CN105976892B - A kind of lanthanum indium codope strontium titanates conductor material and preparation method thereof - Google Patents
A kind of lanthanum indium codope strontium titanates conductor material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of lanthanum indium codope strontium titanates conductor material and preparation method thereof.The materials chemistry formula that the present invention is provided is Sr1‑xLaxTi1‑yInyO3, wherein, 0.1≤x≤0.4,0.03≤y≤0.1.The present invention uses butyl titanate for titanium source, and absolute ethyl alcohol and isopropanol, using the oxide of lanthanum and indium as doping raw material, lanthanum indium codope strontium titanates conductor material are prepared by sol-gal process as solvent.The lanthanum indium codope mixed conductor material that the present invention is provided has single cubic phase perovskite structure, stability is good, and electronic conductance and ionic conductance performance are excellent, disclosure satisfy that fuel cell anode materials, oxygen permeation membrane, the application of the numerous areas such as automobile exhaust sensor needs.The preparation method that the present invention is provided compared with traditional solid-phase sintering method, with the reaction time is short, energy consumption is low, product consistency it is high, the advantages of constituting uniform has broad application prospects.
Description
Technical field
The present invention relates to technical field of function materials, more particularly to a kind of lanthanum indium codope strontium titanates conductor material and its system
Preparation Method.
Background technology
Strontium titanates is Ca-Ti ore type broad stopband oxide, at room temperature energy gap 3.2eV.Because it has dielectric constant
Height, the advantages of low, heat endurance good and excellent catalytic activity is lost becomes a kind of electric function for having an extensive use
Ceramic material, is all presented 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 normal temperature is very low, greatly limit its application in conductive material.
In order to further improve the performance of strontium titanates, in the prior art generally using the method for doping.In strontium titanate material
In, the oxygen octahedra of oxygen element formation connects for concurrent, and its gap is larger, large-size ion can be allowed to insert so that titanium
Equal phase structure can be formed after sour strontium crystal structure doping, i.e., when the size of Doped ions has greater difference with geometry requirement,
It is maintained to strontium titanates Stability Analysis of Structures.At present, mainly adulterated by the list to A and B, that is, doped titanic acid respectively
The Sr positions of strontium and the Ti electric conductivities to adjust strontium titanates.The A positions (Sr) of independent strontium titanate doping are donor doping, are produced
Electronics, promotes the electronic conductivity of material, the B positions (Ti) of independent strontium titanate doping are acceptor doping, produce oxygen ion vacancy,
Promote the ionic conductance of material.
But the strontium titanates of A or B single doping can not improve the electronic conduction and ionic conducting property of material simultaneously.
Therefore, prepare a kind of while the strontium titanates mixed conductor material with good electronic conduction and ionic conducting property turns into ability
Domain technical problem urgently to be resolved hurrily.
The content 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 is carried
The lanthanum indium codope strontium titanates conductor material of confession, stability is good, and electronic conductance and ionic conductance performance are excellent.
The invention provides a kind of lanthanum indium codope strontium titanates conductor material, chemical general formula is shown in formula I：
Sr1-xLaxTi1-yInyO3Formulas I；
Wherein, 0.1≤x≤0.4,0.03≤y≤0.1.
It is preferred that, 0.2≤x≤0.3,0.04≤y≤0.08 in the Formulas I.
The invention provides a kind of preparation method of lanthanum indium codope strontium titanates conductor material described in above-mentioned technical proposal, bag
Include following steps：
(1) butyl titanate, lanthana, indium oxide are mixed with isopropanol and absolute ethyl alcohol, obtains butyl titanate, oxygen
Change the anhydrous mixing precursor liquid of lanthanum and indium oxide；
(2) the anhydrous mixing precursor liquid and strontium salt for butyl titanate, lanthana and the indium oxide for obtaining the step (1)
It is aged after solution mixing, obtains the strontium titanates colloidal sol of lanthanum and indium codope；
(3) solvent in the colloidal sol that the step (2) obtains is removed, the strontium titanates gel of lanthanum and indium codope is obtained；
(4) the strontium titanates gel roasting of the lanthanum and indium codope that obtain the step (3), obtains lanthanum indium codope metatitanic acid
Strontium conductor material.
