CN110817954B - Solid electrolyte, preparation method thereof and solid oxide fuel cell - Google Patents

Solid electrolyte, preparation method thereof and solid oxide fuel cell Download PDF

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CN110817954B
CN110817954B CN201911127725.6A CN201911127725A CN110817954B CN 110817954 B CN110817954 B CN 110817954B CN 201911127725 A CN201911127725 A CN 201911127725A CN 110817954 B CN110817954 B CN 110817954B
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李长久
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Hainan University
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    • C01—INORGANIC CHEMISTRY
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    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G37/00—Compounds of chromium
    • C01G37/006—Compounds containing, besides chromium, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • 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
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    • Y02E60/50—Fuel cells

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Abstract

The invention provides a solid electrolyte, which has a chemical formula shown in formula 1: tixMyTa1‑x‑yO5‑δFormula 1; wherein M is Fe, Al, Ga, Sn, Co, W, Ce, Mo, La, Y, V or Cr, x is more than or equal to 0.05 and less than or equal to 0.30, Y is more than or equal to 0.01 and less than or equal to 0.20, and delta represents the number of oxygen atoms reduced due to the generation of oxygen vacancies. The solid oxide solid electrolyte has high oxygen ion conductivity and low thermal expansion coefficient in the medium temperature range of 600-800 ℃, and the thermal expansion coefficient from room temperature to 800 ℃ is 1.06-4.48 multiplied by 10‑6K; the performance is kept stable when the temperature and the atmosphere change, the internal stress is small, and the method can be applied to sensors of oxygen ion conductance and solid oxide fuel cells under medium-high temperature conditions. The invention also provides a preparation method of the solid electrolyte and a solid oxide fuel cell.

Description

Solid electrolyte, preparation method thereof and solid oxide fuel cell
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a solid electrolyte, a preparation method thereof and a solid oxide fuel cell.
Background
The solid electrolyte is used for Solid Oxide Fuel Cells (SOFC), sensors, electrocatalysis, membrane separation, membrane reactors and the like, and has wide application prospects in the fields of energy, metallurgy, chemical industry, environmental protection and the like. The SOFC has high power generation efficiency, wide adaptability to fuel, NO corrosion, full solidification and extremely low NOXAnd SOXNoise and dust emissions, etc., are known as green energy sources in the 21 st century. The traditional solid oxide fuel cell adopts fluorite yttrium-stabilized zirconia (YSZ) as a solid electrolyte, the working temperature of the traditional solid oxide fuel cell is about 1000 ℃ to reach high enough ionic conductivity (about 0.1S/cm), so the cold-heat cycle service performance of the SOFC is reduced and the service life is greatly shortened due to the difference of the thermal expansion coefficients among the electrolyte, the electrode and the connecting material and the chemical reaction among interfaces at the high temperature. If the working temperature of the SOFC can be reduced to 600-800 ℃, the service life of the SOFC can be prolonged by three times, the selection range of electrodes, sealing and connecting materials is increased, the cost of raw materials and manufacture is reduced, and meanwhile, the operation safety of the SOFC is improved.
A.S.Urusova et al studied oxygen-deficient perovskite type BaFe0.9-xY0.1CoxO3-δPreparation and performance of (a). The perovskite structure can stably exist when the electrolyte with x less than or equal to 0.15 prepared by a sol-gel or solid phase method changes along with the temperature. But the conductivity is relatively low, and the thermal expansion coefficient is high (16-20 multiplied by 10)-6K-1) Have limited their application to fuel cells.
SOFC is an important energy conversion device, and the technical development of SOFC has important meaning for solving the increasingly serious energy crisis current situationAnd (5) defining. The quality of the solid electrolyte performance of the SOFC core component directly influences the service performance of the fuel cell. Currently, there are four systems for solid electrolyte materials that are more studied: ZrO (ZrO)2Base, CeO2Base, Bi2O3Radical and LaGaO3They have limited their use due to their disadvantages, such as low high temperature conductivity, high coefficient of thermal expansion, presence of electronic conduction, high temperature phase transition, and the like.
