CN102515750A - Yb and Y co-doped zirconium barium cerate compound-phase structural proton conductor material and preparation method thereof - Google Patents
Yb and Y co-doped zirconium barium cerate compound-phase structural proton conductor material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the modification for a zirconium barium cerate compound-phase structural proton conductor material and a preparation method thereof. The preparation method comprises the following steps: preparing materials at the molar ratio of BaCO3:(ZrO2+CeO2): Y2O3:Yb2O3 being 1:1:(0.05-0.20):(0.05-0.20); mixing absolute ethyl alcohol as a medium with the materials in a ball-milling manner; calcining at 1100-1500 DEG C, thereby obtaining Y and Yb doped substrate material; additionally adding ZnO with the molar concentration of 1-10%, Na2SO4 with the molar concentration of 3-30% or K2CO3 with the molar concentration of 3-30%, and then mixing in the ball-milling manner, thereby obtaining BZCYYb-Z2-S series and BZCYYb-Z2-C series powder; filling the mixture in a mould, drily pressing and forming, and then performing 150-300MPa isostatic pressing; calcining for 1-10 hours under the air atmosphere at 1200-1600 DEG C; and naturally cooling to room temperature, thereby obtaining the zirconium barium cerate compound-phase structural proton conductor material. The problems of smaller conductivity and inferior calcining performance of barium zirconate grain boundary are solved, and the expected material conductivity is above 10-2S/cm at low temperature.
Description
Technical field
The invention belongs to technical field of ceramic material, particularly Yb and Y co-doped zirconium cerium acid barium multiphase structure proton conductor material and preparation method thereof.
Background technology
Perovskite structural material can be widely used in fields such as SOFC (SOFC) and hydrogen gas sensor as novel proton conductor material.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.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.
Continuous progress along with proton conductor research; People have started the research of inorganic salt composite proton conductor again; People such as scholar Zhu have carried out the research of a large amount of inorganic salt composite proton conductors, have obtained some achievements preferably, and find vitriol; Nitrate salt, phosphoric acid salt and halogenide etc. has higher proton conductivity.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 1S/cm in the time of 600 ℃, has higher proton conductivity.Lunden (Lund é n A, MellanderB-E, Zhu B.Acta Chem.Scand., 1991,45:981-982) once proposed famous " Paddle-Wheel " mechanism and explained.This mechanism is thought, at Li
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.Guo Ruisong (Guo Ruisong, Peng Zhenzhen, Gao Dongyun, etc. multiphase structure designs barium zirconate proton conductor and preparation method, Chinese patent: 101037331A) wait and utilize solid phase method to prepare BaZrO
3/ vitriol complex phase proton conductor material through adding inorganic salt, has improved the crystal boundary specific conductivity, BaZrO
3/ Li
2SO
4Complex phase proton conductor material specific conductivity reaches 5.2 * 10 in the time of 700 ℃
-3S/cm.
The present invention adopts Yb and Y co-doped to prepare zirconium cerium acid barium multiphase structure proton conductor material, reduces the activation energy and the crystal boundary potential barrier of material, makes material under medium and low temperature, have higher specific conductivity.Introduce Na
2SO
4As the liquid phase sintering auxiliary agent and be embedded in the multiphase structure proton conductor ionogen powder and carry out sintering, this sintering processing has reduced the volatilization of inorganic salt and has improved density.Adopt high proton specific conductivity Na
2SO
4And K
2CO
3Add mutually as second and to have improved the crystal boundary specific conductivity, improved conductivity of electrolyte materials.
Summary of the invention
The present invention is a matrix through barium zirconate and the cerium acid barium compound proton conductor that high temperature solid-state method has synthesized Yb and Y co-doped; Further reduce sintering temperature through adding the ZnO sintering aid; Add inorganic salt again as the liquid phase sintering auxiliary agent, reduce sintering temperature and strengthen the interface proton conduction.Employing is imbedded and is carried out sintering in the multiphase structure proton conductor ionogen powder with the volatilization that reduces inorganic salt and improve density through its preparation is studied, in the hope of improve the multiphase structure proton conductor in temperature under specific conductivity.This multiphase structure proton conductor material microstructure characteristic synoptic diagram 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.
Technology of the present invention is following:
The composition and the molar content of Yb and Y co-doped zirconium cerium acid barium multiphase structure proton conductor material and preparation method thereof multiphase structure proton conductor material are following: a kind of Yb and Y co-doped zirconium cerium acid barium multiphase structure proton conductor, and its composition and molar content are following:
Get barium zirconate and cerium acid barium mol ratio and be respectively (8～6): (2～4) are matrix with zirconium cerium acid barium, and 5～20% moles of Yb mix
2O
3With 5～20% moles of Y
2O
3, add 1～10% mole of ZnO and 3～30% moles of Na then
2SO
4Or 3～30% moles of K
2CO
3, wherein ZnO is a sintering aid, Na
2SO
4As the liquid phase sintering auxiliary agent, while Na
2SO
4Or K
2CO
3Has proton conductive.
