CN103367767A - Moderate-temperature solid oxide fuel battery doped double-perovskit-structure cathode material and preparation method thereof - Google Patents

Moderate-temperature solid oxide fuel battery doped double-perovskit-structure cathode material and preparation method thereof Download PDF

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CN103367767A
CN103367767A CN2013102942347A CN201310294234A CN103367767A CN 103367767 A CN103367767 A CN 103367767A CN 2013102942347 A CN2013102942347 A CN 2013102942347A CN 201310294234 A CN201310294234 A CN 201310294234A CN 103367767 A CN103367767 A CN 103367767A
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CN103367767B (en
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夏天
施展
蒙富常
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Heilongjiang University
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Abstract

The invention relates to a cathode material and a preparation method thereof, particularly a moderate-temperature solid oxide fuel battery doped double-perovskit-structure cathode material and a preparation method thereof. The invention aims to solve the problem that the catalytic oxygen reduction reaction capacity of the existing solid oxide fuel battery cathode material La1-xSrxMnO3 acutely reduces under moderate temperature conditions. The moderate-temperature solid oxide fuel battery doped double-perovskit-structure cathode material is an alkaline earth element Sr-doped double-perovskite powder material, and the chemical formula is EuBa1-xSrxCo2O5+delta. The method comprises the following steps: 1. weighing materials according to the chemical formula EuBa1-xSrxCo2O5+delta; 2. grinding to obtain a mixture; and 3. calcining to obtain the alkaline earth element Sr-doped double-perovskite powder material of which the chemical formula is EuBa1-xSrxCo2O5+delta. The invention is mainly used for preparing the moderate-temperature solid oxide fuel battery doped double-perovskit-structure cathode material.

Description

A kind of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material and preparation method thereof
Technical field
The present invention relates to a kind of cathode material and preparation method thereof.
Background technology
Solid Oxide Fuel Cell is a kind of electrochemical appliance of working under hot conditions, and its power conversion is not limited by Carnot cycle, and efficient is the first-selected alternative energy source of thermo-power station, gas turbine and automobile up to about 80%.Traditional Solid Oxide Fuel Cell serviceability temperature is generally 800～1000 ℃, and this can bring series of problems to fuel cell technology: for example material is aging, the phase counterdiffusion between the constituent element, and the processing maintenance cost is more high.The exploitation intermediate temperature solid oxide fuel cell has become one of this area research focus.Traditional cathode material for solid-oxide fuel cell La 1-xSr xMnO 3When being lower than 1000 ℃, lower oxygen ion conduction rate causes the catalytic oxidation-reduction respond sharply to reduce, and no longer is applicable to intermediate temperature solid oxide fuel cell.Warm area high electrocatalytic active cathode material becomes the vital task of fuel cell technology development in the exploitation.
Summary of the invention
The objective of the invention is to solve existing cathode material for solid-oxide fuel cell La 1-xSr xMnO 3The problem of the under mesophilic condition rapid reduction of catalytic oxidation-reduction respond, and a kind of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material and preparation method thereof is provided.
A kind of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material is the double-perovskite powder body material that alkaline earth element Sr mixes, and chemical formula is EuBa 1-xSr xCo 2O 5+ δ, 0＜x≤0.5,0.4≤δ≤0.5 wherein.
A kind of preparation method of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material, chemical formula is EuBa 1-xSr xCo 2O 5+ δThe alkaline earth element Sr double-perovskite powder body material that mixes specifically finish according to the following steps:
One, weighing: according to chemical formula EuBa 1-xSr xCo 2O 5+ δBy Eu:Ba:Sr:Co=1:(1-x): x:2 takes by weighing Eu 2O 3, BaCO 3, SrCO 3And Co 3O 4Described EuBa 1-xSr xCo 2O 5+ δIn 0＜x≤0.5,0.4≤δ≤0.5;
Two, grind: the Eu that step 1 is taken by weighing 2O 3, BaCO 3, SrCO 3And Co 3O 4Put into mortar and carry out ground and mixed, obtain mixed material;
Three, calcining: the mixed material that step 2 is obtained is to calcine 12h～24h under 1100～1250 ℃ of conditions in temperature, and namely obtaining chemical formula is EuBa 1-xSr xCo 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.
