CN105976892A - Lanthanum indium co-doped strontium titanate conductor material and preparation method thereof - Google Patents
Lanthanum indium co-doped strontium titanate conductor material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a lanthanum indium co-doped strontium titanate conductor material and a preparation method thereof. According to the invention, a material chemical general formula is Sr1-xLaxTi1-yInyO3, and 0.1</=x</=0.4 and 0.03</=y</= 0.1; tetrabutyl titanate is used as a titanium source; anhydrous ethanol and isopropyl alcohol are used as solvents; the oxide of lanthanum and indium is used as a dopant raw material; a sol-gel method is used to prepare the lanthanum indium co-doped strontium titanate conductor material; the lanthanum indium co-doped strontium titanate conductor material has a single cubic phase perovskite structure, has the advantages of good stability, excellent electronic conduction and ion conductance, and can satisfy the application needs of many fields such as a fuel cell anode material, an oxygen permeation membrane, an automobile exhaust gas sensor and the like; and compared with a traditional solid-phase sintering method, the preparation method provided by the invention has the advantages of short reaction time, low energy consumption, high product density, uniform composition, wide application prospect and the like.
Description
Technical field
The present invention relates to technical field of function materials, particularly to a kind of lanthanum indium codope strontium titanates conductor material and system thereof
Preparation Method.
Background technology
Strontium titanates is Ca-Ti ore type broad stopband oxide, energy gap 3.2eV under room temperature.Owing to it has dielectric constant
Height, is lost the advantage such as low, Heat stability is good and excellent catalysis activity so that it is become a kind of electric function having extensive use
Ceramic material, all presents good in multiple fields such as sensor, fuel cell electrode, oxidative dehydrogenation, photocatalysis, three-way catalysts
Good application prospect.But, the strontium titanates electrical conductivity under room temperature is the lowest, greatly limit its application in conductive material.
In order to improve the performance of strontium titanates further, the method generally using doping in prior art.At strontium titanate material
In, the oxygen octahedra that oxygen element is formed is that concurrent connects, and its gap is relatively big, large-size ion can be allowed to insert so that titanium
Equal phase structure can be formed after acid strontium crystal structure doping, i.e. when the size of dopant ion requires to have greater difference with geometry,
It is maintained to strontium titanates Stability Analysis of Structures.At present, mainly by the list of A position and B position is adulterated, doped titanic acid the most respectively
The Sr position of strontium and Ti position adjust the electric conductivity of strontium titanates.Individually the A position (Sr position) of strontium titanate doping is donor doping, produces
Electronics, promotes the electronic conductivity of material, and the B position (Ti position) of independent strontium titanate doping is acceptor doping, produces oxygen ion vacancy,
Promote the ionic conductance of material.
But the strontium titanates of the single doping in A position or B position can not improve electronic conduction and the ionic conducting property of material simultaneously.
Therefore, prepare a kind of strontium titanates mixed conductor material with good electronic conduction and ionic conducting property and become ability
The technical problem that territory is urgently to be resolved hurrily.
Summary of the invention
It is an object of the invention to provide a kind of lanthanum indium codope strontium titanates conductor material and preparation method thereof.The present invention carries
The lanthanum indium codope strontium titanates conductor material of confession, good stability, electronic conductance and ionic conductance performance are excellent.
The invention provides a kind of lanthanum indium codope strontium titanates conductor material, chemical general formula shown in formula I:
Sr1-xLaxTi1-yInyO3Formulas I；
Wherein, 0.1≤x≤0.4,0.03≤y≤0.1.
Preferably, 0.2≤x≤0.3 in described Formulas I, 0.04≤y≤0.08.
The invention provides the preparation method of lanthanum indium codope strontium titanates conductor material described in a kind of technique scheme, bag
Include following steps:
(1) butyl titanate, lanthana, Indium sesquioxide. are mixed with isopropanol and dehydrated alcohol, obtain butyl titanate, oxygen
Change lanthanum and the anhydrous mixing precursor liquid of Indium sesquioxide.；
(2) the anhydrous mixing precursor liquid of butyl titanate, lanthana and the Indium sesquioxide. that described step (1) is obtained and strontium salt
It is aged after solution mixing, obtains the strontium titanates colloidal sol of lanthanum and indium codope；
(3) remove the solvent in the colloidal sol that described step (2) obtains, obtain the strontium titanates gel of lanthanum and indium codope；
(4) lanthanum described step (3) obtained and the strontium titanates gel roasting of indium codope, obtain lanthanum indium codope metatitanic acid
Strontium conductor material.
