CN108288723A - A kind of fuel cell nano rare earth zirconic acid salt electrolyte and preparation method - Google Patents

A kind of fuel cell nano rare earth zirconic acid salt electrolyte and preparation method Download PDF

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CN108288723A
CN108288723A CN201810093141.0A CN201810093141A CN108288723A CN 108288723 A CN108288723 A CN 108288723A CN 201810093141 A CN201810093141 A CN 201810093141A CN 108288723 A CN108288723 A CN 108288723A
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陈庆
廖健淞
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Chengdu New Keli Chemical Science Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The present invention proposes a kind of fuel cell nano rare earth zirconates electrolyte preparation method, rare earth oxide is dissolved in dust technology uniformly to mix with zirconium oxychloride solution, solution is mixed into excessive ammonia, gel rubber material aqueous solution is obtained by being co-precipitated, being aged, dispersion grinding is impregnated using alcohol to filter residue after filtering, then carries out low temperature presintering, remaining ammonium ion is set to be desorbed, high temperature sintering is finally carried out, and keeps the temperature 4h at 1500 DEG C or more, nanometer phase rare earth zirconate ceramic powder is obtained after cooling.The present invention provides the above method and solves traditional pyrochlore constitution ceramic post sintering difficulty, easily to ordering phase transformation when middle warm working, the powder problem serious in preparation process reunion degree makes the membrane material of preparation can be with homogeneous film formation, its mechanical property and toughness are higher, to improve electrolyte service life.

Description

A kind of fuel cell nano rare earth zirconic acid salt electrolyte and preparation method
Technical field
The present invention relates to fuel cell material fields, and in particular to a kind of fuel cell nano rare earth zirconic acid salt electrolyte And preparation method.
Background technology
Fuel cell is a kind of energy conversion device based on redox reaction.It can be direct by the chemical energy of fuel It is converted to electric energy, carnot's cycle process is not undergone in conversion process, effect more higher than conventional heat engines electricity generation system can be obtained Rate, have many advantages, such as efficiently, it is low noise, environmental-friendly and safe and reliable.
Fuel cell can be divided into alkaline fuel cell, phosphate fuel electricity by the property of fuel cell electrolyte Pond, molten carbonate fuel cell, Proton Exchange Membrane Fuel Cells and solid oxide fuel cell.With other four kinds of fuel electricity Pond is compared, and solid oxide fuel cell has its unique advantage.First, higher operating temperature has widened the choosing of fuel gas Range is selected, the alkane class A fuel A of relative low price can be reformed in inside battery, oxidation produces electricl energy.Second, solid oxidation A large amount of waste heat is generated when object operation of fuel cells, Co-generation may be implemented, and improves the efficiency of electricity generation system.Third, solid Oxide fuel cell is structure of whole solid state, can mutually be corroded to avoid between battery component existing for other kind of types of fuel cells The problem of.
Main three big component of solid oxide fuel cell is anode, electrolyte and cathode respectively.Wherein, electrolyte is The most crucial component of solid oxide fuel cell, solid-oxide fuel battery electrolyte material, which should meet the following, to be wanted It asks：Good ionic conductivity and simple ionic conductivity（Close to 1 transference number of ions）；In high temperature and redox condition Physics and chemical stability；Air-tightness；Chemical compatibility between electrode；High temperature thermal matching between electrode；Heat The coefficient of expansion matches；Superior performance is cheap.
Pyrochlore constitution has good ionic conductivity high as solid oxide fuel cell electrolyte film, by section Grind the extensive research of worker.Zirconium base pyrochlore system oxide（Ln2ZrO7 , Ln=La、Nd、Gd、Sm）Object has some special Electrical property, in oxygen atmosphere, ionic conductivity when 400-800 DEG C of medium temperature has been more than the zirconium oxide of stabilized with yttrium oxide, in water Proton conductive behavior is shown under vapour-saturated hydrogen atmosphere, it is therein by low price ion such as rare earth or alkaline-earth metal, substitution After rare earth element, conductivity increases, and proton conductivity can be compared with perovskite structure proton conductive oxide, but transition temperature It is lower.However rare earth zirconate is a kind of difficult synthetic material.
