CN108409337A - A method of doped metallic oxide YSZ electrolyte ceramics are prepared based on coprecipitation - Google Patents
A method of doped metallic oxide YSZ electrolyte ceramics are prepared based on coprecipitation Download PDFInfo
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- CN108409337A CN108409337A CN201810105686.9A CN201810105686A CN108409337A CN 108409337 A CN108409337 A CN 108409337A CN 201810105686 A CN201810105686 A CN 201810105686A CN 108409337 A CN108409337 A CN 108409337A
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- metallic oxide
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- ysz electrolyte
- doped metallic
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 51
- 239000000919 ceramic Substances 0.000 title claims abstract description 45
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 31
- 238000000975 co-precipitation Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 238000001556 precipitation Methods 0.000 claims abstract description 33
- 239000002019 doping agent Substances 0.000 claims abstract description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000006228 supernatant Substances 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000084 colloidal system Substances 0.000 claims abstract description 12
- 238000013019 agitation Methods 0.000 claims abstract description 9
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 239000011686 zinc sulphate Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 229910052925 anhydrite Inorganic materials 0.000 claims 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims 1
- -1 metals Salt Chemical class 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 abstract 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 49
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 13
- 150000004706 metal oxides Chemical class 0.000 description 8
- 101710134784 Agnoprotein Proteins 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910017343 Fe2 (SO4)3 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
The invention discloses a kind of methods preparing doped metallic oxide YSZ electrolyte ceramics based on coprecipitation, belong to function ceramics preparing technical field.Yttrium oxide is dissolved in concentrated nitric acid by the present invention, and zirconium oxychloride is added according to the stoichiometric ratio of YSZ, adds dopant salt mixed dissolution and uniformly obtains mixed liquor A；Under agitation, ammonium hydroxide is added dropwise in mixed liquor A to complete precipitation and obtains colloid B；Colloid B is centrifugally separating to obtain supernatant C and precipitation D, adopts and precipitation D is washed with deionized to the supernatant liquor being centrifugally separating to obtain without Cl‑Ion, then absolute ethyl alcohol is used to wash 2 ~ 3 times, dry, grinding, then be placed under the conditions of temperature is 500 ~ 700 DEG C and roast 2 ~ 4h up to doped metallic oxide YSZ electrolyte ceramics.Doped metallic oxide YSZ electrolyte ceramics powder grains prepared by the present invention are tiny, and sintering activity is high, and chemical uniformity is good and easy-sintering, can accurately control the content of each component.
Description
Technical field
The present invention relates to a kind of methods preparing doped metallic oxide YSZ electrolyte ceramics based on coprecipitation, belong to
Function ceramics preparing technical field.
Background technology
8 mol% yttria-stabilized zirconias (yttria stabilized zirconia, YSZ) are that research is widest
One of ceramic material, since sufficiently high ionic conductivity becomes under its good mechanical performance, chemical stability and high temperature
Soild oxide fuel cell (solid oxide fuel cell, SOFC) ideal electrolyte.Pure zirconium oxide has
Three kinds of crystal forms, monoclinic phase, tetragonal phase and fluorite structure cubic phase.By Y2O3Adulterate ZrO2Obtained fluorite cubic phase YSZ
More other two kinds of crystal forms are more suitably applied to the electrolyte of the SOFC as hot operation.Electrolyte YSZ's suitable for SOFC
Sintering needs higher temperature, so the limitation that conductivity caused by its application is often subject to sintering temperature height declines.It is this
Limitation is mainly caused by YSZ crystal grain is easy mutually to merge at high temperature and grow up so that oxygen ion transport channel tails off.It is logical
Crossing appropriate doping can inhibit crystal grain to grow up, to reduce the sintering temperature of YSZ materials, increase its intensity and oxide ion conduction
Rate.
Currently, the process of doped metallic oxide YSZ electrolyte ceramics is mainly mechanical ball mill mixing, however it is this
The ceramic powders that method prepares are easy to reunite, and lead to active reduction.
Invention content
For existing doped metallic oxide YSZ electrolyte ceramics technology of preparing there are the problem of and deficiency, the present invention carry
For a kind of method preparing doped metallic oxide YSZ electrolyte ceramics based on coprecipitation, the present invention is using co-precipitation legal system
Standby doped metallic oxide YSZ electrolyte ceramics, can make doped metallic oxide YSZ electrolyte ceramics powder grains small, be sintered
Active high, chemical uniformity is good and easy-sintering, can accurately control the content of each component, and superfluous precipitating reagent makes in solution
All cation precipitates simultaneously, can avoid the loss of effectively cation.