Advantage of the present invention: one, preparation method of the present invention is simple to operate, the intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material electrode heat treatment temperature lower (700～1000 ℃) of preparation is that polarization resistance is 0.17～0.38 Ω cm in 700 ℃, air atmosphere in temperature 2The time, the intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material of the present invention's preparation has good catalytic oxidation-reduction respond, solves existing cathode material for solid-oxide fuel cell La 1-xSr xMnO 3The problem that the catalytic oxidation-reduction respond sharply reduces under middle temperature (700～1000 ℃) condition; Two, the intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material of the present invention's preparation, chemical formula is EuBa 1-xSr xCo 2O 5+ δThe advantage of the double-perovskite powder body material that mixes of alkaline earth element Sr be that degree of crystallinity is high, conducting power is strong, thereby shows good electro catalytic activity; Three, the intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material of the present invention's preparation utilizes doping ion Sr 2+Has the Ba of ratio 2+The ionic radius that ion is less, thus polarizability to oxonium ion increased, and the electronic conduction ability that this has improved between metal ion and the oxonium ion makes it have higher conductivity and good electro catalytic activity.
Description of drawings
Fig. 1 is XRD figure, and to represent to test the chemical formula of a preparation be EuBaCo to A among the figure 2O 5+ δThe XRD figure of double-perovskite powder body material, to represent to test the chemical formulas of two preparations be EuBa to B among the figure 0.9Sr 0.1Co 2O 5+ δThe XRD figure of the double-perovskite powder body material that mixes of alkaline earth element Sr, to represent to test the chemical formulas of three preparations be EuBa to C among the figure 0.8Sr 0.2Co 2O 5+ δThe XRD figure of the double-perovskite powder body material that mixes of alkaline earth element Sr, to represent to test the chemical formulas of four preparations be EuBa to D among the figure 0.7Sr 0.3Co 2O 5+ δThe XRD figure of the double-perovskite powder body material that mixes of alkaline earth element Sr, to represent to test the chemical formulas of five preparations be EuBa to E among the figure 0.6Sr 0.4Co 2O 5+ δThe XRD figure of the double-perovskite powder body material that mixes of alkaline earth element Sr, to represent to test the chemical formulas of six preparations be EuBa to F among the figure 0.5Sr 0.5Co 2O 5+ δThe XRD figure of the double-perovskite powder body material that mixes of alkaline earth element Sr;
Fig. 2 is temperature-conductivity curve chart, and A represents that chemical property detects the EuBaCo of test 1 preparation among the figure 2O 5+ δThe temperature of pottery-conductivity curve chart, B represents that chemical property detects the EuBa of test 2 preparations among the figure 0.9Sr 0.1Co 2O 5+ δThe temperature of pottery-conductivity curve chart, C represents that chemical property detects the EuBa of test 3 preparations among the figure 0.8Sr 0.2Co 2O 5+ δThe temperature of pottery-conductivity curve chart, D represents that chemical property detects the EuBa of test 4 preparations among the figure 0.7Sr 0.3Co 2O 5+ δThe temperature of pottery-conductivity curve chart, E represents that chemical property detects the EuBa of test 5 preparations among the figure 0.6Sr 0.4Co 2O 5+ δThe temperature of pottery-conductivity curve chart, F represents that chemical property detects the EuBa of test 6 preparations among the figure 0.5Sr 0.5Co 2O 5+ δThe temperature of pottery-conductivity curve chart;
Fig. 3 is the polarization resistance curve chart, among the figure ● the thickness of expression catalytic oxidation-reduction respond detection test 1 preparation is the polarization of electrode resistance plot about 10 μ m, the thickness of zero expression catalytic oxidation-reduction respond detection test, 2 preparations are the polarization of electrode resistance plot about 10 μ m among the figure, among the figure ▲ thickness that expression catalytic oxidation-reduction respond detects test 3 preparations are the polarization of electrode resistance plot about 10 μ m, ■ represents that the thickness of catalytic oxidation-reduction respond detection test 4 preparations are the polarization of electrode resistance plot about 10 μ m among the figure, and represents that the thickness that catalytic oxidation-reduction respond detection test 5 prepares are the polarization of electrode resistance plot about 10 μ m among the figure.
