changed the crystal boundary characteristic, the transport property of ion-electron along crystal boundary improved at the new interface of appearance, thereby improved the ion-electron hybrid conductive performance of material.Utilize the ionic conductance of crystal grain to be the master, the Fe that mixes has improved the electronic conduction of crystal boundary, thereby makes the total conductivity of material obtain raising, from～10
-1.27S/cm brings up to～and 10
-1.16S/cm has showed that the out-phase dopant material improves the potentiality of material property by the crystal boundary engineering.The seventies in last century, people such as Liang (J.Electrochem.Soc., 1973,120 (10): 1289-1292) inorganic salts solid proton conductor ionogen is carried out modification, find in low temperature proton conductor LiI, to mix the Al of high dispersing by the out-phase doping
2O
3Can significantly improve its specific conductivity and reach several magnitude.People such as Maier (Solid State Ionics, 1995,75:139-145; J.Physics ﹠amp; Chemistry of Solids, 1985,46 (3): 309-320; Physica B, 1995,204 (1-4): 57-64) this phenomenon has been carried out detailed mechanism research and elaboration, they find when research disperses oxide compound to be doped in the inorganic ion crystalline material, inorganic ion can produce absorption on the interface of the two, changing between the different ions on the oxide particle surface and the electrochemical potential between the different defectives, the defective at granular boundary place is increased, thereby the Debye layer that occurs a height defective at this place, out-phase doping material system specific conductivity is significantly increased, that is to say in this out-phase dopant material to have produced distribution of space charge on the out-phase interface, the generation of space charge will help to improve boundary's sheet conductance.Another effect is ionic salt compounds at the interface distribution certainly (self-distribution) and " fusion " phenomenon between oxide compound, become the rapid passage (Russ.J.Inorg.Chem. of proton conduction, 2000,45 (Suppl.3): S249-S267; Prog.Solid State Chem., 1995,23 (3): 171-263).
Early stage out-phase is mixed and is studied the doping that mainly concentrates on indifferent oxide and salt, and the indifferent oxide of employing is Al
2O
3, SiO
2Deng, their main effect is as skeleton, play the effect of propping material, self do not have a proton conductive ability, and the oxide content in the component is less, principal phase is the salts substances with proton conductive, and inorganic salt melting transition under working temperature is a superionic phase, and its ion transport characteristic and liquid state are down much at one.After inert substance mixes, why material electric conductivity obtains to improve, and also relies on the generation of electroconductibility interface Contact Effect, and the doping of oxide compound has increased boundary defect concentration, reduced specific conductivity activation energy and superionic phase transition temperature, proton can conduct fast along the interface.
Zhu (Solid State Ionics, 1999,125 (1-4): 397-405; Materials Research Bulletin, 2000,35 (1): 47-52) specialized in Al
2O
3-fused salt hangs down temperature proton conductor material, and the result shows that fused salt forms external phase and distributes at the crystal boundary place, and this material has good proton conductivity, reason is exactly under working temperature, softening or the fusion of fused salt becomes a kind of superionic phase, and proton transport number betwixt improves greatly.If do not add indifferent oxide, then there is not interfacial effect, the superionic phase transition temperature improves, and this moment, proton conductivity reduced.
Up to the present, except above-mentioned be the complex phase proton conductor material of principal phase with the salt, use composite modified research report in perovskite typed solid state electrolyte field extremely rare, before only having several pieces of very few bibliographical informations to start from three, four years, and be primarily aimed at cerate, Zhu (J.Power Sources, 2003,114 (1): 1-9) reported that the doped cerium oxide matrix material has good performance, 400～700 ℃ of specific conductivity are 0.01～1S/cm, and 400～650 ℃ of power of battery density are 300～800mW/cm
2(Electrochem.Solid-State Letters such as Schober, 2005,8 (4): A199～A255) carrying out some research work aspect the out-phase doping of Y doped with cerium acid barium, also obtained certain effect, jumping appears in σ T-1/T curve, cause because the interface superionic phase changes, their result of study is confirmed middle warm area high conductivity and the high current density experimental result of having explained Zhu simultaneously well.The cerate proton conductivity is higher, is exactly its poor stability but there is a deadly defect in cerate.Though the zirconate proton conductivity is lower, its good stability if it is carried out the complex phase doping vario-property, makes its specific conductivity bring up to applicable 10
-2～10
-1More than the S/cm, then its application prospect and meaning highly significant.Because the uhligite proton conductor receives publicity day by day, it is extremely urgent to capture a zirconate low electric conductivity difficult problem, the present invention proposes the research of multiphase structure design high conductivity zirconate proton conductor, by microstructure design and control, solve the restriction of crystal boundary for material electric conductivity, realize the performance hop, yet there are no other people research report so far.
