CN109713347A - A kind of metallic element doping La2Mo2O9Method for preparing solid electrolyte - Google Patents
A kind of metallic element doping La2Mo2O9Method for preparing solid electrolyte Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910002287 La2Mo2O9 Inorganic materials 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000011240 wet gel Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead(II) nitrate Inorganic materials [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 28
- 239000000919 ceramic Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 244000137852 Petrea volubilis Species 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 25
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 25
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011159 matrix material Substances 0.000 abstract description 14
- 230000004913 activation Effects 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 27
- 239000012071 phase Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 230000009466 transformation Effects 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000003608 titanium Chemical class 0.000 description 6
- -1 Oxygen ion Chemical class 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000001453 impedance spectrum Methods 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- DRIUWMIAOYIBGN-UHFFFAOYSA-N lanthanum titanium Chemical compound [Ti][La] DRIUWMIAOYIBGN-UHFFFAOYSA-N 0.000 description 2
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
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- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
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- 239000010416 ion conductor Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 238000009862 microstructural analysis Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Conductive Materials (AREA)
- Fuel Cell (AREA)
Abstract
A kind of metallic element doping La2Mo2O9Method for preparing solid electrolyte is related to solid electrolyte preparation technical field.La (NO first3)3·6H2O、(NH4)6Mo7O24·4H2O、Pb(NO3)2Or butyl titanate is dissolved with distilled water；Then it is uniformly dispersed after citric acid and regulation system pH value being added using ultrasonic washing instrument, is then transferred to heating reaction in microwave chemical reactor and forms wet gel；Finally by wet gel drying, calcining, then film-making is sintered.In La doping Pb of lanthanum molybdate matrix2+, Ti4+ is not onlyThe α/β phase transition that the matrix can be effectively inhibited can also improve Lacking oxygen in crystal structure, improve conductivity.Electrolyte has good ionic conductivity, lower Conductance activation energy, higher sintering activity.Reach maximum conductivity 0.0253S/cm, Conductance activation energy 1.312eV at 800 DEG C.
Description
Technical field
The present invention relates to solid electrolyte preparation technical fields, are specifically related to a kind of metallic element doping La2Mo2O9Gu
Body electrolyte preparation method.
Background technique
Solid oxide fuel cell (SOFC) is because of exclusive structure of whole solid state, energy conversion efficiency is high, it is environmental-friendly, can
By property, fuel use scope is wide, the features such as small, the service life is long is lost, and becomes the research hotspot in new energy field.Traditional SOFC makes
It is higher (800~1000 DEG C) with temperature, it is very high to associated materials performance requirement, the development and application of SOFC are limited, therefore open
Low temperature SOFC has become inexorable trend in hair.Solid electrolyte material is the critical component of SOFC, therefore develops high conductivity
Electrolyte is most important to the development and application of SOFC.
With getting worse for the nowadays energy shortage of social being and problem of environmental pollution, new green environment protection is researched and developed
Material is extremely urgent.And solid oxide fuel cell converts energy in fossil energy to the Thermal Cycling of electric energy.And with
The problems such as YSZ is that the operating temperature of the SOFC of electrolyte is up to 800 DEG C or more, is matched at high cost, difficult sealing, electrode difficulty.
Researching and developing at (500-800 DEG C) of medium temperature there is the novel oxygen ion conductor compared with high ionic conductivity to be of great significance to SOFC.Molybdenum
Sour lanthanum is that Laccore in 2000 reported that conductivity became larger since temperature raises first, since step of preparation process is few, valence
The low candidate material as researcher of lattice is laid a good foundation for further investigation electric conductivity etc..
Mass data shows the lanthanum molybdate for having special construction, and the other elements even if itself undopes, itself can also be aerobic
Vacancy and conductivity are higher than YSZ, along with its preparation process is fairly simple, the advantages that price of raw material is relatively low, still
Also have the shortcomings that very big, high temperature is can to undergo phase transition.I.e. at 580 DEG C, matrix lanthanum molybdate is to occur by high temperature cubic (β-
La2Mo2O9) arrive low temperature monocline (α-La2Mo2O9) phase transformation, this phase transformation not only along with conductivity reduce by 2 orders of magnitude, and
Can also electronic conductance be made to increase.In strongly reducing atmosphere, be changed into completely amorphous posture anoxic it is serious when will lead to La2Mo2O9
It decomposes completely；Thermal expansion coefficient increases, and influences the assembling of electrolyte and electrode material.In summary factor lanthanum molybdate fuel
Battery there are significant limitation, so experiment doping angle and stablize the mutually further improvement of its thermal structure, this experiment
Mainly probing into its ratio and element influences its performance, finds most suitable scheme.
Summary of the invention
For the technical problems in the prior art, the present invention provides a kind of metallic elements to adulterate La2Mo2O9Solid
Electrolyte preparation method.The electrolyte of acquisition can effectively inhibit phase transformation, improve the conductivity of lanthanum molybdate matrix,
It is expected to be applied to intermediate temperature solid oxide fuel cell electrolyte.
