CN108695532A - High stability adulterates strontium cerate/cerium acid zirconium-alkali metal salt composite electrolyte and preparation method thereof - Google Patents

High stability adulterates strontium cerate/cerium acid zirconium-alkali metal salt composite electrolyte and preparation method thereof Download PDF

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CN108695532A
CN108695532A CN201710233110.6A CN201710233110A CN108695532A CN 108695532 A CN108695532 A CN 108695532A CN 201710233110 A CN201710233110 A CN 201710233110A CN 108695532 A CN108695532 A CN 108695532A
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doping
strontium cerate
alkali metal
metal salt
composite electrolyte
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CN108695532B (en
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王洪涛
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Hefei Longzhi Electromechanical Technology Co ltd
Fuyang Normal University
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Fuyang Normal University
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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
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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Abstract

The present invention provides a kind of doping strontium cerate/cerium acid zirconium-alkali metal salt composite electrolytes, first, by the way that further rare earth doped cation obtains high stability high conductivity doping SrCeO in strontium cerate/cerium acid zirconium solid solution material3/SrZrO3Solid solution, it is prepared by sol-gal process, it is carried out under middle low temperature with alkali metal salt again compound, obtained composite electrolyte has excellent chemical stability and conductivity, it is greatly lowered with the operating temperature of the oxidation of solid fuels object battery of its making, and stable output power density can be maintained in a long time.

Description

High stability adulterates strontium cerate/cerium acid zirconium-alkali metal salt composite electrolyte and its preparation Method
Technical field
The invention belongs to the development fields of Solid Oxide Fuel Cells, are related to a kind of suitable for solid oxide fuel High stability doping strontium cerate/cerium acid zirconium-alkali metal salt composite electrolyte of battery and preparation method thereof.
Background technology
Solid oxide fuel cell (SOFC) efficient, clean can convert chemical energy to electric energy and be learned to obtain research The extensive research of person.SOFC electrolytes make the operating temperature of SOFC high at present, so high generally at 1000 DEG C or more Temperature brings a series of problem to the commercialization of SOFC:(1) battery critical material selection has larger limitation;(2) Battery pile sealing is difficult;(3) under hot conditions, electrode material microstructure is easily varied, and is lost so as to cause electrode material performance Effect, leads to battery performance fast decay.(600~800 DEG C) operation trend of middle low temperature of SOFC become inevitable.But with electricity The conductivity of the middle low temperature of pond operation temperature, electrolyte declines, and increases the ohmic loss of battery, has seriously affected electricity The chemical property in pond.
The study found that being expected to the SrCeO adulterated as the positive trivalent rare earth element of SOFC electrolyte3Or BaCeO3In high temperature Down have excellent proton conductive, but its in middle low temperature conductivity usually 10-4~10-3S·cm-1.Meanwhile positive three The rare earth doped SrCeO of valence3Or BaCeO3Electrolyte is easy to decompose with carbon dioxide reaction, and chemical stability is not high, cannot Meet the business application of SOFC.
It would therefore be highly desirable to develop one kind, with electrochemical properties, good, performance is stablized under middle cryogenic conditions, and preparation method The electrolyte of easy-to-use solid oxide fuel cell.
Invention content
To solve the above-mentioned problems, present inventor has performed sharp studies, as a result, it has been found that:By trivalent rare earth element and zirconium (Zr) strontium cerate (SrCeO adulterated3) compound with the eutectic progress of alkali metal salt, obtained compound is used as the electrolysis of SOFC Matter can significantly reduce the operating temperature of solid fuel cell, and the SOFC being assembled by it is in a long time (at least 40h) Output power density, current density, conductivity significantly increase and can stablize and continue, so as to complete the present invention.
The purpose of the present invention is to provide following aspect:
The first aspect of the present invention provides a kind of doping strontium cerate-alkali metal salt composite electrolyte, the doping cerium acid Strontium is that positive trivalent rare earth element adulterates strontium cerate, and the alkali metal salt is alkali metal chloride.
Preferably, also doped with zirconium in the doping strontium cerate;
The positive trivalent rare earth element is indicated with M, is selected from Y3+,Lu3+,Eu3+And Tm3+Any one, the doping strontium cerate Chemical composition be SrCe(1-x-y)ZrxMyO3-α, wherein 0.20≤x≤0.60,0≤y≤0.20,0≤α≤0.1.