Solid phase method (solid-state reaction method, SSM) is by two or more metal salt or metal Oxide is stoichiometrically sufficiently mixed, and calcining occurs solid phase reaction and obtains target product at a certain temperature after grinding, It is the common method for preparing pyrochlore type multiple oxide.When preparing pyrochlore-type compound, oxide raw material and rare earth oxygen Compound（Ln2O3）Deng usually being reacted 1 to 2 days at 1500 DEG C, reacting needs at relatively high temperatures, the longer reaction time, gained The particle size arrived is larger, and Young's modulus is larger after preparing film forming, and the toughness of membrane material is poor, easily opens in use It splits, embrittlement, to seriously affect its service life.Therefore, new synthetic method is found, the performance for improving material has weight The meaning wanted.
Chinese invention patent application number 201210221957.X discloses a kind of preparation side of pyrochlore type rare-earth zirconate Method, uses rare earth nitrades, zirconium nitrate and a small amount of fluxing agent for raw material, and ground and mixed is placed directly in Muffle furnace in a constant temperature The lower calcination of degree for a period of time, can be obtained single-phase product pyrochlore type rare-earth zirconate, the pyrochlore of preparation after washing, drying Type rare earth zirconate purity, crystallinity, thermal stability are very high, still, as electrolyte membrane for fuel cell material, need to make The electric conductivity of standby pyrochlore constitution oxonium ion is higher, and the pyrochlore constitution directly prepared with this solution is not appropriate for directly making It is used for fuel battery electrolyte material, it is still desirable to which new process program improves material property.
It is therefore proposed that a kind of process program is simply controllable, effectively overcome traditional pyrochlore constitution ceramic post sintering difficult, medium temperature When processing easily to ordering phase transformation, the powder problem serious in preparation process reunion degree, for the mechanical property of its membrane material Improving has highly important practical significance.
Invention content
For traditional pyrochlore constitution ceramic post sintering difficulty, easily to ordering phase transformation when middle warm working, prepared by powder The serious problem of Cheng Tuanju degree, the present invention provide a kind of fuel cell nano rare earth zirconic acid salt electrolyte and preparation method, The membrane material of preparation can be with homogeneous film formation, and mechanical property and toughness are higher, to improve its service life.
To solve the above problems, the present invention uses following technical scheme：A kind of fuel cell nano rare earth zirconates electricity The preparation method for solving matter, uses rare earth oxide, zirconium oxychloride for raw material, and ammonium hydroxide is alkaline precipitating agent, and high temperature sintering is made, Specific preparation method is as follows：
（1）Weigh 30-40 mass parts RE oxide powders, 28-37 mass parts zirconium oxychlorides powder, the dilute nitre of 100 mass parts Acid and 120 mass parts ammonium hydroxide are spare；
（2）The rare earth oxide is added in dust technology, is stirred continuously, until completely dissolved, zirconium oxychloride powder is added, Uniformly mixing stands 2-3 hours, obtains hybrid ionic clear liquid；
（3）Under protective atmosphere, excessive ammonia is added to the hybrid ionic clear liquid, what reaction was co-precipitated for 30-150 minutes Filter residue is passed through soaked in absolute ethyl alcohol by rare earth zirconium gel rubber material by ageing 12-20 hours after suction filtration, and ball mill grinding obtains To precursor pulp；
（4）The precursor pulp is subjected to double sintering, first low temperature presintering, sintering temperature is 300-450 DEG C, and sintering time is 2-3 hours, then temperature is increased to 1500 DEG C, 4 hours are kept the temperature, nanometer phase rare earth zirconate ceramics are obtained after cooled to room temperature Powder.
Preferably, the rare earth oxide is one or both of gadolinium oxide, samarium oxide, and the zirconium oxychloride is eight Water zirconium oxychloride or six water zirconium oxychloride powders.
Preferably, a concentration of 1-1.5mol/L of the dust technology, the ammonium hydroxide are ammonia volumetric concentration 18-25%'s Ammonium hydroxide.
Preferably, the stirring frequency is 100-300rpm, keeps temperature to be no more than 45 DEG C in whipping process, the ball milling The rotating speed of machine is controlled in 800-1200rpm, and the time control of ball milling was at 2-5 hours.
Preferably, the protective atmosphere gas is one kind in argon gas, nitrogen, helium atmosphere.
Preferably, the Aging Temperature is 60-70 DEG C.
Preferably, step（4）Described in be sintered heating rate control be 1-3K/min.
Preferably, acid-base neutralization processing is carried out to tail gas in the high-temperature sintering process, avoids decomposing the gas dirt generated Contaminate air.
A kind of fuel cell nano rare earth zirconic acid salt electrolyte is provided, is made of the above method, the rare earth zirconate Electrolyte is nanometer phase rare earth zirconate ceramic powder, and grain size is 8-20 nanometers, and bending strength is 80-124 MPa, and fracture is tough Property 400-670 MPa.