To achieve the goals above, the technical scheme adopted by the invention is as follows: a kind of metallic element adulterates La2Mo2O9Solid
Electrolyte preparation method, using ultrasonic-microwave sol-gal process, steps are as follows:
1., according to target sample (La1-xMx)2Mo2O9-δStoichiometric ratio, weigh La (NO3)3·6H2O、(NH4)6Mo7O24·4H2O、Pb(NO3)2Or butyl titanate is added appropriate distilled water and dissolution is sufficiently stirred in beaker；
2., be added citric acid into beaker again, and adjust pH value to neutrality with ammonium hydroxide, be transferred to CS-BA type digital display ultrasound
Ultrasound 1h is carried out in wave water bath chader, after being uniformly dispersed, is put into 80 DEG C of microwave heatings in WBFY201 type microwave chemical reactor
2h is reacted, evaporation obtains wet gel；
3., gained wet gel sample is put into drying box in 120 DEG C of dry 12h, then will dry that sample is levigate to be put into
Pre-burning 3 times in Muffle furnace, each 10h, temperature is respectively 750 DEG C, 850 DEG C, 950 DEG C three times, takes out sample and is cooled to room temperature
It is fully ground again, to obtain target product (La1-xMx)2Mo2O9-δ；
4., using after grinding electrolyte pre-burning material be added 5wt% PVA solution be granulated as adhesive, then
The powder 0.5g after being granulated is taken, in stainless steel mould, positive 4MPa pressure, reversed 8MPa is pressed into a thickness of 2mm, diameter
For the thin rounded flakes of 12mm；Then it is placed on ceramic wafer, label good position is placed in high-temperature box type temperature control furnace again with 2 DEG C/min
850 DEG C of sintering are warming up to, keep the temperature 2h at 850 DEG C；
5., carry out dumping after natural cooling；Gloss is presented into through sand paper polishing, cleaning, drying rear surface in sample；In print
Upper and lower surface surface uniformly coats DAD-87 silver conductive adhesive, is warming up to 700 DEG C of sintering in high-temperature box type temperature control furnace with 2 DEG C/min and protects
Warm 2h；Sintering obtains (La1-xMx)2Mo2O9-δElectrolyte ceramics piece.
As the optimal technical scheme of preparation method of the invention, step 1. in target product (La1-xMx)2Mo2O9-δMiddle x
=0~0.6, M are Pb or Ti.
The present invention uses the preparation of ultrasonic-microwave auxiliary law with lanthanum molybdate La2Mo2O9For the solid fuel cell electricity of matrix
Material is solved, Pb is selected2+And Ti4+As Doped ions, synthesizing new oxide (La1-xMx)2Mo2O9-δNano ceramic material,
Experiment is granulated, compression moulding, calcination temperature is respectively air atmosphere at 750 DEG C, 850 DEG C, 950 DEG C by three sections of grinding calcinings
In sinter porcelain technique into and be prepared for La2Mo2O9Base novel battery material.Pass through infrared spectroscopy, porosity, relative density, SEM-
The means such as EDS and XRD spectra analysis test and analyze sample surfaces structure with internal performance, are tested and are electrolysed using impedance spectrum
The chemical property of material, it is desirable to which changing lanthanum molybdate matrix electrolyte itself by the angle from doping, there are phase transformations
The defect of point, changes its transformation temperature, avoids using limitation.This experimental data shows:
1, cubic symmetry is presented using the powder that ultrasonic-microwave auxiliary law is prepared, and average grain size exists
25nm or so.
2, the metal ion adulterated is particularly significant, and experiment shows that the sample of Doped with Titanium series can go out in x > 0.4
Existing sintering phenomenon, can be with crucible knot porcelain.
3, by lanthanum molybdate matrix, in La doping Pb2+, Ti4+The α/β phase that the matrix can be effectively inhibited turns
Become.
4、(La1-xMx)2Mo2O9-δSeries of electrolyte material sintering activity with higher, different doped metal ions its most
Good to be consistent substantially at porcelain, the optimum temperature of Doped with Titanium series is to obtain electrolyte ceramics through 850 DEG C of sintered heat insulating 2h
Relative density is 95% or more；And the optimum temperature for adulterating lead series is to obtain electrolyte pottery through 850 DEG C of sintered heat insulating 2h
The relative density of porcelain is 97% or more.
5, shown by impedance test results: (the La of the doping of lanthanum position Pb, Ti1-xMx)2Mo2O9- δ series has good ion
Conductivity, lower Conductance activation energy.Its electrolyte ceramics piece (La0.6Ti0.4)2Mo2O9-δReach maximum conductivity at 800 DEG C
0.0253S/cm, Conductance activation energy 1.312eV.Illustrate that low-valent metal element is selected to be doped while inhibiting phase transformation also
Lacking oxygen in crystal structure can be improved, improve conductivity.