The second aspect of the present invention also provides a kind of side preparing above-mentioned doping strontium cerate-alkali metal salt composite electrolyte Method, wherein the described method comprises the following steps:
1) doping strontium cerate is mixed with alkali metal salt, is suppressed, obtain compound precursor;
2) calcining step 1) obtained compound precursor, doping strontium cerate-alkali metal salt composite electrolyte is made.
According to a kind of high stability doping strontium cerate/cerium acid zirconium-alkali metal salt composite electrolyte provided by the invention and its Preparation method has the advantages that:
(1) doped with zirconium in heretofore described doping strontium cerate, by the way that doping can be improved with the parts Zr substitution Ce SrCeO3The chemical stability of material, to obtain the proton conductor with high conductance and good chemical stability.
(2) present invention prepares doping strontium cerate by sol-gal process, and reactant dissolves in the solution, can reach molecule Or the dispersion of atomic level, calcination temperature have a larger reduction than conventional solid reaction method, prepared powder have purity it is high, Granularity fine uniform, the features such as calcination temperature is low, are conducive to the raising of conductivity or chemical stability.
(3) through the invention in the composite electrolyte compactness for preparing of method it is high, without hole, airtight permeable, grain size is equal It is even consistent, be conducive to the raising of battery safety.
(4) conductivity for the composite electrolyte that through the invention prepared by middle method reaches 1.27 × 10-1S.cm-1;By its group The H dressed up2/O2Fuel cell, temperature be 700 DEG C when, open-circuit voltage 1.07V, fuel cell in a long time, output power Density is up to 0.57~0.58Wcm-2, current density is up to 0.89~0.90Acm-2, voltage maintains 0.63~0.65V.
Description of the drawings
Fig. 1 shows that the XRD spectrum of sample is made in embodiment 1;
Fig. 2 shows the surface topography electron microscopes that sample is made in embodiment 1;
Fig. 3 shows that the cross-section morphology electron microscope of sample is made in embodiment 1;
Fig. 4 shows that sample is made at 700 DEG C in embodiment 1, the Conductivity Results in air atmosphere;
Fig. 5 shows to be assembled into H with composite electrolyte made from embodiment 12/O2Fuel cell, I- under the conditions of 700 DEG C V-P relational graphs.
Specific implementation mode
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations It is clear, clear.
The study found that doping SrCeO3There is proton conductivity of phosphoric acid, so in hydrogeneous at a higher temperature or vapour atmosphere And the doping SrCeO being prepared by dry-pressing-cofiring method or high temperature solid-state method3The conductivity of proton conductor is not high, limitation Its application on H-SOFC.In doping SrCeO3The middle ionic conductivity for introducing inorganic salts and can effectively improve material, from And excellent electric conductivity is obtained at a lower temperature.However the type of inorganic salts is various, selects which kind of inorganic salts and its addition Amount is to influence doping SrCeO3An important factor for salt composite electrolyte electrical property.
The first aspect of the present invention as a result, provides a kind of doping strontium cerate-alkali metal salt composite electrolyte, wherein described It is that positive trivalent rare earth element adulterates strontium cerate to adulterate strontium cerate, and the alkali metal salt is alkali metal chloride.
It has been investigated that the doping SrCeO after addition alkali metal inorganic salts3Conductivity improved, alkali metal salt is Promoted apparent relative to otheralkali metal salt, conductivity when alkali metal chloride.Preferably, alkali metal salt is at least two alkali gold Belong to the eutectic of hydrochloride, more preferable alkali metal salt is the eutectic of potassium chloride and sodium chloride, mole of potassium chloride and sodium chloride The ratio between amount is 1:1, wherein the mole of potassium chloride is with the molar amount of wherein potassium element, and the mole of sodium chloride is with wherein sodium The molar amount of element.
In the present invention, the positive trivalent rare earth element is with M3+It indicates, is selected from Y3+,Lu3+,Eu3+And Tm3+Any one, it is excellent It is selected as Eu3+.Rare earth doped SrCeO3In, M3+Replace Ce4+More Lacking oxygens (being indicated with Vo 〃) are produced, to So that doping strontium cerate is carried out defect qualitative, there is preferable proton conductivity.