Preferably, in described step (1), the volume ratio of isopropanol and dehydrated alcohol is 3～5: 1.
Preferably, in described step (2), the solvent in strontium salt solution is dehydrated alcohol or water.
Preferably, one or more during described strontium salt is strontium nitrate, hydrochloric acid strontium, strontium carbonate and strontium acetate.
Preferably, in described step (2), mixing is carried out under agitation, and described mixing time is 30～60min.
Preferably, in described step (2), digestion time is 12～24h.
Preferably, the mode removing solvent in described step (3) is drying, and the temperature of described drying is 50～80 DEG C.
Preferably, in described step (4), the temperature of roasting is 900～1100 DEG C, and the time of roasting is 8～10h.
The present invention provide lanthanum indium codope strontium titanates conductor material, chemical general formula shown in formula I:
Sr1-xLaxTi1-yInyO3Formulas I；
Wherein, 0.1≤x≤0.4,0.03≤y≤0.1.The lanthanum indium codope strontium titanates conductor material tool of chemical general formula shown in Formulas I
There are single cubic phase perovskite structure, good stability；The present invention passes through lanthanum indium codope, forms Mixed electronic-ionic conduction machine
System, controls lanthanum and the doping of indium simultaneously, makes the A position doping of lanthanum not only promote the electronic conductance of material, also can promote material
Ionic conductance；The strontium titanates conductor material electronics conductance obtained and ionic conductance performance are excellent, it is possible to meet anode of fuel cell
Material, oxygen permeation membrane, the application of the numerous areas such as automobile exhaust sensor needs.Test result indicate that, 100-900 DEG C of scope
In, total conductivity is 0.06-0.08S/cm-1Between, in the range of 600-900 DEG C, ionic conductivity is 0.002-0.014S/
cm-1Between, higher than the simple superposition of the most single strontium titanate doping conductor conductivity of material performance of lanthanum and indium.
Present invention also offers the preparation method of above-mentioned lanthanum indium codope strontium titanates conductor material.It is molten that the present invention provides
Glue-gel method avoids solid-phase synthesis and causes sintering temperature too high (being typically higher than 1500 degree), and the material of synthesis is micro-
See the problem that composition is uneven；The oxide the most directly using alloy is that raw material is directly added into, it is not necessary to deionized water dissolving,
Overcome the technical barrier of butyl titanate hydrolysis, thus simplify sol-gel process, and then reduce sintering temperature, save
The energy, obtains the uniform material of microstructure.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum that the embodiment of the present invention 1,2 and 3 prepares lanthanum indium codope strontium titanates conductor material；
Fig. 2 is the XRD figure spectrum that the embodiment of the present invention 4 and 5 prepares lanthanum indium codope strontium titanates conductor material；
Fig. 3 is the microscopic appearance that the embodiment of the present invention 1 prepares lanthanum indium codope strontium titanates conductor material；
Fig. 4 is the microscopic appearance that the embodiment of the present invention 2 prepares lanthanum indium codope strontium titanates conductor material；
Fig. 5 is the microscopic appearance that the embodiment of the present invention 3 prepares lanthanum indium codope strontium titanates conductor material；
Fig. 6 is the microscopic appearance that the embodiment of the present invention 4 prepares lanthanum indium codope strontium titanates conductor material；
Fig. 7 is the microscopic appearance that the embodiment of the present invention 5 prepares lanthanum indium codope strontium titanates conductor material.