Detailed description of the invention
Fig. 1 is doping lead lanthanum molybdate (La1-XPbx)2Mo2O9-δThe XRD diffraction of (x=0,0.2,0.4,0.6) powder sample
Figure；
Fig. 2 a, b are (La0.4Pb0.6)2Mo2O9-δThe high and low multiplying power electron microscope of powder, Fig. 2 c is (La0.4Pb0.6)2Mo2O9-δ
The energy spectrum diagram of powder；
Fig. 3 is (La1-XPbx)2Mo2O9-&The infrared spectrogram of presoma；
Fig. 4 is (La0.6Pb0.4)2Mo2O9-δThe impedance spectra of ceramics sample at different temperatures；
(La when Fig. 5 is 600 DEG C0.6Pb0.4)2Mo2O9-δImpedance diagram；
Fig. 6 is (La1-xPbx)2Mo2O9-δConductance conductance and temperature relational graph；
Fig. 7 is (La1-xPbx)2Mo2O9-δThe conductivity Arrhenius curve of (x=0.2,0.4,0.6)；
Fig. 8 is Doped with Titanium lanthanum molybdate (La1-XTix)2Mo2O9-δThe XRD diffraction pattern of (x=0.2,0.3,0.4) powder sample；
Fig. 9 a, b are (La0.4Ti0.6)2Mo2O9-δThe high and low multiplying power electron microscope of powder, Fig. 9 c is (La0.4Ti0.6)2Mo2O9-δ
The quantitative analysis results of powder, Fig. 9 d are (La0.4Ti0.6)2Mo2O9-δThe energy spectrum diagram of powder；
Figure 10 is (La1-XTix)2Mo2O9-&The infrared spectrogram of presoma；
Figure 11 is (La1-xTix)2Mo2O9-δAC impedance spectroscopy under different temperatures；
Figure 12 is (La1-xTix)2Mo2O9-δConductance conductance and temperature relational graph；
Figure 13 is (La1-xTix)2Mo2O9-δThe conductivity Arrhenius curve of (x=0.2,0.3,0.4).
Specific embodiment
La is adulterated to metallic element of the invention with attached drawing with reference to embodiments2Mo2O9Method for preparing solid electrolyte
It makes and being discussed further.
Embodiment 1
(La1-xPbx)2Mo2O9-δMethod for preparing solid electrolyte, steps are as follows:
1., total 4 groups of experiment, x is taken respectively from 0,0.2,0.4,0.6.According to target sample (La1-xPbx)2Mo2O9-δChange
Metering ratio is learned, La (NO is weighed3)3·6H2O、(NH4)6Mo7O24·4H2O、Pb(NO3)2In beaker, appropriate distilled water is added and fills
Divide stirring and dissolving.
2., citric acid is added into beaker again, and (mole of citric acid is the 1.5 of the amount of metal ion contained in component
Times), and pH value is adjusted to neutrality with ammonium hydroxide, it is transferred to progress ultrasound 1h in CS-BA type digital display ultrasound bath oscillator, dispersion
After uniformly, it is put into 80 DEG C of microwave heating reaction 2h, evaporation in WBFY201 type microwave chemical reactor and obtains wet gel.
3., gained wet gel sample is put into drying box in 120 DEG C of dry 12h, then will dry that sample is levigate to be put into
Pre-burning 3 times in Muffle furnace, each 10h, temperature is respectively 750 DEG C, 850 DEG C, 950 DEG C three times, takes out sample and is cooled to room temperature
It is fully ground again, to obtain target product (La1-xPbx)2Mo2O9-δ。
4., using after grinding electrolyte pre-burning material be added 5wt% PVA solution be granulated as adhesive, then
The powder 0.5g after being granulated is taken, in stainless steel mould, positive 4MPa pressure, reversed 8MPa is pressed into a thickness of 2mm, diameter
For the thin rounded flakes of 12mm；Then it is placed on ceramic wafer, label good position is placed in high-temperature box type temperature control furnace again with 2 DEG C/min
850 DEG C of sintering are warming up to, keep the temperature 2h at 850 DEG C.
5., carry out dumping after natural cooling；Gloss is presented into through sand paper polishing, cleaning, drying rear surface in sample；In print
Upper and lower surface surface uniformly coats DAD-87 silver conductive adhesive, is warming up to 700 DEG C of sintering in high-temperature box type temperature control furnace with 2 DEG C/min and protects
Warm 2h；Sintering obtains (La1-xPbx)2Mo2O9-δElectrolyte ceramics piece.
Embodiment 2
(La1-xPbx)2Mo2O9-δSolid electrolyte performance characterization
1, characterizing method
1.1.XRD test method principle
XRD diagram spectrum analysis is a kind of very common material analysis method, is the diffraction that X-ray is received using sample,
Different absorption peaks are generated, according to the form at peak to information such as the chemical component of sample, the structure of molecule and interior atoms forms
A kind of research means.Gained powder carries out X-ray diffraction (XRD) test, the survey that this experiment uses after different temperatures calcining
Examination parameter be wavelength (λ) be 0.1542nm, sweep speed is that (V) be 35/min, scanning range (2 θ) is 5 °~80 °.XRD analysis
It is that there is this feature of specific energy, they can be split into spectrum with oring Software on Drawing for different elements according to X-ray
After figure, its corresponding element is found according to the magnitude of different energy.