In the present invention, the chemical composition for adulterating strontium cerate is SrCe(1-y)MyO3-α, wherein 0≤y≤0.20,0≤α≤ 0.1, y is positive trivalent rare earth element M3+The doping of solid solution is formed, α represents the Lacking oxygen number of each doping strontium cerate unit. For the SrCe after doping(1-y)MyO3-α, y is bigger, and Lacking oxygen is more, and electric conductivity is better;But with the increase of y, work as y When > 0.2, start the diffraction maximum for dephasign occur, illustrates that the rare earth element of incorporation is not completely dissolved into SrCeO3Lattice in, can not Obtain the electrolyte of single crystalline phase, SrCe(1-y)MyO3-αStability it is low, sintering temperature is higher.Y is smaller, adulterates and is produced in strontium cerate Raw Lacking oxygen is fewer, is unfavorable for SrCe(1-y)MyO3-αThe raising of electrical property, it is therefore preferable that 0 y≤0.20 <, more preferably 0.01≤y≤0.15.The inventors discovered that as rare earth element (especially Eu3+) doping be y=0.1 when, made from it The chemical properties such as the conductivity of electrolyte, the output power density of battery and stabilization time are best.
In the present invention, the weight ratio for adulterating strontium cerate and alkali metal salt is (3~8):1, preferably (4~5):1.Work as doping The weight ratio of strontium cerate and alkali metal salt is less than 3:When 1, the doping of alkali metal salt is excessive, can reduce the structure of composite electrolyte Stability;And when the weight ratio of doping strontium cerate and alkali metal salt is more than 8:When 1, the doping of alkali metal salt is few, to compound electric The promotion for solving matter conductivity is limited.
Adulterate SrCeO3It is excellent with the conductivity of the composite electrolyte of alkali metal salt formation, if further increasing doping SrCeO3Or the chemical stability and mechanical performance of its composite electrolyte formed, then be conducive to improve final battery product can By property.
Therefore, the present invention in the doping strontium cerate also doped with zirconium.SrZrO3Have as proton conductor preferable Chemical stability, by with Zr part substitution Ce can improve doping SrCeO3The chemical stability of material, to be had There is the proton conductor of high conductance and good chemical stability.
However, the addition of Zr can not only reduce the conductivity of material, but also the sintering temperature that can improve material (is more than 1700 DEG C), make it be difficult to be sintered the electrolyte structure for obtaining densification, while also affecting the cofiring process of galvanic anode and electrolyte. Because under excessively high co-fired temperature, galvanic anode structure, which is easily burnt to death, causes porosity to greatly reduce, and can not obtain porous sun Pole structure, to influence the normal conveying of battery fuel gas so that cell output reduces.Therefore, the choosing of the doping of Zr It is also highly important to select.
Adulterate the SrCeO after Zr and positive trivalent rare earth element3The chemical composition of material is SrCe(1-x-y)ZrxMyO3-α, it is Adulterate SrCeO3/SrZrO3Solid solution, wherein 0.10≤x≤0.60,0≤y≤0.20,0≤α≤0.1, preferably 0.20≤x ≤ 0.30,0.01≤y≤0.15,0.005≤α≤0.05.Positive trivalent rare earth element indicates that x is Zr with M4+Form solid solution Doping, y are positive trivalent rare earth element M3+The doping of solid solution is formed, α represents the Lacking oxygen of each doping strontium cerate unit Number.
SrCeO after above-mentioned doping3, x is smaller, and conductivity is higher, but as x < 0.10, the chemical stability of material It is promoted limited;X is bigger, bigger to the inhibition of its conductivity, as x > 0.6, can obtain good chemical stability, but its Sintering temperature increases obviously, and conductivity inhibits apparent.Thus, when selection Zr adulterates SrCeO3When, Zr4+0.10≤x of doping ≤0.60。
Verified discovery, after doping strontium cerate and alkali metal salt are compound in the present invention, composite electrolyte conductivity obtained It dramatically increases, at 700 DEG C, the conductivity of composite electrolyte can reach 1.27 × 10-1S.cm-1.Meanwhile it being provided with the present invention The SOFC operating temperatures that assemble of composite electrolyte can significantly reduce, the operating temperature of SOFC existing in the prior art is extremely Less at 1000 DEG C or more, and the operating temperature for the SOFC that composite electrolyte assembles in the present invention is only 700 DEG C, compared to existing There is the SOFC in technology to reduce at least 300 DEG C.What is more important, since the chemistry of composite electrolyte provided by the invention is steady Qualitative height, to improve by the battery performance of its SOFC assembled.
