CN101362205B - Preparation method of solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder - Google Patents
Preparation method of solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder Download PDFInfo
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Abstract
The invention relates to a method for preparing solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder, which belongs to the field of electrolytic hydrogen production with high temperature steam and the field of solid oxide electrolytic cell. The invention uses six hydrate nickel nitride, YSZ (yttira stabilized zirconia) powder, and ammonia as raw materials; an in-situ synthesis is adopted; nickel nitrate is adopted as the nickel source, ammonia as precipitant, and YSZ powder as a precipitation-coated core; by the optimized control of conditions of stirring speed, ultrasonic wave processing, pH value of solution, and dropping speed, etc. Ni(OH)2 is deposited on the YSZ grain and the YSZ is coated; then, after processing of curing, filtering, washing, and drying, etc. NiO is generated on the YSZ powder after roasting; therefore, high-performance solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder is obtained. The method has the advantages of good adhesion between NiO and YSZ grains, even distribution, strong catalysis activity, accurate chemical equivalence ratio, and simple operation, etc.
Description
Technical field
The invention belongs to high temperature steam electrolytic hydrogen manufacturing and electrolytic tank of solid oxide field, the preparation method of particularly a kind of solid oxide electrolytic cell NiO-YSZ (zirconia of nickel oxide-stabilized with yttrium oxide) hydrogen electrode powder.
Background technology
SOFC (Solid Oxide Fuel Cells, SOFC) be a kind of device that the chemical energy of fuel is directly changed into electric energy, owing to possess advantages such as efficient, environmental protection and fuel is applied widely, more and more be subject to people's attention in fields such as the distributed power generation and the vehicles in recent years.Electrolytic tank of solid oxide (Solid OxideElectrolytic Cells with the preparation of SOFC antikinesis, SOEC), at high temperature the efficient of the hydrogen manufacturing of brine electrolysis steam can be up to 45～59% (hydrogen production efficiency is defined as the ratio of the energy that the hydrogen contained energy that makes and hydrogen manufacturing consumed), be considered to one of extensive hydrogen production process of following Hydrogen Energy economy era, also become the research focus in current international energy field.
Ni-YSZ (zirconia of nickel-stabilized with yttrium oxide) cermet since possess electronic conductivity height, catalytic capability strong, with other component machinery of battery and chemical property advantage such as compatibility mutually, be considered to be applicable to the best hydrogen electrode of pure hydrogen fuel.But, being converted to the process of SOEC from SOFC, hydrogen electrode environment of living in becomes high temperature, high humidity atmosphere by strong reducing property atmosphere, and this weatherability to hydrogen electrode is had higher requirement.Denmark
The current research of National Laboratory shows, under the SOFC pattern, utilize ripe Ni-YSZ/YSZ/LSM (lanthanum manganate of strontium doping) pile operation 1500 hours, the polarization resistance of battery does not obviously change, but operation is 90 hours under the SOEC pattern, its polarization resistance increases to original more than 3 times, and the battery performance decay rapidly.
At present, the unstability that generally believes electrode microstructure is the main cause that causes the battery performance decay, and is especially true for the Ni-YSZ hydrogen electrode.In order to improve the performance of hydrogen electrode, Ni-YSZ should be meticulous as far as possible on micro-structural, to increase the quantity of three phase boundary.But at high temperature the Ni particle trends towards reducing specific surface energy and reunites in the Ni-YSZ cermet.Although YSZ has the effect that suppresses Ni particle agglomeration, alligatoring in the electrode as support frame, but wettability is relatively poor between metal and the ceramic material (Ni and YSZ contact angle in the time of 1500 ℃ is 117 °), when the Ni particle hour, its reunion, coarsening phenomenon are still very serious.
The performance of Ni-YSZ hydrogen electrode depends primarily on microstructure and the Ni and the distribution situation of YSZ in electrode of electrode, and this depends on particle properties and the preparation process of NiO and YSZ.Ni-YSZ hydrogen electrode powder preparation method commonly used at present is generally solid phase method and liquid phase method.Solid phase method is directly NiO powder and YSZ powder to be mixed, exist NiO and YSZ in conjunction with poor, disperse inhomogeneous, easily introduce shortcoming such as impurity; Liquid phase method comprises coprecipitation, sol-gel process, cushioning liquid method etc., though these methods can be prepared meticulous NiO-YSZ powder and improve the uniformity of powder, but these methods need precipitate multiple metal ion in solution of the same race, and existence condition control is complicated, the product stoichiometric proportion is inaccurate and be prone to shortcoming such as metal ion segregation.