1.2.SEM-EDS test method principle
SEM-EDS combination is the most wide microscopic analysis instrument of existing social application, principle be using material electromagnetically not
Together, it is radiated at detected sample surfaces using electron beam, leads to the interaction of electronics and sample, it is existing to generate light and shade difference
As.It can reflect the various information such as specimen surface pattern, structure in this way.It can be simultaneously to member contained in the tiny area of sample
Element is qualitatively and quantitatively analyzed.Electron microscope analysis within the scope of cubic nanometer, belongs to microstructural analysis in spatial resolution.
1.3.IR test method principle
Examination of infrared spectrum is according to the different connection type of meeting and unequal energy between different molecular and molecule.Draw
It plays intramolecular chemical composition and space structure differs greatly.Thus each molecule has its corresponding infrared absorption spectrum.Cause
This can carry out physical property identification and structural analysis to molecule.Testing procedure weighs 2mg powder sample first, is placed in the Ma of drying
In Nao mortar, 99% potassium bromide solution of about 200mg is added.Under being irradiated under infrared baking lamp, it is fully ground.It is placed in stainless steel again
In infrared compression mold, with positive 10Pa pressure, thin rounded flakes are pressed on infrared tablet press machine, then carry out infrared test.
1.4. porosity and density calculation method and principle
The test method of common several porositys has weight method, densimetry, gas adsorption method, press pump method.This paper is adopted
Porosity is tested with weight method, sample is weighed and soaks the weight change before and after deionized water to determine sample porosity.It is basis
Archimedes principle, sample are equal to the gravity of water by buoyancy.This experiment determines various kinds using hydrostatic balance weight method
The porosity and density of product.Density and porosity are calculated according to following equation (1) and (2) formula respectively.
(1) in formula, G1For the quality of dry ceramic sample, G2For ceramics sample, (sample internal voids are satisfied by water after boiling
With) suspending weight in water, the moisture on the ceramics sample surface after having surveyed suspending weight is then blotted with filter paper, and it is aerial to test its
Quality, as G3.Then (G3-G1) be into the water in stomata quality, (G3-G2) it is that the buoyancy that sample is subject to accelerates divided by gravity
The value of degree, (G3-G2) it can indicate that sample arranges the quality of water, then by (2) formula, (G3-G2) it is the quality that sample arranges water, ρ water
For the density of water, therefore (G3-G2)/ρWaterIt can indicate that sample arranges the volume of water namely the volume of sample, then G1ρWater/(G3-G2) can table
Show the density of ceramics sample.
1.5. impedance method analytical calculation conductivity
AC impedence method analysis is to be designed according to battery electrode using alternating voltage or electric current by a small margin electrode perturbation,
Simulate equivalent circuit devices and carry out electro-chemical test, calculates the parameters of the electrode reaction.
Potsherd is put into high temperature resistance furnace, electrochemical analyser is linked.Starting software starts to test, after the completion of test
Converting text format saves, and is mapped using data.The standard AC impedance analysis spectrum drawn out by searching for literature oring
Scheme, is made of in figure 3 sections of camber lines, horizontal axis is shown from high-frequency to low frequency.Fitting in obtained impedance spectra is obtained into sample
Resistance value, it may appear that the abscissa intersection point on semicircle and figure, is exactly the R of ceramics sample under the test temperaturegiWith brilliant RgbIt is added
Obtain resistance R.Then conductivity value is converted into the calculating of (3) formula.
(3) in formula: r is the radius of sample；σ is the ionic conductivity of sample；D is the thickness of potsherd.
(4) in formula: A is characterized constant；Ea is ion activation energy；K is Boltzmann coefficient；T is absolute temperature.
It is developed through formula (4) and obtains following equation:
Energy Si Tetu is made, can be according to slopeConductance activation energy is calculated, activation energy is that it is chemomotive force
Key concept.
2、(La1-xPbx)2Mo2O9-δSolid electrolyte experimental result
2.1.XRD test
Fig. 1 is doping lead lanthanum molybdate (La1-XPbx)2Mo2O9-δThe XRD diffraction of (x=0,0.2,0.4,0.6) powder sample
Figure carries out object using MDI Jade6.5 software and mutually retrieves, provides search condition and element certain or that may be present, then by institute
The standard card of known object phase compares one by one in the spectrogram PDF card library of sample, is fitted, finds corresponding object and mutually mark
It is quasi-.Sample spectrogram matches with PDF card (28-0509) after fitting, has not seen Pb3O4Or other impurity peaks, that indicates that doping
Lead ion not only completely inhibits phase transformation, has not been changed La2Mo2O9Cubic crystal structure.
Start MDI Jade6.5 software and diffraction maximum contrast standard card main in the XRD of sample is marked each spread out
The corresponding crystal face in peak is penetrated, the corresponding interplanar of the crystal face can be found on card by then being integrated to the indices of crystallographic plane (210)
Away from other parameters such as, half-peak breadths.As table 1 indicates.Cell parameter is calculated further according to the formula (6) of interplanar distance, is utilized
Cell parameter is calculated in Delphi program, input interplanar crystal spacing.
Crystallite dimension is calculated according to Scherrer formula (7).Wherein, D-grain size (unit: nm)；The half of β-(111) peak
Gao Kuan；θ-the angle of diffraction；K- Scherrer constant, K=0.89；λ-x-ray wavelength (λ=0.15405nm).