Disclosure of Invention
The invention aims to provide a solid electrolyte, a preparation method thereof and a solid oxide fuel cell.
The invention provides a solid electrolyte, which has a chemical formula shown in a formula 1:
TixMyTa1-x-yO5-δformula 1;
wherein M is Fe, Al, Ga, Sn, Co, W, Ce, Mo, La, Y, V or Cr, x is more than or equal to 0.05 and less than or equal to 0.30, Y is more than or equal to 0.01 and less than or equal to 0.20, and delta represents the number of oxygen atoms reduced due to the generation of oxygen vacancies.
Preferably, M is Fe, and y is more than or equal to 0.01 and less than or equal to 0.2;
m is Al, and y is more than or equal to 0.01 and less than or equal to 0.20;
m is Ga, and y is more than or equal to 0.01 and less than or equal to 0.20;
m is Cr, and y is more than or equal to 0.01 and less than or equal to 0.20.
The invention provides a preparation method of a solid electrolyte, which comprises the following steps:
A) mixing Ta powder, Ti powder and MiOjDissolving metal powder in hydrofluoric acid, and then mixing the metal powder with an oxalic acid solution to obtain a mixed metal ion solution;
B) titrating an ammonia water solution containing polyethylene glycol into the mixed metal ion solution, carrying out precipitation reaction, and roasting the obtained precipitate to obtain nano mixed powder;
C) sintering the obtained nano mixed powder to obtain a solid electrolyte;
the solid electrolyte has a chemical formula shown in formula 1:
TixMyTa1-x-yO5-δformula 1;
wherein M is Fe, Al, Ga, Sn, Co, W, Ce, Mo, La, Y, V or Cr, x is more than or equal to 0.05 and less than or equal to 0.30, Y is more than or equal to 0.01 and less than or equal to 0.20, and delta represents the number of oxygen atoms reduced due to the generation of oxygen vacancies.
Preferably, the mass concentration of the oxalic acid solution is 10-15%.
Preferably, the total concentration of the metal particles in the mixed metal ion solution is 0.001-0.5 mol/L.
Preferably, in the ammonia water solution, the mass fraction of the polyethylene glycol is 1-5%.
Preferably, the roasting temperature in the step B) is 500-1000 ℃;
the roasting time in the step B) is 1-4 h.
Preferably, the sintering temperature in the step C) is 1400-1600 ℃;
the sintering time is 1-5 hours.
Preferably, after the mixed nano powder in the step B) is obtained, the mixed nano powder is mixed with an organic binder, and is subjected to dry pressing forming to obtain a blank, and then the blank is sintered.
The present invention provides a solid oxide fuel cell characterized by comprising the solid electrolyte described above.
The invention provides a solid electrolyte, which has a chemical formula shown in formula 1: tixMyTa1-x-yO5-δFormula 1; wherein M is Fe, Al, Ga, Sn, Co, W, Ce, Mo, La, Y, V or Cr, x is more than or equal to 0.05 and less than or equal to 0.30, Y is more than or equal to 0.01 and less than or equal to 0.20, and delta represents the number of oxygen atoms reduced due to the generation of oxygen vacancies. The solid oxide solid electrolyte has high oxygen ion conductivity (6.24 multiplied by 10) in the medium temperature range of 600-800 DEG C-7～2.6×10-1S/cm) and a low coefficient of thermal expansion, the coefficient of thermal expansion being 1.06-4.48 x 10 at room temperature to 800 DEG C-6K; stable performance in temperature and atmosphere change, small internal stress, and applicability to middle and high temperature stripA sensor for oxygen ion conductance under the device and a solid oxide fuel cell.
The invention also provides a preparation method of the solid electrolyte, and Ta is prepared by adopting an oxalate precipitation method2O5、TiO2And MiOjThe nano mixed powder can keep the three metal oxides uniform in microscopic size, reduce sintering temperature and shorten sintering time.
