CN101168486A - Preparation method of zirconia-based electrolyte material - Google Patents

Preparation method of zirconia-based electrolyte material Download PDF

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Publication number
CN101168486A
CN101168486A CNA200710150258XA CN200710150258A CN101168486A CN 101168486 A CN101168486 A CN 101168486A CN A200710150258X A CNA200710150258X A CN A200710150258XA CN 200710150258 A CN200710150258 A CN 200710150258A CN 101168486 A CN101168486 A CN 101168486A
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preparation
powder
electrolyte material
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slurry
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黄新春
李敦钫
曾克里
冀晓鹃
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Beijing General Research Institute of Mining and Metallurgy
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Beijing General Research Institute of Mining and Metallurgy
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Abstract

A method for preparing a zirconia-based solid electrolyte material for thermal spraying. The method is to add Y to zirconia2O3、Sc2O3、Yb2O3High oxygen ion conductive material powder is subjected to spray drying and high-temperature sintering to obtain the electrolyte material for thermal spraying with high apparent density. The prepared electrolyte material has high apparent density and good fluidity. The coating formed by spraying the electrolyte prepared by the method is compact, low in porosity, good in stability and high in ionic conductivity; meanwhile, the method has the advantages of simple process, large production capacity, economy, reliability, industrial popularization and the like. The preparation method of the electrolyte material for thermal spraying provided by the invention is also suitable for preparing other electrolyte material systems for thermal spraying.