The preparation method of multiphase structure proton conductor of the present invention is with BaCO
3: (ZrO
2+ CeO
2): Y
2O
3: Yb
2O
3Being 1: 1: 0.05～0.20: 0.05～0.20 mole batching, is the medium ball mill mixing with the absolute ethyl alcohol, calcines at 1100～1500 ℃ through dry, the back of grinding, sieve and obtains Yb and Y co-doped body material in 3～10 hours; With the body material is benchmark, adds ZnO and 3～30% moles of Na of 1～10% mole
2SO
4Or 3～30% moles of K
2CO
3, ball mill mixing 2～8 hours; Mixed powder through dry, the mould 50～100MPa that packs into after grinding, sieving is dry-pressing formed; Obtain the green compact sample through static pressure such as 150～300MPa again; Then at 1200～1600 ℃ of sintering 1～10 hour in air atmosphere; 2～10 ℃/minute of temperature rise rates naturally cool to room temperature then, make Yb and Y co-doped zirconium cerium acid barium multiphase structure proton conductor material.
In aforesaid method, sample is embedded in the multiphase structure proton conductor ionogen powder carries out sintering, to suppress inorganic salt Na in the sample
2SO
4Or K
2CO
3Decomposition or volatilization, improve density.
Na
2SO
4, K
2CO
3For having the inorganic salt of high proton electroconductibility, be evenly distributed on the crystal boundary place behind the sintering, play and improve the effect that the crystal boundary electricity is led.
The present invention has prepared Yb and Y co-doped barium zirconate and cerium acid barium multiphase structure proton conductor material and preparation method thereof 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 adulterated barium zirconate of Y and cerium acid barium compound body material basis, to introduce Yb as alloying element, in the hope of further reducing the crystal boundary potential barrier, under medium and low temperature, obtains high conductance; Introduce inorganic salt Na simultaneously with proton conductive
2SO
4Or K
2CO
3, make its uniform distribution to improve the crystal boundary characteristic, the salts substances melting transition is a superionic phase under working temperature, improves protolysis reaction speed, improves the material total conductivity, some proton conductor material specific conductivity graphic representation is as shown in Figure 2.Fig. 3 has provided and do not added and the proton conductor material section microtexture photo that adds inorganic salt, and is obvious through the contrast photo, 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.In addition, from adding the proton conductor material section EDX ability spectrogram (Fig. 4) of inorganic salt,, proved the existence of inorganic salt in the crystal boundary through finding that to the face scanned photograph of sodium element inorganic salt evenly are present in the crystal boundary.
Preparing method provided by the present invention is simple, and is with low cost.The present invention proposes on Yb and Y co-doped zirconium cerium acid barium body material basis, to carry out the new approaches of multiphase structure and doping vario-property simultaneously, adopts to bury and burns decomposition or the volatilization that suppresses inorganic salt in the sample, and under medium and low temperature, make the desired material specific conductivity reach 10
-2More than the S/cm, lay a good foundation for developing hydrogen and water vapor sensor, SOFC.
Description of drawings
Fig. 1: multiphase structure zirconium cerium acid barium proton conductor material microtexture synoptic diagram behind zirconium cerium acid barium proton conductor material and the interpolation inorganic salt.
Fig. 2: different content Na
2SO
4Modification Y, Yb doping proton conductor material specific conductivity graphic representation.
Fig. 3: sample section pattern stereoscan photograph.(a) do not add the inorganic salt sample section; (b) add inorganic salt sample sections (low range); (c) add inorganic salt sample sections (high magnification)
Fig. 4: adding inorganic salt sample section EDX can spectrogram.
Specific embodiments
Embodiment 1
With 1 mole of BaCO
3, 0.6 mole of ZrO
2, 0.4 mole of CeO
2, 0.05 mole of Y
2O
3With 0.05 mole of Yb
2O
3, be medium ball mill mixing 6 hours with the absolute ethyl alcohol, through dry, grind, sieve, obtained Y, the adulterated zirconium cerium acid of Yb barium body material in 4 hours 1300 ℃ of calcinings.In body material, add 0.02 mole of ZnO and 0.10 mole of Na then
2SO
4, ball mill mixing 2 hours, again through dry, grind, sieve after, carry out the compound mould of packing into dry-pressing formed, pressure is 100MPa, passes through static pressure such as 200MPa again; Imbed in the BZCYYb-Z2-S ionogen powder sintering in 1370 ℃ of air, 4 ℃/minute of temperature rise rates are incubated 2 hours, naturally cool to room temperature then, make the zirconium cerium acid barium multiphase structure proton conductor material with excellent conductive performance.Specific conductivity reaches 7.85 * 10 in the time of 700 ℃
-3S/cm makes material obtain high conductance at a lower temperature.