Detailed description of the invention
The invention provides a kind of lanthanum indium codope strontium titanates conductor material, chemical general formula shown in formula I:
Sr1-xLaxTi1-yInyO3Formulas I；
Wherein, 0.1≤x≤0.4,0.03≤y≤0.1.In the present invention, in described Formulas I the value of x and y be preferably 0.2≤
X≤0.3,0.04≤y≤0.08.In an embodiment of the present invention, described lanthanum indium codope strontium titanates conductor material can be specially
Sr0.7La0.3Ti0.96In0.04O3、Sr0.7La0.3Ti0.94In0.06O3、Sr0.7La0.3Ti0.92In0.08O3、
Sr0.7La0.3Ti0.94In0.06O3Or Sr0.8La0.2Ti0.92In0.08O3。
In the present invention, the Sr of A position is replaced by described La, forms donor doping, improves the electronic conductance of material；Institute
State In the Ti of B position is replaced, form acceptor doping, improve example conductance and the catalysis activity of material；La and In codope,
Formation Mixed electronic-ionic conduction mechanism, makes the A position doping of La not only promote the electronic conductance of material, also can promote material
Ionic conductance.
Present invention also offers the preparation method of lanthanum indium codope strontium titanates conductor material described in a kind of technique scheme,
Comprise the following steps:
(1) butyl titanate, lanthana, Indium sesquioxide. are mixed with isopropanol and dehydrated alcohol, obtain butyl titanate, oxygen
Change lanthanum and the anhydrous mixing precursor liquid of Indium sesquioxide.；
(2) the anhydrous mixing precursor liquid of butyl titanate, lanthana and the Indium sesquioxide. that described step (1) is obtained and strontium salt
It is aged after solution mixing, obtains the strontium titanates colloidal sol of lanthanum and indium codope；
(3) remove the solvent in the colloidal sol that described step (2) obtains, obtain the strontium titanates gel of lanthanum and indium codope；
(4) lanthanum described step (3) obtained and the strontium titanates gel roasting of indium codope, obtain lanthanum indium codope metatitanic acid
Strontium conductor material.
Butyl titanate, lanthana, Indium sesquioxide. are mixed by the present invention with isopropanol and dehydrated alcohol, obtain metatitanic acid four fourth
The anhydrous mixing precursor liquid of ester, lanthana and Indium sesquioxide..In the present invention, described lanthana, Indium sesquioxide. and butyl titanate
Mol ratio is preferably 1～1.5: 0.2～0.4: 4.6～4.8.The present invention does not has special restriction to the operation of described mixing, adopts
Technical scheme with mixing well known to those skilled in the art.In the present invention, it is preferred to first by butyl titanate with different
The mixed solvent mixing of propanol and dehydrated alcohol, obtains the anhydrous solution of butyl titanate.In the present invention, described isopropanol and
The volume ratio of dehydrated alcohol is preferably 3～5: 1；The molar concentration of described butyl titanate anhydrous solution be preferably 0.09～
0.12mol/L。
The anhydrous solution obtaining butyl titanate is preferably mixed by the present invention with lanthana and Indium sesquioxide., obtains metatitanic acid four fourth
The anhydrous mixing precursor liquid of ester, lanthana and Indium sesquioxide..In the present invention, described mixing is preferably carried out under conditions of stirring.
In the present invention, described stirring is preferably magnetic agitation；The speed of described stirring is preferably 500～700r/min, more preferably
550～650r/min；The time of described stirring is preferably 2～4h, more preferably 2.5～3.5h.
After obtaining the anhydrous mixing precursor liquid of butyl titanate, lanthana and Indium sesquioxide., the present invention is by precursor liquid and strontium salt
It is aged after solution mixing, obtains the strontium titanates colloidal sol of lanthanum and indium codope.In the present invention, described strontium salt be preferably strontium nitrate,
One or more in hydrochloric acid strontium, strontium carbonate and strontium acetate.Described strontium salt solution is mixed to get with dehydrated alcohol or water by strontium salt；
In described strontium salt solution, the molar concentration of strontium salt is preferably 1～2mol/L.In the present invention, described mixing is preferably at stirring condition
Under carry out；Described stirring is preferably magnetic agitation；The speed of described stirring be preferably 500～700r/min, more preferably 550～
650r/min；The time of described stirring is preferably 30～60min, more preferably 40～50min.In the present invention, described stirring
Strontium salt can be accelerated and form colloidal sol with butyl titanate.In the present invention, the time of described ageing is preferably 12～24h, more preferably
It is 16～20h.