Detailed Description
The invention provides a solid electrolyte, which has a chemical formula shown in formula 1:
TixMyTa1-x-yO5-δformula 1;
wherein M is Fe, Al, Ga, Sn, Co, W, Ce, Mo, La, Y, V or Cr, x is more than or equal to 0.05 and less than or equal to 0.30, Y is more than or equal to 0.01 and less than or equal to 0.20, and delta represents the reduced number of oxygen atoms due to the generation of oxygen vacancies.
Preferably, 0.06. ltoreq. x.ltoreq.0.25, more preferably, 0.06. ltoreq. x.ltoreq.0.20, in particular, in embodiments of the invention, x is 0.06, 0.10 or 0.20.
Preferably, when M is Fe, 0.01. ltoreq. y.ltoreq.0.20, preferably, 0.02. ltoreq. y.ltoreq.0.15, and in particular, in the examples of the present invention, may be 0.02, 0.08 or 0.15;
m is Al, y is more than or equal to 0.01 and less than or equal to 0.20, preferably, y is more than or equal to 0.02 and less than or equal to 0.15, and specifically, in the embodiment of the invention, the M can be 0.02, 0.04, 0.06, 0.08, 0.10, 0.12 or 0.15;
m is Ga, 0.01-y-0.20, preferably 0.02-y-0.15, and specifically can be 0.02, 0.05, 0.07, 0.10, 0.13 or 0.15 in the embodiment of the invention;
m is Cr, and y is 0.01. ltoreq. y.ltoreq.0.20, preferably 0.02. ltoreq. y.ltoreq.0.15, and specifically, in the embodiment of the present invention, may be 0.02, 0.05, 0.07, 0.10, 0.13 or 0.15.
And M is Sn, Co, W, Ce, Mo, La, Y and V, Y is more than or equal to 0.01 and less than or equal to 0.20, preferably, Y is more than or equal to 0.02 and less than or equal to 0.15.
Specifically, in the embodiment of the present invention, the solid electrolyte has any one of the followingThe chemical formula is as follows: ti0.06Fe0.02Ta0.92O5-δ、Ti0.1Fe0.08Ta0.82O5-δ、Ti0.2Fe0.15Ta0.65O5-δ、Ti0.06Al0.02Ta0.92O5-δ、Ti0.08Al0.04Ta0.88O5-δ、Ti0.1Al0.06Ta0.84O5-δ、Ti0.12Al0.08Ta0.8O5-δ、Ti0.014Al0.1Ta0.76O5-δ、Ti0.17Al0.12Ta0.71O5-δ、Ti0.2Al0.15Ta0.65O5-δ、Ti0.6 Ga0.2Ta0.92O5-δ、Ti0.09 Ga0.05Ta0.86O5-δ、Ti0.12Ga0.07Ta0.81O5-δ、Ti0.15 Ga0.1Ta0.75O5-δ、Ti0.18 Ga0.13Ta0.69O5-δ、Ti0.2 Ga0.15Ta0.65O5-δ、Ti0.6Cr0.2Ta0.92O5-δ、Ti0.09 Cr0.05Ta0.86O5-δ、Ti0.12 Cr0.07Ta0.81O5-δ、Ti0.18 Cr0.13Ta0.69O5-δOr Ti0.2Cr0.15Ta0.65O5-δ。
The invention also provides a preparation method of the solid electrolyte, which comprises the following steps:
A) mixing Ta powder, Ti powder and MiOjDissolving metal powder in hydrofluoric acid, and then mixing the metal powder with an oxalic acid solution to obtain a mixed metal ion solution;
B) titrating an ammonia water solution containing polyethylene glycol into the mixed metal ion solution, carrying out precipitation reaction, and roasting the obtained precipitate to obtain nano mixed powder;
C) sintering the obtained nano mixed powder to obtain a solid electrolyte;
the solid electrolyte has a chemical formula shown in formula 1:
TixMyTa1-x-yO5-δformula 1;
wherein M is Fe, Al, Ga, Sn, Co, W, Ce, Mo, La, Y, V or Cr, x is more than or equal to 0.05 and less than or equal to 0.30, Y is more than or equal to 0.01 and less than or equal to 0.20, and delta represents the reduced number of oxygen atoms due to the generation of oxygen vacancies.