A method of doped metallic oxide YSZ electrolyte ceramics are prepared based on coprecipitation, are as follows：
（1）Under the conditions of temperature is 40 ~ 60 DEG C, yttrium oxide is dissolved in concentrated nitric acid, oxygen is added according to the stoichiometric ratio of YSZ
Zirconium chloride adds dopant salt mixed dissolution and uniformly obtains mixed liquor A；Wherein dopant salt is metal salt；
（2）Under agitation, ammonium hydroxide is added dropwise to step（1）In gained mixed liquor A colloid B is obtained to complete precipitation；
（3）By step（2）Gained colloid B be centrifugally separating to obtain supernatant C and precipitation D, adopt be washed with deionized precipitation D to from
The isolated supernatant liquor of the heart is without Cl-Ion, then washed 2 ~ 4 times using absolute ethyl alcohol, dry, grinding, then be placed in temperature and be
2 ~ 4 h are roasted under the conditions of 500 ~ 700 DEG C up to doped metallic oxide YSZ electrolyte ceramics；
Further, the step（1）The solid-to-liquid ratio g of middle yttrium oxide and concentrated nitric acid:ML is 1:(2.2~4.4)；
Further, the mass ratio of the dopant salt and yttrium oxide is 1:(2.1~5.4)；
Further, the step（1）Middle metal salt is the metal salt of Al, Fe, Ca or Mg；
Further, the step（1）Middle Al metal salts are Al2(SO4)3, Fe metal salts be Fe2(SO4)3, Ca metal salts be
Ca(NO3)2, Zn metal salts be ZnSO4；
The concentrated nitric acid is commercially available concentrated nitric acid.
Beneficial effects of the present invention：
（1）The present invention prepares doped metallic oxide YSZ electrolyte ceramics using coprecipitation, can make doped metallic oxide
YSZ electrolyte ceramics powder grains are small, and sintering activity is high, and chemical uniformity is good and easy-sintering, can accurately control each component
Content, and superfluous precipitating reagent makes all cations in solution while precipitating, and can avoid the loss of effectively cation；
（2）Doped metallic oxide YSZ electrolyte ceramics prepared by the present invention, compared with undoped YSZ electrolyte ceramics, conductance
Rate is improved significantly.
Description of the drawings
Fig. 1 is 1 Al of embodiment2O3Adulterate AC impedance spectroscopy of the YSZ electrolyte ceramics when temperature is 800 DEG C；
Fig. 2 is 1 Al of embodiment2O3Adulterate the scanning electron microscope (SEM) photograph of YSZ electrolyte ceramics；
Fig. 3 is 2 Al of embodiment2O3Adulterate the transmission electron microscope picture of YSZ electrolyte ceramics.
Specific implementation mode
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1：One kind preparing Al based on coprecipitation2O3The method for adulterating YSZ electrolyte ceramics, is as follows：
（1）Under the conditions of temperature is 40 DEG C, by 0.68 g yttrium oxides Y2O3It is dissolved in concentrated nitric acid, according to the stoichiometry of YSZ
Than 11.39 g zirconium oxychlorides ZrOCl are added2·9H2O adds dopant salt（Dopant salt is aluminum sulfate Al2(SO4)3·
9H2O）Mixed dissolution uniformly obtains mixed liquor A；The wherein solid-to-liquid ratio g of yttrium oxide and concentrated nitric acid:ML is 1:2.2；Dopant salt
（Aluminum sulfate Al2(SO4)3·9H2O）Mass ratio with yttrium oxide is 1:2.1；
（2）Under the conditions of magnetic agitation, ammonium hydroxide is added dropwise to step（1）In gained mixed liquor A glue is obtained to complete precipitation
Body B；Wherein ammonium hydroxide is excessive；
（3）By step（2）Gained colloid B be centrifugally separating to obtain supernatant C and precipitation D, adopt be washed with deionized precipitation D to from
The isolated supernatant liquor of the heart is without Cl-Ion, then washed 2 times using absolute ethyl alcohol, it spontaneously dries, grinds, then set at room temperature
Roasting 2h is up to metal oxide Al under the conditions of being 700 DEG C in temperature2O3Adulterate YSZ electrolyte ceramics；
The present embodiment step（3）Middle Cl-The detection of ion uses the AgNO of a concentration of 0.1 mol/L3Solution is titrated, nothing