The solid that doping strontium cerate-alkali metal salt composite electrolyte is high-crystallinity, size of microcrystal is uniform, compactness is high is multiple Object is closed, especially with Eu3+,Zr4+Doping strontium cerate and the homogeneous electrolysis of the densification that sodium chloride and potassium chloride eutectic are combined Matter (SrCe0.7Zr0.2M0.1O3-α- NaCl-KCl) it is assembled into H2/O2Fuel cell, at 700 DEG C, the open-circuit voltage of battery is 1.07V, at least 40 hours, output power density can maintain 0.57~0.58Wcm-2, corresponding current density maintenance In 0.89~0.90Acm-2, voltage maintains 0.63~0.65V.
The second aspect of the present invention also provides a kind of side preparing above-mentioned doping strontium cerate-alkali metal salt composite electrolyte Method, wherein the described method comprises the following steps:
1) doping strontium cerate is mixed with alkali metal salt, is suppressed, compound precursor is obtained;
2), calcining step 1) obtained compound precursor, doping strontium cerate-alkali metal salt composite electrolyte is made.
In step 1), doping strontium cerate is mixed into mixing, compacting with alkali metal salt, obtains compound precursor.
In the present invention, SrCeO is adulterated3Chemical composition be SrCe(1-x-y)ZrxMyO3-α, for doping SrCeO3/SrZrO3 Solid solution, wherein 0.10≤x≤0.60,0≤y≤0.20,0≤α≤0.1, preferably 0.20≤x≤0.30,0.01≤y≤ 0.15,0.005≤α≤0.05.Positive trivalent rare earth element indicates that x is Zr with M4+The doping of solid solution is formed, y is that trivalent is dilute Earth elements M3+The doping of solid solution is formed, α represents the Lacking oxygen number of each doping strontium cerate unit.
Alkali metal salt is alkali metal chloride, the eutectic of preferably at least two kinds alkali metal chlorides, more preferable alkali gold Belong to salt for the eutectic of potassium chloride and sodium chloride, the ratio between the mole of potassium chloride and sodium chloride is 1:1.
The weight ratio for adulterating strontium cerate and alkali metal salt is (3~8):1, preferably (4~5):1.
In the present invention, doping strontium cerate is mixed with alkali metal salt using the method for grinding, on the one hand reduces each original On the other hand the grain size of material makes each raw material mix more abundant and uniformly, finally obtained sheet electrolyte is made to be more uniformly distributed.
The present invention is not specially limited the time of grinding, is subject to and is sufficiently mixed each raw material uniformly.
After doping strontium cerate is sufficiently mixed uniformly with alkali metal salt, by mixture according to difference under larger pressure action The needing of fuel cell is pressed into specific shape, to be prepared into the solid electrolyte in solid fuel cell.Before Material synthesis Compressing tablet process need be carried out, the consistency and uniformity of electrolyte after being calcined with raising.
In the present invention, to used in pressing mixt pressure and the pressing time be not specially limited, preferably compacting have It is 8~10MPa to have pressure when specific shape electrolyte, and the pressing time is 2~3min;The thickness of electrolytic thin-membrane is after compacting The density of 1~3mm, composite electrolyte are 3.0~4.5gcm-3, preferably 4.0~4.2gcm-3.Thin dense electrolyte film Effect be isolation fuel gas and oxic gas the rupture of electrolyte can be effectively prevent to cause within the scope of above-mentioned film thickness Gas leaks in SOFC structures.
In the present invention, the doping strontium cerate is that positive trivalent rare earth element adulterates strontium cerate, preferably positive trivalent rare earth member Element and zr element adulterate strontium cerate.The doping strontium cerate can be commercially available or be voluntarily prepared, and preferably voluntarily prepares.