It is preferred that, the volume ratio of isopropanol and absolute ethyl alcohol is 3~5: 1 in the step (1).
It is preferred that, the solvent in the step (2) in strontium salt solution is absolute ethyl alcohol or water.
It is preferred that, the strontium salt is the one or more in strontium nitrate, hydrochloric acid strontium, strontium carbonate and strontium acetate.
It is preferred that, mixing is carried out under agitation in the step (2), and the mixing time is 30~60min.
It is preferred that, digestion time is 12~24h in the step (2).
It is preferred that, it is drying that the mode of solvent is removed in the step (3), and the temperature of the drying is 50~80 DEG C.
It is preferred that, the temperature of roasting is 900~1100 DEG C in the step (4), and the time of roasting is 8~10h.
The lanthanum indium codope strontium titanates conductor material that the present invention is provided, chemical general formula is 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 of chemical general formula shown in Formulas I is led
Body material has single cubic phase perovskite structure, and stability is good；The present invention is formed electron-ion and mixed by lanthanum indium codope
Conductive mechanism is closed, while controlling the doping of lanthanum and indium, the A positions of lanthanum is adulterated and not only promotes the electronic conductance of material, can also promote
Enter the ionic conductance of material；Obtained strontium titanates conductor material electronicses conductance and ionic conductance performance is excellent, disclosure satisfy that fuel
Battery anode material, oxygen permeation membrane, the application of the numerous areas such as automobile exhaust sensor needs.Test result indicates that, in 100-900
In the range of DEG C, 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 lanthanum and the simple superposition of the single strontium titanate doping conductor conductivity of material performance of indium difference.
Present invention also offers the preparation method of above-mentioned lanthanum indium codope strontium titanates conductor material.It is molten that the present invention is provided
Glue-gel method, which avoids solid-phase synthesis, causes sintering temperature too high (being typically higher than 1500 degree), and the material of synthesis is micro-
See the problem of composition is uneven；Directly the oxide of dopant is used to be directly added into for raw material simultaneously, without deionized water dissolving,
The technical barrier of butyl titanate hydrolysis is overcome, so as to simplify sol-gel process, and then sintering temperature is reduced, saved
The energy, obtains the uniform material of microstructure.
Brief description of the drawings
Fig. 1 is the XRD 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 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.
Embodiment
The invention provides a kind of lanthanum indium codope strontium titanates conductor material, chemical general formula is shown in formula I：
Sr1-xLaxTi1-yInyO3Formulas I；
Wherein, 0.1≤x≤0.4,0.03≤y≤0.1.In the present invention, in the Formulas I x and y value be preferably 0.2≤
X≤0.3,0.04≤y≤0.08.In an embodiment of the present invention, the 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 La is replaced to the Sr of A, forms donor doping, improves the electronic conductance of material；Institute
The Ti that In is stated to B is replaced, and forms acceptor doping, improves the example conductance and catalytic activity of material；La and In codopes,
Mixed electronic- ionic conduction mechanism is formed, La A positions is adulterated and not only promotes the electronic conductance of material, can also promote material
Ionic conductance.
Present invention also offers a kind of preparation method of lanthanum indium codope strontium titanates conductor material described in above-mentioned technical proposal,
Comprise the following steps：
(1) butyl titanate, lanthana, indium oxide are mixed with isopropanol and absolute ethyl alcohol, obtains butyl titanate, oxygen
Change the anhydrous mixing precursor liquid of lanthanum and indium oxide；
(2) the anhydrous mixing precursor liquid and strontium salt for butyl titanate, lanthana and the indium oxide for obtaining the step (1)
It is aged after solution mixing, obtains the strontium titanates colloidal sol of lanthanum and indium codope；
(3) solvent in the colloidal sol that the step (2) obtains is removed, the strontium titanates gel of lanthanum and indium codope is obtained；
(4) the strontium titanates gel roasting of the lanthanum and indium codope that obtain the step (3), obtains lanthanum indium codope metatitanic acid
Strontium conductor material.
