CN111408729A - Preparation method of Ni-BaZrY composite powder - Google Patents
Preparation method of Ni-BaZrY composite powder Download PDFInfo
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- CN111408729A CN111408729A CN201910009073.XA CN201910009073A CN111408729A CN 111408729 A CN111408729 A CN 111408729A CN 201910009073 A CN201910009073 A CN 201910009073A CN 111408729 A CN111408729 A CN 111408729A
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- 239000000843 powder Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 title claims description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910002648 Ni-Y2O3 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
Abstract
The invention provides a preparation method of a Ni-BaZrY powder material. Selecting YSZ powder as a Zr source and a Y source, dissolving the YSZ powder, a Ni source and a Ba source in a solvent to form a raw material solution, and heating the raw material solution to evaporate the solvent to obtain a precursor; and heating the precursor to the heat treatment temperature, preserving the heat, cooling to room temperature, and finally grinding to obtain the Ni-BaZrY powder material. The Ni-BaZrY powder material which is regular in morphology, uniform in dispersion, good in phase formation and good in ammonia catalytic decomposition efficiency can be obtained under the condition of low heat treatment temperature by using the method, and the Ni-BaZrY powder material has the advantages of low cost, simple process and low phase formation temperature.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a preparation method of Ni-BaZrY composite powder.
Background
Ni — BaZrY powder materials have recently attracted attention in the field of anode materials for proton-conducting fuel cells because of their advantages such as good electrical conductivity. In addition, the powder material can be used for catalyzing ammonia decomposition reaction.
At present, the preparation method of the Ni-BaZrY powder material mainly comprises a sol-gel method, a solid-phase reaction method, a solid-liquid method, Flame Spray Synthesis (FSS) and the like. The main disadvantages of the sol-gel method are that the process flow is complex and not suitable for large-scale production; the main disadvantage of the solid phase reaction method is that Ba and Ni elements are lost, so that a phase with high purity cannot be obtained; the solid-liquid method cannot obtain pure phase at low temperature in the experiment; the flame spraying synthesis also has the defects of complex process flow and suitability for small-scale production.
In addition, in the preparation of the existing Ni-BaZrY powder material, raw materials comprise a Ni source, a Ba source, a Zr source and a Y source, but the synthesis of the Zr element and the Y element is generally difficult, so that the problems of irregular shape, uneven dispersion and the like of the powder material are caused.
Besides, the preparation of the Ni-BaZrY powder material comprises a heat treatment phase forming process. However, because the sintering activity ratio of the Zr element is poor, a very high sintering temperature is often needed, so that the phase forming temperature in the heat treatment in the preparation is high, the cost is high, and the energy consumption is high.
Disclosure of Invention
In view of the above technical situation, the present invention aims to provide a method for preparing Ni-doped BaZrY powder, i.e., Ni-BaZrY composite powder, which can obtain Ni-BaZrY powder material with regular morphology, uniform dispersion and good phase formation under the condition of low heat treatment temperature.
In order to achieve the technical purpose, the invention adopts the technical scheme that: a preparation method of Ni-BaZrY powder material comprises the following steps:
(1) selecting YSZ powder as a Zr source and a Y source, dissolving the YSZ powder, a Ni source and a Ba source in a solvent, and uniformly dispersing to obtain a raw material solution;
(2) heating the raw material solution to evaporate the solvent to obtain a precursor;
(3) and heating the precursor to the heat treatment temperature, preserving the heat, cooling to room temperature, and finally grinding to obtain the Ni-BaZrY powder material.
In the step (1), the Ni source is not limited and includes nickel nitrate and the like.
In the step (1), the Ba source is not limited and includes barium nitrate and the like.
Preferably, in the step (2), in order to heat the raw material solution uniformly, the raw material solution is heated by constant-temperature steam, and the solvent in the raw material solution is heated and evaporated, which is beneficial to the synthesis of the Ni source, the Ba source, the Zr source and the Y source in the heat treatment process. As an implementation mode, a water bath device is adopted, the raw material solution is placed in a culture dish, and the culture dish is heated by using water vapor generated after water bath heating, so that the solvent in the culture dish is heated and evaporated to obtain a powder precursor.
Preferably, the water vapor temperature is 60 to 100 ℃, preferably 70 to 90 ℃.