Summary of the invention
In view of the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder, technical scheme is as follows:
This method is the nickel source with the nickel nitrate, ammoniacal liquor is precipitating reagent, YSZ (zirconia of stabilized with yttrium oxide) powder adopts in-situ synthesis as the core of precipitated parcel, and the step of preparation solid oxide electrolytic cell NiO-YSZ (zirconia of nickel oxide-stabilized with yttrium oxide) hydrogen electrode powder is as follows:
(1) with Nickelous nitrate hexahydrate (Ni (NO
3)
26H
2O) and deionized water preparation 0.3～1mol/L nickel nitrate solution, the YSZ powder of adding aequum in the nickel nitrate solution under the condition of 15～50 ℃ of water-baths, ultrasonic oscillation and high-speed stirred, is uniformly dispersed the YSZ particle, as Ni (OH) in solution again
2The precipitation core of adhering to, adopting denseer solution is degree of supersaturation in order to ensure system, makes Ni (OH)
2The particle of precipitation is tiny;
(2) drip precipitating reagent, regulating the pH value is 7.5～9.5, makes Ni (OH)
2Be deposited on the YSZ, and YSZ is coated, carry out high-speed stirred simultaneously and suppress Ni (OH)
2Crystal growth and ultrasonic oscillation stop Ni (OH)
2Reunion between crystal;
(3) under continuous stirring condition, be 50～80 ℃ of slakings 0.5～4 hour in temperature with the gained precipitated product, again through filtering, clean, drying, be 300～800 ℃ of roastings 1～4 hour in temperature at last, synthetic NiO makes high-performance solid oxidate electrolytic cell NiO-YSZ hydrogen electrode powder on the YSZ powder.
The particle diameter of described YSZ powder is at 0.1～2 μ m.
The described solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder that makes, NiO coats the full coating of YSZ or half.
Described precipitating reagent also has urea, oxalic acid, carbonic hydroammonium or NaOH etc. except that ammoniacal liquor.
Beneficial effect of the present invention: with respect to prior art, method provided by the invention have between NiO and YSZ particle tack good, be uniformly dispersed, catalytic activity is strong, stoichiometric proportion is accurate, simple operation and other advantages.
Description of drawings
Fig. 1 is the X-ray diffractogram (XRD) of the synthetic NiO-YSZ powder of ammonia precipitation process original position.
Fig. 2 is ESEM (SEM) photo of the synthetic NiO-YSZ powder of ammonia precipitation process original position.
Fig. 3 is the X-ray diffractogram (XRD) of the synthetic NiO-YSZ powder of ultrasonic auxiliary ammonia precipitation process original position.
Fig. 4 is ESEM (SEM) photo of the synthetic NiO-YSZ powder of ultrasonic auxiliary ammonia precipitation process original position.
Fig. 5 is the electrolytic cell 300mA constant-current electrolysis curve map of the synthetic NiO-YSZ powder preparation of ammonia precipitation process original position.
The specific embodiment
The present invention proposes a kind of preparation method of novel, high-performance solid oxidate electrolytic cell NiO-YSZ hydrogen electrode powder, this method is the nickel source with the nickel nitrate, and ammoniacal liquor is as precipitating reagent, and the YSZ powder is made the core of precipitated parcel, adopt the described powder of in-situ synthesis efficient production, its step is as follows:
(1) with Nickelous nitrate hexahydrate and deionized water preparation 0.3～1mol/L nickel nitrate solution, the YSZ powder that adds aequum again in the nickel nitrate solution, under the condition of 15～50 ℃ of water-baths, ultrasonic oscillation and high-speed stirred, the YSZ particle is uniformly dispersed, in solution as Ni (OH)
2The precipitation core of adhering to, adopting denseer solution is degree of supersaturation in order to ensure system, makes Ni (OH)
2The particle of precipitation is tiny;
(2) drip precipitating reagent, regulating the pH value is 7.5～9.5, makes Ni (OH)
2Be deposited on the YSZ, and YSZ is coated, carry out high-speed stirred simultaneously and suppress Ni (OH)
2Crystal growth and ultrasonic oscillation stop Ni (OH)
2Reunion between crystal;
(3) under continuous stirring condition, be 50～80 ℃ of slakings 0.5～4 hour in temperature with the gained precipitated product, again through filtering, clean, drying, be 300～800 ℃ of roastings 1～4 hour in temperature at last, synthetic NiO on the YSZ powder, make high-performance solid oxidate electrolytic cell NiO-YSZ hydrogen electrode powder, NiO coats the full coating of YSZ or half in the powder.