The present invention mixes butyl titanate, lanthana, indium oxide with isopropanol and absolute ethyl alcohol, obtains the fourth of metatitanic acid four
The anhydrous mixing precursor liquid of ester, lanthana and indium oxide.In the present invention, the lanthana, indium oxide and butyl titanate
Mol ratio is preferably 1~1.5: 0.2~0.4: 4.6~4.8.The present invention, without special restriction, is adopted to the operation of the mixing
With the technical scheme of mixing well known to those skilled in the art.In the present invention, it is preferred to first by butyl titanate with it is different
The mixed solvent mixing of propyl alcohol and absolute ethyl alcohol, obtains the anhydrous solution of butyl titanate.In the present invention, the isopropanol and
The volume ratio of absolute ethyl alcohol is preferably 3~5: 1；The molar concentration of the butyl titanate anhydrous solution is preferably 0.09~
0.12mol/L。
The present invention preferably mixes the anhydrous solution for obtaining butyl titanate with lanthana and indium oxide, obtains the fourth of metatitanic acid four
The anhydrous mixing precursor liquid of ester, lanthana and indium oxide.In the present invention, the mixing is carried out preferably under conditions of stirring.
In the present invention, the stirring is preferably magnetic agitation；The speed of the stirring is preferably 500~700r/min, more preferably
550~650r/min；The time of the stirring is preferably 2~4h, more preferably 2.5~3.5h.
It is of the invention by precursor liquid and strontium salt after the anhydrous mixing precursor liquid for obtaining butyl titanate, lanthana and indium oxide
It is aged after solution mixing, obtains the strontium titanates colloidal sol of lanthanum and indium codope.In the present invention, the strontium salt be preferably strontium nitrate,
One or more in hydrochloric acid strontium, strontium carbonate and strontium acetate.The strontium salt solution is mixed to get by strontium salt with absolute ethyl alcohol or water；
The molar concentration of strontium salt is preferably 1~2mol/L in the strontium salt solution.In the present invention, the mixing is preferably in stirring condition
It is lower to carry out；The stirring is preferably magnetic agitation；The speed of the stirring is preferably 500~700r/min, more preferably 550~
650r/min；The time of the stirring is preferably 30~60min, more preferably 40~50min.In the present invention, the stirring
Strontium salt and butyl titanate formation colloidal sol can be accelerated.In the present invention, the time of the ageing is preferably 12~24h, more preferably
For 16~20h.
After the strontium titanates colloidal sol for obtaining lanthanum and indium codope, the present invention by the colloidal sol solvent remove, obtain lanthanum and
The strontium titanates gel of indium codope.The present invention is operated without special restriction to the removal solvent, using art technology
The technical scheme of gel is prepared 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 the drying is preferably 50~80 DEG C, more preferably 60~70 DEG C；The time of the drying is preferably 24~
36h, more preferably 28~32h.
Complete after the drying, the present invention is preferably crushed the strontium titanates gel of obtained lanthanum and indium codope.
In the present invention, the granularity of the strontium titanates gel of lanthanum and indium codope is preferably 100~200 mesh, more preferably 140 after the crushing
~160 mesh.The present invention is operated without special restriction to the crushing, using the skill of crushing well known to those skilled in the art
Art scheme.In the present invention, it is preferred to be crushed using lapping mode.
After the strontium titanates gel for obtaining lanthanum and indium codope, the present invention enters the strontium titanates gel of the lanthanum and indium codope
Row roasting, obtains lanthanum indium codope strontium titanates conductor powder after cooling.In the present invention, the temperature of the roasting is preferably 900
~1100 DEG C, more preferably 980~1020 DEG C；The time of the roasting is preferably 8~10h, more preferably 8.5~9.5h.
In the present invention, the roasting can be with organics removal.In the present invention, the mode of the cooling is preferably furnace cooling.
The present invention preferably after the roasting is completed, obtained lanthanum indium codope strontium titanates conductor powder is carried out tabletting,
Sintering and cooling, obtain lanthanum indium codope strontium titanates conductor material.The present invention is operated without special restriction to the tabletting,
Using the technical scheme of tabletting well known to those skilled in the art.In the present invention, the tabletting is preferred to use single shaft and added
Pressure compacting；The pressure of the tabletting is preferably 5~10MPa, more preferably 7~8MPa.In the present invention, product after the tabletting
It is preferably dimensioned to be 8~10mm of diameter, 1~2mm of thickness.In the present invention, the temperature of the sintering is preferably 1200~1500
DEG C, more preferably 1300~1400 DEG C, most preferably 1340~1370 DEG C；The time of the sintering is preferably 3~6h, more preferably
For 4~5h.In the present invention, the sintering can improve the compactness of material.In the present invention, the mode of the cooling is preferred
For furnace cooling.