AgCl precipitations generate；
3 g the present embodiment doped metallic oxide YSZ electrolyte ceramics powder are taken, 6 wt% polyvinyl butyrals (PVB) are added
Ethanol solution be ground in agate mortar ethyl alcohol volatilization, obtain being easy to dry-pressing formed powder, by powder stainless steel mold
Tool is pressed into a diameter of 1.3 cm under 300 MPa pressure, and thickness is the disk of 0.5 mm, is 1400 DEG C of 4 h of sintering through temperature
Keep electrolyte sheet fine and close；Be put into tube furnace after electrolyte sheet two sides even application silver paste (DAD-87), in air atmosphere with
The heating rate of 20 DEG C/min rises to 800 DEG C from room temperature, and 1 h of heat preservation drops to room temperature to get to fine and close, bright and clean, uniform with stove
Silver electrode, silver electrode effective area are 0.25cm2；Between sintered electrolyte sheet is fixed on two ceramic tubes, made with filamentary silver
It for conducting wire, puts into the quartz ampoule being put into tube furnace in advance, in air atmosphere, is heated up with the heating rate of 10 DEG C/min
It to 800 DEG C and keeps the temperature, tests its AC impedance under open-circuit condition, the frequency range of testing impedance is 0.1 ~ 105 Hz；Such as figure
Shown in 1, test shows that the Ohmic resistance of electrolyte sheet when temperature is 800 DEG C is 1.74 Ω cm2, it is converted into the electricity of electrolyte
Conductance is 0.0334 Scm-1；The analysis of microstructure is carried out to the surface of electrolyte sheet simultaneously, the surface of electrolyte sheet is swept
Electron microscope is retouched as shown in Fig. 2, from figure 2 it can be seen that Al manufactured in the present embodiment2O3It is fine and close to adulterate YSZ bath surfaces, table
There is the particle aggregation more smaller than its between the YSZ crystal grain of face or intersperse among surface, whole surface there are a large amount of little particles
Distribution, to provide more particle contact surfaces, these little particles are evenly distributed in YSZ grain boundaries, prevent YSZ crystal grain
Grow up.
Embodiment 2：One kind preparing Al based on coprecipitation2O3The method for adulterating YSZ electrolyte ceramics, is as follows：
（1）Under the conditions of temperature is 60 DEG C, by 0.68 g yttrium oxides Y2O3It is dissolved in concentrated nitric acid, according to the stoichiometry of YSZ
Than 11.39 g zirconium oxychlorides ZrOCl are added2·9H2O adds dopant salt（Dopant salt is aluminum sulfate Al2(SO4)3·
9H2O）Mixed dissolution uniformly obtains mixed liquor A；The wherein solid-to-liquid ratio g of yttrium oxide and concentrated nitric acid:ML is 1:4.4；Dopant salt
（Aluminum sulfate Al2(SO4)3·9H2O）Mass ratio with yttrium oxide is 1:4.1；
（2）Under the conditions of magnetic agitation, ammonium hydroxide is added dropwise to step（1）In gained mixed liquor A glue is obtained to complete precipitation
Body B；Wherein ammonium hydroxide is excessive；
（3）By step（2）Gained colloid B be centrifugally separating to obtain supernatant C and precipitation D, adopt be washed with deionized precipitation D to from
The isolated supernatant liquor of the heart is without Cl-Ion, then washed 3 times using absolute ethyl alcohol, it spontaneously dries, grinds, then set at room temperature
Roasting 4h is up to metal oxide Al under the conditions of being 500 DEG C in temperature2O3Adulterate YSZ electrolyte ceramics；
The present embodiment step（3）Middle Cl-The detection of ion uses the AgNO of a concentration of 0.1 mol/L3Solution is titrated, nothing
AgCl precipitations generate；
The present embodiment metal oxide Al2O3The transmission electron microscope picture of YSZ electrolyte ceramics is adulterated as shown in figure 3, can from Fig. 3
Know, the present embodiment metal oxide Al2O3Doping YSZ electrolyte ceramics powder is nanometer grade powder, average grain size 15
The lattice fringe of nm, YSZ are clear.
