CN105088316A - Preparation method of rare earth doped ceria membrane - Google Patents
Preparation method of rare earth doped ceria membrane Download PDFInfo
- Publication number
- CN105088316A CN105088316A CN201510503083.0A CN201510503083A CN105088316A CN 105088316 A CN105088316 A CN 105088316A CN 201510503083 A CN201510503083 A CN 201510503083A CN 105088316 A CN105088316 A CN 105088316A
- Authority
- CN
- China
- Prior art keywords
- cerium
- rare earth
- earth
- dioxide film
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Cosmetics (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a preparation method of a rare earth doped ceria membrane. The method comprises the steps that a rare earth oxide is dissolved in nitric acid to obtain a rare earth salt solution; the pH value of the rare earth salt solution is adjusted by ammonium hydroxide to be 6.3-7.8, ethylene glycol is added, ammonium hydroxide is added with stirring, and an electrolyte is obtained; silicon carbide waterproof abrasive paper wet by absolute ethyl alcohol is used for polishing a cerium sheet, the polished cerium sheet is cleaned by absolute ethyl alcohol, a diamond spray polishing agent is sprayed on lint, the cerium sheet is polished on the lint sprayed with the diamond spray polishing agent till being a mirror plane, and the polished cerium sheet is placed in absolute ethyl alcohol for ultrasonic cleaning; the cerium sheet to be anodized is placed into the electrolyte to be anodized, and the anodized part is washed with water and air-dried; and the anodized part is placed in a muffle furnace to be roasted, cooled and taken out, and therefore the rare earth doped ceria membrane with the two faces with multiple nanometer straight holes and the compact middle is obtained. The diameters of the multiple nanometer straight holes in the two faces are tested by a Fisher MPO thickness tester to range from 15 micrometers to 97 micrometers.
Description
Technical field
The invention belongs to materialogy field, relate to a kind of cerium dioxide film, specifically a kind of preparation method of rear-earth-doped cerium dioxide film.
Background technology
Due to doping
twocerium oxide has high oxygen storage capacity and oxygen ionic conductivity, can be used for the ionogen of Solid Oxide Fuel Cell.The ionogen of current Solid Oxide Fuel Cell to be supported on electrode especially on anode usually, existing silk screen print method, casting method, altogether platen press, spin coating method, dip-coating method, sol-gel membrane formation process, spray decomposition method etc.These film preparing technologies obtain very large development in electrolytical preparation and application process, but still there is certain deficiency, as electrolyte thin film thickness controllability, sticking power and there is defect etc. when usually need sinter more than 1000 DEG C and burn till.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of preparation method of rear-earth-doped cerium dioxide film, the preparation method of described this rear-earth-doped cerium dioxide film solves the electrolyte thin film thickness of prior art, sticking power is uncontrollable, and easily occurs the technical problem of defect during sintering.
The invention provides a kind of preparation method of rear-earth-doped cerium dioxide film, comprise the steps:
(1) rare earth oxide is dissolved in nitric acid, is mixed with rare earths salt;
Its middle rare earth is the mixture of one or more the rare earth oxide in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium rare earth oxide; The concentration of rare earths salt middle-weight rare earths is 300 ~ 500g/L;
(2) regulate the pH value of above-mentioned rare earths salt to be 6.3 ~ 7.8 with ammonia soln, add ethylene glycol, under agitation add ammoniacal liquor, make electrolytic solution; In ethylene glycol, the concentration of ammoniacal liquor is 2.5 ~ 400g/L, the concentration of rare-earth salts is 30 ~ 50g/L;
(3) be that 0.1 ~ 0.3mm cerium tablet is polished and clean with washes of absolute alcohol with the wetting silicon carbide waterproof abrasive paper of dehydrated alcohol to thickness, be sprayed on flannelette with the diamond spraying rumbling compound of 0.5 ~ 1.5 μm, cerium tablet after polishing, until be minute surface, is put into anhydrous alcohol solution ultrasonic cleaning by cerium tablet polishing on the flannelette having diamond spraying rumbling compound;
(4) will treat that anodised cerium tablet puts into electrolytic solution Anodic Oxidation, negative electrode is platinum or lead, and cerium tablet is anode, and anodised processing condition are current density 8 ~ 200mA/dm
2, oxidizing temperature 0 ~ 20 DEG C, mixing speed 100 ~ 600rpm, oxidization time 3 ~ 17h, after anodic oxidation, anodic oxidation part use water rinse, air-dry;
(5) anodic oxidation part is put into retort furnace, with 0.4`0.6 DEG C/min temperature programming to 320 ~ 800 DEG C, at 320 ~ 400 DEG C of roasting 0.5 ~ 2h, be chilled to room temperature, taking out and obtaining two sides is be fine and close rear-earth-doped cerium dioxide film in the middle of many nanometers straight hole.