After obtaining the strontium titanates colloidal sol of lanthanum and indium codope, the present invention by described colloidal sol solvent remove, obtain lanthanum and
The strontium titanates gel of indium codope.The present invention does not has special restriction to the operation of described removal solvent, uses art technology
The technical scheme preparing gel known to personnel.In the present invention, it is preferred to by drying the solvent removed in colloidal sol.At this
In invention, the temperature of described drying is preferably 50～80 DEG C, more preferably 60～70 DEG C；The time of described drying be preferably 24～
36h, more preferably 28～32h.
After completing described drying, the strontium titanates gel of the lanthanum obtained and indium codope is preferably pulverized by the present invention.?
In the present invention, after described pulverizing, the granularity of the strontium titanates gel of lanthanum and indium codope is preferably 100～200 mesh, and more preferably 140
～160 mesh.The present invention does not has special restriction to the operation of described pulverizing, uses the skill of pulverizing well known to those skilled in the art
Art scheme.In the present invention, it is preferred to use lapping mode to pulverize.
After obtaining the strontium titanates gel of lanthanum and indium codope, the strontium titanates gel of described lanthanum and indium codope is entered by the present invention
Row roasting, obtains lanthanum indium codope strontium titanates conductor powder after cooling.In the present invention, the temperature of described roasting is preferably 900
～1100 DEG C, more preferably 980～1020 DEG C；The time of described roasting is preferably 8～10h, more preferably 8.5～9.5h.?
In the present invention, described roasting can be with organics removal.In the present invention, the mode of described cooling is preferably furnace cooling.
The present invention preferably after completing described roasting, the lanthanum indium codope strontium titanates conductor powder obtained is carried out tabletting,
Sintering and cooling, obtain lanthanum indium codope strontium titanates conductor material.The present invention does not has special restriction to the operation of described tabletting,
Use the technical scheme of tabletting well known to those skilled in the art.In the present invention, described tabletting preferably employs single shaft and adds
Pressure compacting；The pressure of described tabletting is preferably 5～10MPa, more preferably 7～8MPa.In the present invention, product after described tabletting
It is preferably dimensioned to be diameter 8～10mm, thickness 1～2mm.In the present invention, the temperature of described sintering is preferably 1200～1500
DEG C, more preferably 1300～1400 DEG C, most preferably 1340～1370 DEG C；The time of described sintering is preferably 3～6h, more preferably
It is 4～5h.In the present invention, described sintering can improve the compactness of material.In the present invention, the mode of described cooling is preferred
For furnace cooling.
In order to further illustrate the present invention, the lanthanum indium codope strontium titanates conductor present invention provided below in conjunction with embodiment
Material and preparation method thereof is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1:
The doping content of lanthanum is 30%, and the doping content of indium is 4%:
(1) first according to Sr0.7La0.3Ti0.96In0.04O3In stoichiometric proportion (strontium, lanthanum mol ratio are 70: 30；Titanium, indium
Mol ratio is 96: 4) to weigh 1.63g butyl titanate, 0.24g lanthana and 0.028g Indium sesquioxide. then molten by butyl titanate
In the mixed solvent of 30mL isopropanol and 10mL dehydrated alcohol, after being stirred until homogeneous, lanthana and Indium sesquioxide. are put into metatitanic acid
In the mixed solution of four butyl esters, i.e. can get butyl titanate, lanthana and Indium sesquioxide. in 600r/min speed magnetic agitation 3h
Anhydrous mixing precursor liquid.
(2) according to Sr0.7La0.3Ti0.96In0.04O3In stoichiometric proportion (strontium, lanthanum mol ratio are 70: 30) weigh 0.75g
Strontium acetate, is then dissolved in 3mL deionized water by strontium acetate, and stirring is to being completely dissolved formation strontium salt solution；By butyl titanate, oxygen
Change lanthanum and the anhydrous mixing precursor liquid of Indium sesquioxide. and strontium acetate solution mixes, and magnetic agitation under 600r/min speed
30min, obtains adulterate lanthanum and the strontium titanates colloidal sol of indium after being aged 24 hours.