In order to further illustrate the present invention, the lanthanum indium codope strontium titanates conductor provided with reference to embodiment the present invention
Material and preparation method thereof is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1：
The doping concentration of lanthanum is 30%, and the doping concentration of indium is 4%：
(1) first according to Sr0.7La0.3Ti0.96In0.04O3In stoichiometric proportion (strontium, lanthanum mol ratio be 70: 30；Titanium, indium
Mol ratio is 96: 4) weighs 1.63g butyl titanates, 0.24g lanthanas and 0.028g indium oxides and then butyl titanate is molten
In the in the mixed solvent of 30mL isopropanols and 10mL absolute ethyl alcohols, after being stirred until homogeneous, lanthana and indium oxide are put into metatitanic acid
It is that can obtain butyl titanate, lanthana and indium oxide in 600r/min speed magnetic agitations 3h in the mixed solution of four butyl esters
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 waters by strontium acetate, and stirring to form strontium salt solution to being completely dissolved；By butyl titanate, oxygen
The anhydrous mixing precursor liquid and strontium acetate solution for changing lanthanum and indium oxide are mixed, and the magnetic agitation under 600r/min speed
30min, ageing obtains the strontium titanates colloidal sol of doped lanthanum and indium after 24 hours.
(3) 30h will be dried at 50 DEG C of the strontium titanates colloidal sol of the doped lanthanum of gained and indium, is adulterated after removing organic solvent
The strontium titanates gel of lanthanum and indium.
(4) the strontium titanates xerogel of doped lanthanum and indium is ground to form after 100 mesh powders, the constant temperature calcining under the conditions of 900 DEG C
Doped lanthanum, the Sr titanate powder of indium are obtained after 10h, furnace cooling.
(5) Sr titanate powder of doped lanthanum, indium is subjected to single shaft pressurization under 5MPa pressure, after being compressed into tablet form,
The strontium titanates mixed conductor material that lanthanum, indium codope are obtained after 5h, furnace cooling is incubated under the conditions of 1300 DEG C.
Strontium acetate in step (2) can be substituted with the strontium nitrate, strontium titanates or hydrochloric acid strontium of same molar.
Obtained lanthanum, the strontium titanates mixed conductor material of indium codope are carried out using CHI660B types electrochemical workstation
Electrical conductivity is detected.In frequency range 10-2-105In Hz, the impedance spectrum of test sample.
Starched with platinum and coat on 2 surfaces of sample uniformly, then be stained with after platinum filament, 30min is calcined at 800 DEG C, you can
To membrane electrode, the measurement of total conductivity is carried out.
Ionic conductivity is measured using the method for electronics blocking electrode, YSZ is pure oxygen ion conductor, regard YSZ as electronics
The electrolyte sheet of blocking electrode, uniformly fills platinum slurry by the coupons sintered one side, is pasted onto on YSZ pieces；By the examination posted
Sample-YSZ composite sheets are put into tube furnace, and 30min is calcined at 800 DEG C, and two thin slices are linked together using platinum slurry；It will burn again
The edge of sample is covered with encapsulant after good, and the edge of sample and air is completely isolated, makes the gap at two thin slice borders
It is completely enclosed；Platinum pulp layer is finally coated on sample-YSZ composite sheets two sides, platinum filament is stained with, 30min is sintered at 800 DEG C, you can
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 concentration of lanthanum is 30%, and the doping concentration of indium is 6%：
(1) first according to Sr0.7La0.3Ti0.94In0.06O3In stoichiometric proportion weigh 1.6g butyl titanates, 0.24g
Lanthana and 0.042g indium oxides；Then butyl titanate is dissolved in the mixed solvent of 40mL isopropanols and 10mL absolute ethyl alcohols
In, after being stirred until homogeneous, lanthana and indium oxide are put into the mixed solution of butyl titanate, in 600r/min speed magnetic force
It is the anhydrous mixing precursor liquid that can obtain butyl titanate, lanthana and indium oxide to stir 3h.