Summary of the invention
The present invention selected Stability Analysis of Structures, have the doping barium zirconate proton conductor that higher crystal grain electricity leads is matrix, by adding the ZnO sintering aid, add vitriol or oxyhydroxide again, be evenly distributed on crystal boundary, form multiphase structure, strengthen the interface proton conduction, its preparation is studied, in the hope of improving the specific conductivity of multiphase structure proton conductor.
Technology of the present invention is as follows:
Multi-phase structure designed high-conductive electrical zirconate barium proton conductor of the present invention is to coat one deck NaOH or vitriol around the crystal grain of barium zirconate, as depicted in figs. 1 and 2.
Multi-phase structure designed high-conductive electrical zirconate barium proton conductor of the present invention, the composition and the molar content of its conductor are as follows:
With 5～30% Y
2O
3Adulterated BaZrO
3Be matrix, chemical formula is BaZr
1-2xY
2xO
3-x, wherein x=0.05～0.30 adds 1～10% ZnO and 5～50% NaOH or K
2SO
4Or Na
2SO
4Or Li
2SO
4
The preparation method of multi-phase structure designed high-conductive electrical zirconate barium proton conductor of the present invention is, with BaCO
3, ZrO
2And Y
2O
3Being raw material, by 1:(1-2x): x (x=0.05～0.30) the preparation body material of preparing burden, is that the medium ball milling mixed 4～10 hours with water, drying, grinds, sieves, 1200～1400 ℃ of calcinings 4～12 hours; Add 1 then～ZnO of mole 10%, ball milling mixed 4～10 hours, again drying, grind, sieve after, add 5～50 moles of % NaOH or K in the mode of hand lapping
2SO
4Or Na
2SO
4Or Li
2SO
4, be ground to mixture to even; Carry out the compound mould of packing into dry-pressing formed, pressure is 50～120MPa, again through static pressure such as 200～350MPa; At 1200～1500 ℃ of sintering in air atmosphere, 2～10 ℃/minute of temperature rise rates are incubated 2～10 hours, naturally cool to room temperature then, make high conductivity zirconate proton conductor material.
The present invention has adopted multiphase structure design new approaches, has prepared the barium zirconate 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 multiphase structure design new approaches, in crystal boundary, introduce vitriol or oxyhydroxide with proton conductive, by compound and 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, improves proton shifting speed, forms space charge on the crystal boundary out-phase interface simultaneously, strengthen the interface proton conduction, make the material proton conductivity bring up to applicable 10
-2～10
-1More than the S/cm.
Description of drawings
Fig. 1: multiphase structure schema of the present invention.
Fig. 2: electromicroscopic photograph figure of the present invention.
Specific embodiments
Embodiment 1
Get 1 mole of BaCO
3, 0.95 mole of ZrO
2, 0.05 mole of Y
2O
3, be that with water the medium ball milling mixed 4 hours, drying, grind, sieve, obtained body material in 12 hours in 1200 calcinings.Add 0.01 mole of ZnO then, ball milling mixed 4 hours, again drying, grind, sieve after, add 0.05 moles of NaOH in the mode of hand lapping, 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 1200 ℃ of sintering in air atmosphere, 2 ℃/minute of temperature rise rates are incubated 10 hours, naturally cool to room temperature then, make the zirconate proton conductor material with excellent conductive performance, and specific conductivity reaches 5.86 * 10 in the time of 700 ℃
-5S/cm.