In the present invention, said MiOjPreferably Fe2O3、Al2O3、Ga2O3、SnO2、Co2O3、WO2、CeO2、Mo2O3、La2O3、Y2O3、V2O5Or Cr2O3(ii) a The Ta powder, Ti powder and MiOjThe molar amount of the metal powder is determined according to the molar ratio of each element in the chemical formula 1.
In the present invention, the hydrofluoric acid is preferably analytically pure HF in an amount of not less than 0.5L of hydrofluoric acid per mole of sample.
The mass concentration of the oxalic acid solution is preferably 10-15%, and more preferably 12-13%; according to the invention, oxalic acid solution is added into the metal ion solution of the hydrofluoric acid solution to prepare a mixed solution with the metal ion concentration of 0.001-0.5 mol/L, and more preferably 0.005-0.2 mol/L.
After obtaining the mixed metal ion solution, titrating an ammonia water solution containing polyethylene glycol into the mixed metal ion solution, and carrying out precipitation reaction to obtain a precipitate, wherein preferably, in the titration process, the titration speed is controlled, and mechanical stirring is carried out simultaneously to keep the pH of the solution to be more than or equal to 11; during the titration a suspension is formed, preferably by ultrasonic dispersion.
In the invention, the mass concentration of polyethylene glycol in the ammonia water is preferably 1-3%; the polyethylene glycol is used as a dispersing agent, preferably PEG10000, the dosage of the ammonia water solution of the polyethylene glycol is not particularly limited, and the titration is carried out until no precipitate is generated.
After titration is carried out until no precipitate is generated, filtering is carried out to obtain a precipitate, the precipitate is preferably washed by deionized water, then dehydrated by absolute ethyl alcohol, and then dried and roasted to obtain the nano mixed powder.
In the invention, the drying temperature is preferably 70-90 ℃, more preferably 75-85 ℃, and most preferably 80 ℃; the drying time is preferably 12 to 24 hours, and more preferably 15 to 20 hours.
The roasting temperature is preferably 500-1000 ℃, more preferably 600-900 ℃, and most preferably 650-850 ℃; the roasting time is preferably 1-4 h.
After the nano mixed powder is obtained, the powder is preferably mixed with the organic binder, and the mixture is subjected to dry pressing, demolding and drying to obtain a blank.
In the invention, the organic binder is preferably a polyvinyl alcohol organic binder, and the mass fraction of the organic binder is preferably 2-8%, and more preferably 3-7%; the pressure of the dry pressing molding is preferably more than 100 MPa; the drying temperature after demolding is preferably 80-100 ℃.
After the green body is obtained, the green body is sintered to obtain the solid electrolyte, the green body is preferably sintered under neutral and oxidizing atmosphere, and the sintering is preferably pressureless sintering.
The sintering temperature is preferably 1400-1700 ℃, and more preferably 1500-1600 ℃; the sintering time is preferably 1 to 5 hours, and more preferably 2 to 4 hours. In the pressureless reaction sintering process of the present invention, Ta2O5And a dopant TiO2And MiOjSolid phase reaction is carried out to generate solid solution, and nanocrystalline TiO is prepared2And MiOjDoped Ta2O5A solid electrolyte of a oxygen ion conductor.
The present invention also provides a solid oxide fuel cell comprising the solid electrolyte described above. The invention is not limited to the anode, cathode and other components of the fuel cell, and the anode, cathode and other components of the fuel cell commonly used in the art may be used.