Embodiment
Embodiment one: present embodiment is that a kind of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material is the double-perovskite powder body material that alkaline earth element Sr mixes, and chemical formula is EuBa 1-xSr xCo 2O 5+ δ, 0＜x≤0.5,0.4≤δ≤0.5 wherein.
The described intermediate temperature solid oxide fuel cell doping of present embodiment structure of double perovskite cathode material, chemical formula is EuBa 1-xSr xCo 2O 5+ δThe advantage of the double-perovskite powder body material that mixes of alkaline earth element Sr be that degree of crystallinity is high, conducting power is strong, thereby shows good electro catalytic activity.
The described intermediate temperature solid oxide fuel cell doping of present embodiment structure of double perovskite cathode material utilizes doping ion Sr 2+Has the Ba of ratio 2+The ionic radius that ion is less, thus polarizability to oxonium ion increased, and the electronic conduction ability that this has improved between metal ion and the oxonium ion makes it have higher conductivity and good electro catalytic activity.
Embodiment two: present embodiment is a kind of preparation method of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material, and chemical formula is EuBa 1-xSr xCo 2O 5+ δThe alkaline earth element Sr double-perovskite powder body material that mixes specifically finish according to the following steps:
One, weighing: according to chemical formula EuBa 1-xSr xCo 2O 5+ δBy Eu:Ba:Sr:Co=1:(1-x): x:2 takes by weighing Eu 2O 3, BaCO 3, SrCO 3And Co 3O 4Described EuBa 1-xSr xCo 2O 5+ δIn 0＜x≤0.5,0.4≤δ≤0.5;
Two, grind: the Eu that step 1 is taken by weighing 2O 3, BaCO 3, SrCO 3And Co 3O 4Put into mortar and carry out ground and mixed, obtain mixed material;
Three, calcining: the mixed material that step 2 is obtained is to calcine 12h～24h under 1100～1250 ℃ of conditions in temperature, and namely obtaining chemical formula is EuBa 1-xSr xCo 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.
The preparation method of present embodiment is simple to operate, the intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material electrode heat treatment temperature lower (700～1000 ℃) of preparation is that polarization resistance is 0.17～0.38 Ω cm in 700 ℃, air atmosphere in temperature 2The time, the intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material of present embodiment preparation has good catalytic oxidation-reduction respond, solves existing cathode material for solid-oxide fuel cell La 1-xSr xMnO 3The problem that the catalytic oxidation-reduction respond sharply reduces under middle temperature (700～1000 ℃) condition;
The synthetic chemical formula of present embodiment is EuBa 1-xSr xCo 2O 5+ δThe advantage of the double-perovskite powder body material that mixes of alkaline earth element Sr be that degree of crystallinity is high, conducting power is strong, thereby shows good electro catalytic activity.
The intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material of present embodiment preparation utilizes doping ion Sr 2+Has the Ba of ratio 2+The ionic radius that ion is less, thus polarizability to oxonium ion increased, and the electronic conduction ability that this has improved between metal ion and the oxonium ion makes it have higher conductivity and good electro catalytic activity.
Embodiment three: present embodiment with the difference of embodiment two is: the mill mixing concrete operations described in the step 2 are as follows: the Eu that step 1 is taken by weighing 2O 3, BaCO 3, SrCO 3And Co 3O 4Put into agate mortar ground and mixed 8min～12min, obtain initial mixed material, then in initial mixed material, add absolute ethyl alcohol, continue ground and mixed 25min～35min, namely obtain mixed material; The volume of described absolute ethyl alcohol and the mass ratio of initial mixed material are 10mL:(4g～7g).Other embodiments two are identical.
Embodiment four: present embodiment and one of embodiment two or three difference are: the mixed material that in the step 3 step 2 is obtained is to calcine 24h under 1100 ℃ of conditions in temperature, and namely obtaining chemical formula is EuBa 1-xSr xCo 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.Other embodiments two or three are identical.