For traditional pyrochlore constitution ceramic post sintering difficulty, easily to ordering phase transformation when middle warm working, prepared by powder The serious problem of Cheng Tuanju degree, the present invention provide a kind of fuel cell nano rare earth zirconic acid salt electrolyte and preparation method, Rare earth oxide is dissolved in dust technology uniformly to mix with zirconium oxychloride solution, solution is mixed into excessive ammonia, by being co-precipitated, Ageing obtains gel rubber material aqueous solution, impregnates dispersion grinding using alcohol to filter residue after filtering, then carries out low temperature presintering, make residual The ammonium ion desorption stayed, finally carries out high temperature sintering, and 4h is kept the temperature at 1500 DEG C or more, and nanometer phase rare earth zirconium is obtained after cooling Hydrochlorate ceramic powder.Since the electric conductivity of oxonium ion in its pyrochlore constitution depends on oxonium ion disordering degree, pass through doping And high temperature（1500 DEG C of ＞）Sintering form the class fluorite structure of disordered structure after, by cation disordering promote anion without Sequence, to improve the diffusion rate of oxonium ion.It is higher that the lattice of nanosizing can be such that powder body material shows at low temperature Toughness reduces the difficulty of processing of membrane material and the mechanical property of film forming.
The present invention provides a kind of fuel cell nano rare earth zirconic acid salt electrolyte and preparation method, with prior art phase Than the feature and excellent effect protruded is：
1, the present invention proposes a kind of fuel cell nano rare earth zirconates electrolyte preparation method, is burnt by doping and high temperature Knot form the class fluorite structure of disordered structure after, by cation disordering promote anion disordering, to improve oxygen from The diffusion rate of son, it is difficult that the present invention solves traditional pyrochlore constitution ceramic post sintering, easily to ordering phase transformation when middle warm working, The powder problem serious in preparation process reunion degree makes the membrane material of preparation that can reduce sintering difficulty with homogeneous film formation.
2, the lattice crystal grain of nanosizing prepared by the present invention is tiny, and no dephasign can make nano rare earth zirconic acid salt electrolyte Powder body material shows higher toughness at low temperature, reduces the difficulty of processing of membrane material and the mechanical property of film forming, improves thin The mechanical property and toughness of film, to extend the service life of electrolyte.
3, present invention process method is simple, and the membrane structure of preparation is uniform, and performance is stablized, and manufacturing cost is reduced, and pushes The development of pyrochlore constitution dielectric film application.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）Weigh 30 mass parts samarium oxide powders, 37 mass parts, eight water zirconium oxychloride powder, 100 mass parts dust technologies and 120 Mass parts ammonia volumetric concentration is spare in 18% ammonium hydroxide；
（2）The rare earth oxide is added in 1mol/L dust technologies, is stirred continuously, stirring frequency 300rpm, whipping process Middle holding temperature is no more than 45 DEG C, until completely dissolved, eight water zirconium oxychloride powders is added, uniformly mix, stand 2 hours, Obtain hybrid ionic clear liquid；
（3）Under argon atmosphere, excessive ammonia is added to the hybrid ionic clear liquid, reaction is co-precipitated for 150 minutes Rare earth zirconium gel rubber material be aged within 12 hours through being excessively 60 DEG C, filter residue passed through into soaked in absolute ethyl alcohol, ball milling after suction filtration Machine is ground, and obtains precursor pulp；
（4）The precursor pulp is subjected to double sintering, first low temperature presintering, sintering temperature is 450 DEG C, and sintering time is 2 small When, then temperature is increased to 1500 DEG C, heating rate control is 1K/min, keeps the temperature 4 hours, grain size is obtained after cooled to room temperature For 20 nanometers of nanometer phase rare earth zirconate ceramic powder, acid-base neutralization processing is carried out to tail gas in warm sintering process, is avoided point Solve the gaseous contamination air generated.
100g powder body materials are added in the water containing dispersant, for 24 hours, the PVA solution of 9wt% is added in ball milling, PP and the third two Alcohol is mixed into uniform sizing material and is stirred, and obtained slurry is prolonged stream naturally, is surveyed to mechanical property and conductivity after dry Examination, is sintered together with membrane electrode after test, is assembled into fuel cell, hydrogen is fuel, and air is oxidant, is in test temperature Under the conditions of 400 DEG C, record parameter is as shown in table 1.