Preferably, the preparation method of the doping strontium cerate includes the following steps:
1-1), barium source, cerium source, zirconium source are weighed by setting molar ratio and are dissolved in concentrated nitric acid containing rare-earth compound, Ligand compound is added;
1-2), regulation system pH value forms it into colloidal sol, is heated to forming gel;
1-3), gel is calcined, obtains doping strontium cerate.
In the present invention, the preparation method for adulterating strontium cerate is sol-gal process, is had the following advantages:It is reacted in this method Object dissolves in the solution, can reach the dispersion of molecule or atomic level, calcination temperature has larger than conventional solid reaction method It reduces, and the uniformity is higher, stoichiometric ratio is accurate, other will not be introduced other than organic principle in whole preparation process It is not easy the impurity metal ion removed, therefore prepared powder has the spies such as purity height, granularity fine uniform, calcination temperature be low Point is conducive to the raising of conductivity or chemical stability.
Step 1-1), it weighs barium source, cerium source, zirconium source and rare-earth compound by setting molar ratio and is dissolved in concentrated nitric acid In, ligand compound is added, wherein
What the barium source was selected from that strontium oxide strontia, strontium acetate or strontium nitrate etc. dissolve in nitric acid contains strontium compound, preferably acetic acid Strontium;
The cerium source is selected from the cerium-containing compound that cerium oxide, cerous carbonate, cerous nitrate or ammonium ceric nitrate etc. dissolve in nitric acid, excellent It is selected as ammonium ceric nitrate;
The zirconium source is selected from the zirconium-containing compound that zirconium carbonate, zirconium nitrate etc. dissolve in nitric acid, preferably zirconium nitrate;
The rare-earth compound is selected from oxide, acetate or the nitrate etc. of rare earth element, preferably rare earth member The oxide of element.
In the present invention, the weight fraction of the concentrated nitric acid is more than 65%.In barium source, cerium source and rare-earth compound It is one or more be selected from oxide when, oxide is first preferably dissolved in concentrated nitric acid, then concentrated nitric acid is added in non-oxide compound Middle dissolving avoids the dilution of concentrated nitric acid, is allowed to quickly dissolve oxide.
In the present invention, ligand is introduced by ligand compound into above-mentioned system, make Ce elements in system, strontium element, Zr element and rare earth element are matched, form complex, and the complex compound for being easy to ageing can be formed after regulation system pH.Institute It states complex not limit, is subject to that above-mentioned element, preferably citric acid and/or ethylenediamine tetra-acetic acid can be complexed in it (EDTA)。
Citric acid is bidentate ligand, it can coordinate each citric acid molecule with two metallic atoms, for make citric acid with The complex reaction of metallic atom fully carries out, and it is preferably the 3 of total metal ion that the present invention, which selects the addition of citric acid, ~4 times;And EDTA is a sexadentate ligand, can chelate various metals ion, usually with metal ion with 1:1 or 1:2 huge legendary turtles Close, to make the complex reaction of EDTA and metallic atom fully carry out, the present invention select the addition of EDTA be preferably total metal from 5~6 times of sub- molal quantity.
Step 1-2), regulation system pH value forms it into colloidal sol, is heated to forming gel.
In the present invention, regulation system pH value to 8~9 makes the metal ion in system that complex reaction occur with ligand, generates Stable complex.
Preferably, using ammonium hydroxide or the pH of organic base (such as triethylamine) regulation system.Ammonium hydroxide or organic base can be by rear Remaining alkali in continuous calcining removing system, without the remaining hetero atom in system.According to inorganic base, alkali metal therein or Alkaline-earth metal can remain in system and can not remove effectively, and cause to be mixed with miscellaneous metallic element in product obtained, to change The chemical composition for having become product influences its mechanical performance or chemical property.
In the present invention, adjoint whipping process during pH is adjusted.System after the completion of being adjusted to pH is at 70~90 DEG C 10~20h is heated, is allowed to form vitreosol.
5~20h is heated at 100~130 DEG C to colloidal sol, is allowed to form gel
Step 1-3), gel is calcined, doping strontium cerate is obtained.