Further, the thickness of cerium tablet is 0.2mm.
Further, be sprayed on flannelette with the diamond spraying rumbling compound of 1 μm.
Further, described rare earth oxide is any one in lanthanum trioxide, Samarium trioxide, Neodymium trioxide, lutecium oxide, gadolinium sesquioxide, europium sesquioxide, terbium sesquioxide or Praseodymium trioxide.
It is be fine and close rear-earth-doped cerium dioxide film in the middle of many nanometers straight hole that the present invention has prepared two sides.The hole length adopting FisherMPO thickness tester to measure two sides many nanometers straight hole is respectively 15 ~ 97 μm.It is 5.2 ~ 27.1% that the content adopting BrukerAXSMicroanalysisGmbH energy spectrometer to measure rear-earth-doped cerium dioxide film middle-weight rare earths is calculated by mass percentage.
The present invention compares with prior art, and its technical progress is significant.It is be fine and close rear-earth-doped cerium dioxide film in the middle of many nanometers straight hole that the present invention adopts anonizing and heat treating process to prepare two sides.The present invention by controlling the anodizing time of cerium paper tinsel, thus can control the thickness of rear-earth-doped cerium dioxide film film.
Embodiment
Below by specific embodiment, the present invention is set forth further, but do not limit the present invention.
Embodiment 1
Take 35.1840g lanthanum trioxide in 100mL small beaker, under agitation add 50mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, la concn is 300g/L.The solution 100mL that above-mentioned la concn is 300g/L is added in the beaker of 2L, be 7.8 by ammonia soln regulator solution pH value, add 785mL ethylene glycol, under agitation add 2.5g ammoniacal liquor, dissolve and form lanthanum nitrate-ammonia water-ethylene glycol mixing solutions, move in 1L volumetric flask, spent glycol is diluted to scale, obtained electrolytic solution.With dehydrated alcohol wetting silicon carbide waterproof abrasive paper, 100mm × 100mm × 0.1mm is treated that anodised cerium paper tinsel is polished and clean with washes of absolute alcohol, be sprayed on flannelette with the diamond of 0.5 μm spraying rumbling compound, by cerium tablet have diamond spray rumbling compound flannelette on polishing until be minute surface.Cerium paper tinsel after polishing is put into anhydrous alcohol solution ultrasonic cleaning.Above-mentioned electrolytic solution is proceeded in the beaker of 2L, above-mentioned 100mm × 100mm × 0.1mm treated that electrolytic solution put into by anodic oxidation cerium paper tinsel and for anode, negative electrode is the platinum plate of 150mm × 150mm × 0.5mm, magnetic agitation, mixing speed is 100rpm, and current density is 8mA/dm
2, oxidizing temperature 0 DEG C, oxidization time 3h, takes out anodic oxidation part, clean with deionized water rinsing, air-dry, puts into crucible, puts into retort furnace, with 0.5 DEG C/min temperature programming to 400 DEG C, at 400 DEG C of roasting 0.5h.Be chilled to room temperature, taking out and obtaining two sides is be fine and close lanthanum doping cerium dioxide film in the middle of many nanometers straight hole.The hole length that the MPO thickness tester adopting Fisher company to produce measures two sides many nanometers straight hole is respectively 15 μm.It is 5.2% that the content adopting BrukerAXSMicroanalysisGmbH energy spectrometer to measure lanthanum in lanthanum doping cerium dioxide film is calculated by mass percentage.