Embodiment five: present embodiment and one of embodiment two or three difference are: the mixed material that in the step 3 step 2 is obtained is to calcine 24h under 1250 ℃ of conditions in temperature, and namely obtaining chemical formula is EuBa 1-xSr xCo 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.Other embodiments two or three are identical.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of preparation method of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material, chemical formula is EuBaCo 2O 5+ δThe double-perovskite powder body material specifically finish according to the following steps:
One, weighing: according to chemical formula EuBaCo 2O 5+ δTake by weighing Eu by Eu:Ba:Co=1:1:2 2O 3, BaCO 3And Co 3O 4Described EuBaCo 2O 5+ δMiddle δ=0.5
Two, grind: the Eu that step 1 is taken by weighing 2O 3, BaCO 3, and Co 3O 4Put into mortar and carry out ground and mixed, obtain mixed material;
Three, calcining: the mixed material that step 2 is obtained is to calcine 24h under 1250 ℃ of conditions in temperature, and namely obtaining chemical formula is EuBaCo 2O 5+ δThe double-perovskite powder body material.
Test two: a kind of preparation method of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material, chemical formula is EuBa 0.9Sr 0.1Co 2O 5+ δThe alkaline earth element Sr double-perovskite powder body material that mixes specifically finish according to the following steps:
One, weighing: according to chemical formula EuBa 0.9Sr 0.1Co 2O 5+ δTake by weighing Eu by Eu:Ba:Sr:Co=1:0.9:0.1:2 2O 3, BaCO 3, and Co 3O 4Described EuBa 0.9Sr 0.1Co 2O 5+ δMiddle δ=0.47
Two, grind: the Eu that step 1 is taken by weighing 2O 3, BaCO 3, SrCO 3And Co 3O 4Put into mortar and carry out ground and mixed, obtain mixed material;
Three, calcining: the mixed material that step 2 is obtained is to calcine 24h under 1250 ℃ of conditions in temperature, and namely obtaining chemical formula is EuBa 0.9Sr 0.1Co 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.
Test three: a kind of preparation method of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material, chemical formula is EuBa 0.8Sr 0.2Co 2O 5+ δThe alkaline earth element Sr double-perovskite powder body material that mixes specifically finish according to the following steps:
One, weighing: according to chemical formula EuBa 0.8Sr 0.2Co 2O 5+ δTake by weighing Eu by Eu:Ba:Sr:Co=1:0.8:0.2:2 2O 3, BaCO 3, and Co 3O 4Described EuBa 0.8Sr 0.2Co 2O 5+ δMiddle δ=0.45
Two, grind: the Eu that step 1 is taken by weighing 2O 3, BaCO 3, SrCO 3And Co 3O 4Put into mortar and carry out ground and mixed, obtain mixed material;
Three, calcining: the mixed material that step 2 is obtained is to calcine 24h under 1250 ℃ of conditions in temperature, and namely obtaining chemical formula is EuBa 0.8Sr 0.2Co 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.
Test four: a kind of preparation method of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material, chemical formula is EuBa 0.7Sr 0.3Co 2O 5+ δThe alkaline earth element Sr double-perovskite powder body material that mixes specifically finish according to the following steps:
One, weighing: according to chemical formula EuBa 0.7Sr 0.3Co 2O 5+ δTake by weighing Eu by Eu:Ba:Sr:Co=1:0.7:0.3:2 2O 3, BaCO 3, and Co 3O 4Described EuBa 0.7Sr 0.3Co 2O 5+ δMiddle δ=0.42
Two, grind: the Eu that step 1 is taken by weighing 2O 3, BaCO 3, SrCO 3And Co 3O 4Put into mortar and carry out ground and mixed, obtain mixed material;
Three, calcining: the mixed material that step 2 is obtained is to calcine 24h under 1250 ℃ of conditions in temperature, and namely obtaining chemical formula is EuBa 0.7Sr 0.3Co 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.