Adulterate the parameters of the lead difference mole potsherd indices of crystallographic plane (210) in 1 lanthanum position of table
According to DDA analysis in table 1:
(1), by (210) crystal face angle corresponding 2 θ of different proportion sample it is found that the main peak overall positions of each sample are at 27 °
Left and right, as the trend of slight shift can occur for doping variation main peak.
(2), the cell parameter of doped samples is different from cell parameter (0.72014nm) than parent, with Doped ions
Molal quantity increases, and lattice number can change.When doping ratio is larger, charge number imbalance out can be caused, by extra
Oxygen ion vacancy causes main function, and cell parameter generation appropriate can also expand.
(3), very big on unit cell dimension influence with the difference of lead doping, interplanar distance d becomes with the variation of ratio mole
Gesture first reduces and increases afterwards.This it appears that interplanar distance is smaller in figure, the lattice point arrangement on crystal face is more sparse.But
Can also be seen in figure the characteristic peak of the sample of different proportion in angle and standard PDF card spectrogram slightly deviation, whole diffraction
Peak deviates high angle direction.
2.2.SEM-EDS test
Fig. 2 a, b are (La0.4Pb0.6)2Mo2O9-δThe high and low multiplying power electron microscope of powder, Fig. 2 c is (La0.4Pb0.6)2Mo2O9-δ
The energy spectrum diagram of powder.From Fig. 2 a significantly find out sequence rule and gap very little, from Fig. 2 b can clearly from be sintered
Powder granule afterwards is in ellipsoid.The external morphology for sintering porcelain potsherd sample into comes from the SEM photograph that specification is 50 μm
It sees, it can be seen that inside precursor powder, the particle diameter distribution of crystal grain is uniform, and crystal Jian Jie circle is obvious and porosity.Meet
Ceramic material property requirement, this image also comply with relative density calculated above (>=99%) measurement result.
2.3.IR test
Fig. 3 is (La1-XPbx)2Mo2O9-&The infrared spectrogram of presoma is indicated using T- δ curve.Abscissa indicates wave
Number, ordinate indicate transmitance.By Fig. 3 it can be observed that in 3400~3200cm-1Inside there is absorption peak, shows there is-OH (to form
Closing) group occurs, with the presence of hydrone in the sample；Doping difference absorption peak is different, illustrates physical property and doping mole
Number is related.In 794cm-1There is absorption peak, show the characteristic peak of Pb-O stretching vibration, illustrates that metal ion comes into lanthanum molybdate
In matrix.
2.4. porosity and density calculate
Sample consistency is mainly characterized by weighing porosity and the relative density of the sample of sample re-computation, is weighed
Method weighs the dry weight of sample, weight in wet base and buoyant weight.The porosity and relative density of each sample are calculated in formula.According to above-mentioned
Formula (1) (2) calculates porosity and relative density is as shown in table 2
2 (La of table1-xPbx)2Mo2O9-δThe porosity and relative density of sample
As shown in Table 2, the sample of 2h is kept the temperature at 850 DEG C, its relative density is up to 97% or more after tested.Doping
Ratio gets over that high porosity is smaller, and relative density is higher.This shows that the Ceramic Like for mixing lead series utilizes mixing oxides method synthesis
(La1-xPbx)2Mo2O9-δ(0≤x≤0.6) can be obtained with the lanthanum position doping of good sintering activity, especially x=0.6
99.74% consistency, this compares 97% or more the ceramics sample relative density of the acquisition synthesized with sol-gel method, fine and close
Degree improves 2%.This and Pb3O4Structure have many relationships, (Pbo)2Pbo2Lead therein is deposited with 2+divalent, one+4 valence
With high oxidation state (Pb in sample2+And Pb4+) coexist, this phenomenon is similar with the result of document, can more preferably fill up oxygen
Vacancy.It is very big that this more illustrates that the spatial shape of doped chemical influences, while the experimental method also reduces conventional junction and burns temperature 1100
℃。
2.5. impedance method analytical calculation conductivity
Electrolyte is solid fuel cell chief component, seriously affects the performance of battery material.AC impedance
The resistance value for measuring out sample calculates to obtain conductivity further according to formula (3), and conductivity height shows (La1-xPbx)2Mo2O9-δSeries
The oxygen ion transport performance of sample is good.The conductivity of sample is not only increased after lanthanum position doping lead ion, and improves solid
The redox reaction of fuel cell electrode makes material have good catalytic activity, and Fig. 4 is (La0.6Pb0.4)2Mo2O9-δCeramics
The impedance spectra of sample at different temperatures.