In the present invention, first time calcining is carried out to gel at 1150 DEG C~1250 DEG C, removes organic impurities therein, It carries out calcining for second at 1500~1600 DEG C, obtains doping strontium cerate.By calcining twice, doping cerium is further improved The purity of sour strontium, crystallinity and compactness are more preferable.Preferably, the time of gel calcining for the first time is 4~6 hours, second The time of calcining is 4~8 hours.
Processing is crushed to the doping strontium cerate after the completion of calcining, obtains powder body material, is handled convenient for following process.
In the present invention, when alkali metal salt is the eutectic of potassium chloride and sodium chloride, the eutectic passes through following methods It prepares:
Step 2-1 weighs each alkali metal chloride by setting ratio, carries out first time calcining;
Step 2-2 crushes the product after calcining, carries out second and calcines.
Step 2-1 weighs each alkali metal chloride by setting ratio, grinds, is uniformly mixed, calcined.
Above-mentioned grinding is uniformly mixed and successively can carry out or be carried out at the same time, and achievees the effect that mixing by co-ground.
In the present invention, the temperature of calcining selects 600 DEG C~800 DEG C, preferably 650 DEG C~750 DEG C for the first time;When calcining Between selection selection 20~60min, preferably 30~40min;Sodium chloride and potassium chloride can form stabilization under this temperature, time Eutectic.
Product after calcining is crushed, is calcined again by step 2-2.
The inventors discovered that after burning product crushing by one, then second of calcining is carried out, it is more equal Elemental redistribution can be obtained Even eutectic.
In the present invention, the temperature of second of calcining selects 600 DEG C~800 DEG C, preferably 650 DEG C~750 DEG C;When calcining Between selection selection 20~60min, preferably 30~40min.
It is taken out after second of calcining postcooling to room temperature, grind to fine powdered and is run through 200 mesh sieve.
Step 2), calcining step 1) obtained compound precursor, doping strontium cerate-alkali metal salt composite electrolyte is made.
In the present invention, solid electrolyte have passed through green compact molding, be provided with certain shape and intensity, but substantially also The only loose combination of powder, intensity and performance cannot all reach demand, therefore must also be sintered to it.The mesh of sintering Be that dusty material is transformed into bulk material, assign material characteristic property, obtain the polycrystalline material of block.
Preferably, compound precursor step 1) obtained is calcined 1~2 hour at 700 DEG C~800 DEG C, you can makes to mix Miscellaneous strontium cerate is compound with alkali metal salt, forms uniform electrolyte.
Embodiment
Embodiment 1
(1) preparation of strontium cerate is adulterated
It weighs 0.05moL europium oxides and is dissolved in concentrated nitric acid, then weigh 1moL strontium acetates, 0.7moL ammonium ceric nitrates and 0.2moL nitre Sour zirconium dissolving, is added 6moL citric acids, adjusts pH value to 9 with ammonium hydroxide, is sufficiently stirred, is heated to forming vitreosol at 80 DEG C. It is positioned in baking oven, gel is formed in 110 DEG C of constant temperature 10h.Gel is subjected to ashing processing, the calcination 5h at 1200 DEG C, 1540 After being sintered 5h crushing at DEG C, SrCe is obtained0.7Zr0.2Eu0.1O3-αPowder (SCZE-SG).
(2) preparation of sodium chloride-potassium chloride eutectic
1moL sodium chloride and 1moL potassium chloride are weighed, is ground, is uniformly mixed, is placed in chamber type electric resistance furnace and heats, temperature is set 720 DEG C are set to, heating 30min or so takes out after being cooled to room temperature, grinds to fine powdered.By eutectic powder obtained above End is heated again by above-mentioned condition, is taken out after being cooled to room temperature, and is ground to fine powdered and is put after being sieved with 200 mesh standard sieves Enter in hermetic bag and labelled spare.