The invention provides a solid electrolyte, which has a chemical formula shown in formula 1: tixMyTa1-x-yO5-δFormula 1; wherein M is Fe, Al, Ga, Sn, Co, W, Ce, Mo, La, Y, V or Cr, x is more than or equal to 0.05 and less than or equal to 0.30, Y is more than or equal to 0.01 and less than or equal to 0.20, and delta represents the reduced number of oxygen atoms due to the generation of oxygen vacancies. The solid oxide solid electrolyte has high oxygen ion conductivity (6.24 multiplied by 10) in the medium temperature range of 600-800 DEG C-7～2.6×10-1S/cm) and a low coefficient of thermal expansion, the coefficient of thermal expansion from room temperature to 830 ℃ being 1.06-4.48X 10-6K; the performance is kept stable when the temperature and the atmosphere change, the internal stress is small, and the method can be applied to sensors of oxygen ion conductance and solid oxide fuel cells under medium-high temperature conditions.
The invention also provides a preparation method of the solid electrolyte, and Ta is prepared by adopting an oxalate precipitation method2O5、TiO2And MxOyThe nano mixed powder can keep the three metal oxides uniform in microscopic size, reduce sintering temperature and shorten sintering time.
In order to further illustrate the present invention, the following examples are provided to describe the solid electrolyte, the preparation method thereof and the solid oxide fuel cell in detail, but should not be construed as limiting the scope of the present invention.
Example 1
Firstly, preparing a precursor solution, namely dissolving Ta powder, Ti powder and Fe by using a proper amount of analytically pure HF2O3Powder is mixed with 10 to 15 weight percent oxalic acid solution to prepare solution with the total concentration of metal ions being 0.1 mol/L; wherein the molar content of Ti powder is 6 percent and Fe2O3The powder molar content is 2 percent, and the Ta powder molar content is 92 percent.
Gradually titrating an ammonia water solution containing 1 wt% of PEG10000 dispersing agent into the mixed solution at room temperature, and carrying out hydrolysis reaction; in the titration process, controlling the titration speed, carrying out mechanical stirring, and controlling the pH to be more than or equal to 11; dispersing the generated suspension by ultrasonic waves, carrying out centrifugal treatment to obtain a precipitate, cleaning by using deionized water, dehydrating by using absolute ethyl alcohol, drying for 20 hours at 85 ℃, and roasting at 500 ℃ to obtain nano mixed powder;
adding 3 wt% of polyvinyl alcohol organic binder into the obtained nano mixed powder, and performing dry pressing forming under the pressure of more than 100MPa to obtain the nano composite material
Figure BDA0002277381320000061
Demoulding, drying at 85 ℃ to obtain a blank;
the sintering temperature of the green body is 1400 ℃, the sintering atmosphere is air atmosphere, and the heat preservation time is 5 hours, so as to prepare the Ti with the chemical formula0.06Fe0.02Ta0.92O5-δThe solid electrolyte of (1).
Examples 2 to 3
A solid electrolyte was prepared as in example 1, except that the metal powders in examples 2 to 3 were different in molar ratio:
example 2: ti powder of 10 mol% and Fe2O3The powder molar content is 8 percent, and the Ta powder molar content is 82 percent; to obtain the chemical formula of Ti0.1Fe0.08Ta0.82O5-δThe solid electrolyte of (1);
example 3: ti powder of 20 mol% and Fe2O3The powder molar content is 15 percent, and the Ta powder molar content is 65 percent; to obtain the chemical formula of Ti0.2Fe0.15Ta0.65O5-δThe solid electrolyte of (1).
The ionic conductivity of the solid electrolyte in examples 1 to 3 at 400 to 800 ℃ was tested, and the results are shown in table 1; the thermal expansion coefficient of the solid electrolyte of examples 1 to 3 was measured at 30 to 800 ℃ and the results are shown in Table 2.