Embodiment 2
Take 57.9800g Samarium trioxide in 200mL small beaker, under agitation add 80mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, samarium concentration is 500g/L.The solution 100mL that above-mentioned samarium concentration is 500g/L is added in the beaker of 2L, be 6.9 by ammonia soln regulator solution pH value, add 375mL ethylene glycol, under agitation add 400g ammoniacal liquor, dissolve and form samaric nitrate-ammonia water-ethylene glycol mixing solutions, move in 1L volumetric flask, spent glycol is diluted to scale, obtained electrolytic solution.With dehydrated alcohol wetting silicon carbide waterproof abrasive paper, 100mm × 100mm × 0.3mm is treated that anodised cerium paper tinsel is polished and clean with washes of absolute alcohol, be sprayed on flannelette with the diamonds of 1.5 μm spraying rumbling compound, by cerium tablet have diamond spray rumbling compound flannelette on polishing until be minute surface.Cerium paper tinsel after polishing is put into anhydrous alcohol solution ultrasonic cleaning.Above-mentioned electrolytic solution is proceeded in the beaker of 2L, above-mentioned 100mm × 100mm × 0.3mm treated that electrolytic solution put into by anodic oxidation cerium paper tinsel and for anode, negative electrode is the stereotype of 150mm × 150mm × 2mm, magnetic agitation, mixing speed is 600rpm, and current density is 200mA/dm
2, oxidizing temperature 20 DEG C, oxidization time 17h, takes out anodic oxidation part, clean with deionized water rinsing, air-dry, puts into crucible, puts into retort furnace, with 0.5 DEG C/min temperature programming to 320 DEG C, at 320 DEG C of roasting 2h.Be chilled to room temperature, taking out and obtaining two sides is be fine and close samarium doping cerium dioxide film in the middle of many nanometers straight hole.The hole length that the MPO thickness tester adopting Fisher company to produce measures two sides many nanometers straight hole is respectively 97 μm.It is 27.1% that the content adopting BrukerAXSMicroanalysisGmbH energy spectrometer to measure samarium in samarium doping cerium dioxide film is calculated by mass percentage.
Embodiment 3
Take 46.6560g Neodymium trioxide in 200mL small beaker, under agitation add 80mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, neodymium concentration is 400g/L.Take 50.8000g yttrium oxide in 100mL small beaker, under agitation add 80mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, yttrium concentration is 400g/L.The solution 50mL that solution 50mL that above-mentioned neodymium concentration is 400g/L and above-mentioned yttrium concentration are 400g/L is added in the beaker of 2L, be 6.9 by ammonia soln regulator solution pH value, add 575mL ethylene glycol, under agitation add 200g ammoniacal liquor, dissolve and form neodymium nitrate-Yttrium trinitrate-ammonia water-ethylene glycol mixing solutions, move in 1L volumetric flask, spent glycol is diluted to scale, obtained electrolytic solution.With dehydrated alcohol wetting silicon carbide waterproof abrasive paper, 100mm × 100mm × 0.2mm is treated that anodised cerium paper tinsel is polished and clean with washes of absolute alcohol, be sprayed on flannelette with the diamond of 1 μm spraying rumbling compound, by cerium tablet have diamond spray rumbling compound flannelette on polishing until be minute surface.Cerium paper tinsel after polishing is put into anhydrous alcohol solution ultrasonic cleaning.Above-mentioned electrolytic solution is proceeded in the beaker of 2L, above-mentioned 100mm × 100mm × 0.2mm treated that electrolytic solution put into by anodic oxidation cerium paper tinsel and for anode, negative electrode is the platinum plate of 150mm × 150mm × 0.5mm, magnetic agitation, mixing speed is 300rpm, and current density is 100mA/dm
2, oxidizing temperature 10 DEG C, oxidization time 10h, takes out anodic oxidation part, clean with deionized water rinsing, air-dry, puts into crucible, puts into retort furnace, with 0.5 DEG C/min temperature programming to 360 DEG C, at 360 DEG C of roasting 1h.Be chilled to room temperature, taking out and obtaining two sides is be fine and close neodymium and doped yttrium cerium dioxide film in the middle of many nanometers straight hole.The hole length that the MPO thickness tester adopting Fisher company to produce measures two sides many nanometers straight hole is respectively 68 μm.The content adopting BrukerAXSMicroanalysisGmbH energy spectrometer to measure neodymium and yttrium in neodymium and doped yttrium cerium dioxide film is calculated by mass percentage and is respectively 8.6% and 6.2%.