Preferably, in the water bath apparatus, the culture dish is placed above the water bath so as not to contact the water bath, and the steam generated after heating in the water bath contacts the culture dish.
Compared with the prior art, the invention has the following beneficial effects:
in the invention, industrial YSZ powder is directly used as a Zr source and a Y source, and because the YSZ powder contains two elements of Zr and Y which are well synthesized in the YSZ powder, the problem that the two elements of Zr and Y are difficult to synthesize is solved, and then Ni and Ba elements are synthesized into a YSZ crystal lattice by impregnation; moreover, experiments show that the YSZ powder, the Ni source and the Ba source are mixed to form a raw material solution, then the raw material solution is heated to evaporate a solvent, then the heat treatment is carried out to form a phase, and finally the Ni-BaZrY powder obtained by grinding is regular in shape, uniform and stable, and is also beneficial to reducing the heat treatment phase forming temperature in the heat treatment process, the phase forming is good below 1100 ℃, and the phase forming of the Ni-BaZrY powder can be realized even at 900 ℃, so that the heat treatment temperature is reduced by the method, the cost is saved, and the prepared Ni-BaZrY powder has good ammonia catalytic decomposition efficiency.
Drawings
FIG. 1 is an XRD pattern of Ni-BaZrY powder obtained at 900-.
FIG. 2 shows the variation of ammonia catalytic decomposition efficiency with temperature of Ni-BaZrY powder obtained in example 1 of the present invention and Ni/Y ratio with Ni-doped metal oxide powder2O3、Ni/Al2O3、Ni/La2O3、Ni/CeO2The powder is additionally arranged inDecomposition efficiency at 550 ℃ was compared.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, which are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way.
In this example, the Ni — BaZrY powder was prepared as follows:
(1) the water bath adopts a constant temperature water bath HH-6-02577 model of Pongxi instruments science and technology (Shanghai) Limited company, and the spherical glass culture dish
The type of the glass rod is
YSZ powder is selected as a Zr source and a Y source, nickel nitrate is selected as a nickel source, and barium nitrate is selected as a Ba source.
(2) Adding YSZ powder, nickel nitrate and barium nitrate with corresponding weight into a spherical glass vessel, adding a proper amount of distilled water, stirring by using a glass rod, and completely dissolving and uniformly dispersing to obtain a raw material solution; the spherical glass ware is erected above the water bath and is not contacted with the water bath; adjusting the temperature of the water bath to 90 ℃, and slowly heating the culture dish by contacting water vapor generated after water bath heating until the solvent in the raw material solution is evaporated to dryness, and leaving a white powder precursor at the bottom of the spherical glass dish, wherein if a residual powder sample exists on the wall of the spherical culture dish, the residual powder sample is gently scraped off by a glass rod and falls into the bottom of the culture dish.
(3) And heating the precursor to the heat treatment temperature, preserving the heat for 180min, cooling to room temperature, and finally grinding to obtain the Ni-BaZrY powder material.
FIG. 1 is an XRD pattern of the Ni-BaZrY powder material obtained by selecting the heat treatment temperatures of 900 deg.C, 1000 deg.C, 1100 deg.C, 1200 deg.C, 1300 deg.C, and 1400 deg.C, respectively, in the step (3) above. It can be seen from fig. 1 that the Ni-BaZrY powder material has formed a good phase already under the 900 ℃ heat treatment condition.
FIG. 2 isThe ammonia catalytic decomposition efficiency of the Ni-BaZrY powder sample prepared under the condition of 900 ℃ heat treatment changes along with the temperature and is mixed with other four Ni-doped metal oxide powders Ni-Y2O3、Ni-Al2O3、Ni-La2O3、Ni-CeO2Comparison of the decomposition efficiency at 550 ℃ shows that the ammonia catalytic decomposition efficiency of the Ni-BaZrY powder sample prepared under the 900 ℃ heat treatment condition in this example gradually increased with increasing temperature and tended to be stable at 600 ℃. The ammonia catalytic decomposition efficiency of the Ni-BaZrY powder was higher than the remaining four Ni-doped metal oxide powders at 550 ℃.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of Ni-BaZrY composite powder is characterized by comprising the following steps: the method comprises the following steps:
(1) selecting YSZ powder as a Zr source and a Y source, dissolving the YSZ powder, a Ni source and a Ba source in a solvent, and uniformly dispersing to obtain a raw material solution;
(2) heating the raw material solution to evaporate the solvent to obtain a precursor;
(3) and heating the precursor to the heat treatment temperature, preserving the heat, cooling to room temperature, and finally grinding to obtain the Ni-BaZrY powder material.