TABLE 1 Ti in examples 1 to 3xFeyTa1-x-yO5-δConductivity of solid electrolyte
Figure BDA0002277381320000071
TABLE 2 Ti in examples 1 to 3xFeyTa1-x-yO5-δThermal expansion coefficient of solid electrolyte
Figure BDA0002277381320000072
As can be seen from Table 1, the TiO prepared by the process of the present invention2、Fe2O3Doped with Ta2O5The solid electrolyte has conductivity over 10 at over 600 deg.C-2S/cm, can meet the working requirement of serving as an SOFC fuel cell. And has a thermal expansion coefficient of 3.72 to 3.79X 10 in the range of 30 to 800 ℃ as shown in Table 2-6K-1And belongs to a low-thermal expansion solid electrolyte material. And Y2O3Stabilized ZrO2(YSZ) solid electrolyte phase comparison of TiO prepared by the method of the present invention2、Fe2O3Doped with Ta2O5The solid electrolyte has a higher oxygen ion conductivity and a lower thermal expansion coefficient.
Examples 4 to 10
A solid electrolyte was prepared by the method of example 1, except that the kinds and molar ratios of the metal powders in examples 4 to 10 were different from those in example 1:
example 4: ti powder of 6 mol% and Al2O3The powder molar content is 2 percent, and the Ta powder molar content is 92 percent; to obtain the chemical formula of Ti0.06Al0.02Ta0.92O5-δThe solid electrolyte of (1);
example 5: ti powder of 8 mol% and Al2O3The powder molar content is 4 percent, and the Ta powder molar content is 88 percent; to obtain the chemical formula of Ti0.08Al0.04Ta0.88O5-δThe solid electrolyte of (1);
example 6: ti powder of 10 mol% and Al2O3The powder molar content is 6 percent, and the Ta powder molar content is 84 percent; to obtain the chemical formula of Ti0.1Al0.06Ta0.84O5-δThe solid electrolyte of (1);
example 7: ti powder of 12 mol% and Al2O3The powder molar content is 8 percent, and the Ta powder molar content is 80 percent; to obtain the chemical formula of Ti0.12Al0.08Ta0.8O5-δThe solid electrolyte of (1);
example 8: ti powder 14 mol% and Al2O3The powder molar content is 10 percent, and the Ta powder molar content is 76 percent; to obtain the chemical formula of Ti0.014Al0.1Ta0.76O5-δThe solid electrolyte of (1);
example 9: the molar content of Ti powder is 17 percent and Al is2O3The powder molar content is 12 percent, and the Ta powder molar content is 71 percent; to obtain the chemical formula of Ti0.17Al0.12Ta0.71O5-δThe solid electrolyte of (1);
example 10: ti powder 20 mol% and Al2O3The powder molar content is 15 percent, and the Ta powder molar content is 65 percent; to obtain the chemical formula of Ti0.2Al0.15Ta0.65O5-δThe solid electrolyte of (1);
the ionic conductivity of the solid electrolyte in examples 4-10 at 400-800 ℃ was tested, and the results are shown in table 3; the thermal expansion coefficients of the solid electrolytes of examples 4 to 10 at 30 to 800 ℃ were measured, and the results are shown in Table 4.
TABLE 3 Ti in examples 4 to 10xAlyTa1-x-yO5-δConductivity of solid electrolyte
Figure BDA0002277381320000081
TABLE 4 Ti in examples 4 to 10xAlyTa1-x-yO5-δThermal expansion coefficient of solid electrolyte
Figure BDA0002277381320000082
As can be seen from Table 3, the TiO prepared by the process of the present invention2、Al2O3Doped with Ta2O5The solid electrolyte has conductivity over 10 at over 600 deg.C-2S/cm, can meet the working requirement of serving as an SOFC fuel cell. And has a thermal expansion coefficient of 1.06-2.60 × 10 in the range of 30-800 deg.C as shown in Table 4-6K-1And belongs to a low-thermal expansion solid electrolyte material. And Y2O3Stabilized ZrO2(YSZ) solid electrolyte phase comparison of TiO prepared by the method of the present invention2、Al2O3Doped with Ta2O5The solid electrolyte has a higher oxygen ion conductivity and a lower thermal expansion coefficient.
