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 PDFInfo
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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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- 239000000446 fuel Substances 0.000 title claims abstract description 53
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 50
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 48
- 239000003792 electrolyte Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002253 acid Substances 0.000 title claims description 11
- 150000003839 salts Chemical class 0.000 title claims description 10
- 239000000843 powder Substances 0.000 claims abstract description 48
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 16
- 238000005516 engineering process Methods 0.000 claims abstract description 16
- 239000000428 dust Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000011109 contamination Methods 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 5
- 229940075613 gadolinium oxide Drugs 0.000 claims description 5
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 5
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229940075630 samarium oxide Drugs 0.000 claims description 4
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 16
- 239000000243 solution Substances 0.000 abstract description 11
- 230000009466 transformation Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 230000002035 prolonged effect Effects 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- -1 rare earth oxygen Compound Chemical class 0.000 description 5
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B82—NANOTECHNOLOGY
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
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
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.
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Cited By (2)
| 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 its preparation method |
| 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 (3)
| 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 its preparation method |
| CN116023133B (en) * | 2021-10-26 | 2024-04-05 | 国家能源投资集团有限责任公司 | Composite zirconium oxide 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 |