Embodiment 2
（1）Weigh 35 mass parts gadolinium oxide powders, 32 mass parts, six water zirconium oxychloride powder, 100 mass parts dust technologies and 120 Mass parts ammonia volumetric concentration is spare in 19% ammonium hydroxide；
（2）The rare earth oxide is added in 1.3mol/L dust technologies, is stirred continuously, stirring frequency 300rpm is stirred It keeps temperature to be no more than 45 DEG C in journey, until completely dissolved, six water zirconium oxychloride powders is added, uniformly mix, it is small to stand 2 When, obtain hybrid ionic clear liquid；
（3）Under helium protective atmosphere, excessive ammonia is added to the hybrid ionic clear liquid, what reaction was co-precipitated for 50 minutes Rare earth zirconium gel rubber material is aged through being excessively 62 DEG C, filter residue is passed through soaked in absolute ethyl alcohol, ball mill after suction filtration for 20 hours Grinding, obtains precursor pulp；
（4）The precursor pulp is subjected to double sintering, first low temperature presintering, sintering temperature is 320 DEG C, sintering time 2.4 Hour, then temperature is increased to 1500 DEG C, heating rate control is 3K/min, keeps the temperature 4 hours, grain is obtained after cooled to room temperature Diameter is 8 nanometers of nanometer phase rare earth zirconate ceramic powder, and acid-base neutralization processing is carried out to tail gas in warm sintering process, is avoided point Solve the gaseous contamination air generated.
120g powder body materials are added in the water containing dispersant, for 24 hours, the PVA solution of 9wt% is added in ball milling, PP and the third two Alcohol is mixed into uniform sizing material and is stirred, and obtained slurry is prolonged stream naturally, is surveyed to mechanical property and conductivity after dry Examination, is sintered together with membrane electrode after test, is assembled into fuel cell, hydrogen is fuel, and air is oxidant, is in test temperature Under the conditions of 400 DEG C, record parameter is as shown in table 1.
Embodiment 3
（1）Weigh 35 mass parts samarium oxide powders, 33 mass parts, six water zirconium oxychloride powder, 100 mass parts dust technologies and 120 Mass parts ammonia volumetric concentration is spare in 19% ammonium hydroxide；
（2）The rare earth oxide is added in 1.4mol/L dust technologies, is stirred continuously, stirring frequency 210rpm is stirred It keeps temperature to be no more than 45 DEG C in journey, until completely dissolved, six water zirconium oxychloride powders is added, uniformly mix, it is small to stand 2.7 When, obtain hybrid ionic clear liquid；
（3）Under nitrogen protection atmosphere, excessive ammonia is added to the hybrid ionic clear liquid, what reaction was co-precipitated for 50 minutes Rare earth zirconium gel rubber material is aged through being excessively 66 DEG C, filter residue is passed through soaked in absolute ethyl alcohol, ball mill after suction filtration for 20 hours Grinding, obtains precursor pulp；
（4）The precursor pulp is subjected to double sintering, first low temperature presintering, sintering temperature is 450 DEG C, sintering time 2.4 Hour, then temperature is increased to 1500 DEG C, heating rate control is 2K/min, keeps the temperature 4 hours, grain is obtained after cooled to room temperature Diameter is 16 nanometers of nanometer phase rare earth zirconate ceramic powder, carries out acid-base neutralization processing to tail gas in warm sintering process, avoids Decompose the gaseous contamination air generated.
140g powder body materials are added in the water containing dispersant, for 24 hours, the PVA solution of 9wt% is added in ball milling, PP and the third two Alcohol is mixed into uniform sizing material and is stirred, and obtained slurry is prolonged stream naturally, is surveyed to mechanical property and conductivity after dry Examination, is sintered together with membrane electrode after test, is assembled into fuel cell, hydrogen is fuel, and air is oxidant, is in test temperature Under the conditions of 400 DEG C, record parameter is as shown in table 1.