Examples 11 to 16
A solid electrolyte was prepared by following the procedure of example 1, except that the kinds and molar ratios of the metal powders in examples 11 to 16 were different from those in example 1:
example 11: ti powder of 6 mol% and Ga2O3The powder molar content is 2 percent, and the Ta powder molar content is 92 percent; to obtain the chemical formula of Ti0.6 Ga0.2Ta0.92O5-δThe solid electrolyte of (1);
example 12: 9% of Ti powder by mol and Ga2O3The powder molar content is 5 percent, and the Ta powder molar content is 86 percent; to obtain the chemical formula of Ti0.09 Ga0.05Ta0.86O5-δThe solid electrolyte of (1);
example 13: ti powder of 12 mol% and Ga2O3The powder molar content is 7 percent, and the Ta powder molar content is 81 percent; to obtain the chemical formula of Ti0.12 Ga0.07Ta0.81O5-δThe solid electrolyte of (1);
example 14: ti powder of 15 mol% and Ga2O3The powder molar content is 10 percent, and the Ta powder molar content is 75 percent; to obtain the chemical formula of Ti0.15 Ga0.1Ta0.75O5-δThe solid electrolyte of (1);
example 15: ti powder has a molar content of18％、Ga2O3The powder molar content is 13 percent, and the Ta powder molar content is 69 percent; to obtain the chemical formula of Ti0.18 Ga0.13Ta0.69O5-δThe solid electrolyte of (1);
example 16: ti powder molar content of 20%, Ga2O3The powder molar content is 15 percent, and the Ta powder molar content is 65 percent; to obtain the chemical formula of Ti0.2 Ga0.15Ta0.65O5-δThe solid electrolyte of (1);
the ionic conductivity of the solid electrolytes of examples 11 to 16 at 400 to 800 ℃ was tested, and the results are shown in table 5; the thermal expansion coefficients of the solid electrolytes of examples 11 to 16 at 30 to 800 ℃ were measured, and the results are shown in Table 6.
TABLE 5 Ti in examples 11 to 16 of the present inventionxGayTa1-x-yO5-δConductivity of solid electrolyte
Figure BDA0002277381320000091
Figure BDA0002277381320000101
TABLE 6 Ti in examples 11 to 16 of the present inventionxGayTa1-x-yO5-δThermal expansion coefficient of solid electrolyte
Figure BDA0002277381320000102
As can be seen from Table 5, TiO prepared by the process of the present invention2、Ga2O3Doped with Ta2O5The solid electrolyte has conductivity over 10 at over 600 deg.C-3S/cm, can meet the working requirement of serving as an SOFC fuel cell. And has a thermal expansion coefficient of 2.50 to 3.04X 10 in the range of 30 to 800 ℃ as shown in Table 6-6K-1And belongs to a low-thermal expansion solid electrolyte material. And Y2O3Stabilized ZrO2(YSZ) solid electrolyte phase comparison of TiO prepared by the method of the present invention2、Ga2O3Doped with Ta2O5The solid electrolyte has a higher oxygen ion conductivity and a lower thermal expansion coefficient.
Examples 17 to 22
A solid electrolyte was prepared by following the procedure of example 1, except that the kinds and molar ratios of the metal powders in examples 11 to 16 were different from those in example 1:
example 17: ti powder with 6% mol content and Cr2O3The powder molar content is 2 percent, and the Ta powder molar content is 92 percent; to obtain the chemical formula of Ti0.6 Cr0.2Ta0.92O5-δThe solid electrolyte of (1);
example 18: ti powder 9 mol% and Cr2O3The powder molar content is 5 percent, and the Ta powder molar content is 86 percent; to obtain the chemical formula of Ti0.09 Cr0.05Ta0.86O5-δThe solid electrolyte of (1);
example 19: ti powder with 12% mol content and Cr2O3The powder molar content is 7 percent, and the Ta powder molar content is 81 percent; to obtain the chemical formula of Ti0.12 Cr0.07Ta0.81O5-δThe solid electrolyte of (1);
example 21: ti powder 18 mol% and Cr2O3The powder molar content is 13 percent, and the Ta powder molar content is 69 percent; to obtain the chemical formula of Ti0.18 Cr0.13Ta0.69O5-δThe solid electrolyte of (1);
example 22: ti powder of 20 mol% and Cr2O3The powder molar content is 15 percent, and the Ta powder molar content is 65 percent; to obtain the chemical formula of Ti0.2 Cr0.15Ta0.65O5-δThe solid electrolyte of (1);
the ionic conductivity of the solid electrolytes of examples 17 to 22 at 400 to 800 ℃ was tested, and the results are shown in table 7; the thermal expansion coefficients of the solid electrolytes of examples 17 to 22 at 30 to 800 ℃ were measured, and the results are shown in Table 8.