Test five: a kind of preparation method of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material, chemical formula is EuBa 0.6Sr 0.4Co 2O 5+ δThe alkaline earth element Sr double-perovskite powder body material that mixes specifically finish according to the following steps:
One, weighing: according to chemical formula EuBa 0.6Sr 0.4Co 2O 5+ δTake by weighing Eu by Eu:Ba:Sr:Co=1:0.6:0.4:2 2O 3, BaCO 3, and Co 3O 4Described EuBa 0.6Sr 0.4Co 2O 5+ δMiddle δ=0.41
Two, grind: the Eu that step 1 is taken by weighing 2O 3, BaCO 3, SrCO 3And Co 3O 4Put into mortar and carry out ground and mixed, obtain mixed material;
Three, calcining: the mixed material that step 2 is obtained is to calcine 24h under 1250 ℃ of conditions in temperature, and namely obtaining chemical formula is EuBa 0.6Sr 0.4Co 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.
Test six: a kind of preparation method of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material, chemical formula is EuBa 0.5Sr 0.5Co 2O 5+ δThe alkaline earth element Sr double-perovskite powder body material that mixes specifically finish according to the following steps:
One, weighing: according to chemical formula EuBa 0.5Sr 0.5Co 2O 5+ δTake by weighing Eu by Eu:Ba:Sr:Co=1:0.6:0.4:2 2O 3, BaCO 3, and Co 3O 4Described EuBa 0.5Sr 0.5Co 2O 5+ δMiddle δ=0.4;
Two, grind: the Eu that step 1 is taken by weighing 2O 3, BaCO 3, SrCO 3And Co 3O 4Put into mortar and carry out ground and mixed, obtain mixed material;
Three, calcining: the mixed material that step 2 is obtained is to calcine 24h under 1250 ℃ of conditions in temperature, and namely obtaining chemical formula is EuBa 0.5Sr 0.5Co 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.
Utilize the X-ray diffraction analysis instrument to detect test one to the intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode materials of test five preparations, testing result as shown in Figure 1, Fig. 1 is XRD figure, to represent to test the chemical formula of a preparation be EuBaCo to A among the figure 2O 5+ δThe XRD figure of double-perovskite powder body material, to represent to test the chemical formulas of two preparations be EuBa to B among the figure 0.9Sr 0.1Co 2O 5+ δThe XRD figure of the double-perovskite powder body material that mixes of alkaline earth element Sr, to represent to test the chemical formulas of three preparations be EuBa to C among the figure 0.8Sr 0.2Co 2O 5+ δThe XRD figure of the double-perovskite powder body material that mixes of alkaline earth element Sr, to represent to test the chemical formulas of four preparations be EuBa to D among the figure 0.7Sr 0.3Co 2O 5+ δThe XRD figure of the double-perovskite powder body material that mixes of alkaline earth element Sr, to represent to test the chemical formulas of five preparations be EuBa to E among the figure 0.6Sr 0.4Co 2O 5+ δThe XRD figure of the double-perovskite powder body material that mixes of alkaline earth element Sr, to represent to test the chemical formulas of six preparations be EuBa to F among the figure 0.5Sr 0.5Co 2O 5+ δThe XRD figure of the double-perovskite powder body material that mixes of alkaline earth element Sr, the intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material of testing as shown in Figure 1 one to five preparation is the structure of double perovskite material, does not find that other generate mutually.
Chemical property detects:
Chemical property detects test 1: the chemical formula that will test a preparation is EuBaCo 2O 5+ δThe double-perovskite powder body material put into tablet press machine, compressing under 200 MPas, then place high temperature Muffle furnace, sintering is 18 hours in 1250 ℃, air atmosphere, obtain fine and close ceramics sample, then be coated with the platinum slurry in the both sides of ceramics sample, again 700 ℃ of heat treatments 1.5 hours, obtain the double-perovskite pottery, i.e. EuBaCo 2O 5+ δPottery.
Chemical property detects test 2: the chemical formula that will test two preparations is EuBa 0.9Sr 0.1Co 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr put into tablet press machine, compressing under 200 MPas, then place high temperature Muffle furnace, sintering is 18 hours in 1250 ℃, air atmosphere, obtain fine and close ceramics sample, then be coated with the platinum slurry in the both sides of ceramics sample, again 700 ℃ of heat treatments 1.5 hours, obtain the double-perovskite pottery, i.e. EuBa 0.9Sr 0.1Co 2O 5+ δPottery.