Embodiment 2
Get 1 mole of BaCO
3, 0.70 mole of ZrO
2, 0.30 mole of Y
2O
3The preparation body material is that with water the medium ball milling mixed 10 hours, drying, grinds, sieves, 1400 calcinings 4 hours.Add 0.10 mole of ZnO then, ball milling mixed 10 hours, again drying, grind, sieve after, add 0.50 moles of NaOH in the mode of hand lapping, 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 350MPa again; At 1500 ℃ of sintering in air atmosphere, 10 ℃/minute of temperature rise rates are incubated 2 hours, naturally cool to room temperature then, make the zirconate proton conductor material with excellent conductive performance, and specific conductivity reaches 4.29 * 10 in the time of 700 ℃
-4S/cm.。
Embodiment 3
Get 1 mole of BaCO
3, 0.90 mole of ZrO
2, 0.10 mole of Y
2O
3, be that with water the medium ball milling mixed 6 hours, drying, grind, sieve, obtained body material in 6 hours in 1400 calcinings.Add 0.03 mole of ZnO then, ball milling mixed 6 hours, again drying, grind, sieve after, add 0.40 moles of NaOH in the mode of hand lapping, 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 1350 ℃ of sintering in air atmosphere, 2 ℃/minute of temperature rise rates are incubated 4 hours, naturally cool to room temperature then, make high conductivity zirconate proton conductor material, and specific conductivity reaches 3.25 * 10 in the time of 700 ℃
-4S/cm.
Embodiment 4
Get 1 mole of BaCO
3, 0.90 mole of ZrO
2, 0.10 mole of Y
2O
3, be that with water the medium ball milling mixed 4 hours, drying, grind, sieve, 1200 calcinings 12 hours.Add 0.01 mole of ZnO then, ball milling mixed 4 hours, again drying, grind, sieve after, add 0.05 mole of K in the mode of hand lapping
2SO
4, grind 1 hour to guarantee 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 1200 ℃ of sintering in air atmosphere, 2 ℃/minute of temperature rise rates are incubated 10 hours, naturally cool to room temperature then, make the zirconate proton conductor material with excellent conductive performance, and specific conductivity reaches 7.96 * 10 in the time of 700 ℃
-5S/cm.
Embodiment 5
Get 1 mole of BaCO
3, 0.90 mole of ZrO
2, 0.10 mole of Y
2O
3, be that with water the medium ball milling mixed 10 hours, drying, grind, sieve, obtained body material in 4 hours in 1400 calcinings.Add 0.10 mole of ZnO then, ball milling mixed 10 hours, again drying, grind, sieve after, add 0.50 mole of K in the mode of hand lapping
2SO
4, 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 1500 ℃ of sintering in air atmosphere, 10 ℃/minute of temperature rise rates are incubated 2 hours, naturally cool to room temperature then, make the zirconate proton conductor material with excellent conductive performance, and specific conductivity reaches 9.41 * 10 in the time of 700 ℃
-3S/cm.
Embodiment 6
Get 1 mole of BaCO
3, 0.90 mole of ZrO
2, 0.10 mole of Y
2O
3The preparation body material is that with water the medium ball milling mixed 6 hours, drying, grinds, sieves, 1400 calcinings 10 hours.Add 0.03 mole of ZnO then, ball milling mixed 6 hours, again drying, grind, sieve after, add 0.10 mole of K in the mode of hand lapping
2SO
4, 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 the zirconate proton conductor material, and specific conductivity reaches 0.36 * 10 in the time of 700 ℃
-2S/cm.
Embodiment 7
Get 1 mole of BaCO
3, 0.90 mole of ZrO
2, 0.10 mole of Y
2O
3, be that with water the medium ball milling mixed 6 hours, drying, grind, sieve, obtained body material in 10 hours in 1400 calcinings.Add 0.03 mole of ZnO then, ball milling mixed 6 hours, again drying, grind, sieve after, add 0.10 mole of Na in the mode of hand lapping
2SO
4, 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 the zirconate proton conductor material, and specific conductivity reaches 0.18 * 10 in the time of 700 ℃
-2S/cm.
Embodiment 8
Get 1 mole of BaCO
3, 0.90 mole of ZrO
2, 0.10 mole of Y
2O
3, be that with water the medium ball milling mixed 6 hours, drying, grind, sieve, 1400 calcinings 10 hours.Add 0.03 mole of ZnO then, ball milling mixed 6 hours, again drying, grind, sieve after, add 0.10 mole of Li in the mode of hand lapping
2SO
4, 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 the zirconate proton conductor material, and specific conductivity reaches 0.52 * 10 in the time of 700 ℃
-2S/cm.