TABLE 7 Ti in examples 17 to 22 of the present inventionxCryTa1-x-yO5-δConductivity of solid electrolyte
Figure BDA0002277381320000111
TABLE 8 Ti in examples 17 to 22 of the present inventionxCryTa1-x-yO5-δThermal expansion coefficient of solid electrolyte
Figure BDA0002277381320000112
As can be seen from Table 7, TiO prepared by the process of the present invention2、Cr2O3Doped with Ta2O5The solid electrolyte has conductivity over 10 at over 600 deg.C-1S/cm, can meet the working requirement of serving as an SOFC fuel cell. And has a thermal expansion coefficient of 2.33 to 4.48X 10 in the range of 30 to 800 ℃ as shown in Table 8-6K-1And belongs to a low-thermal expansion solid electrolyte material. And Y2O3Stabilized ZrO2(YSZ) solid electrolyte phase comparison of TiO prepared by the method of the present invention2、Cr2O3Doped with Ta2O5The solid electrolyte has a higher oxygen ion conductivity and a lower thermal expansion coefficient.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A solid electrolyte having a chemical formula of formula 1:
TixCryTa1-x-yO5-δformula 1;
x is more than or equal to 0.05 and less than or equal to 0.30, y is more than or equal to 0.01 and less than or equal to 0.20, and delta represents the number of oxygen atoms reduced due to the generation of oxygen vacancies.
2. A method of preparing a solid electrolyte comprising the steps of:
A) mixing Ta powder, Ti powder and Cr powder2O3Dissolving metal powder in hydrofluoric acid, and then mixing the metal powder with an oxalic acid solution to obtain a mixed metal ion solution;
B) titrating an ammonia water solution containing polyethylene glycol into the mixed metal ion solution, carrying out precipitation reaction, and roasting the obtained precipitate to obtain nano mixed powder;
C) sintering the obtained nano mixed powder to obtain a solid electrolyte;
the solid electrolyte has a chemical formula shown in formula 1:
TixCryTa1-x-yO5-δformula 1;
x is more than or equal to 0.05 and less than or equal to 0.30, y is more than or equal to 0.01 and less than or equal to 0.20, and delta represents the number of oxygen atoms reduced due to the generation of oxygen vacancies.
3. The method according to claim 2, wherein the oxalic acid solution has a mass concentration of 10 to 15%.
4. The method according to claim 2, wherein the total concentration of the metal particles in the mixed metal ion solution is 0.001 to 0.5 mol/L.
5. The method according to claim 2, wherein the mass fraction of polyethylene glycol in the aqueous ammonia solution is 1 to 5%.
6. The preparation method according to claim 2, wherein the roasting temperature in the step B) is 500-1000 ℃;
the roasting time in the step B) is 1-4 h.
7. The preparation method according to claim 2, wherein the sintering temperature in the step C) is 1400-1600 ℃;
the sintering time is 1-5 hours.
8. The preparation method according to any one of claims 2 to 7, wherein after the mixed nanopowder obtained in step B) is obtained, the mixed nanopowder is mixed with an organic binder, and then dry pressing and forming are carried out to obtain a green body, and then the green body is sintered.
9. A solid oxide fuel cell comprising the solid electrolyte according to claim 1 or the solid electrolyte obtained by the production method according to any one of claims 2 to 8.
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