Description

The preparation method of zirconium oxide base electrolyte material
[technical field]: the invention belongs to hot-spraying techniques and material processing field.Be particularly related to a kind of preparation method of used for hot spraying zirconia base solid electrolyte material.
[background technology]: SOFC is the Conversion of energy system that a kind of chemical energy that will be stored under constant working temperature (800-1000 ℃) in the fuel is converted into electric energy.Compare with traditional thermoelectric conversion system, this system crossed over chemical energy to heat energy and heat energy to the intermediate steps of electric energy, be not subjected to the restriction of carnot's working cycle, transformation efficiency can be up to 60%, cooperation is to utilize the combined cycle system of waste heat, and the utilization ratio of its fuel potential reaches as high as 90%; The quantity discharged of gas pollutant is very low in the conversion process simultaneously, approaches zero release, is a kind of energy conversion system of high-efficiency cleaning.World developed country all takes much count of the development work of SOFC for this reason, as " the TARGET plan " of the U.S. and " Moonlight Plan " of Japan etc.Scholarly forecast, 10 years from now on will be the important period that SOFC turns to practicability, simplify preparation technology, reduce cost, improving stability test will be its important topic that obtains application.
Core among the SOFC is the solid electrolyte material with oxygen conduction, as ZrO 2-Y 2O 3, ZrO 2-Sc 2O 3, ZrO 2-Ce 2O 3, ZrO 2-Yb 2O 3, ZrO 2-Al 2O 3Deng, yttria-stabilized zirconia (ZrO wherein 2-Y 2O 3), be called for short YSZ, be that application is the most general among the present SOFC, study the most deep a kind of solid electrolyte.Dielectric substrate is one of key stratum structure of SOFC, the technology that is used to prepare dielectric substrate at present mainly comprises electrochemical vapour deposition (EVD) (EVD), low-voltage plasma spraying (VPS) and metal-organic chemical vapor deposition equipment methods such as (MOCVD), and manufacturing cost height, the complex process of current electrolysis matter layer are to cause SOFC manufacturing cost height, the business-like one of the main reasons of restriction SOFC.Hot-spraying techniques can prepare metal and metal one ceramic composite coating neatly, and coat-thickness control is easy, has become one of gordian technique of preparation SOFC.As having adopted air plasma spraying (APS) preparation SOFC anode, negative electrode and the connection utmost point etc. at present, and for the also main expensive low-voltage plasma spraying of cost that adopts of the preparation method of SOFC dielectric substrate, this mainly is because the exploitation of the used for hot spraying electrolyte relevant with this technology does not catch up with.When adopting air plasma spraying to make the ionogen coating, there are pore in traditional electrolyte such as yttria-stabilized zirconia inevitably in the coating, this will cause the leakage of fuel gas and oxygenant.Document points out that its released gas rate at least should be less than 10 as the dielectric substrate that is used for SOFC -6Cm 4G -1S -1(referring to IDET, NAMIKAWAt, YAMAZAKIY[J], Denki Kagaku, 1996,64:681-683), and the released gas rate of YSZ coating that adopts the preparation of conventional hot spray powder is usually greater than this value, in order to utilize the ionogen coating of APS preparation, require spraying high loose density to be arranged with electrolyte, good fluidity is beneficial to the void content that reduces coating.
[summary of the invention]: the present invention seeks to solve existing electrolyte such as yttria-stabilized zirconia, when adopting air plasma spraying to make the ionogen coating, there is pore in the coating inevitably, and cause the problem that fuel gas and oxygenant leak, a kind of preparation method of used for hot spraying zirconia base solid electrolyte material is provided.
Technical scheme of the present invention is by add Y in zirconium white 2O 3, Sc 2O 3, Yb 2O 3Contour oxygen-ion conduction material powder, spray-dried-high temperature sintering is to obtain the used for hot spraying electrolyte of high apparent density.The preparation method of the used for hot spraying electrolyte that the present invention is given is equally applicable to other used for hot spraying electrolyte material system preparation.
The preparation method of used for hot spraying zirconia base solid electrolyte material provided by the invention, its prepared zirconium oxide base electrolyte material is ZrO 2-M 2O 3, wherein, M is any or several among Sm, Y, Sc, Ce, Yb, Al, Er, the Dy, the preparation method comprises following each step:
The first, raw material is prepared: with granularity between 5nm～55 μ m, purity is the ZrO more than 99.9% 2And M 2O 3Be raw material, M is any or several among Sm, Y, Sc, Ce, Yb, Al, Er, the Dy, ZrO 2And M 2O 3The batching mol ratio be 8: 1 to 12: 1, will drop into agitating ball mill according to the raw material of the required preparing product of above stoichiometric ratio weighing;
The second, slurry preparation: institute joins that abrading-ball and raw material ratio are 1: 1～1: 1.5 in the slurry, and used abrading-ball is a zirconia ball; Add deionized water in last step agitating ball mill, the mass ratio of raw material and deionized water is 1: 2～2: 1; Add macromolecular compound simultaneously as binding agent, the binding agent that is added is any in polyvinyl alcohol, polyacrylic acid, Xylo-Mucine or the polyvinylpyrrolidone, its mass percent is 5%～20% of a raw material, and ball milling obtained the suspension slurry in 0.5～10 hour;
Three, spraying drying: adopt drying process with atomizing will go up the suspension slurry that the step obtains and make micron order Conglobation type spherical powder;
Four, powder sintered: as will to go up the Conglobation type spherical powder that obtains of step 500～1600 ℃ of sintering 4～24 hours;
