CN101974763A - Method for preparing hydrogen electrode composite powder of solid oxide electrolyzer - Google Patents
Method for preparing hydrogen electrode composite powder of solid oxide electrolyzer Download PDFInfo
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- CN101974763A CN101974763A CN 201010527683 CN201010527683A CN101974763A CN 101974763 A CN101974763 A CN 101974763A CN 201010527683 CN201010527683 CN 201010527683 CN 201010527683 A CN201010527683 A CN 201010527683A CN 101974763 A CN101974763 A CN 101974763A
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Abstract
The invention relates to a method for preparing hydrogen electrode composite powder of a solid oxide electrolyzer, belonging to the field of high-temperature steam electrolysis hydrogen preparation and solid oxide electrolyzer. The preparation method comprises the steps of: with nickel nitrate, YSZ (Yttria Stabilized Zirconia) powder and urea as raw materials, controlling reaction conditions of the addition of the urea, the hydrolysis temperature of the urea and ultrasonic time when the powder is prepared, depositing NiO on a YSZ particle through two-step reactions of homogeneous precipitation and low-temperature spontaneous combustion, and finally preparing the NiO-YSZ hydrogen electrode composite powder of the solid oxide electrolyzer through roasting, wherein the nickel nitrate is used as a nickel source, the YSZ powder is used as a core of a composite powder and the urea is a settling agent in a uniform settling process and a combustion improver in a combustion process. The NiO-YSZ composite powder prepared by using the method has the advantages of good adhering property of two phases of NiO and YSZ, uniform dispersing, accurate stoichiometric proportion, strong catalytic activity, high utilization ratio of the nickel, and the like. The invention is suitable for preparing the NiO-YSZ hydrogen electrode composite powder of the solid oxide electrolyzer.
Description
Technical field
The invention belongs to the high temperature steam electrolytic hydrogen manufacturing field, particularly relate to a kind of preparation method of electrolytic tank of solid oxide hydrogen electrode composite granule.
Background technology
Electrolytic tank of solid oxide (Solid oxide electrolysis cell, SOEC) be a kind of energy conversion device that electric energy and heat energy is converted into chemical energy, be to study more Solid Oxide Fuel Cell (Solid oxide fuel cell, inverse process SOFC) at present on the principle.Utilizing the efficient of the SOEC hydrogen manufacturing of brine electrolysis steam at high temperature can be up to 45～59% (ratio of the energy that the energy content that hydrogen production efficiency is defined as obtained hydrogen and hydrogen manufacturing are used), be one of extensive hydrogen production process of potential.But, this technology will realize commercialization scale operation, except the problems such as coupling that will solve hydrogen manufacturing unit and reactor, for hydrogen manufacturing unit itself, improve the electrolysis performance of electrolytic tank of solid oxide and the stability of hot operation, the cost that further reduces hydrogen manufacturing is the subject matter that its development is at present faced.
At present, SOEC is a technology of continuing to use the comparatively sophisticated high temperature SOFC of research on material is selected.Wherein the Ni-YSZ/YSZ/LSM-YSZ electrolyzer is considered to the SOEC of at present tool some commercial potential because the high temperature between each parts is better compatible.But, be transformed into the SOEC pattern from the SOFC pattern after, water vapour content brings up to 70% from 3% in the air inlet of Ni-YSZ hydrogen electrode, high temperature, high humidity environment easily cause Ni particle agglomeration, alligatoring, cause the increase of hydrogen electrode activation polarization.Therefore, the weathering resistance to hydrogen electrode is had higher requirement among the SOEC.
The performance of Ni-YSZ hydrogen electrode depends primarily on microtexture 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.NiO-YSZ composite granule preparation method commonly used at present is generally mechanical mixing and liquid phase method.Mechanical mixing is directly two kinds of powder ball millings of NiO and YSZ to be mixed, though preparation is simple, exist between NiO and the YSZ in conjunction with poor, dispersion is inhomogeneous, easily introduce shortcoming such as impurity.Liquid phase method comprises coprecipitation method, sol-gel method, buffered soln method etc., though these methods can be prepared meticulous, uniform NiO-YSZ composite granule, but need in solution of the same race, precipitate multiple metal ion during preparation, synthesis condition is wayward, exists the product stoichiometric ratio inaccurate and be prone to shortcoming such as metal ion segregation.