As shown in Figure 4, when having apparent scatterplot in 400 DEG C of images, as temperature constantly increases, image curve obviously becomes
In half arc shape.Make oxonium ion obtain higher energy since temperature raises, oxonium ion is promoted to overcome resistance energy.Conducive to ion
Between conduct, oxonium ion capacitation is bigger, conductivity increase.And in T < 500 DEG C temperature, lead to crystal grain conductance process, crystal boundary electricity
The reaction time for leading process and electrode process is different, as can be seen from Figure 500 DEG C when, only occur in impedance spectra two it is bright
Aobvious semi arch corresponds to crystal grain process and crystal boundary process in crystal.Due at low temperature, carrier O2-Movement speed it is slow
Slowly, electrode interface process is unobvious.When temperature is increased to 600 DEG C, body phase conductive process gradually weakens in crystal, electrolyte electricity
Resistive is small.Crystal conduction process is caused gradually to be controlled by electrode interface procedure, corresponding crystal grain process and crystal boundary process
Semi arch gradually becomes smaller, and is in collapsed state, and reclinate trend is presented in ray portion.
Starting Zsimpwin software is fitted data, resistance Rd=Rgi+Rgb.(La when Fig. 5 is 600 DEG C0.6Pb0.4)2Mo2O9-δImpedance diagram.Fig. 6 is (La1-xPbx)2Mo2O9-δConductance conductance and temperature relational graph.Doping (x=0.2,
0.4,0.6), as can be seen from the figure: (1) conductance of sample increases with the raising of temperature；(2) when temperature is in 400-600
The conductivity very little of DEG C sample and unrelated with Doped ions molal quantity；(3) when x=0.4 temperature be 800 DEG C when sample conductivity
It is up to 0.024S/cm.
Fig. 7 is (La1-xPbx)2Mo2O9-δWith the linear graph that the value of 1000/T and ln (σ T) are made for horizontal, ordinate, indicate
Lanthanum position doping is the conductivity Arrhenius curve of (x=0.2,0.4,0.6) respectively.As can be seen from Figure 7 lanthanum position is mixed
Miscellaneous lead ion can overcome lanthanum molybdate high-temperature and reversible phase transformation, show its conductivity at 580 DEG C or so and occur not declining suddenly, scheme
In three Arrhenius curves all show regular decline curve and become.And can also be seen that curve downward trend with mole
Number relationship is little, entire lowering similar rate.Lanthanum position is doped with Pb in summary2+La2Mo2O9Matrix may indicate that well
Inhibit La2Mo2O9The generation of matrix phase transformation.
Embodiment 3
(La1-xTix)2Mo2O9-δMethod for preparing solid electrolyte, steps are as follows:
1., total 3 groups of experiment, x is taken respectively from 0.2,0.3,0.4.According to target sample (La1-xTix)2Mo2O9-δChemistry
Ratio is measured, La (NO is weighed3)3·6H2O、(NH4)6Mo7O24·4H2O, butyl titanate is added appropriate distilled water and fills in beaker
Divide stirring and dissolving.
2., citric acid is added into beaker again, and (mole of citric acid is the 1.5 of the amount of metal ion contained in component
Times), and pH value is adjusted to neutrality with ammonium hydroxide, it is transferred to progress ultrasound 1h in CS-BA type digital display ultrasound bath oscillator, dispersion
After uniformly, it is put into 80 DEG C of microwave heating reaction 2h, evaporation in WBFY201 type microwave chemical reactor and obtains wet gel.
3., gained wet gel sample is put into drying box in 120 DEG C of dry 12h, then will dry that sample is levigate to be put into
Pre-burning 3 times in Muffle furnace, each 10h, temperature is respectively 750 DEG C, 850 DEG C, 950 DEG C three times, takes out sample and is cooled to room temperature
It is fully ground again, to obtain target product (La1-xTix)2Mo2O9-δ。
4., using after grinding electrolyte pre-burning material be added 5wt% PVA solution be granulated as adhesive, then
The powder 0.5g after being granulated is taken, in stainless steel mould, positive 4MPa pressure, reversed 8MPa is pressed into a thickness of 2mm, diameter
For the thin rounded flakes of 12mm；Then it is placed on ceramic wafer, label good position is placed in high-temperature box type temperature control furnace again with 2 DEG C/min
850 DEG C of sintering are warming up to, keep the temperature 2h at 850 DEG C.
5., carry out dumping after natural cooling；Gloss is presented into through sand paper polishing, cleaning, drying rear surface in sample；In print
Upper and lower surface surface uniformly coats DAD-87 silver conductive adhesive, is warming up to 700 DEG C of sintering in high-temperature box type temperature control furnace with 2 DEG C/min and protects
Warm 2h；Sintering obtains (La1-xTix)2Mo2O9-δElectrolyte ceramics piece.
Embodiment 4
(La1-xTix)2Mo2O9-δSolid electrolyte performance characterization
1, characterizing method
With embodiment 2
2、(La1-xTix)2Mo2O9-δSolid electrolyte experimental result
2.1.XRD test
Fig. 8 is Doped with Titanium lanthanum molybdate (La1-XTix)2Mo2O9-δThe XRD diffraction pattern of (x=0.2,0.3,0.4) powder sample.
Start MD I Jade6.5 software and XRD spectrum fitting is carried out to test data, call the PDF Ka Ku of standard, setting is necessary and can
After energy material element, carries out object and mutually retrieve.It is observed that after comparison, it was therefore concluded that, the intensity of each diffraction maximum of the sample and position
Set with the JCPDS of standard (28-0509) card image, it is found that its information is almost the same without other diffraction maximums.This illustrates that lanthanum is to mix
The powder of miscellaneous titanium ion after oversintering and have not been changed lanthanum molybdate-based body spatial cuboids structure and document in record molybdenum position mix
Miscellaneous phase is same, and all getable is uniform solid solution.It also indicates that doping titanium ion not only completely inhibits phase transformation simultaneously, and does not have
Change La2Mo2O9Cube structure.