Chemical property detects test 3: the chemical formula that will test three preparations is EuBa 0.8Sr 0.2Co 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr put into tablet press machine, compressing under 200 MPas, then place high temperature Muffle furnace, sintering is 18 hours in 1250 ℃, air atmosphere, obtain fine and close ceramics sample, then be coated with the platinum slurry in the both sides of ceramics sample, again 700 ℃ of heat treatments 1.5 hours, obtain the double-perovskite pottery, i.e. EuBa 0.8Sr 0.2Co 2O 5+ δPottery.
Chemical property detects test 4: the chemical formula that will test four preparations is EuBa 0.7Sr 0.3Co 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr put into tablet press machine, compressing under 200 MPas, then place high temperature Muffle furnace, sintering is 18 hours in 1250 ℃, air atmosphere, obtain fine and close ceramics sample, then be coated with the platinum slurry in the both sides of ceramics sample, again 700 ℃ of heat treatments 1.5 hours, obtain the double-perovskite pottery, i.e. EuBa 0.7Sr 0.3Co 2O 5+ δPottery.
Chemical property detects test 5: the chemical formula that will test five preparations is EuBa 0.6Sr 0.4Co 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr put into tablet press machine, compressing under 200 MPas, then place high temperature Muffle furnace, sintering is 18 hours in 1250 ℃, air atmosphere, obtain fine and close ceramics sample, then be coated with the platinum slurry in the both sides of ceramics sample, again 700 ℃ of heat treatments 1.5 hours, obtain the double-perovskite pottery, i.e. EuBa 0.6Sr 0.4Co 2O 5+ δPottery.
Chemical property detects test 6: the chemical formula that will test six preparations is EuBa 0.5Sr 0.5Co 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr put into tablet press machine, compressing under 200 MPas, then place high temperature Muffle furnace, sintering is 18 hours in 1250 ℃, air atmosphere, obtain fine and close ceramics sample, then be coated with the platinum slurry in the both sides of ceramics sample, again 700 ℃ of heat treatments 1.5 hours, obtain the double-perovskite pottery, i.e. EuBa 0.5Sr 0.5Co 2O 5+ δPottery.
Adopt the direct current four point probe technique that chemical property is detected the double-perovskite pottery that test 1-6 obtains and carry out the conductivity test, testing result as shown in Figure 2, Fig. 2 is temperature-conductivity curve chart, A represents that chemical property detects the EuBaCo of test 1 preparation among the figure 2O 5+ δThe temperature of pottery-conductivity curve chart, B represents that chemical property detects the EuBa of test 2 preparations among the figure 0.9Sr 0.1Co 2O 5+ δThe temperature of pottery-conductivity curve chart, C represents that chemical property detects the EuBa of test 3 preparations among the figure 0.8Sr 0.2Co 2O 5+ δThe temperature of pottery-conductivity curve chart, D represents that chemical property detects the EuBa of test 4 preparations among the figure 0.7Sr 0.3Co 2O 5+ δThe temperature of pottery-conductivity curve chart, E represents that chemical property detects the EuBa of test 5 preparations among the figure 0.6Sr 0.4Co 2O 5+ δThe temperature of pottery-conductivity curve chart, F represents that chemical property detects the EuBa of test 6 preparations among the figure 0.5Sr 0.5Co 2O 5+ δThe temperature of pottery-conductivity curve chart, the double-perovskite ceramic electrical conductance of chemical property detection test 2-6 preparation is 100～955Scm when temperature is 600 ℃ in air atmosphere as shown in Figure 2 -1, be 141～1246Scm when temperature is 500 ℃ -1, be 143～1255Scm when temperature is 400 ℃ -1, be 188～1384Scm when temperature is 300 ℃ -1, high conductivity numerical value is respectively 11 times (600 ℃) that the respective electrical chemical property detects the porous platinum electrode conductivity of test 1 preparation, 13 times (500 ℃), 13 times (400 ℃), 17 times (300 ℃) illustrate Sr 2+The doping of ion has improved the conductive performance of double perovskite materials, increased conductivity, improved the chemical property of double perovskite materials, when therefore the intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material of the present invention's preparation is for the preparation of the double-perovskite pottery, in air atmosphere, temperature can guarantee when being 300 ℃～600 ℃ that the double-perovskite pottery has high conductivity.