Above-mentioned precipitating reagent also has urea, oxalic acid, carbonic hydroammonium or NaOH etc. except that ammoniacal liquor.
The particle diameter of above-mentioned YSZ powder is at 0.1～2 μ m.
The present invention will be further described below in conjunction with embodiment.
Embodiment 1: the ammonia precipitation process original position is synthesized the NiO-YSZ powder
Take by weighing 72.70g Ni (NO
3)
26H
2O, be mixed with the nickel nitrate solution of 0.5mol/L with deionized water, in nickel nitrate solution, add 12.00g YSZ powder (Japanese Tosoh 8YSZ) again, the process ultrasonic wave was handled after 15 minutes, under the condition of 20 ℃ of water-baths and magnetic agitation, in mixed liquor, dropwise add ammoniacal liquor, the pH value of solution is transferred to 7.6, produce the light green color precipitation.After ammoniacal liquor dropwises bath temperature is adjusted to 70 ℃, allows precipitation continue slaking 40 minutes, afterwards the sediment with slaking filter, clean, 105 ℃ of oven dry, insert in the Muffle furnace 800 ℃ of roastings 2 hours at last, obtain 24.66g NiO-YSZ powder.The mass ratio of NiO and YSZ is about 1: 1 in the powder.
Fig. 1 is under the above-mentioned condition being the X-ray diffractogram (XRD) of the synthetic NiO-YSZ powder of ammonia precipitation process original position.As can be seen, the crystal formation of YSZ and NiO is comparatively complete in the powder from the figure, there is no dephasign and produces.ESEM (SEM) photo of the synthetic NiO-YSZ powder of ammonia precipitation process original position as shown in Figure 2.
Embodiment 2: ultrasonic auxiliary ammonia precipitation process original position is synthesized the NiO-YSZ powder
Take by weighing 36.35g Ni (NO
3)
26H
2O, be mixed with the nickel nitrate solution of 0.5mol/L with deionized water, in nickel nitrate solution, add 6.00g YSZ powder (Japanese Tosoh 8YSZ) again, under the stirring condition of 25 ℃ of water-baths and ultrasonic oscillation and 600r/min, in mixed liquor, dropwise add ammoniacal liquor, the pH value of solution is transferred to 8.0, produce the light green color precipitation.After ammoniacal liquor dropwises bath temperature is adjusted to 70 ℃, allows precipitation continue slaking 2 hours, afterwards the sediment with slaking filter, clean, 110 ℃ of oven dry, insert in the Muffle furnace 400 ℃ of roastings 2 hours at last, obtain 12.86g NiO-YSZ powder.The mass percentage content of NiO is about 53% in the powder.The X-ray diffractogram (XRD) of gained NiO-YSZ powder and ESEM (SEM) photo are respectively as shown in Figure 3 and Figure 4.
Example 3: the performance of the electrolytic cell of the synthetic NiO-YSZ powder of ammonia precipitation process original position
The hydrogen electrode of Ni-YSZ/YSZ/YSZ-LSM electrolytic cell adopts the dry pressing preparation.The hydrogen electrode powder is the synthetic NiO-YSZ powder of ammonia precipitation process original position, and the hydrogen electrode film diameter is 17mm, and thickness is 0.5mm, and pressure is 250MPa in flakes.The mass ratio of NiO and YSZ is 1: 1 in the hydrogen electrode, possesses sufficient hole conduction gas in order to make hydrogen electrode, and the starch that adds NiO-YSZ powder quality 25% is as pore creating material.YSZ electrolyte and YSZ-LSM oxygen electrode adopt the silk screen print method preparation, and binding agent is mixed by the ethyl cellulose of 5wt% and the terpinol of 95wt% in the serigraphy slurry.Fig. 5 is the curve map of the Ni-YSZ/YSZ/YSZ-LSM electrolytic cell 300mA constant-current electrolysis test of the synthetic NiO-YSZ powder preparation of ammonia precipitation process original position, as can be seen from Figure 5, decomposition voltage 1.44V from the beginning descends gradually, be stabilized in about 0.98V at last, illustrate that there is the process of an activation in this electrolytic cell in the process of electrolysis, and electrolytic cell possesses good stable.