Embodiment 4
Take 19.8972g lutecium oxide in 100mL small beaker, under agitation add 35mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 50mL, be diluted with water to scale, in this solution, lutetium concentration is 350g/L.Get 20.0115g Erbium trioxide in 100mL small beaker, under agitation add 35mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 50mL, be diluted with water to scale, in this solution, erbium concentration is 350g/L.The solution 50mL that solution 50mL that above-mentioned lutetium concentration is 350g/L and above-mentioned erbium concentration are 350g/L is added in the beaker of 2L, be 6.3 by ammonia soln regulator solution pH value, add 775mL ethylene glycol, under agitation add 100g ammoniacal liquor, dissolve and form lutecium nitrate-Erbium trinitrate-ammonia water-ethylene glycol mixing solutions, move in 1L volumetric flask, spent glycol is diluted to scale, obtained electrolytic solution.With dehydrated alcohol wetting silicon carbide waterproof abrasive paper, 100mm × 100mm × 0.2mm is treated that anodised cerium paper tinsel is polished and clean with washes of absolute alcohol, be sprayed on flannelette with the diamond of 1 μm spraying rumbling compound, by cerium tablet have diamond spray rumbling compound flannelette on polishing until be minute surface.Cerium paper tinsel after polishing is put into anhydrous alcohol solution ultrasonic cleaning.Above-mentioned electrolytic solution is proceeded in the beaker of 2L, above-mentioned 100mm × 100mm × 0.2mm treated that electrolytic solution put into by anodic oxidation cerium paper tinsel and for anode, negative electrode is the stereotype of 150mm × 150mm × 2mm, magnetic agitation, mixing speed is 200rpm, and current density is 50mA/dm
2, oxidizing temperature 5 DEG C, oxidization time 6h, takes out anodic oxidation part, clean with deionized water rinsing, air-dry, puts into crucible, puts into retort furnace, with 0.5 DEG C/min temperature programming to 380 DEG C, at 380 DEG C of roasting 0.75h.Be chilled to room temperature, taking out and obtaining two sides is be fine and close lutetium and Er ions cerium dioxide film in the middle of many nanometers straight hole.The hole length that the MPO thickness tester adopting Fisher company to produce measures two sides many nanometers straight hole is respectively 45 μm.The content adopting BrukerAXSMicroanalysisGmbH energy spectrometer to measure lutetium and erbium in lutetium and Er ions cerium dioxide film is calculated by mass percentage and is respectively 7.8% and 5.1%.
Embodiment 5
Take 51.8625g gadolinium sesquioxide in 200mL small beaker, under agitation add 90mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, gadolinium concentration is 450g/L.The solution 100mL that above-mentioned gadolinium concentration is 450g/L is added in the beaker of 2L, be 6.8 by ammonia soln regulator solution pH value, add 575mL ethylene glycol, under agitation add 300g ammoniacal liquor, dissolve and form Gadolinium trinitrate-ammonia water-ethylene glycol mixing solutions, move in 1L volumetric flask, spent glycol is diluted to scale, obtained electrolytic solution.With dehydrated alcohol wetting silicon carbide waterproof abrasive paper, 100mm × 100mm × 0.2mm is treated that anodised cerium paper tinsel is polished and clean with washes of absolute alcohol, be sprayed on flannelette with the diamond of 1 μm spraying rumbling compound, by cerium tablet have diamond spray rumbling compound flannelette on polishing until be minute surface.Cerium paper tinsel after polishing is put into anhydrous alcohol solution ultrasonic cleaning.Above-mentioned electrolytic solution is proceeded in the beaker of 2L, above-mentioned 100mm × 100mm × 0.2mm treated that electrolytic solution put into by anodic oxidation cerium paper tinsel and for anode, negative electrode is the platinum plate of 150mm × 150mm × 0.5mm, magnetic agitation, mixing speed is 500rpm, and current density is 150mA/dm
2, oxidizing temperature 15 DEG C, oxidization time 15h, takes out anodic oxidation part, clean with deionized water rinsing, air-dry, puts into crucible 5, puts into retort furnace, with 0.5 DEG C/min temperature programming to 340 DEG C, at 340 DEG C of roasting 1.75h.Be chilled to room temperature, taking out and obtaining two sides is be fine and close Gd2 O3 cerium dioxide film in the middle of many nanometers straight hole.The hole length that the MPO thickness tester adopting Fisher company to produce measures two sides many nanometers straight hole is respectively 89.3 μm.It is 21.6% that the content adopting BrukerAXSMicroanalysisGmbH energy spectrometer to measure gadolinium in Gd2 O3 cerium dioxide film is calculated by mass percentage.