The partial size of powder can carry out calculating by above-mentioned formula (7) Debye Scherrer formula its grain size 1.68
Between~27.9nm, therefore obtain the superfines with cubic crystal structure.The following table 3 lists the doping titanium ion indices of crystallographic plane
(210) parameters.
The parameters of the 3 lanthanum position Doped with Titanium difference mole potsherd indices of crystallographic plane (210) of table
According to DDA analysis in table 3:
(1), by (210) crystal face angle corresponding 2 θ of different proportion sample it is found that the main peak overall positions of each sample are at 27 °
Left and right, as the trend of slight shift can occur for doping variation main peak.
(2), the cell parameter of doped samples is different from cell parameter (0.72014nm) than parent, with Doped ions
Molal quantity increases, and lattice number can change.When doping ratio is larger, charge number imbalance out can be caused, by extra
Oxygen ion vacancy causes main function, and cell parameter generation appropriate can also expand.
(3), very big on unit cell dimension influence with the difference of titanium doped amount, interplanar distance d becomes with the variation of ratio mole
Gesture first reduces and increases afterwards.This it appears that interplanar distance is smaller in figure, the lattice point arrangement on crystal face is more sparse.But
Can also be seen in figure the characteristic peak of the sample of different proportion in angle and standard PDF card spectrogram slightly deviation, whole diffraction
Peak deviates high angle direction.
2.2.SEM-EDS test
Fig. 9 a, b are (La0.4Ti0.6)2Mo2O9-δThe high and low multiplying power electron microscope of powder, Fig. 9 c is (La0.4Ti0.6)2Mo2O9-δ
The quantitative analysis results of powder, Fig. 9 d are (La0.4Ti0.6)2Mo2O9-δThe energy spectrum diagram of powder.The SEM photograph for being 50 μm from specification
It can be seen that the partial size of crystal grain is closely arranged, and the crystal boundary of sample is clear, and light and shade, which connects, to be shown inside precursor powder on (Fig. 9 a)
Powder has protrusion phenomenon, and bright face represents raised position.Concave-convex orderly structure more reduces porosity, this image and formula (1)
Relative density (>=97%) measurement result is calculated to match.What can be apparent from Fig. 9 b sees sintered particles in ellipsoid
Shape, and surface is smooth, illustrates that crystallization degree is very good.From in Fig. 9 c it can be seen that sample in titaniferous amount be about 15%, but
Not can determine that its content, EDS can only qualitative analysis, quantitative analysis is unable to, because the data that different time sections are surveyed are different.
2.3.IR test
Figure 10 is (La1-XTix)2Mo2O9-&The infrared spectrogram of presoma is indicated using T- δ curve.Abscissa indicates
Wave number, ordinate indicate transmitance.By Figure 10 it can be observed that in 697cm-1Absorption peak is can be attributed to M-O stretching vibration
Characteristic peak, illustrate that metal ion comes into lanthanum molybdate matrix.Meanwhile it can be seen from fig. 10 that 1500cm in figure-1
There is no the appearance at other infrared ray diffraction peaks later, illustrate sample in contained hydrone after high-temperature calcination three times, second
Impurity volatilizees or decomposes completely in the air such as alcohol, and crystalline formation process is not affected by influence, forms complete cubic fluorite
Structure.
2.4. porosity and density calculate
Sample consistency is mainly characterized by weighing porosity and the relative density of the sample of sample re-computation, is weighed
Method weighs the dry weight of sample, weight in wet base and buoyant weight.The porosity and relative density of each sample are calculated in formula.According to above-mentioned
Formula (1) (2) calculates porosity and relative density is as shown in table 2
4 (La of table1-xTix)2Mo2O9-δThe porosity and relative density of sample
As shown in Table 4, Doped with Titanium series lanthanum molybdate potsherd keeps the temperature the sample of 2h at 850 DEG C, it is relatively close after tested
Degree is up to 95% or more.Doping ratio more high porosity is bigger, and relative density is smaller.This shows the Ceramic Like for mixing titanium series
(the La synthesized using mixing oxides method1-xTix)2Mo2O9-δ(0.2≤x≤0.4) has good sintering activity, although this is compared
97% or more titanium series ceramic sample relative density is mixed in the molybdenum position of the acquisition synthesized with sol-gel method, and consistency is few
2%, but its ratio is controlled to the potsherd that 97% or more consistency can be equally obtained below x < 0.3.This more shows to adulterate
Ratio and matrix location influence it is very big, with document record ratio should x < 0.3 meet.The sintering temperature that the method needs also relatively passes
System solid phase method reduces 150 DEG C or so, and lower sintering has temperature to help the preparation that activity loads with type electrolyte.But ratio is necessary
Control can just effectively reduce the preparation cost of solid oxide fuel in x < 0.3.