Embodiment 2
With 1 mole of BaCO
3, 0.6 mole of ZrO
2, 0.4 mole of CeO
2, 0.1 mole of Y
2O
3With 0.1 mole of Yb
2O
3, be medium ball mill mixing 8 hours with the absolute ethyl alcohol, through dry, grind, sieve, obtained Y, Yb doping zirconium cerium acid barium body material in 10 hours 1100 ℃ of calcinings.In body material, add 0.01 mole of ZnO and 0.03 mole of Na then
2SO
4, ball mill mixing 4 hours, again through dry, grind, sieve after, carry out the compound mould of packing into dry-pressing formed, pressure is 50MPa, passes through static pressure such as 150MPa again; Imbed BZCYYb-Z2-S ionogen powder sintering in 1200 ℃ of air, 10 ℃/minute of temperature rise rates are incubated 10 hours, naturally cool to room temperature then, make the zirconium cerium acid barium multiphase structure proton conductor material with excellent conductive performance.
Embodiment 3
With 1 mole of BaCO
3, 0.7 mole of ZrO
2, 0.3 mole of CeO
2, 0.2 mole of Yb
2O
3With 0.2 mole of Y
2O
3, be medium ball mill mixing 6 hours with the absolute ethyl alcohol, through dry, grind, sieve, obtained the adulterated zirconium cerium acid of Yb barium body material in 5 hours 1300 ℃ of calcinings.In body material, add 0.02 mole of ZnO and 0.15 mole of Na then
2SO
4, ball mill mixing 2 hours, again through dry, grind, sieve after, carry out the compound mould of packing into dry-pressing formed, pressure is 75MPa, passes through static pressure such as 300MPa again; Imbed in the BZCYYb-Z2-S ionogen powder 1350 ℃ in air calcination, 2 ℃/minute of temperature rise rates are incubated 3 hours, naturally cool to room temperature then, make the zirconium cerium acid barium multiphase structure proton conductor material with excellent conductive performance.Specific conductivity reaches 6.95 * 10 in the time of 700 ℃
-3S/cm makes material obtain high conductance at a lower temperature.
Embodiment 4
With 1 mole of BaCO
3, 0.7 mole of ZrO
2, 0.3 mole of CeO
2, 0.2 mole of Y
2O
3With 0.2 mole of Yb
2O
3, be medium ball mill mixing 6 hours with the absolute ethyl alcohol, through dry, grind, sieve, obtained Y, the adulterated zirconium cerium acid of Yb barium body material in 6 hours 1350 ℃ of calcinings.In body material, add 0.02 mole of ZnO and 0.15 mole of K then
2CO
3, ball mill mixing 2 hours, again through dry, grind, sieve after, carry out the compound mould of packing into dry-pressing formed, pressure is 70MPa, passes through static pressure such as 200MPa again; Imbed in the BZCYYb-Z2-C ionogen powder sintering in 1370 ℃ of air, 5 ℃/minute of temperature rise rates are incubated 4 hours, naturally cool to room temperature then, make the zirconium cerium acid barium multiphase structure proton conductor material with excellent conductive performance.Specific conductivity reaches 5.62 * 10 in the time of 750 ℃
-3S/cm.
Embodiment 5
With 1 mole of BaCO
3, 0.7 mole of ZrO
2, 0.3 mole of CeO
2, 0.1 mole of Y
2O
3With 0.1 mole of Yb
2O
3, be medium ball mill mixing 6 hours with the absolute ethyl alcohol, through dry, grind, sieve, obtained Y, the adulterated zirconium cerium acid of Yb barium body material in 4 hours 1300 ℃ of calcinings.In body material, add 0.02 mole of ZnO and 0.1 mole of K then
2CO
3, ball mill mixing 4 hours, again through dry, grind, sieve after, carry out the compound mould of packing into dry-pressing formed, pressure is 100MPa, passes through static pressure such as 250MPa again; Imbed in the BZCYYb-Z2-C ionogen powder sintering in 1500 ℃ of air; 8 ℃/minute of temperature rise rates are incubated 2 hours, naturally cool to room temperature then; Make the zirconium cerium acid barium multiphase structure proton conductor material with excellent conductive performance, 750 ℃ of specific conductivity reach 5.85 * 10
-3S/cm.