(3) preparation of composite electrolyte
Take 4.0g SrCe0.7Zr0.2Eu0.1O3-αIt with 1.0g sodium chloride-potassium chloride eutectics, is mixed in mortar, and fully Grinding is uniform, and under 9MPa pressure, tabletting time 3min is tabletted rapidly with tablet press machine, and the disk of the 2-3mm pressed is put In on gasket, ceramic crucible is covered, is put in electric furnace that calcination 1h obtains SrCe at 750 DEG C0.7Zr0.2Eu0.1O3-α-NaCl-KCl (SCZE-SG-NK).It is reprocessed into the electrolyte disk that thickness is 1.0mm.It is multiple when temperature is 700 DEG C in air atmosphere The conductivity for closing electrolyte reaches maximum value 1.27 × 10-1S.cm-1。
Embodiment 2
The present embodiment method therefor is similar to Example 1, differs only in and 0.05moL europium oxides, 1moL are added in (one) Strontium acetate, 0.6moL ammonium ceric nitrates and 0.3moL zirconium nitrates, the chemical composition that product is made are SrCe0.6Zr0.3Eu0.1O3-α, With potassium chloride and sodium chloride it is compound after, be made SrCe0.6Zr0.3Eu0.1O3-α- NaCl-KCl composite electrolytes.
In air atmosphere, when temperature is 700 DEG C, the conductivity of above-mentioned composite electrolyte can reach maximum value 1 × 10- 1S.cm-1.It is made the solid oxide fuel cell that composite electrolyte assembles with embodiment 2, open-circuit voltage 1.07V, Peak power output density is 450~460mWcm at 700 DEG C-2, power is density stabilized in 40 hours.
Experimental example
The XRD characterization of 1 sample of experimental example
The XRD that sample is made in embodiment 1 is measured, the results are shown in Figure 1.
As shown in Figure 1, thus the comparison of collection of illustrative plates and standard diffraction collection of illustrative plates card can be seen that, the intensity at peak and position with undoped with when It is cube consistent, 2 θ be respectively present at 20.75 °, 29.48 °, 42.18 ° and 61.13 ° (110), (112), (220) and (224) crystallographic plane diffraction peak.
There is strongest diffraction maximum when as can be seen from Figure near 2 θ=30 °, and peak type is more sharp, and half-peak breadth It is narrow, show that the sample has very high crystallinity.It can also be seen that sample has newly increased the diffraction maximum of NaCl, KCl, explanation NaCl, KCl and SrCe0.7Zr0.2Eu0.1O3-αThat any chemical reaction does not occur after compound.
The electron microscope analysis of 2 sample of experimental example
The scanning electron microscope of sample surfaces and section is made in testing example 1 respectively, as a result as shown in Figures 2 and 3 respectively, In,
Fig. 2 shows the surface topography electron microscopes that sample is made in embodiment 1;
Fig. 3 shows that the cross-section morphology electron microscope of sample is made in embodiment 1.
By Fig. 2 and Fig. 3 it is found that composite electrolyte SrCe made from embodiment 10.7Zr0.2Eu0.1O3-α- NaCl-KCl is fine and close Property high, no hole, uniform particle sizes are consistent.
The conductivity of 3 sample of experimental example is analyzed
Sample is made at 500-700 DEG C in testing example 1, and the conductivity in air atmosphere, the results are shown in Figure 4.
As shown in Figure 4, as temperature gradually rises, conductivity gradually increases, and illustrates that composite electrolyte has and preferably leads Electrically.The logarithm of conductivity and temperature be not linear, consolidates fusing point as temperature increases to NaCl, KCl, is further continued for Increase temperature, slope reduces, and slope is big, and the activation energy of sample is big, slope, and the activation energy of sample is small, is conducive to proton conducting Conduction, when temperature is 700 DEG C, the conductivity of composite electrolyte reaches 1.27 × 10-1S.cm-1。
The performance of 4 fuel cell of experimental example
Respectively using hydrogen as fuel gas, oxygen is oxidant, and H is assembled into composite electrolyte made from embodiment 12/O2Combustion Expect battery, and tests I-V-P relationships under the conditions of 700 DEG C, the results are shown in Figure 5
As shown in Figure 5, open-circuit voltage 1.07V illustrates that the composite electrolyte of synthesis is very fine and close close to theoretical value.It opens Road voltage continuously decreases, and current density gradually increases, and power gradually increases, and fuel cell is in 40 hours, peak power output Density maintains 0.57~0.58Wcm-2, corresponding current density maintains 0.89~0.90Acm-2, voltage maintains 0.63~0.65V.
It is described the invention in detail above in association with detailed description and exemplary example, but these explanations are simultaneously It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention, Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention In the range of.Scope of protection of the present invention is subject to the appended claims.