Embodiment 4
（1）Weigh 32 mass parts gadolinium oxide powders, 29 mass parts, six water zirconium oxychloride powder, 100 mass parts dust technologies and 120 Mass parts ammonia volumetric concentration is spare in 25% ammonium hydroxide；
（2）The rare earth oxide is added in 1.4mol/L dust technologies, is stirred continuously, stirring frequency 120rpm is stirred It keeps temperature to be no more than 45 DEG C in journey, until completely dissolved, six water zirconium oxychloride powders is added, uniformly mix, it is small to stand 2.1 When, obtain hybrid ionic clear liquid；
（3）Under nitrogen protection atmosphere, excessive ammonia is added to the hybrid ionic clear liquid, reaction is co-precipitated for 135 minutes Rare earth zirconium gel rubber material be aged within 20 hours through being excessively 67 DEG C, filter residue passed through into soaked in absolute ethyl alcohol, ball milling after suction filtration Machine is ground, and obtains precursor pulp；
（4）The precursor pulp is subjected to double sintering, first low temperature presintering, sintering temperature is 350 DEG C, sintering time 2.4 Hour, then temperature is increased to 1500 DEG C, heating rate control is 3K/min, keeps the temperature 4 hours, grain is obtained after cooled to room temperature Diameter is 12 nanometers of nanometer phase rare earth zirconate ceramic powder, carries out acid-base neutralization processing to tail gas in warm sintering process, avoids Decompose the gaseous contamination air generated.
160g powder body materials are added in the water containing dispersant, for 24 hours, the PVA solution of 9wt% is added in ball milling, PP and the third two Alcohol is mixed into uniform sizing material and is stirred, and obtained slurry is prolonged stream naturally, is surveyed to mechanical property and conductivity after dry Examination, is sintered together with membrane electrode after test, is assembled into fuel cell, hydrogen is fuel, and air is oxidant, is in test temperature Under the conditions of 400 DEG C, record parameter is as shown in table 1.
Embodiment 5
（1）40 mass parts samarium oxides and gadolinium oxide powder are weighed, 28 mass parts, eight water zirconium oxychloride powder, 100 mass parts are dilute Nitric acid and 120 mass parts ammonia volumetric concentrations are spare in 25% ammonium hydroxide；
（2）The rare earth oxide is added in 1.5mol/L dust technologies, is stirred continuously, stirring frequency 100rpm is stirred It keeps temperature to be no more than 45 DEG C in journey, until completely dissolved, eight water zirconium oxychloride powders is added, uniformly mix, it is small to stand 3 When, obtain hybrid ionic clear liquid；
（3）Under argon atmosphere, excessive ammonia is added to the hybrid ionic clear liquid, reaction is co-precipitated for 125 minutes Rare earth zirconium gel rubber material be aged within 15 hours through being excessively 70 DEG C, filter residue passed through into soaked in absolute ethyl alcohol, ball milling after suction filtration Machine is ground, and obtains precursor pulp；
（4）The precursor pulp is subjected to double sintering, first low temperature presintering, sintering temperature is 300 DEG C, sintering time 2.7 Hour, then temperature is increased to 1500 DEG C, heating rate control is 1.5K/min, keeps the temperature 4 hours, is obtained after cooled to room temperature Grain size is 16 nanometers of nanometer phase rare earth zirconate ceramic powder, carries out acid-base neutralization processing to tail gas in warm sintering process, keeps away Exempt to decompose the gaseous contamination air generated.
200g powder body materials are added in the water containing dispersant, for 24 hours, the PVA solution of 9wt% is added in ball milling, PP and the third two Alcohol is mixed into uniform sizing material and is stirred, and obtained slurry is prolonged stream naturally, is surveyed to mechanical property and conductivity after dry Examination, is sintered together with membrane electrode after test, is assembled into fuel cell, hydrogen is fuel, and air is oxidant, is in test temperature Under the conditions of 400 DEG C, record parameter is as shown in table 1.
Comparative example
Raw material rare earth nitrades, zirconium nitrate or zirconyl nitrate and fluxing agent are placed according to a certain ratio in mortar be fully ground or in Ball milling in ball mill is then placed in Muffle furnace with 10oThe heating rate of C/min is warming up to 1400 oC, it is small to keep the temperature 60 When, it cools to room temperature with the furnace, after drying is washed with deionized, obtains rare earth zirconate electrolyte powder material.By 100g powder Body material is added in the water containing dispersant, and ball milling for 24 hours, is added the PVA solution of 9wt%, PP and propylene glycol, is mixed into uniform sizing material It is stirred, obtained slurry is prolonged into stream naturally, conductivity is tested after dry, is sintered together with membrane electrode after test, It is assembled into fuel cell, hydrogen is fuel, and air is oxidant, under the conditions of test temperature is 400 DEG C, record parameter such as table 1 It is shown.