(2) according to Sr0.7La0.3Ti0.94In0.06O3In stoichiometric proportion weigh 0.75g strontium acetates, then by strontium acetate
3mL deionized waters are dissolved in, stirring to form strontium salt solution to being completely dissolved；By the anhydrous of butyl titanate, lanthana and indium oxide
Mixing precursor liquid and strontium acetate solution are mixed, and the magnetic agitation 60min under 600r/min speed, and ageing is obtained after 12 hours
To doped lanthanum and the strontium titanates colloidal sol of indium.
(3) the strontium titanates colloidal sol of the doped lanthanum of gained and indium is dried into 30h at 50 DEG C, mixed after removing organic solvent
The strontium titanates gel of miscellaneous lanthanum and indium.
(4) the strontium titanates xerogel of doped lanthanum and indium is ground to form after 100 mesh powders, the constant temperature calcining under the conditions of 1100 DEG C
Doped lanthanum, the Sr titanate powder of indium are obtained after 8h, furnace cooling.
(5) Sr titanate powder of doped lanthanum, indium is subjected to single shaft pressurization under 5MPa pressure, after being compressed into tablet form,
The strontium titanates mixed conductor material that lanthanum, indium codope are obtained after 6h, furnace cooling is incubated under the conditions of 1200 DEG C.
Strontium acetate in step (2) can be substituted with the strontium nitrate, strontium titanates or hydrochloric acid strontium of same molar.
Using described in embodiment 1 to obtain lanthanum, indium codope strontium titanates mixed conductor material carry 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 concentration of lanthanum is 30%, and the doping concentration of indium is 8%：
(1) first according to Sr0.7La0.3Ti0.92In0.08O3In stoichiometric proportion weigh 1.56g butyl titanates, 0.24g
Lanthana and 0.056g indium oxides；Then butyl titanate is dissolved in the mixed solvent of 30mL isopropanols and 10mL absolute ethyl alcohols
In, after being stirred until homogeneous, lanthana and indium oxide are put into the mixed solution of butyl titanate, in 600r/min speed magnetic force
It is the anhydrous mixing precursor liquid that can obtain butyl titanate, lanthana and indium oxide to stir 3h.
(2) first according to Sr0.7La0.3Ti0.92In0.08O3In stoichiometric proportion weigh 0.75g strontium acetates, then by second
Sour strontium is dissolved in 3mL deionized waters, and stirring to form strontium salt solution to being completely dissolved；By butyl titanate, lanthana and indium oxide
Anhydrous mixing precursor liquid and strontium acetate solution are mixed, and the magnetic agitation 30min under 600r/min speed, are aged 24 hours
The strontium titanates colloidal sol of doped lanthanum and indium is obtained afterwards.
(3) 24h will be dried at 70 DEG C of the strontium titanates colloidal sol of the doped lanthanum of gained and indium, is adulterated after removing organic solvent
The strontium titanates gel of lanthanum and indium.
(4) the strontium titanates xerogel of doped lanthanum and indium is ground to form after 200 mesh powders, the constant temperature calcining under the conditions of 1000 DEG C
Doped lanthanum, the Sr titanate powder of indium are obtained after 9h, furnace cooling.
(5) Sr titanate powder of doped lanthanum, indium is subjected to single shaft pressurization under 10MPa pressure, after being compressed into tablet form,
The strontium titanates mixed conductor material that lanthanum, indium codope are obtained after 5h, furnace cooling is incubated under the conditions of 1300 DEG C.
Strontium acetate in step (2) can be substituted with the strontium nitrate, strontium titanates or hydrochloric acid strontium of same molar.
Using described in embodiment 1 to obtain lanthanum, indium codope strontium titanates mixed conductor material carry 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 concentration of lanthanum is 30%, and the doping concentration of indium is 6%：
(1) first according to Sr0.7La0.3Ti0.94In0.06O3In stoichiometric proportion weigh 1.6g butyl titanates, 0.24g
Lanthana and 0.042g indium oxides；Then butyl titanate is dissolved in the mixed solvent of 50mL isopropanols and 10mL absolute ethyl alcohols
In, after being stirred until homogeneous, lanthana and indium oxide are put into the mixed solution of butyl titanate, in 600r/min speed magnetic force
It is the anhydrous mixing precursor liquid that can obtain butyl titanate, lanthana and indium oxide to stir 3h.