In February, 2009, people such as Tsing-Hua University's Liang Mingde disclose a kind of preparation method of solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder, this method is the nickel source with the nickelous nitrate, ammoniacal liquor is precipitation agent, YSZ (zirconium white of stabilized with yttrium oxide) powder is made the core of compound powder, optimal control by conditions such as stirring velocity, ultrasonication, pH value of solution value and rate of addition deposits Ni (OH) on the YSZ particle
2And YSZ coated, again through processing such as overcuring, filtration, cleaning, oven dry,, make high-performance solid oxidate electrolytic cell NiO-YSZ hydrogen electrode composite granule after on the YSZ powder, generate NiO after the roasting.This method have between NiO and YSZ particle tack good, be uniformly dispersed, catalytic activity is strong, simple operation and other advantages.The present invention sees Chinese invention patent " preparation method of solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder " (publication number: CN 101362205A) for details.But meticulous for the particle that guarantees NiO in the present invention, the deposition reaction of nickel need be carried out under higher degree of supersaturation, and when the pH of solution value was too high, ammoniacal liquor can produce Ni (NH with the nickel ion complexing
3)
6 2+, the feasible Ni (OH) that is precipitated out
2Dissolving reduces the NiO productive rate, makes that also NiO and YSZ mass ratio are difficult for accurately control in the composite granule.In addition, the precipitation process of dropping precipitation agent commonly used is owing to material concentration inequality in the solution, and sedimentary formation speed is fast, causes the size distribution broad of deposit seeds easily.
Summary of the invention:
In view of the deficiencies in the prior art, the object of the present invention is to provide the preparation method of electrolytic tank of solid oxide hydrogen electrode composite granule, technical scheme is as follows:
At first by sluggish precipitation with Ni (NO
3)
2Most of nickel ion in the solution is with Ni (OH)
2Form be deposited on the YSZ particle, by the low temperature auto-combustion method nickel ion in the solution all is converted into NiO then, make the NiO-YSZ composite granule, its step is;
1) preparation 0.2～1.0mol/L nickel nitrate solution, the urea and the YSZ powder that add aequum again in the nickel nitrate solution, wherein the mol ratio of urea and nickelous nitrate is 1.6: 1～4: 1, the quality of YSZ and be 0.8: 1～2: 1 with the ratio of the NiO Theoretical Mass that generates was with the mixture ultrasonication of preparation 5～30 minutes;
2) under 80～100 ℃ of water-baths, quick stirring condition, reacted 1～10 hour, make a part of hydrolysis of urea, the nickel ion in the solution is deposited on the YSZ particle, then mixture is transferred to heating evaporation in the furnace pot, make the mixture gel;
3) continue the described jelly of heating and obtain first powder, be 300～1100 ℃ in temperature then and carried out calcination process 1～5 hour, make the solid oxide electrolytic cell NiO-YSZ hydrogen electrode composite granule to the low-temperature self-propagating burning takes place.
Described nickel nitrate solution is for using Ni (NO
3)
26H
2O dissolves in the deionized water preparation.
The particle diameter of described YSZ powder is at 0.05～2 μ m.
The described solid oxide electrolytic cell NiO-YSZ hydrogen electricity complex poles powder that makes, NiO coats the full coating of YSZ or half.
Beneficial effect of the present invention is: with sluggish precipitation with close the low temperature auto-combustion method and combine and prepare the NiO-YSZ composite granule, the meticulous advantage of NiO structure that had both kept Preparation by Uniform Precipitation, adopt the low temperature auto-combustion method to remedy the low shortcoming of NiO productive rate in the precipitator method again, the productive rate of NiO is near 100%, and the NiO-YSZ composite granule of preparation has NiO and YSZ two alternate tacks are good, be uniformly dispersed, stoichiometric ratio is accurate, catalytic activity is strong and the utilization ratio advantages of higher of nickel.
Description of drawings:
The mol ratio of Fig. 1 urea and nickelous nitrate is the XRD figure spectrum of 2: 1 o'clock synthetic NiO-YSZ composite granules.