Five, screening: will go up the powder of step behind the sintering and cross 140 orders and 325 mesh sieves, gained 140～325 orders partly are the used for hot spraying zirconium oxide base electrolyte material.
The 3rd step, used spray drying process can be centrifugal or one of press spray desiccating method.The spray-drier inlet temperature is 250～350 ℃, and temperature out is 120～200 ℃, and feeding speed is 20～100ml/min.
Advantage of the present invention and positively effect:
The electrolyte of the inventive method preparation has the loose density height, and good fluidity adopts the coating densification of the ionogen spraying back formation of this method preparation, and void content is low, good stability, ionic conductivity height; This preparation method has that technology is simple simultaneously, turnout is big, economic and reliable, can the industry popularization etc. advantage.
[embodiment]:
Embodiment 1:
1) takes by weighing 10.0kgZrO 2With Y 2O 3Premix powder (ZrO 2With Y 2O 3Mol ratio is 11.5: 1) drop into and stir in the mill, and add polyvinyl alcohol 0.1kg and 10.0kg deionized water, wet-milling 4 hours.
2) the gained slip is sprayed in the drying tower with the centrifugal atomizing nozzle, the spraying gun rotating speed is 1500r/min, 280 ℃ of inlet temperatures, and 170 ℃ of temperature outs will be collected in the dried powder suction cyclonic separator.
3) with powder high temperature sintering furnace internal heating to 1450 ℃ sintering 4 hours.
4) powder behind the sintering is sieved with mechanical sub-sieve, get the powder between 140～325 orders, obtain the used for hot spraying ZrO of densification 2-Y 2O 3Electrolyte.
Embodiment 2:
1) takes by weighing 10.0kgZrO 2With Sm 2O 3Premix powder (ZrO 2With Sm 2O 3Mol ratio is 9: 1) drop into and stir in the mill, and add polyethylene than pyrrolidone 0.1kg and 10.0kg deionized water, wet-milling 6 hours.
2) the gained slip is sprayed in the drying tower with the centrifugal atomizing nozzle, the spraying gun rotating speed is 2000r/min, 300 ℃ of inlet temperatures, and 170 ℃ of temperature outs will be collected in the dried powder suction cyclonic separator.
3) with powder high temperature sintering furnace internal heating to 1500 ℃ sintering 6 hours.
4) powder behind the sintering is sieved with mechanical sub-sieve, get the powder between 140～325 orders, obtain the used for hot spraying ZrO of densification 2-Sm 2O 3Electrolyte
Embodiment 3:
1) takes by weighing 10.0kgZrO 2With Sc 2O 3Premix powder (ZrO 2With Sc 2O 3Mol ratio is 11.5: 1) drop into and stir in the mill, and add Xylo-Mucine 0.1kg and 10.0kg deionized water, wet-milling 4 hours.
2) the gained slip is sprayed in the drying tower with the centrifugal atomizing nozzle, the spraying gun rotating speed is 1800r/min, 350 ℃ of inlet temperatures, and 170 ℃ of temperature outs will be collected in the dried powder suction cyclonic separator.
3) with powder high temperature sintering furnace internal heating to 1450 ℃ sintering 6 hours.
4) powder behind the sintering is sieved with mechanical sub-sieve, get the powder between 140～325 orders, obtain the used for hot spraying ZrO of densification 2-Sc 2O 3Electrolyte.
Embodiment 4:
1) takes by weighing 10.0kg ZrO 2With Yb 2O 3Premix powder (ZrO 2With Yb 2O 3Mol ratio is 11.5: 1) drop into and stir in the mill, and add polyvinyl alcohol 0.1kg and 10.0kg deionized water, wet-milling 4 hours.
2) the gained slip is sprayed in the drying tower with the centrifugal atomizing nozzle, the spraying gun rotating speed is 2000r/min, 350 ℃ of inlet temperatures, and 170 ℃ of temperature outs will be collected in the dried powder suction cyclonic separator.
3) with powder high temperature sintering furnace internal heating to 1500 ℃ sintering 4 hours.
4) powder behind the sintering is sieved with mechanical sub-sieve, get the powder between 140～325 orders, obtain the used for hot spraying ZrO of densification 2-Yb 2O 3Electrolyte.
Embodiment 5:
1) takes by weighing 10.0kgZrO 2With Er 2O 3Premix powder (ZrO 2With Er 2O 3Mol ratio is 10.1: 1) drop into and stir in the mill, and add polyvinyl alcohol 0.1kg and 10.0kg deionized water, wet-milling 8 hours.
2) the gained slip is sprayed in the drying tower with the centrifugal atomizing nozzle, the spraying gun rotating speed is 1800r/min, 300 ℃ of inlet temperatures, and 170 ℃ of temperature outs will be collected in the dried powder suction cyclonic separator.
3) with powder high temperature sintering furnace internal heating to 1500 ℃ sintering 4 hours.
4) powder behind the sintering is sieved with mechanical sub-sieve, get the powder between 140～325 orders, obtain the used for hot spraying ZrO of densification 2-Er 2O 3Electrolyte.
Embodiment 6:
1) takes by weighing 10.0kgZrO 2With Dy 2O 3Premix powder (ZrO 2With Dy 2O 3Mol ratio is 10.1: 1) drop into and stir in the mill, and add polyvinylpyrrolidone 0.1kg and 10.0kg deionized water, wet-milling 8 hours.
2) the gained slip is sprayed in the drying tower with the centrifugal atomizing nozzle, the spraying gun rotating speed is 1500r/min, 300 ℃ of inlet temperatures, and 170 ℃ of temperature outs will be collected in the dried powder suction cyclonic separator.
3) with powder high temperature sintering furnace internal heating to 1450 ℃ sintering 4 hours.
4) powder behind the sintering is sieved with mechanical sub-sieve, get the powder between 140～325 orders, obtain the used for hot spraying ZrO of densification 2-Dy 2O 3Electrolyte.
Embodiment 7:
1) takes by weighing 10.0kg ZrO 2With S C2O 3And Al 2O 3Premix powder (ZrO 2: Sc 2O 3: Al 2O 3Mol ratio 8: 1: 0.1) drops in the stirring mill, and add polyvinylpyrrolidone 0.1kg and 10.0kg deionized water, wet-milling 8 hours.
2) the gained slip is sprayed in the drying tower with the centrifugal atomizing nozzle, the spraying gun rotating speed is 1500r/min, 300 ℃ of inlet temperatures, and 170 ℃ of temperature outs will be collected in the dried powder suction cyclonic separator.
3) with powder high temperature sintering furnace internal heating to 1450 ℃ sintering 4 hours.
4) powder behind the sintering is sieved with mechanical sub-sieve, get the powder between 140～325 orders, obtain the used for hot spraying ZrO of densification 2-11%S C2O 3-1%Al 2O 3Electrolyte.