The catalytic oxidation-reduction respond detects test
The catalytic oxidation-reduction respond detects test 1: the chemical formula that will test two preparations is EuBa 0.9Sr 0.1Co 2O 5+ δThe double-perovskite powder body material high-energy ball milling that mixes of alkaline earth element Sr 10 hours, be EuBa with the 1g chemical formula behind the ball milling 0.9Sr 0.1Co 2O 5+ δAlkaline earth element Sr the double-perovskite powder body material powder and the 1g terpinol mixed grinding that mix obtain cathode slurry, cathode slurry is coated in uniformly the Ce of densification by spin coating method 0.9Gd 0.1O 1.95(CGO) ceramic disks both sides form the symmetry electrode structure, and electrode area is 1.6cm 2, again in baking oven in 120 ℃ of oven dry 2 hours, at last in high temperature Muffle furnace in 900 ℃ of heat treatments 1.5 hours, obtain thickness and be the electrode about 10 μ m.
The catalytic oxidation-reduction respond detects test 2: the chemical formula that will test three preparations is EuBa 0.8Sr 0.2Co 2O 5+ δThe double-perovskite powder body material high-energy ball milling that mixes of alkaline earth element Sr 10 hours, be EuBa with the 1g chemical formula behind the ball milling 0.8Sr 0.2Co 2O 5+ δAlkaline earth element Sr the double-perovskite powder body material powder and the 1g terpinol mixed grinding that mix obtain cathode slurry, cathode slurry is coated in uniformly the Ce of densification by spin coating method 0.9Gd 0.1O 1.95(CGO) ceramic disks both sides form the symmetry electrode structure, and electrode area is 1.6cm 2, again in baking oven in 120 ℃ of oven dry 2 hours, at last in high temperature Muffle furnace in 900 ℃ of heat treatments 1.5 hours, obtain thickness and be the electrode about 10 μ m.
The catalytic oxidation-reduction respond detects test 3: the chemical formula that will test four preparations is EuBa 0.7Sr 0.3Co 2O 5+ δThe double-perovskite powder body material high-energy ball milling that mixes of alkaline earth element Sr 10 hours, be EuBa with the 1g chemical formula behind the ball milling 0.7Sr 0.3Co 2O 5+ δAlkaline earth element Sr the double-perovskite powder body material powder and the 1g terpinol mixed grinding that mix obtain cathode slurry, cathode slurry is coated in uniformly the Ce of densification by spin coating method 0.9Gd 0.1O 1.95(CGO) ceramic disks both sides form the symmetry electrode structure, and electrode area is 1.6cm 2, again in baking oven in 120 ℃ of oven dry 2 hours, at last in high temperature Muffle furnace in 900 ℃ of heat treatments 1.5 hours, obtain thickness and be the electrode about 10 μ m.
The catalytic oxidation-reduction respond detects test 4: the chemical formula that will test five preparations is EuBa 0.6Sr 0.4Co 2O 5+ δThe double-perovskite powder body material high-energy ball milling that mixes of alkaline earth element Sr 10 hours, be EuBa with the 1g chemical formula behind the ball milling 0.6Sr 0.4Co 2O 5+ δAlkaline earth element Sr the double-perovskite powder body material powder and the 1g terpinol mixed grinding that mix obtain cathode slurry, cathode slurry is coated in uniformly the Ce of densification by spin coating method 0.9Gd 0.1O 1.95(CGO) ceramic disks both sides form the symmetry electrode structure, and electrode area is 1.6cm 2, again in baking oven in 120 ℃ of oven dry 2 hours, at last in high temperature Muffle furnace in 900 ℃ of heat treatments 1.5 hours, obtain thickness and be the electrode about 10 μ m.