(2) according to Sr0.7La0.3Ti0.94In0.06O3In stoichiometric proportion weigh 0.75g strontium acetates, then by strontium acetate
3mL deionized waters are dissolved in, stirring to form strontium salt solution to being completely dissolved；By the anhydrous of butyl titanate, lanthana and indium oxide
Mixing precursor liquid and strontium acetate solution are mixed, and the magnetic agitation 60min under 600r/min speed, and ageing is obtained after 12 hours
To doped lanthanum and the strontium titanates colloidal sol of indium.
(3) the strontium titanates colloidal sol of the doped lanthanum of gained and indium is dried into 36h at 50 DEG C, mixed after removing organic solvent
The strontium titanates gel of miscellaneous lanthanum and indium.
(4) the strontium titanates xerogel of doped lanthanum and indium is ground to form after 150 mesh powders, the constant temperature calcining under the conditions of 1100 DEG C
Doped lanthanum, the Sr titanate powder of indium are obtained after 8h, furnace cooling.
(5) Sr titanate powder of doped lanthanum, indium is subjected to single shaft pressurization under 5MPa pressure, after being compressed into tablet form,
The strontium titanates mixed conductor material that lanthanum, indium codope are obtained after 4h, furnace cooling is incubated under the conditions of 1400 DEG C.
Strontium acetate in step (2) can be substituted with the strontium nitrate, strontium titanates or hydrochloric acid strontium of same molar.
Using described in embodiment 1 to obtain lanthanum, indium codope strontium titanates mixed conductor material carry out electrical conductivity inspection
Survey.After testing, in the range of 100-900 DEG C, total conductivity is 0.036~0.06S/cm-1Between, in 600~900 DEG C of scopes
Interior, ionic conductivity is 0.002~0.014S/cm-1Between.
Embodiment 5：
The doping concentration of lanthanum is 20%, and the doping concentration of indium is 8%：
(1) first according to Sr0.8La0.2Ti0.92In0.08O3In stoichiometric proportion weigh 1.56g butyl titanates, 0.16g
Lanthana and 0.056g indium oxides；Then butyl titanate is dissolved in the mixed solvent of 40mL isopropanols and 10mL absolute ethyl alcohols
In, after being stirred until homogeneous, lanthana and indium oxide are put into the mixed solution of butyl titanate, in 600r/min speed magnetic force
It is the anhydrous mixing precursor liquid that can obtain butyl titanate, lanthana and indium oxide to stir 3h.
(2) according to Sr0.8La0.2Ti0.92In0.08O3In stoichiometric proportion weigh 0.86g strontium acetates, then by strontium acetate
5mL deionized waters are dissolved in, stirring to form strontium salt solution to being completely dissolved；By the anhydrous of butyl titanate, lanthana and indium oxide
Mixing precursor liquid and strontium acetate solution are mixed, and the magnetic agitation 30min under 600r/min speed, and ageing is obtained after 24 hours
To doped lanthanum and the strontium titanates colloidal sol of indium.
(3) 36h will be dried at 50 DEG C of the strontium titanates colloidal sol of the doped lanthanum of gained and indium, is adulterated after removing organic solvent
The strontium titanates gel of lanthanum and indium.
(4) the strontium titanates xerogel of doped lanthanum and indium is ground to form after 200 mesh powders, the constant temperature calcining under the conditions of 900 DEG C
Doped lanthanum, the Sr titanate powder of indium are obtained after 10h, furnace cooling.
(5) Sr titanate powder of doped lanthanum, indium is subjected to single shaft pressurization under 5MPa pressure, after being compressed into tablet form,
It is incubated under the conditions of 1500 DEG C after 3h, furnace cooling and obtains lanthanum indium codope strontium titanates mixed conductor material.
Strontium acetate in step (2) can be substituted with the strontium nitrate, strontium titanates or hydrochloric acid strontium of same molar.