Embodiment 3：One kind preparing Al based on coprecipitation2O3The method for adulterating YSZ electrolyte ceramics, is as follows：
（1）Under the conditions of temperature is 50 DEG C, by 0.68 g yttrium oxides Y2O3It is dissolved in concentrated nitric acid, according to the stoichiometry of YSZ
Than 11.39 g zirconium oxychlorides ZrOCl are added2·9H2O adds dopant salt（Dopant salt is aluminum sulfate Al2(SO4)3·
9H2O）Mixed dissolution uniformly obtains mixed liquor A；The wherein solid-to-liquid ratio g of yttrium oxide and concentrated nitric acid:ML is 1:3.3；Dopant salt
（Aluminum sulfate Al2(SO4)3·9H2O）Molar ratio with yttrium oxide is 1:2.1；
（2）Under the conditions of magnetic agitation, ammonium hydroxide is added dropwise to step（1）In gained mixed liquor A glue is obtained to complete precipitation
Body B；Wherein ammonium hydroxide is excessive；
（3）By step（2）Gained colloid B be centrifugally separating to obtain supernatant C and precipitation D, adopt be washed with deionized precipitation D to from
The isolated supernatant liquor of the heart is without Cl-Ion, then washed 4 times using absolute ethyl alcohol, it spontaneously dries, grinds, then set at room temperature
Roasting 3h is up to metal oxide Al under the conditions of being 600 DEG C in temperature2O3Adulterate YSZ electrolyte ceramics；
The present embodiment step（3）Middle Cl-The detection of ion uses the AgNO of a concentration of 0.1 mol/L3Solution is titrated, nothing
AgCl precipitations generate.
Embodiment 4：One kind preparing Fe based on coprecipitation2O3The method for adulterating YSZ electrolyte ceramics, is as follows：
（1）Under the conditions of temperature is 60 DEG C, by 0.68 g yttrium oxides Y2O3It is dissolved in concentrated nitric acid, according to the stoichiometry of YSZ
Than 11.39 g zirconium oxychlorides ZrOCl are added2·9H2O adds dopant salt（Dopant salt is ferric sulfate Fe2(SO4)3）Mixing
It is uniformly dissolved to obtain mixed liquor A；The wherein solid-to-liquid ratio g of yttrium oxide and concentrated nitric acid:ML is 1:2.6；Dopant salt（Ferric sulfate Fe2
(SO4)3）Mass ratio with yttrium oxide is 1:5.4；
（2）Under the conditions of magnetic agitation, ammonium hydroxide is added dropwise to step（1）In gained mixed liquor A glue is obtained to complete precipitation
Body B；Wherein ammonium hydroxide is excessive；
（3）By step（2）Gained colloid B be centrifugally separating to obtain supernatant C and precipitation D, adopt be washed with deionized precipitation D to from
The isolated supernatant liquor of the heart is without Cl-Ion, then washed 2 times using absolute ethyl alcohol, it spontaneously dries, grinds, then set at room temperature
Roasting 3h is up to metal oxide Fe under the conditions of being 550 DEG C in temperature2O3Adulterate YSZ electrolyte ceramics；
The present embodiment step（3）Middle Cl-The detection of ion uses the AgNO of a concentration of 0.1 mol/L3Solution is titrated, nothing
AgCl precipitations generate.
Embodiment 5：A method of CaO is prepared based on coprecipitation and adulterates YSZ electrolyte ceramics, is as follows：
（1）Under the conditions of temperature is 55 DEG C, by 0.68 g yttrium oxides Y2O3It is dissolved in concentrated nitric acid, according to the stoichiometry of YSZ
Than 11.39 g zirconium oxychlorides ZrOCl are added2·9H2O adds dopant salt（Dopant salt is calcium nitrate Ca (NO3)2·
4H2O）Mixed dissolution uniformly obtains mixed liquor A；The wherein solid-to-liquid ratio g of yttrium oxide and concentrated nitric acid:ML is 1:3.6；Dopant salt
（Calcium nitrate Ca (NO3)2·4H2O）Mass ratio with yttrium oxide is 1:3.2；
（2）Under the conditions of magnetic agitation, ammonium hydroxide is added dropwise to step（1）In gained mixed liquor A glue is obtained to complete precipitation
Body B；Wherein ammonium hydroxide is excessive；
（3）By step（2）Gained colloid B be centrifugally separating to obtain supernatant C and precipitation D, adopt be washed with deionized precipitation D to from
The isolated supernatant liquor of the heart is without Cl-Ion, then washed 3 times using absolute ethyl alcohol, it spontaneously dries, grinds, then set at room temperature
Roasting 2.5h adulterates YSZ electrolyte ceramics up to metal oxide CaO under the conditions of being 650 DEG C in temperature；
The present embodiment step（3）Middle Cl-The detection of ion uses the AgNO of a concentration of 0.1 mol/L3Solution is titrated, nothing
AgCl precipitations generate.