2. The method for preparing Ni-BaZrY composite powder according to claim 1, wherein: in the step (1), the Ni source comprises nickel nitrate.
3. The method for preparing Ni-BaZrY composite powder according to claim 1, wherein: in the step (1), the Ba source includes barium nitrate.
4. The method for preparing Ni-BaZrY composite powder according to claim 1, wherein: in the step (2), the raw material solution is heated by constant-temperature steam, so that the solvent in the raw material solution is heated and evaporated.
5. The method for preparing Ni-BaZrY composite powder as claimed in claim 4, wherein: a water bath device is adopted, the raw material solution is contained in a culture dish, and the culture dish is heated by water vapor generated after water bath heating, so that the solvent in the culture dish is heated and evaporated.
6. The method for preparing Ni-BaZrY composite powder as claimed in claim 4, wherein: the temperature of the water vapor is 60-100 ℃.
7. The method for preparing Ni-BaZrY composite powder as claimed in claim 6, wherein: the steam temperature is 70-90 deg.C.
8. The method for preparing Ni-BaZrY composite powder as claimed in claim 4, wherein: in the water bath device, the culture dish is erected above the water bath and does not contact the water bath, and water vapor generated after the water bath heating contacts the culture dish.
9. The method for producing Ni-BaZrY composite powder according to any one of claims 1 to 8, characterized by: the heat treatment temperature is lower than 1100 ℃.
10. The method for preparing Ni-BaZrY composite powder according to claim 9, wherein: the heat treatment temperature is 900-1000 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113952979A (en) * | 2020-07-21 | 2022-01-21 | 中国科学院宁波材料技术与工程研究所 | Catalyst for ammonia decomposition hydrogen production |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006063441A (en) * | 2004-07-30 | 2006-03-09 | Jfe Mineral Co Ltd | Ultrafine metal powder slurry |
| CN103000908A (en) * | 2011-09-08 | 2013-03-27 | 中国科学院过程工程研究所 | Metal/YSZ Composite electrode preparation method |
| KR20160087516A (en) * | 2015-01-14 | 2016-07-22 | 창원대학교 산학협력단 | Low and intermediate-temperature type proton-conducting ceramic fuel cells containing bi-layer electrolyte structure for preventing performance degradation and method for manufacturing the same |
| CN107206356A (en) * | 2014-12-19 | 2017-09-26 | 庄信万丰股份有限公司 | Catalyst manufacture method |
| CN108424142A (en) * | 2018-04-28 | 2018-08-21 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of BaZrY dusty materials |
-
2019
- 2019-01-04 CN CN201910009073.XA patent/CN111408729A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006063441A (en) * | 2004-07-30 | 2006-03-09 | Jfe Mineral Co Ltd | Ultrafine metal powder slurry |
| CN103000908A (en) * | 2011-09-08 | 2013-03-27 | 中国科学院过程工程研究所 | Metal/YSZ Composite electrode preparation method |
| CN107206356A (en) * | 2014-12-19 | 2017-09-26 | 庄信万丰股份有限公司 | Catalyst manufacture method |
| KR20160087516A (en) * | 2015-01-14 | 2016-07-22 | 창원대학교 산학협력단 | Low and intermediate-temperature type proton-conducting ceramic fuel cells containing bi-layer electrolyte structure for preventing performance degradation and method for manufacturing the same |
| CN108424142A (en) * | 2018-04-28 | 2018-08-21 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of BaZrY dusty materials |
Non-Patent Citations (2)
| Title |
|---|
| FRANCESCO BOZZA等: "Effects of Ni doping on the sintering and electrical properties of BaZr0.8Y0.2O3−δ proton conducting electrolyte prepared by Flame Spray Synthesis", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
| 毛宗强等: "《低温固体氧化物燃料电池》", 31 January 2013, 上海科学技术出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113952979A (en) * | 2020-07-21 | 2022-01-21 | 中国科学院宁波材料技术与工程研究所 | Catalyst for ammonia decomposition hydrogen production |
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Application publication date: 20200714 |