Claims (5)

1. the preparation method of a used for hot spraying zirconia base solid electrolyte material is characterized in that, prepared zirconium oxide base electrolyte material is ZrO 2-M 2O 3, wherein, M is any among Sm, Y, Sc, Ce, Yb, Al, Er, the Dy, the preparation method comprises following each step:
The first, raw material is prepared: with granularity between 5nm～5 μ m, purity is the ZrO more than 99.9% 2And M 2O 3Be raw material, wherein M is any or several among Sm, Y, Sc, Ce, Yb, Al, Er, the Dy, ZrO 2And M 2O 3The batching mol ratio be 8: 1 to 12: 1, above-mentioned raw materials is dropped into agitating ball mill;
The second, slurry preparation: institute joins that abrading-ball and raw material ratio are 1: 1～1: 1.5 in the slurry, and used abrading-ball is a zirconia ball; Add deionized water in last step agitating ball mill, and add macromolecular compound as binding agent, ball milling obtained the suspension slurry in 0.5～10 hour;
Three, spraying drying: adopt drying process with atomizing will go up the suspension slurry that the step obtains and make micron order Conglobation type spherical powder;
Four, powder sintered: as will to go up the Conglobation type spherical powder that obtains of step 500～1600 ℃ of sintering 4～24 hours;
Five, screening: will go up the powder of step behind the sintering and cross 140 orders and 325 mesh sieves, gained 140～325 orders partly are the used for hot spraying zirconium oxide base electrolyte material.
2. preparation method according to claim 1 is characterized in that the mass ratio of raw material and deionized water in the second step slurry is 1: 2～2: 1.
3. preparation method according to claim 1, it is characterized in that binding agent that second step added in the slurry is any in polyvinyl alcohol, polyacrylic acid, Xylo-Mucine or the polyvinylpyrrolidone, its mass percent is 5%～20% of a raw material.
4. according to right 1 described preparation method, it is characterized in that used spray drying process of the 3rd step is centrifugal or one of press spray desiccating method.
5. according to right 1 described preparation method, it is characterized in that the 3rd one step spray-drying machine inlet temperature is 250～350 ℃, temperature out is 120～200 ℃, and feeding speed is 20～100ml/min.
CNA200710150258XA 2007-11-21 2007-11-21 Preparation method of zirconia-based electrolyte material Pending CN101168486A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106216690A (en) * 2016-08-24 2016-12-14 洛阳金鹭硬质合金工具有限公司 A kind of preparation method of slug type thermal spraying tungsten powder of reuniting
CN108329026A (en) * 2018-03-30 2018-07-27 东北大学 The preparation method of lambda sensor electrolyte layer and fine and close diffusion layer double-layer structure
CN108531842A (en) * 2018-05-04 2018-09-14 广东省新材料研究所 The preparation method of ultrathin nanometer SOFC electrolyte layers
CN110061274A (en) * 2012-11-20 2019-07-26 博隆能源股份有限公司 The Zirconia electrolytic composition of doped scandia stabilized
CN112430087A (en) * 2020-11-26 2021-03-02 安徽盈锐优材科技有限公司 Preparation method of zirconia-based solid electrolyte material for thermal spraying
CN113773076A (en) * 2021-09-26 2021-12-10 苏州正义新能源科技有限公司 Fuel cell electrolyte membrane with low sintering temperature and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110061274A (en) * 2012-11-20 2019-07-26 博隆能源股份有限公司 The Zirconia electrolytic composition of doped scandia stabilized
CN106216690A (en) * 2016-08-24 2016-12-14 洛阳金鹭硬质合金工具有限公司 A kind of preparation method of slug type thermal spraying tungsten powder of reuniting
CN108329026A (en) * 2018-03-30 2018-07-27 东北大学 The preparation method of lambda sensor electrolyte layer and fine and close diffusion layer double-layer structure
CN108531842A (en) * 2018-05-04 2018-09-14 广东省新材料研究所 The preparation method of ultrathin nanometer SOFC electrolyte layers
CN112430087A (en) * 2020-11-26 2021-03-02 安徽盈锐优材科技有限公司 Preparation method of zirconia-based solid electrolyte material for thermal spraying
CN113773076A (en) * 2021-09-26 2021-12-10 苏州正义新能源科技有限公司 Fuel cell electrolyte membrane with low sintering temperature and preparation method thereof

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