Embodiment 6：A method of ZnO doping YSZ electrolyte ceramics are prepared based on coprecipitation, are as follows：
（1）Under the conditions of temperature is 45 DEG C, by 0.68 g yttrium oxides Y2O3It is dissolved in concentrated nitric acid, according to the stoichiometry of YSZ
Than 11.39 g zirconium oxychlorides ZrOCl are added2·9H2O adds dopant salt（Dopant salt is zinc sulfate ZnSO4·7H2O）
Mixed dissolution uniformly obtains mixed liquor A；The wherein solid-to-liquid ratio g of yttrium oxide and concentrated nitric acid:ML is 1:3.9；Dopant salt（Zinc sulfate
ZnSO4·7H2O）Mass ratio with yttrium oxide is 1:3.8；
（2）Under the conditions of magnetic agitation, ammonium hydroxide is added dropwise to step（1）In gained mixed liquor A glue is obtained to complete precipitation
Body B；Wherein ammonium hydroxide is excessive；
（3）By step（2）Gained colloid B be centrifugally separating to obtain supernatant C and precipitation D, adopt be washed with deionized precipitation D to from
The isolated supernatant liquor of the heart is without Cl-Ion, then washed 4 times using absolute ethyl alcohol, it spontaneously dries, grinds, then set at room temperature
Roasting 3.5h is up to metal oxide ZnO doping YSZ electrolyte ceramics under the conditions of being 600 DEG C in temperature；
The present embodiment step（3）Middle Cl-The detection of ion uses the AgNO of a concentration of 0.1 mol/L3Solution is titrated, nothing
AgCl precipitations generate.
Claims (5)
1. a kind of method preparing doped metallic oxide YSZ electrolyte ceramics based on coprecipitation, which is characterized in that specific step
It is rapid as follows：
（1）Under the conditions of temperature is 40 ~ 60 DEG C, yttrium oxide is dissolved in concentrated nitric acid, oxygen is added according to the stoichiometric ratio of YSZ
Zirconium chloride adds dopant salt mixed dissolution and uniformly obtains mixed liquor A；Wherein dopant salt is metal salt；
（2）Under agitation, ammonium hydroxide is added dropwise to step（1）In gained mixed liquor A colloid B is obtained to complete precipitation；
（3）By step（2）Gained colloid B be centrifugally separating to obtain supernatant C and precipitation D, adopt be washed with deionized precipitation D to from
The isolated supernatant liquor of the heart is without Cl-Ion, then washed 2 ~ 4 times using absolute ethyl alcohol, dry, grinding, then be placed in temperature and be
2 ~ 4h is roasted under the conditions of 500 ~ 700 DEG C up to doped metallic oxide YSZ electrolyte ceramics.
2. the method for preparing doped metallic oxide YSZ electrolyte ceramics based on coprecipitation according to claim 1, special
Sign is：Step（1）The solid-to-liquid ratio g of middle yttrium oxide and concentrated nitric acid:ML is 1:(2.2~4.4).
3. the method for preparing doped metallic oxide YSZ electrolyte ceramics based on coprecipitation according to claim 1, special
Sign is：The mass ratio of dopant salt and yttrium oxide is 1:(2.1~5.4).
4. the method for preparing doped metallic oxide YSZ electrolyte ceramics based on coprecipitation according to claim 1, special
Sign is：Step（1）Middle metal salt is the metal salt of Al, Fe, Ca or Zn.
5. the method for preparing doped metallic oxide YSZ electrolyte ceramics based on coprecipitation according to claim 4, special
Sign is：Step（1）Middle Al metal salts are Al2(SO4)3, Fe metal salts be Fe2(SO4)3, Ca metal salts be CaSO4, Zn metals
Salt is ZnSO4。
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Application publication date: 20180817 |