Be by the foregoing description characteristics of the present invention as can be seen: the synthetic operation that this method prepares the NiO-YSZ powder is simple, the content that makes NiO in the NiO-YSZ powder can be controlled according to the addition of YSZ powder and the pH value of precipitation, tack is good and be uniformly dispersed between NiO and YSZ particle, utilize the hydrogen electrode catalytic activity of this powder preparation strong, good stability meets the electrolytic tank of solid oxide needs that move steady in a long-term.
Claims (3)
1. the preparation method of a solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder, it is characterized in that, this method is the nickel source with the nickel nitrate, ammoniacal liquor is as precipitating reagent, the YSZ powder is as the core of precipitated parcel, adopt in-situ synthesis, the step of preparation solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder is as follows:
(1) with Nickelous nitrate hexahydrate and deionized water preparation 0.3～1mol/L nickel nitrate solution, the YSZ powder that adds aequum again in the nickel nitrate solution, under the condition of 15～50 ℃ of water-baths, ultrasonic oscillation and high-speed stirred, the YSZ particle is uniformly dispersed, in solution as Ni (OH)
2The core that precipitation is adhered to;
(2) drip precipitating reagent, regulating the pH value is 7.5～9.5, makes Ni (OH)
2Be deposited on the YSZ, and YSZ is coated, carry out high-speed stirred simultaneously and suppress Ni (OH)
2Crystal growth, ultrasonic oscillation stops Ni (OH)
2Reunion between crystal;
(3) under continuous stirring condition, be 50～80 ℃ of slakings 0.5～4 hour in temperature with the gained precipitated product, again through filtering, clean, drying, be 300～800 ℃ of roastings 1～4 hour in temperature at last, synthetic NiO makes high-performance solid oxidate electrolytic cell NiO-YSZ hydrogen electrode powder on the YSZ powder.
2. the preparation method of solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder according to claim 1 is characterized in that, the particle diameter of described YSZ powder is at 0.1～2 μ m.
3. the preparation method of solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder according to claim 1 is characterized in that, the described solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder that makes, and NiO coats the full coating of YSZ or half.
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| US20110111230A1 (en) * | 2008-06-27 | 2011-05-12 | Sumitomo Osaka Cement Co., Ltd. | Composite ceramic powder, process of producing the same, and solid-oxide fuel cell |
| JP5375063B2 (en) * | 2008-12-10 | 2013-12-25 | 住友大阪セメント株式会社 | Composite ceramic powder, method for producing the same, and solid oxide fuel cell |
| CN101974763A (en) * | 2010-10-27 | 2011-02-16 | 清华大学 | Method for preparing hydrogen electrode composite powder of solid oxide electrolyzer |
| CN102185148A (en) * | 2011-04-01 | 2011-09-14 | 景德镇陶瓷学院 | NiO-based SOFC (Solid Oxide Fuel Cell) composite anode film material with nano-sheet microcellular structure and preparation method thereof |
| CN104060293B (en) * | 2014-06-20 | 2016-08-24 | 清华大学 | Electrolytic tank of solid oxide of electrolyte-supported and preparation method thereof |
| CN108110263A (en) * | 2017-12-20 | 2018-06-01 | 新奥科技发展有限公司 | A kind of SMR catalyst and solid oxide fuel cell anode material |
| CN109319942A (en) * | 2018-09-20 | 2019-02-12 | 江苏理工学院 | A kind of application of the construction method and processing Copper in Electroplating Waste Water, nickel of bioelectrochemistry processing system |
| CN113097511B (en) * | 2021-03-30 | 2022-04-12 | 太原理工大学 | Ni(OH)2/ZrO2Preparation method of heterostructure fuel cell cathode oxygen reduction catalyst |
| CN113285178A (en) * | 2021-05-12 | 2021-08-20 | 山东宏匀纳米科技有限公司 | Oxide-coated lithium lanthanum zirconium oxide material, diaphragm material, lithium battery and preparation method |
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Patent Citations (2)
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| CN1226090A (en) * | 1998-02-12 | 1999-08-18 | 中国科学院大连化学物理研究所 | Anode fundamental mode for cell of middle-temp. solid oxide fuel and preparation thereof |
| CN1293459A (en) * | 2000-09-30 | 2001-05-02 | 吉林大学 | Composite anode materials for solid oxide fuel battery and method for making its electrode |
Non-Patent Citations (2)
| Title |
|---|
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