2.5. impedance method analytical calculation conductivity
Figure 11 is (La1-xTix)2Mo2O9-δAC impedance spectroscopy under different temperatures, ac impedance spectroscopy are generally divided into three
Part: the grain resistance in high frequency region；Grain boundary resistance in intermediate frequency zone；Between electrode and electrolyte in low frequency range
Charge diffusion, transfer resistance.As shown in Figure 11:
(1) resistance change rate of Doped with Titanium series ceramic sample varies with temperature very big；
(2) when temperature is increased to 600 DEG C, the semicircle of high frequency region becomes smaller in AC impedance spectroscopy, is in collapsed state, this says
Body phase conductive process gradually weakens in bright crystal, and reclinate trend is presented in ray portion.
Figure 12 is (La1-xTix)2Mo2O9-δConductance conductance and temperature relational graph (x=0.2,03,0.4), can from figure
To find out:
(1) conductance of sample increases with the raising of temperature；
(2) when temperature is in the conductivity very little of 400-600 DEG C of sample and unrelated with Doped ions molal quantity；
(3) when x=0.4 temperature is 800 DEG C, the conductivity of sample is up to 0.0253S/cm.
Figure 13 is (La1-xPbx)2Mo2O9-δThe linear graph made with the value of 1000/T and ln (σ T) for horizontal, ordinate.Doping
Measure (x=0.2,0.3,0.4) conductivity Arrhenius curve.As can be seen from the figure the curvilinear motion of x=0.3 and x=0.4
Trend is almost the same, but three curves are whole all on a declining curve.Do not occur gliding suddenly.This shows according to La2Mo2O9?
580 DEG C or so high-temperature and reversible phase transformation can not occur, because unexpected near the temperature spot for conductivity on Arrhenius curve
It reduces.It is doped with Ti4+La2Mo2O9Arrhenius curve show that conductivity is not observed on regular decline curve is prominent
So decline phenomenon, it is possible thereby to show that La can be inhibited well by adulterating titanium ion2Mo2O9Matrix is undergone phase transition.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Design or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (3)
1. a kind of metallic element adulterates La2Mo2O9Method for preparing solid electrolyte, using ultrasonic-microwave sol-gal process,
It is characterized in that, steps are as follows:
1., according to target sample (La1-xMx)2Mo2O9-δStoichiometric ratio, weigh La (NO3)3·6H2O、(NH4)6Mo7O24·
4H2O、Pb(NO3)2Or butyl titanate is added appropriate distilled water and dissolution is sufficiently stirred in beaker；
2., be added citric acid into beaker again, and adjust pH value to neutrality with ammonium hydroxide, be transferred to CS-BA type digital display ultrasonic water
It bathes and carries out ultrasound 1h in oscillator, after being uniformly dispersed, be put into 80 DEG C of microwave heating reactions in WBFY201 type microwave chemical reactor
2h, evaporation obtain wet gel；
3., gained wet gel sample is put into drying box in 120 DEG C of dry 12h, then will dry that sample is levigate to be put into Muffle
Pre-burning 3 times in furnace, each 10h, temperature is respectively 750 DEG C, 850 DEG C, 950 DEG C three times, take out sample be cooled to room temperature again into
Row is fully ground, to obtain target product (La1-xMx)2Mo2O9-δ；
4., using after grinding electrolyte pre-burning material be added 5wt% PVA solution be granulated as adhesive, then take and make
Powder 0.5g after grain, in stainless steel mould, positive 4MPa pressure, reversed 8MPa is pressed into a thickness of 2mm, and diameter is
The thin rounded flakes of 12mm；Then it is placed on ceramic wafer, label good position is placed in high-temperature box type temperature control furnace again with 2 DEG C/min liter
Temperature keeps the temperature 2h at 850 DEG C to 850 DEG C of sintering；
5., carry out dumping after natural cooling；Gloss is presented into through sand paper polishing, cleaning, drying rear surface in sample；Above and below print
Two sides surface uniformly coats DAD-87 silver conductive adhesive, is warming up to 700 DEG C of sintered heat insulatings in high-temperature box type temperature control furnace with 2 DEG C/min
2h；Sintering obtains (La1-xMx)2Mo2O9-δElectrolyte ceramics piece.
2. preparation method as described in claim 1, which is characterized in that step 1. in target product (La1-xMx)2Mo2O9-δMiddle x
=0~0.6, M are Pb or Ti.
3. a kind of (La of method preparation as claimed in claim 1 or 21-xMx)2Mo2O9-δElectrolyte ceramics piece, which is characterized in that
Powder granule is in ellipsoid, sequence rule and gap very little；The particle diameter distribution of crystal grain is uniform, and crystal Jian Jie circle is obvious and porosity
It is smaller.
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| CN111517783A (en) * | 2020-04-30 | 2020-08-11 | 合肥学院 | Method for preparing calcium carbonate-YSZ composite solid electrolyte by ultrasonic microwave combination method |
| CN111517783B (en) * | 2020-04-30 | 2022-04-22 | 合肥学院 | Method for preparing calcium carbonate-YSZ composite solid electrolyte by ultrasonic microwave combination method |
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