(3) by drying 30h at the doping lanthanum of gained and the strontium titanates colloidal sol 50 DEG C of indium, adulterated after removing organic solvent
The strontium titanates gel of lanthanum and indium.
(4) after the strontium titanates xerogel of doping lanthanum and indium being ground to form 100 mesh powder body, constant temperature calcining under the conditions of 900 DEG C
10h, obtains adulterate lanthanum, the Sr titanate powder of indium after furnace cooling.
(5) doping lanthanum, the Sr titanate powder of indium are carried out single shaft pressurization under the pressure of 5MPa, after being compressed into tablet form,
It is incubated 5h under the conditions of 1300 DEG C, after furnace cooling, obtains the strontium titanates mixed conductor material of lanthanum, indium codope.
Strontium acetate in step (2) can use the strontium nitrate of same molar, strontium titanates or hydrochloric acid strontium to substitute.
The CHI660B type electrochemical workstation lanthanum to obtaining, the strontium titanates mixed conductor material of indium codope is used to carry out
Electrical conductivity detects.In frequency range 10-2-105In Hz, the impedance spectrum of test sample.
With platinum slurry, 2 surface-coated of sample are uniform, then after being stained with platinum filament, at 800 DEG C, calcine 30min,
To membrane electrode, carry out the measurement of total conductivity.
The method using electronics blocking electrode measures ionic conductivity, and YSZ is pure oxygen ion conductor, using YSZ as electronics
The electrolyte sheet of blocking electrode, uniformly fills platinum slurry by the coupons sintered one side, is pasted onto on YSZ sheet；The examination that will post
Sample-YSZ composite sheet is put in tube furnace, calcines 30min at 800 DEG C, utilizes platinum slurry to be linked together by two thin slices；To burn again
After good, the edge of sample encapsulant covers, and by completely isolated to the edge of sample and air, makes the gap at two thin slice junction
Completely enclosed；Finally platinum pulp layer is all coated on sample-YSZ composite sheet two sides, is stained with platinum filament, sinter 30min at 800 DEG C,
Obtain sample to be tested.
After testing, in the range of 100～900 DEG C, total conductivity is 0.06～0.08S/cm-1Between, at 600～900 DEG C
In the range of, ionic conductivity is 0.001～0.008S/cm-1Between.
Embodiment 2:
The doping content of lanthanum is 30%, and the doping content of indium is 6%:
(1) first according to Sr0.7La0.3Ti0.94In0.06O3In stoichiometric proportion weigh 1.6g butyl titanate, 0.24g
Lanthana and 0.042g Indium sesquioxide.；Then butyl titanate is dissolved in 40mL isopropanol and the mixed solvent of 10mL dehydrated alcohol
In, after being stirred until homogeneous, lanthana and Indium sesquioxide. are put in the mixed solution of butyl titanate, at 600r/min speed magnetic force
Stirring 3h i.e. can get the anhydrous mixing precursor liquid of butyl titanate, lanthana and Indium sesquioxide..
(2) according to Sr0.7La0.3Ti0.94In0.06O3In stoichiometric proportion weigh 0.75g strontium acetate, then by strontium acetate
Being dissolved in 3mL deionized water, stirring is to being completely dissolved formation strontium salt solution；Anhydrous by butyl titanate, lanthana and Indium sesquioxide.
Mixing precursor liquid and strontium acetate solution mix, and magnetic agitation 60min under 600r/min speed, after being aged 12 hours
To doping lanthanum and the strontium titanates colloidal sol of indium.
(3) the doping lanthanum of gained and the strontium titanates colloidal sol of indium are dried 30h at 50 DEG C, mixed after removing organic solvent
The strontium titanates gel of miscellaneous lanthanum and indium.
(4) after the strontium titanates xerogel of doping lanthanum and indium being ground to form 100 mesh powder body, constant temperature calcining under the conditions of 1100 DEG C
8h, obtains adulterate lanthanum, the Sr titanate powder of indium after furnace cooling.