The mol ratio of Fig. 2 urea and nickelous nitrate is scanning electron microscope (SEM) photo of 2: 1 o'clock synthetic NiO-YSZ composite granules
Fig. 3 Ni-YSZ/YSZ/YSZ-LSM electrolyzer is with 0.33A/cm
2Constant-current electrolysis test curve figure
Embodiment
The present invention proposes a kind of preparation method of electrolytic tank of solid oxide hydrogen electrode composite granule, this method is made the core of compound powder with the YSZ powder, NiO makes coating layer, urea is as precipitation agent and ignition dope in the preparation journey, deposit NiO by precipitation from homogeneous solution and low temperature auto-combustion two-step reaction on the YSZ particle, concrete step is as follows:
(1) preparation 0.2～1.0mol/L nickel nitrate solution, the urea and the YSZ powder that add aequum again in the nickel nitrate solution, wherein the mol ratio of urea and nickelous nitrate is 1.6: 1～4: 1, the quality of YSZ and be 0.8: 1～2: 1 with the ratio of the NiO Theoretical Mass that generates was with the mixture ultrasonication of preparation 5～30 minutes;
(2) under 80～100 ℃ of water-baths, quick stirring condition, reacted 1～10 hour, make a part of hydrolysis of urea, the nickel ion in the solution is deposited on the YSZ particle, then mixture is transferred to heating evaporation in the furnace pot, make the mixture gel;
(3) continue the described jelly of heating and obtain first powder, be 300～1100 ℃ in temperature then and carried out calcination process 1～5 hour, make the solid oxide electrolytic cell NiO-YSZ hydrogen electrode composite granule to the low-temperature self-propagating burning takes place.
Described nickel nitrate solution is for using Ni (NO
3)
26H
2O dissolves in the deionized water preparation.
The particle diameter of described YSZ powder is at 0.05～2 μ m.
The described solid oxide electrolytic cell NiO-YSZ hydrogen electrode composite granule that makes, NiO coats the full coating of YSZ or half.
Embodiment 1:
With Ni (NO
3)
26H
2O dissolves in deionized water and is mixed with the 0.5mol/L nickel nitrate solution, the urea and the YSZ powder that add aequum again in the nickel nitrate solution, wherein the mol ratio of urea and nickelous nitrate is 2: 1, the quality of YSZ and be 1: 1 with the ratio of the NiO Theoretical Mass that generates, mixture ultrasonication 15 minutes with preparation, open the reunion between the YSZ powder granule and make it to be dispersed in the solution, as Ni (OH)
2Sedimentary core.Reaction is 4 hours under 90 ℃ of water-baths, quick stirring condition, makes a part of hydrolysis of urea, and the nickel ion in the solution is deposited on the YSZ particle.Then the gained mixture is transferred in the porcelain circle furnace pot, in heating evaporation, constantly stir, become jelly until suspension liquid, continue to be heated to and burn, obtain the first powder of NiO-YSZ, be 800 ℃ in temperature then and carried out calcination process 2 hours, make the solid oxide electrolytic cell NiO-YSZ hydrogen electrode composite granule.
Fig. 1 is the XRD figure spectrum of 2: 1 o'clock synthetic NiO-YSZ composite granules for the mol ratio of urea and nickelous nitrate.As can be seen from Figure 1, sample all presents crystal form preferably, and the peak position of NiO and YSZ conforms in the diffraction peak of sample and the JCPDS standard card, there is no dephasign in the composite granule and produces.Fig. 2 is scanning electron microscope (SEM) photo of 2: 1 o'clock synthetic NiO-YSZ composite granules for the mol ratio of urea and nickelous nitrate.As can be seen from Figure 2, in the NiO-YSZ composite granule NiO with nano particle attached on the YSZ.
The performance of example 2:Ni-YSZ/YSZ/YSZ-LSM electrolyzer
The hydrogen electrode of Ni-YSZ/YSZ/YSZ-LSM electrolyzer adopts the dry pressing preparation.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.In order to make hydrogen electrode possess competent hole conduction gas, the starch that adds NiO and YSZ total mass 25% is as pore-forming material.YSZ ionogen and YSZ-LSM oxygen electrode adopt the silk screen print method preparation, and the mass ratio of powder and organic binder bond is 1: 2 in the silk screen printing slurry.Organic binder bond is mixed by the ethyl cellulose of 5wt% and the Terpineol 350 of 95wt%.The electrolytical sintering temperature of YSZ is 1400 ℃, and thickness is 15 μ m.The calcining temperature of YSZ-LSM oxygen electrode is 1150 ℃, and thickness is 50 μ m.Fig. 3 for the preparation the Ni-YSZ/YSZ/YSZ-LSM electrolyzer at 900 ℃ with 0.33A/cm
250 hours graphic representation of constant-current electrolysis.As can be seen from Figure 3, in 50 hours process of constant-current electrolysis, electrolysis voltage is stabilized in 0.93～0.95V, and decay does not appear in the stable performance of SOEC.The hydrogen-producing speed that calculates according to current density is 138Nml/cm
2H (that is, milliliter every square centimeter per hour).