Using described in embodiment 1 to obtain lanthanum, indium codope strontium titanates mixed conductor material carry out electrical conductivity inspection
Survey.After testing, in the range of 100-900 DEG C, total conductivity is 0.032~0.052S/cm-1Between, in 600~900 DEG C of scopes
Interior, ionic conductivity is 0.0016~0.012S/cm-1Between.
Rigaku D/max-A types X-ray diffraction (XRD) instrument and the type electron scanning Electronic Speculum of Quanta FEG 650 are used respectively
(SEM) the indium codope strontium titanates mixed conductor material prepared to embodiment 1~5 carries out phase structure and microscopic appearance inspection
Survey.
The XRD spectrum for the indium codope strontium titanates mixed conductor material that embodiment 1~3 is prepared is as shown in figure 1, wherein
(1), (2), (3) are respectively the XRD spectrum of embodiment 1,2,3, are as a result shown：The doping concentration of indium is 4% lanthanum, 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 concentration of indium is respectively 6%, and 8% diffracting spectrum, which is also corresponded to, to be stood
Square perovskite structure, diffraction maximum is clear, and small skew occurs for diffraction maximum.
The XRD spectrum for the indium codope strontium titanates mixed conductor material that embodiment 4 and 5 is prepared is as shown in Fig. 2 wherein
(4), (5) are respectively the XRD spectrum of embodiment 4,5, maintain single cubic phase perovskite structure, and diffraction maximum is clear.
The microscopic appearance figure for the indium codope strontium titanates mixed conductor material that embodiment 1~5 is prepared respectively as Fig. 3~
Shown in 7, as a result show：All sample sintered densities are all more than 90%.
As can be seen from the above embodiments, the material that the present invention is provided has single cubic phase perovskite structure, stability
Good, electronic conductance and ionic conductance performance are excellent, in the range of 100-900 DEG C, and 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.
Described above is only the preferred embodiment of the present invention, not makees any formal limitation to the present invention.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention, if can also make
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of lanthanum indium codope strontium titanates conductor material, comprises the following steps：
(1) butyl titanate, lanthana, indium oxide are mixed with isopropanol and absolute ethyl alcohol, obtains butyl titanate, lanthana
With the anhydrous mixing precursor liquid of indium oxide；
(2) the anhydrous mixing precursor liquid and strontium salt solution for butyl titanate, lanthana and the indium oxide for obtaining the step (1)
It is aged after mixing, obtains the strontium titanates colloidal sol of lanthanum and indium codope；
(3) solvent in the colloidal sol that the step (2) obtains is removed, the strontium titanates gel of lanthanum and indium codope is obtained；
(4) the strontium titanates gel roasting of the lanthanum and indium codope that obtain the step (3), obtains lanthanum indium codope strontium titanates and leads
Body material；
The chemical general formula of the lanthanum indium codope strontium titanates conductor material is as shown in formula I：
Sr1-xLaxTi1-yInyO3Formula I；
Wherein, 0.1≤x≤0.4,0.03≤y≤0.1.
2. preparation method according to claim 1, it is characterised in that 0.2≤x≤0.3,0.04≤y in the formula I≤
0.08。
3. preparation method according to claim 1 or 2, it is characterised in that isopropanol and absolute ethyl alcohol in the step (1)
Volume ratio be 3~5:1.
4. preparation method according to claim 1 or 2, it is characterised in that the solvent in the step (2) in strontium salt solution
For absolute ethyl alcohol or water.
5. preparation method according to claim 4, it is characterised in that the strontium salt be strontium nitrate, hydrochloric acid strontium, strontium carbonate and
One or more in strontium acetate.
6. preparation method according to claim 1 or 2, it is characterised in that mixed under agitation in the step (2)
Carry out, the mixing time is 30~60min.
7. preparation method according to claim 1 or 2, it is characterised in that in the step (2) digestion time be 12~
24h。
8. preparation method according to claim 1 or 2, it is characterised in that the mode of removal solvent is in the step (3)
Drying, the temperature of the drying is 50~80 DEG C.
9. preparation method according to claim 1 or 2, it is characterised in that the temperature of roasting is 900 in the step (4)
~1100 DEG C, the time of roasting is 8~10h.
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