Multi-phase structure designed high-conductive electrical zirconate barium proton conductor 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. a multi-phase structure designed high-conductive electrical zirconate barium proton conductor is characterized in that coating one deck NaOH or K around the crystal grain of barium zirconate
2SO
4Or Na
2SO
4Or Li
2SO
4The composition and the molar content of conductor are as follows:
With 5～30%Y
2O
3Adulterated BaZrO
3Be matrix, chemical formula is BaZr
1-2xY
2xO
3-x, wherein x=0.05～0.30 adds 1～10%ZnO and 5～50%NaOH or K
2SO
4Or Na
2SO
4Or Li
2SO
4
2. the preparation method of multi-phase structure designed high-conductive electrical zirconate barium proton conductor as claimed in claim 1 is characterized in that BaCO
3, ZrO
2And Y
2O
3By 1:(1-2x): x prepares burden, x=0.05～0.30; Is that with water the medium ball milling mixed 4～10 hours, drying, grinds, sieve,, obtain body material 1200～1400 ℃ of calcinings 4～12 hours; Add the ZnO of 1～10 mole of % then, ball milling mixed 4～10 hours, again drying, grind, sieve after, add 5～50 moles of %NaOH or K in the mode of hand lapping
2SO
4Or Na
2SO
4Or Li
2SO
4, be ground to mixture to even; Carry out the compound mould of packing into dry-pressing formed, pressure is 50～120MPa, again through static pressure such as 200～350MPa; At 1200～1500 ℃ of sintering in air atmosphere, 2～10 ℃/minute of temperature rise rates are incubated 2～10 hours, naturally cool to room temperature then, make high conductivity barium zirconate proton conductor material.
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Families Citing this family (11)
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|---|---|---|---|---|
| CN102180667A (en) * | 2011-02-28 | 2011-09-14 | 天津大学 | Barium zirconate proton conductor with multi-phase structure and preparation method thereof |
| CN102408233A (en) * | 2011-08-18 | 2012-04-11 | 天津大学 | Barium zirconate cerate complex phase structure proton conductor material and preparation method thereof |
| CN102515750A (en) * | 2011-11-14 | 2012-06-27 | 天津大学 | Yb and Y co-doped zirconium barium cerate compound-phase structural proton conductor material and preparation method thereof |
| JP5936898B2 (en) | 2012-03-28 | 2016-06-22 | 住友電気工業株式会社 | Solid electrolyte laminate, method for producing solid electrolyte laminate, and fuel cell |
| JP5936897B2 (en) | 2012-03-28 | 2016-06-22 | 住友電気工業株式会社 | Solid electrolyte, method for producing solid electrolyte, solid electrolyte laminate, method for producing solid electrolyte laminate, and fuel cell |
| CN103086714B (en) * | 2013-02-06 | 2014-06-04 | 哈尔滨工业大学 | Barium zirconate-zirconium oxide composite proton conductor material and preparation method thereof |
| CN103864419B (en) * | 2014-03-12 | 2017-01-04 | 华东师范大学 | A kind of preparation method of high fine and close barium zirconate pottery |
| CN108832136B (en) * | 2018-06-21 | 2020-10-23 | 中国科学院上海应用物理研究所 | Composite oxygen electrode for solid oxide battery and preparation method thereof |
| CN112062153A (en) * | 2020-09-15 | 2020-12-11 | 吉林大学 | Improve BaZrO3Method of electrical conductivity |
| CN112062567A (en) * | 2020-09-17 | 2020-12-11 | 中国科学院上海应用物理研究所 | Method for preparing zirconium-yttrium-doped barium cerate powder by using molten salt and powder obtained by method |
| CN113666415B (en) * | 2021-06-22 | 2022-10-28 | 南京工业大学 | High-conductivity perovskite-type BaZrO with controllable grain size 3 Preparation method of proton conductor material |
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| US20070012975A1 (en) * | 2005-07-13 | 2007-01-18 | The Regents Of The University Of California | Coated conductors |
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