Embodiment 6
Take 37.0536g europium sesquioxide in 100mL small beaker, under agitation add 60mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, europium concentration is 320g/L.The solution 100mL that above-mentioned europium concentration is 320g/L is added in the beaker of 2L, be 6.8 by ammonia soln regulator solution pH value, add 715mL ethylene glycol, under agitation add 150g ammoniacal liquor, dissolve and form europium nitrate-ammonia water-ethylene glycol mixing solutions, move in 1L volumetric flask, spent glycol is diluted to scale, obtained electrolytic solution.With dehydrated alcohol wetting silicon carbide waterproof abrasive paper, 100mm × 100mm × 0.2mm is treated that anodised cerium paper tinsel is polished and clean with washes of absolute alcohol, be sprayed on flannelette with the diamond of 1 μm spraying rumbling compound, by cerium tablet have diamond spray rumbling compound flannelette on polishing until be minute surface.Cerium paper tinsel after polishing is put into anhydrous alcohol solution ultrasonic cleaning.Above-mentioned electrolytic solution is proceeded in the beaker of 2L, above-mentioned 100mm × 100mm × 0.2mm treated that electrolytic solution put into by anodic oxidation cerium paper tinsel and for anode, negative electrode is the platinum plate of 150mm × 150mm × 0.5mm, magnetic agitation, mixing speed is 250rpm, and current density is 75mA/dm
2, oxidizing temperature 7 DEG C, oxidization time 9h, takes out anodic oxidation part, clean with deionized water rinsing, air-dry, puts into crucible 5, puts into retort furnace, with 0.5 DEG C/min temperature programming to 350 DEG C, at 350 DEG C of roasting 1.5h.Be chilled to room temperature, taking out and obtaining two sides is be fine and close europium doping cerium dioxide film in the middle of many nanometers straight hole.The hole length that the MPO thickness tester adopting Fisher company to produce measures two sides many nanometers straight hole is respectively 60.3 μm.It is 13.7% that the content adopting BrukerAXSMicroanalysisGmbH energy spectrometer to measure europium in europium doping cerium dioxide film is calculated by mass percentage.
Embodiment 7
Take 35.6810g terbium sesquioxide in 100mL small beaker, under agitation add 60mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, terbium concentration is 310g/L.The solution 100mL that above-mentioned terbium concentration is 310g/L is added in the beaker of 2L, be 6.8 by ammonia soln regulator solution pH value, add 735mL ethylene glycol, under agitation add 130g ammoniacal liquor, dissolve and form Terbium trinitrate-ammonia water-ethylene glycol mixing solutions, move in 1L volumetric flask, spent glycol is diluted to scale, obtained electrolytic solution.With dehydrated alcohol wetting silicon carbide waterproof abrasive paper, 100mm × 100mm × 0.2mm is treated that anodised cerium paper tinsel is polished and clean with washes of absolute alcohol, be sprayed on flannelette with the diamond of 1 μm spraying rumbling compound, by cerium tablet have diamond spray rumbling compound flannelette on polishing until be minute surface.Cerium paper tinsel after polishing is put into anhydrous alcohol solution ultrasonic cleaning.Above-mentioned electrolytic solution is proceeded in the beaker of 2L, above-mentioned 100mm × 100mm × 0.2mm treated that electrolytic solution put into by anodic oxidation cerium paper tinsel and for anode, negative electrode is the platinum plate of 150mm × 150mm × 0.5mm, magnetic agitation, mixing speed is 150rpm, and current density is 30mA/dm
2, oxidizing temperature 3 DEG C, oxidization time 5h, takes out anodic oxidation part, clean with deionized water rinsing, air-dry, puts into crucible 5, puts into retort furnace, with 0.5 DEG C/min temperature programming to 370 DEG C, at 370 DEG C of roasting 0.9h.Be chilled to room temperature, taking out and obtaining two sides is be fine and close terbium doped cerium dioxide film in the middle of many nanometers straight hole.The hole length that the MPO thickness tester adopting Fisher company to produce measures two sides many nanometers straight hole is respectively 37.8 μm.It is 9.8% that the content adopting BrukerAXSMicroanalysisGmbH energy spectrometer to measure terbium in terbium doped cerium dioxide film is calculated by mass percentage.