The catalytic oxidation-reduction respond detects test 5: the chemical formula that will test six preparations is EuBa 0.5Sr 0.5Co 2O 5+ δThe double-perovskite powder body material high-energy ball milling that mixes of alkaline earth element Sr 10 hours, be EuBa with the 1g chemical formula behind the ball milling 0.5Sr 0.5Co 2O 5+ δAlkaline earth element Sr the double-perovskite powder body material powder and the 1g terpinol mixed grinding that mix obtain cathode slurry, cathode slurry is coated in uniformly the Ce of densification by spin coating method 0.9Gd 0.1O 1.95(CGO) ceramic disks both sides form the symmetry electrode structure, and electrode area is 1.6cm 2, again in baking oven in 120 ℃ of oven dry 2 hours, at last in high temperature Muffle furnace in 900 ℃ of heat treatments 1.5 hours, obtain thickness and be the electrode about 10 μ m.
The thickness that adopts ac impedance spectroscopy that catalytic oxidation-reduction respond detection test 1-5 is prepared is that the electrode electrocatalysis characteristic about 10 μ m is tested, testing result as shown in Figure 3, Fig. 3 is the polarization resistance curve chart, among the figure ● the thickness of expression catalytic oxidation-reduction respond detection test 1 preparation is the polarization of electrode resistance plot about 10 μ m, the thickness of zero expression catalytic oxidation-reduction respond detection test, 2 preparations are the polarization of electrode resistance plot about 10 μ m among the figure, among the figure ▲ thickness that expression catalytic oxidation-reduction respond detects test 3 preparations are the polarization of electrode resistance plot about 10 μ m, ■ represents that the thickness of catalytic oxidation-reduction respond detection test 4 preparations are the polarization of electrode resistance plot about 10 μ m among the figure, represents that the thickness of catalytic oxidation-reduction respond detection test 5 preparations are the polarization of electrode resistance plot about 10 μ m among the figure, proving by Fig. 3, is 700 ℃ in temperature, polarization resistance is 0.17～0.38 Ω cm in the air atmosphere 2, shown that testing the two intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode materials to test six preparations has good catalytic oxidation-reduction respond.

Claims (5)

1. an intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material is characterized in that intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material is the double-perovskite powder body material that alkaline earth element Sr mixes, and chemical formula is EuBa 1-xSr xCo 2O 5+ δ, 0＜x≤0.5,0.4≤δ≤0.5 wherein.
2. the preparation method of a kind of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material as claimed in claim 1 is characterized in that chemical formula is EuBa 1-xSr xCo 2O 5+ δThe alkaline earth element Sr double-perovskite powder body material that mixes specifically finish according to the following steps:
One, weighing: according to chemical formula EuBa 1-xSr xCo 2O 5+ δBy Eu:Ba:Sr:Co=1:(1-x): x:2 takes by weighing Eu 2O 3, BaCO 3, SrCO 3And Co 3O 4Described EuBa 1-xSr xCo 2O 5+ δIn 0＜x≤0.5,0.4≤δ≤0.5;
Two, grind: the Eu that step 1 is taken by weighing 2O 3, BaCO 3, SrCO 3And Co 3O 4Put into mortar and carry out ground and mixed, obtain mixed material;
Three, calcining: the mixed material that step 2 is obtained is to calcine 12h～24h under 1100～1250 ℃ of conditions in temperature, and namely obtaining chemical formula is EuBa 1-xSr xCo 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.
3. the preparation method of a kind of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material according to claim 2 is characterized in that the mill mixing concrete operations described in the step 2 are as follows: the Eu that step 1 is taken by weighing 2O 3, BaCO 3, SrCO 3And Co 3O 4Put into agate mortar ground and mixed 8min～12min, obtain initial mixed material, then in initial mixed material, add absolute ethyl alcohol, continue ground and mixed 25min～35min, namely obtain mixed material; The volume of described absolute ethyl alcohol and the mass ratio of initial mixed material are 10mL:(4g～7g).
4. the preparation method of a kind of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material according to claim 2, it is characterized in that the mixed material that in the step 3 step 2 is obtained is to calcine 24h under 1100 ℃ of conditions in temperature, namely obtaining chemical formula is EuBa 1-xSr xCo 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.
5. the preparation method of a kind of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material according to claim 2, it is characterized in that the mixed material that in the step 3 step 2 is obtained is to calcine 24h under 1250 ℃ of conditions in temperature, namely obtaining chemical formula is EuBa 1-xSr xCo 2O 5+ δThe double-perovskite powder body material that mixes of alkaline earth element Sr.
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