Embodiment 6
With 1 mole of BaCO
3, 0.7 mole of ZrO
2, 0.3 mole of CeO
2, 0.05 mole of Y
2O
3With 0.05 mole of Yb
2O
3, be medium ball mill mixing 6 hours with the absolute ethyl alcohol, through dry, grind, sieve, obtained Y, the adulterated zirconium cerium acid of Yb barium body material in 3 hours 1500 ℃ of calcinings.In body material, add 0.1 mole of ZnO and 0.30 mole of K then
2CO
3, ball mill mixing 4 hours, again through dry, grind, sieve after, carry out the compound mould of packing into dry-pressing formed, pressure is 50MPa, passes through static pressure such as 200MPa again; Imbed in the BZCYYb-Z2-C ionogen powder sintering in 1300 ℃ of air, 2 ℃/minute of temperature rise rates are incubated 5 hours, naturally cool to room temperature then, make the zirconium cerium acid barium multiphase structure proton conductor material with excellent conductive performance.
Embodiment 7
With 1 mole of BaCO
3, 0.8 mole of ZrO
2, 0.2 mole of CeO
2, 0.1 mole of Y
2O
3With 0.1 mole of Yb
2O
3, be medium ball mill mixing 6 hours with the absolute ethyl alcohol, through dry, grind, sieve, obtained Y, the adulterated zirconium cerium acid of Yb barium body material in 3 hours 1400 ℃ of calcinings.In body material, add 0.02 mole of ZnO and 0.03 mole of K then
2CO
3, ball mill mixing 4 hours, again through dry, grind, sieve after, carry out the compound mould of packing into dry-pressing formed, pressure is 80MPa, passes through static pressure such as 150MPa again; Imbed in the BZCYYb-Z2-C ionogen powder sintering in 1600 ℃ of air, 2 ℃/minute of temperature rise rates are incubated 1 hour, naturally cool to room temperature then, make the zirconium cerium acid barium multiphase structure proton conductor material with excellent conductive performance.
Yb that the present invention proposes and Y co-doped zirconium cerium acid barium multiphase structure proton conductor material and preparation method thereof multiphase structure proton conductor material 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. Yb and Y co-doped zirconium cerium acid barium multiphase structure proton conductor, it is characterized in that: get barium zirconate and cerium acid barium mol ratio and be respectively (8～6): (2～4) are matrix with barium zirconate and the sour barium of cerium, and 5～20% moles of Yb mix
2O
3With 5～20% moles of Y
2O
3, add 1～10% mole of ZnO and 3～30% moles of Na then
2SO
4Or 3～30% moles of K
2CO
3, wherein ZnO is a sintering aid, Na
2SO
4As the liquid phase sintering auxiliary agent, while Na
2SO
4Or K
2CO
3Has proton conductive; Multiphase structure proton conductor specific conductivity reaches 10
-2More than the S/cm.
2. the preparation method of multiphase structure proton conductor according to claim 1 is characterized in that BaCO
3: (ZrO
2+ CeO
2): Y
2O
3: Yb
2O
3Being 1: 1: 0.05～0.20: 0.05～0.20 mole batching, is the medium ball mill mixing with the absolute ethyl alcohol, calcines at 1100～1500 ℃ through dry, the back of grinding, sieve and obtains Yb and Y co-doped body material in 3～10 hours; With the body material is benchmark, adds ZnO and 3～30% moles of Na of 1～10% mole
2SO
4Or 3～30% moles of K
2CO
3, ball mill mixing 2～8 hours; Mixed powder through dry, the mould 50～100MPa that packs into after grinding, sieving is dry-pressing formed; Obtain sample through static pressure such as 150～300MPa again; Then at 1200～1600 ℃ of sintering 1～10 hour in air atmosphere; 2～10 ℃/minute of temperature rise rates naturally cool to room temperature then, make Yb and Y co-doped zirconium cerium acid barium multiphase structure proton conductor material.
3. like the preparation method of the said multiphase structure proton conductor of claim 2, it is characterized in that sample is embedded in the multiphase structure proton conductor ionogen powder and carry out sintering, to suppress inorganic salt Na in the sample
2SO
4Or K
2CO
3Decomposition or volatilization, improve density.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US11661660B2 (en) | 2017-03-16 | 2023-05-30 | Battelle Energy Alliance, Llc | Methods for producing hydrocarbon products and protonation products through electrochemical activation of ethane |
| US11668012B2 (en) * | 2017-12-11 | 2023-06-06 | Battelle Energy Alliance, Llc | Methods for producing hydrocarbon products and hydrogen gas through electrochemical activation of methane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11661660B2 (en) | 2017-03-16 | 2023-05-30 | Battelle Energy Alliance, Llc | Methods for producing hydrocarbon products and protonation products through electrochemical activation of ethane |
| US11668012B2 (en) * | 2017-12-11 | 2023-06-06 | Battelle Energy Alliance, Llc | Methods for producing hydrocarbon products and hydrogen gas through electrochemical activation of methane |
| 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 |
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Application publication date: 20120627 |