Claims (10)

1. a kind of doping strontium cerate-alkali metal salt composite electrolyte, which is characterized in that the doping strontium cerate is positive trivalent rare earth Element doping strontium cerate, the alkali metal salt are alkali metal chloride.
2. composite electrolyte according to claim 1, which is characterized in that the positive trivalent rare earth element is selected from Y3+,Lu3+, Eu3+And Tm3+Any one, preferably Eu3+;And/or
The chemical composition of the doping strontium cerate is SrCe(1-y)MyO3-α, wherein 0≤y≤0.20,0≤α≤0.1, y are positive three Valence rare earth element M forms the doping of solid solution, and α represents the Lacking oxygen number of each doping strontium cerate unit.
3. composite electrolyte according to claim 1 or 2, which is characterized in that
Also doped with zirconium in the doping strontium cerate;And/or
The chemical composition of the doping strontium cerate is SrCe(1-x-y)ZrxMyO3-α, wherein 0.10≤x≤0.60,0≤y≤0.20, 0≤α≤0.1, x are the dopings that Zr forms solid solution, and y is the doping that positive trivalent rare earth element M forms solid solution, and α is represented The Lacking oxygen number of each doping strontium cerate unit.
4. the composite electrolyte according to one of claims 1 to 3, which is characterized in that doping strontium cerate and alkali metal salt Weight ratio is (3~8):1, preferably (4~5):1.
5. a kind of method preparing one of Claims 1 to 4 doping strontium cerate-alkali metal salt composite electrolyte, the side Method includes the following steps:
1) doping strontium cerate is mixed with alkali metal salt, is suppressed, obtain compound precursor;
2) calcining step 1) obtained compound precursor, doping strontium cerate-alkali metal salt composite electrolyte is made.
6. according to the method described in claim 5, it is characterized in that, in step 1),
Adulterate SrCeO3Chemical composition be SrCe(1-x-y)ZrxMyO3-α, wherein 0.10≤x≤0.60,0≤y≤0.20,0≤α ≤ 0.1, x are the dopings that Zr forms solid solution, and y is the doping that positive trivalent rare earth element M forms solid solution, and α represents each Adulterate the Lacking oxygen number of strontium cerate unit.
7. method according to claim 5 or 6, which is characterized in that described in step 1) adulterate strontium cerate according to include with What the method for lower step was prepared:
1-1), barium source, cerium source, zirconium source are weighed by setting molar ratio and be dissolved in concentrated nitric acid containing rare-earth compound, is added Ligand compound;
1-2), regulation system pH value forms it into colloidal sol, is heated to forming gel;
1-3), gel is calcined, obtains doping strontium cerate.
8. the method according to one of claim 5~7, which is characterized in that step 1-3) in, at 1150 DEG C~1250 DEG C First time calcining is carried out to gel, second is carried out at 1500~1600 DEG C and is calcined, the time of calcining is 4~6 small for the first time When, the time of second of calcining is 4~8 hours.
9. the method according to one of claim 5~8, which is characterized in that in step 2), doping strontium cerate-alkali gold is made Belong to salt composite electrolyte 2 θ be 20.75 °, 29.48 °, 42.18 ° and 61.13 ° at be respectively present (110), (112), (220) and (224) crystallographic plane diffraction peak;And/or
When temperature is 700 DEG C, the conductivity in air atmosphere reaches 1.27 × 10-1S.cm-1。
10. the method according to one of claim 5~9, which is characterized in that in step 2), using obtained doping strontium cerate- The H that alkali metal salt composite electrolyte is assembled into2/O2Fuel cell, when temperature is 700 DEG C, open-circuit voltage 1.07V,
Fuel cell is at least 40 hours, and output power density is up to 0.57~0.58Wcm-2, current density up to 0.89~ 0.90A·cm-2, voltage maintains 0.63~0.65V.
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CN114829003A (en) * 2020-01-07 2022-07-29 株式会社村田制作所 Hydrocarbon reforming catalyst and hydrocarbon reforming apparatus
CN118231719A (en) * 2024-05-20 2024-06-21 内蒙古科学技术研究院 Sr/Mg co-doped LaAlO3Method for preparing electrolyte material battery

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