(5) doping lanthanum, the Sr titanate powder of indium are carried out single shaft pressurization under the pressure of 5MPa, after being compressed into tablet form,
It is incubated 6h under the conditions of 1200 DEG C, after furnace cooling, obtains the strontium titanates mixed conductor material of lanthanum, indium codope.
Strontium acetate in step (2) can use the strontium nitrate of same molar, strontium titanates or hydrochloric acid strontium to substitute.
Described in employing embodiment 1, the strontium titanates mixed conductor material to the lanthanum obtained, indium codope carries out electrical conductivity inspection
Survey.After testing, in the range of 100-900 DEG C, total conductivity is 0.03～0.05S/cm-1Between, in the range of 600～900 DEG C,
Ionic conductivity is 0.0012～0.01S/cm-1Between.
Embodiment 3:
The doping content of lanthanum is 30%, and the doping content of indium is 8%:
(1) first according to Sr0.7La0.3Ti0.92In0.08O3In stoichiometric proportion weigh 1.56g butyl titanate, 0.24g
Lanthana and 0.056g Indium sesquioxide.；Then butyl titanate is dissolved in 30mL isopropanol and the mixed solvent of 10mL dehydrated alcohol
In, after being stirred until homogeneous, lanthana and Indium sesquioxide. are put in the mixed solution of butyl titanate, at 600r/min speed magnetic force
Stirring 3h i.e. can get the anhydrous mixing precursor liquid of butyl titanate, lanthana and Indium sesquioxide..
(2) first according to Sr0.7La0.3Ti0.92In0.08O3In stoichiometric proportion weigh 0.75g strontium acetate, then by second
Acid strontium is dissolved in 3mL deionized water, and stirring is to being completely dissolved formation strontium salt solution；By butyl titanate, lanthana and Indium sesquioxide.
Anhydrous mixing precursor liquid and strontium acetate solution mix, and magnetic agitation 30min under 600r/min speed, are aged 24 hours
After obtain adulterate lanthanum and the strontium titanates colloidal sol of indium.
(3) by drying 24h at the doping lanthanum of gained and the strontium titanates colloidal sol 70 DEG C of indium, adulterated after removing organic solvent
The strontium titanates gel of lanthanum and indium.
(4) after the strontium titanates xerogel of doping lanthanum and indium being ground to form 200 mesh powder body, constant temperature calcining under the conditions of 1000 DEG C
9h, obtains adulterate lanthanum, the Sr titanate powder of indium after furnace cooling.
(5) doping lanthanum, the Sr titanate powder of indium are carried out single shaft pressurization under the pressure of 10MPa, after being compressed into tablet form,
It is incubated 5h under the conditions of 1300 DEG C, after furnace cooling, obtains the strontium titanates mixed conductor material of lanthanum, indium codope.
Strontium acetate in step (2) can use the strontium nitrate of same molar, strontium titanates or hydrochloric acid strontium to substitute.
Described in employing embodiment 1, the strontium titanates mixed conductor material to the lanthanum obtained, indium codope carries out electrical conductivity inspection
Survey.After testing, in the range of 100-900 DEG C, total conductivity is 0.03～0.05S/cm-1Between, in the range of 600～900 DEG C,
Ionic conductivity is 0.0014～0.012S/cm-1Between.
Embodiment 4:
The doping content of lanthanum is 30%, and the doping content of indium is 6%:
(1) first according to Sr0.7La0.3Ti0.94In0.06O3In stoichiometric proportion weigh 1.6g butyl titanate, 0.24g
Lanthana and 0.042g Indium sesquioxide.；Then butyl titanate is dissolved in 50mL isopropanol and the mixed solvent of 10mL dehydrated alcohol
In, after being stirred until homogeneous, lanthana and Indium sesquioxide. are put in the mixed solution of butyl titanate, at 600r/min speed magnetic force
Stirring 3h i.e. can get the anhydrous mixing precursor liquid of butyl titanate, lanthana and Indium sesquioxide..
(2) according to Sr0.7La0.3Ti0.94In0.06O3In stoichiometric proportion weigh 0.75g strontium acetate, then by strontium acetate
Being dissolved in 3mL deionized water, stirring is to being completely dissolved formation strontium salt solution；Anhydrous by butyl titanate, lanthana and Indium sesquioxide.