Table 1:
Bending strength MPa Fracture toughness MPa Conductivity（S/cm） Open-circuit voltage（V） Electric current（A）
Embodiment 1 85 420 0.85 1.81 18
Embodiment 2 80 400 0.92 1.74 25
Embodiment 3 92 510 0.91 1.89 21
Embodiment 4 103 600 0.80 1.67 16
Embodiment 5 124 670 0.82 1.78 19
Comparative example 52 95 0.04 0.64 9.2

Claims (9)

1. a kind of fuel cell nano rare earth zirconates electrolyte preparation method, which is characterized in that using rare earth oxide, Zirconium oxychloride is raw material, and ammonium hydroxide is alkaline precipitating agent, and high temperature sintering is made, and specific preparation method is as follows：
（1）Weigh 30-40 mass parts RE oxide powders, 28-37 mass parts zirconium oxychlorides powder, the dilute nitre of 100 mass parts Acid and 120 mass parts ammonium hydroxide are spare；
（2）The rare earth oxide is added in dust technology, is stirred continuously, until completely dissolved, zirconium oxychloride powder is added, Uniformly mixing stands 2-3 hours, obtains hybrid ionic clear liquid；
（3）Under protective atmosphere, excessive ammonia is added to the hybrid ionic clear liquid, what reaction was co-precipitated for 30-150 minutes Filter residue is passed through soaked in absolute ethyl alcohol by rare earth zirconium gel rubber material by ageing 12-20 hours after suction filtration, and ball mill grinding obtains To precursor pulp；
（4）The precursor pulp is subjected to double sintering, first low temperature presintering, sintering temperature is 300-450 DEG C, and sintering time is 2-3 hours, then temperature is increased to 1500 DEG C, 4 hours are kept the temperature, nanometer phase rare earth zirconate ceramics are obtained after cooled to room temperature Powder.
2. a kind of fuel cell nano rare earth zirconates electrolyte preparation method as described in claim 1, feature exist In the rare earth oxide is one or both of gadolinium oxide, samarium oxide, and the zirconium oxychloride is eight water zirconium oxychlorides Or six water zirconium oxychloride powder.
3. a kind of fuel cell nano rare earth zirconates electrolyte preparation method as described in claim 1, feature exist In a concentration of 1-1.5mol/L of the dust technology, the ammonium hydroxide is ammonium hydroxide of the ammonia volumetric concentration in 18-25%.
4. a kind of fuel cell nano rare earth zirconates electrolyte preparation method as described in claim 1, feature exist In the stirring frequency is 100-300rpm, keeps temperature to be no more than 45 DEG C in whipping process, the rotating speed of the ball mill controls In 800-1200rpm, the time control of ball milling was at 2-5 hours.
5. a kind of fuel cell nano rare earth zirconates electrolyte preparation method as described in claim 1, feature exist In the protective atmosphere gas is one kind in argon gas, nitrogen, helium atmosphere.
6. a kind of fuel cell nano rare earth zirconates electrolyte preparation method as described in claim 1, feature exist In the Aging Temperature is 60-70 DEG C.
7. a kind of fuel cell nano rare earth zirconates electrolyte preparation method as described in claim 1, feature exist In step（4）Described in be sintered heating rate control be 1-3K/min.
8. a kind of fuel cell nano rare earth zirconates electrolyte preparation method as described in claim 1, feature exist In, to tail gas progress acid-base neutralization processing in the high-temperature sintering process, the gaseous contamination air for avoiding decomposition from generating.
9. a kind of fuel cell nano rare earth zirconic acid salt electrolyte, which is characterized in that described in any claims of claim 1-9 Method be made, the rare earth zirconate electrolyte is nanometer phase rare earth zirconate ceramic powder, and grain size is 8-20 nanometer, anti- Curved intensity is 80-124 MPa, fracture toughness 400-670 MPa.
CN201810093141.0A 2018-01-31 2018-01-31 A kind of fuel cell nano rare earth zirconic acid salt electrolyte and preparation method Withdrawn CN108288723A (en)

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CN116023133A (en) * 2021-10-26 2023-04-28 国家能源投资集团有限责任公司 Composite zirconia powder and preparation method thereof
CN116514541A (en) * 2023-05-09 2023-08-01 有研资源环境技术研究院(北京)有限公司 Preparation method of composite ceramic absorber material and application of material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116023133A (en) * 2021-10-26 2023-04-28 国家能源投资集团有限责任公司 Composite zirconia powder and preparation method thereof
CN116023133B (en) * 2021-10-26 2024-04-05 国家能源投资集团有限责任公司 Composite zirconia powder and preparation method thereof
CN116514541A (en) * 2023-05-09 2023-08-01 有研资源环境技术研究院(北京)有限公司 Preparation method of composite ceramic absorber material and application of material

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Application publication date: 20180717