Be by the foregoing description characteristics of the present invention as can be seen: the synthetic operation for preparing NiO-YSZ hydrogen electrode composite granule by present method is simple, the NiO-YSZ hydrogen electrode composite granule that makes has NiO and YSZ two alternate tacks are good, be uniformly dispersed, stoichiometric ratio is accurate, utilize the hydrogen electrode catalytic activity of this powder preparing strong, good stability meets the electrolytic tank of solid oxide needs that move steady in a long-term.
The present invention is applicable to the preparation of the NiO-YSZ hydrogen electrode composite granule of electrolytic tank of solid oxide and Solid Oxide Fuel Cell.
Claims (3)
1. the preparation method of an electrolytic tank of solid oxide hydrogen electrode composite granule is characterized in that, at first by sluggish precipitation with Ni (NO
3)
2Most of nickel ion in the solution is with Ni (OH)
2Form be deposited on the YSZ particle, by the low temperature auto-combustion method nickel ion in the solution all is converted into NiO then, make the NiO-YSZ composite granule, its step is as follows:
1) preparation 0.2～1.0mol/L nickel nitrate solution, the urea and the YSZ powder that add aequum again in the nickel nitrate solution, wherein the mol ratio of urea and nickelous nitrate is 1.6: 1～4: 1, the quality of YSZ and be 0.8: 1～2: 1 with the ratio of the NiO Theoretical Mass that generates was with the mixture ultrasonication of preparation 5～30 minutes;
2) under 80～100 ℃ of water-baths, quick stirring condition, reacted 1～10 hour, make a part of hydrolysis of urea, the nickel ion in the solution is deposited on the YSZ particle, then mixture is transferred to heating evaporation in the furnace pot, make the mixture gel;
3) continue the described jelly of heating and obtain first powder, be 300～1100 ℃ in temperature then and carried out calcination process 1～5 hour, make the solid oxide electrolytic cell NiO-YSZ hydrogen electrode composite granule to the low-temperature self-propagating burning takes place.
2. the preparation method of a kind of electrolytic tank of solid oxide hydrogen electrode composite granule according to claim 1 is characterized in that, the particle diameter of described YSZ powder is at 0.05～2 μ m.
3. the preparation method of a kind of electrolytic tank of solid oxide hydrogen electrode composite granule according to claim 1 is characterized in that, the described solid oxide electrolytic cell NiO-YSZ hydrogen electricity complex poles powder that makes, and NiO coats the full coating of YSZ or half.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035936A (en) * | 2012-12-27 | 2013-04-10 | 清华大学 | Preparation method of composite electrolyte powder for medium-and-low-temperature solid oxide fuel cell |
| 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 |
| CN113851660A (en) * | 2021-09-22 | 2021-12-28 | 南京工业大学 | Method for improving low-temperature catalytic performance of cathode of solid oxide fuel cell |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307461A (en) * | 2008-06-16 | 2008-11-19 | 清华大学 | Method for preparing YSZ-LSM oxygen electrode powder of solid oxidate electrolytic cell |
| CN101362205A (en) * | 2008-05-19 | 2009-02-11 | 清华大学 | Preparation method of solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder |
| CN101698600A (en) * | 2009-10-30 | 2010-04-28 | 广东工业大学 | Method for preparing Nano-NiO-YSZ composite ceramics |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362205A (en) * | 2008-05-19 | 2009-02-11 | 清华大学 | Preparation method of solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder |
| CN101307461A (en) * | 2008-06-16 | 2008-11-19 | 清华大学 | Method for preparing YSZ-LSM oxygen electrode powder of solid oxidate electrolytic cell |
| CN101698600A (en) * | 2009-10-30 | 2010-04-28 | 广东工业大学 | Method for preparing Nano-NiO-YSZ composite ceramics |
Non-Patent Citations (2)
| Title |
|---|
| 《International Journal of Hydrogen Energy》 20090612 Mingde Liang等 Preparation of NiO-YSZ composite powder by a combustion method and its application for cathode of SOEC 2852-2857 1-3 第35卷, 2 * |
| 《硅酸盐通报》 20040331 王凤华等 SOFC阳极用NiO-YSZ粉末的制备技术 81-84 1-3 , 第3期 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035936A (en) * | 2012-12-27 | 2013-04-10 | 清华大学 | Preparation method of composite electrolyte powder for medium-and-low-temperature solid oxide fuel cell |
| 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 |
| CN113851660A (en) * | 2021-09-22 | 2021-12-28 | 南京工业大学 | Method for improving low-temperature catalytic performance of cathode of solid oxide fuel cell |
| CN113851660B (en) * | 2021-09-22 | 2023-07-07 | 南京工业大学 | Method for improving low-temperature catalytic performance in cathode of solid oxide fuel cell |
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