Mixing precursor liquid and strontium acetate solution mix, and magnetic agitation 60min under 600r/min speed, after being aged 12 hours
To doping lanthanum and the strontium titanates colloidal sol of indium.
(3) the doping lanthanum of gained and the strontium titanates colloidal sol of indium are dried 36h at 50 DEG C, mixed after removing organic solvent
The strontium titanates gel of miscellaneous lanthanum and indium.
(4) after the strontium titanates xerogel of doping lanthanum and indium being ground to form 150 mesh powder body, constant temperature calcining under the conditions of 1100 DEG C
8h, obtains adulterate lanthanum, the Sr titanate powder of indium after furnace cooling.
(5) doping lanthanum, the Sr titanate powder of indium are carried out single shaft pressurization under the pressure of 5MPa, after being compressed into tablet form,
It is incubated 4h under the conditions of 1400 DEG C, after furnace cooling, obtains the strontium titanates mixed conductor material of lanthanum, indium codope.
Strontium acetate in step (2) can use the strontium nitrate of same molar, strontium titanates or hydrochloric acid strontium to substitute.
Described in employing embodiment 1, the strontium titanates mixed conductor material to the lanthanum obtained, indium codope carries out electrical conductivity inspection
Survey.After testing, in the range of 100-900 DEG C, total conductivity is 0.036～0.06S/cm-1Between, 600～900 DEG C of scopes
In, ionic conductivity is 0.002～0.014S/cm-1Between.
Embodiment 5:
The doping content of lanthanum is 20%, and the doping content of indium is 8%:
(1) first according to Sr0.8La0.2Ti0.92In0.08O3In stoichiometric proportion weigh 1.56g butyl titanate, 0.16g
Lanthana and 0.056g Indium sesquioxide.；Then butyl titanate is dissolved in 40mL isopropanol and the mixed solvent of 10mL dehydrated alcohol
In, after being stirred until homogeneous, lanthana and Indium sesquioxide. are put in the mixed solution of butyl titanate, at 600r/min speed magnetic force
Stirring 3h i.e. can get the anhydrous mixing precursor liquid of butyl titanate, lanthana and Indium sesquioxide..
(2) according to Sr0.8La0.2Ti0.92In0.08O3In stoichiometric proportion weigh 0.86g strontium acetate, then by strontium acetate
Being dissolved in 5mL deionized water, stirring is to being completely dissolved formation strontium salt solution；Anhydrous by butyl titanate, lanthana and Indium sesquioxide.
Mixing precursor liquid and strontium acetate solution mix, and magnetic agitation 30min under 600r/min speed, after being aged 24 hours
To doping lanthanum and the strontium titanates colloidal sol of indium.
(3) by drying 36h at the doping lanthanum of gained and the strontium titanates colloidal sol 50 DEG C of indium, adulterated after removing organic solvent
The strontium titanates gel of lanthanum and indium.
(4) after the strontium titanates xerogel of doping lanthanum and indium being ground to form 200 mesh powder body, constant temperature calcining under the conditions of 900 DEG C
10h, obtains adulterate lanthanum, the Sr titanate powder of indium after furnace cooling.
(5) doping lanthanum, the Sr titanate powder of indium are carried out single shaft pressurization under the pressure of 5MPa, after being compressed into tablet form,
It is incubated 3h under the conditions of 1500 DEG C, after furnace cooling, obtains lanthanum indium codope strontium titanates mixed conductor material.
Strontium acetate in step (2) can use the strontium nitrate of same molar, strontium titanates or hydrochloric acid strontium to substitute.
Described in employing embodiment 1, the strontium titanates mixed conductor material to the lanthanum obtained, indium codope carries out electrical conductivity inspection
Survey.After testing, in the range of 100-900 DEG C, total conductivity is 0.032～0.052S/cm-1Between, 600～900 DEG C of scopes
In, ionic conductivity is 0.0016～0.012S/cm-1Between.
Respectively by Rigaku D/max-A type X-ray diffraction (XRD) instrument and Quanta FEG 650 type electron scanning Electronic Speculum
(SEM) the indium codope strontium titanates mixed conductor material prepared embodiment 1～5 carries out phase structure and microscopic appearance inspection
Survey.
The XRD figure spectrum of the indium codope strontium titanates mixed conductor material that embodiment 1～3 prepares is as it is shown in figure 1, wherein
(1), (2), (3) be respectively embodiment 1,2,3 XRD figure spectrum, result shows: the doping content of indium is the lanthanum of 4%, indium codope
Strontium titanates mixed conductor material is single cubic phase perovskite structure, and the clear face of diffraction maximum is discrete, without any miscellaneous peak, shows doping
Indium ion enter strontium titanates lattice, formed solid solution；The doping content of indium is respectively 6%, and the diffracting spectrum of 8% is also corresponding vertical
Side's perovskite structure, diffraction maximum is clear, and diffraction maximum occurs small skew.
The XRD figure spectrum of the indium codope strontium titanates mixed conductor material that embodiment 4 and 5 prepares is as in figure 2 it is shown, wherein
(4), (5) be respectively embodiment 4,5 XRD figure spectrum, all maintain single cubic phase perovskite structure, diffraction maximum is clear.
The microscopic appearance figure of the indium codope strontium titanates mixed conductor material that embodiment 1～5 prepares respectively such as Fig. 3～
Shown in 7, result shows: all of sample sintered density is all more than 90%.
As can be seen from the above embodiments, the material that the present invention provides has single cubic phase perovskite structure, stability
Good, electronic conductance and ionic conductance performance are excellent, and in the range of 100-900 DEG C, total conductivity is 0.03-0.08S/cm-1Between,
In the range of 600-900 DEG C, ionic conductivity is 0.001-0.014S/cm-1Between.
The above is only the preferred embodiment of the present invention, and the present invention not makees any pro forma restriction.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to if making
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a lanthanum indium codope strontium titanates conductor material, chemical general formula shown in formula I:
Sr1-xLaxTi1-yInyO3Formulas I；
Wherein, 0.1≤x≤0.4,0.03≤y≤0.1.
Material the most according to claim 1, it is characterised in that 0.2≤x≤0.3 in described Formulas I, 0.04≤y≤0.08.
3. a preparation method for lanthanum indium codope strontium titanates conductor material described in claim 1 or 2, comprises the following steps:
(1) butyl titanate, lanthana, Indium sesquioxide. are mixed with isopropanol and dehydrated alcohol, obtain butyl titanate, lanthana
Anhydrous mixing precursor liquid with Indium sesquioxide.；
(2) the anhydrous mixing precursor liquid of butyl titanate, lanthana and the Indium sesquioxide. that described step (1) is obtained and strontium salt solution
It is aged after mixing, obtains the strontium titanates colloidal sol of lanthanum and indium codope；
(3) remove the solvent in the colloidal sol that described step (2) obtains, obtain the strontium titanates gel of lanthanum and indium codope；
(4) lanthanum described step (3) obtained and the strontium titanates gel roasting of indium codope, obtain lanthanum indium codope strontium titanates and lead
Body material.
Preparation method the most according to claim 3, it is characterised in that isopropanol and dehydrated alcohol in described step (1)
Volume ratio is 3～5: 1.
Preparation method the most according to claim 3, it is characterised in that in described step (2), the solvent in strontium salt solution is
Dehydrated alcohol or water.
Preparation method the most according to claim 5, it is characterised in that described strontium salt be strontium nitrate, hydrochloric acid strontium, strontium carbonate and
One or more in strontium acetate.
Preparation method the most according to claim 3, it is characterised in that in described step (2), mixing is entered under agitation
OK, described mixing time is 30～60min.
Preparation method the most according to claim 3, it is characterised in that in described step (2), digestion time is 12～24h.
Preparation method the most according to claim 3, it is characterised in that remove the mode of solvent in described step (3) for drying
Dry, the temperature of described drying is 50～80 DEG C.
Preparation method the most according to claim 3, it is characterised in that in described step (4) temperature of roasting be 900～
1100 DEG C, the time of roasting is 8～10h.
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