Embodiment 8
Take 35.6972g Praseodymium trioxide in 200mL small beaker, under agitation add 60mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, praseodymium concentration is 305g/L.The solution 100mL that above-mentioned praseodymium concentration is 310g/L is added in the beaker of 2L, be 7.3 by ammonia soln regulator solution pH value, add 705mL ethylene glycol, under agitation add 140g ammoniacal liquor, dissolve and form praseodymium nitrate-ammonia water-ethylene glycol mixing solutions, move in 1L volumetric flask, spent glycol is diluted to scale, obtained electrolytic solution.With dehydrated alcohol wetting silicon carbide waterproof abrasive paper, 100mm × 100mm × 0.2mm is treated that anodised cerium paper tinsel is polished and clean with washes of absolute alcohol, be sprayed on flannelette with the diamond of 1 μm spraying rumbling compound, by cerium tablet have diamond spray rumbling compound flannelette on polishing until be minute surface.Cerium paper tinsel after polishing is put into anhydrous alcohol solution ultrasonic cleaning.Above-mentioned electrolytic solution is proceeded in the beaker of 2L, above-mentioned 100mm × 100mm × 0.2mm treated that electrolytic solution put into by anodic oxidation cerium paper tinsel and for anode, negative electrode is the platinum plate of 150mm × 150mm × 0.5mm, magnetic agitation, mixing speed is 350rpm, and current density is 20mA/dm
2, oxidizing temperature 9 DEG C, oxidization time 13h, takes out anodic oxidation part, clean with deionized water rinsing, air-dry, puts into crucible 5, puts into retort furnace, with 0.5 DEG C/min temperature programming to 390 DEG C, at 390 DEG C of roasting 0.7h.Be chilled to room temperature, taking out and obtaining two sides is be fine and close praseodymium doped cerium dioxide film in the middle of many nanometers straight hole.The hole length that the MPO thickness tester adopting Fisher company to produce measures two sides many nanometers straight hole is respectively 79.3 μm.It is 7.2% that the content adopting BrukerAXSMicroanalysisGmbH energy spectrometer to measure praseodymium in praseodymium doped cerium dioxide film is calculated by mass percentage.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (4)
1. a preparation method for rear-earth-doped cerium dioxide film, is characterized in that comprising the steps:
(1) rare earth oxide is dissolved in nitric acid, is mixed with rare earths salt;
Its middle rare earth is the mixture of one or more the rare earth oxide in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium rare earth oxide; The concentration of rare earths salt middle-weight rare earths is 300 ~ 500g/L;
(2) regulate the pH value of above-mentioned rare earths salt to be 6.3 ~ 7.8 with ammonia soln, add ethylene glycol, under agitation add ammoniacal liquor, make electrolytic solution; In ethylene glycol, the concentration of ammoniacal liquor is 2.5 ~ 400g/L, the concentration of rare-earth salts is 30 ~ 50g/L;
(3) be that 0.1 ~ 0.3mm cerium tablet is polished and clean with washes of absolute alcohol with the wetting silicon carbide waterproof abrasive paper of dehydrated alcohol to thickness, be sprayed on flannelette with the diamond spraying rumbling compound of 0.5 ~ 1.5 μm, cerium tablet after polishing, until be minute surface, is put into anhydrous alcohol solution ultrasonic cleaning by cerium tablet polishing on the flannelette having diamond spraying rumbling compound;
(4) will treat that anodised cerium tablet puts into electrolytic solution Anodic Oxidation, negative electrode is platinum or lead, and cerium tablet is anode, and anodised processing condition are current density 8 ~ 200mA/dm
2, oxidizing temperature 0 ~ 20 DEG C, mixing speed 100 ~ 600rpm, oxidization time 3 ~ 17h, after anodic oxidation, anodic oxidation part use water rinse, air-dry;
(5) anodic oxidation part is put into retort furnace, with 0.4`0.6 DEG C/min temperature programming to 320 ~ 800 DEG C, at 320 ~ 400 DEG C of roasting 0.5 ~ 2h, be chilled to room temperature, taking out and obtaining two sides is be fine and close rear-earth-doped cerium dioxide film in the middle of many nanometers straight hole.
2. the preparation method of a kind of rear-earth-doped cerium dioxide film according to claim 1, is characterized in that: the thickness of cerium tablet is 0.2mm.
3. the preparation method of a kind of rear-earth-doped cerium dioxide film according to claim 1, is characterized in that: be sprayed on flannelette with the diamond spraying rumbling compound of 1 μm.
4. the preparation method of a kind of rear-earth-doped cerium dioxide film according to claim 1, is characterized in that: described rare earth oxide is any one in lanthanum trioxide, Samarium trioxide, Neodymium trioxide, lutecium oxide, gadolinium sesquioxide, europium sesquioxide, terbium sesquioxide or Praseodymium trioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510503083.0A CN105088316B (en) | 2015-08-17 | 2015-08-17 | A kind of preparation method of rear-earth-doped ceria film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510503083.0A CN105088316B (en) | 2015-08-17 | 2015-08-17 | A kind of preparation method of rear-earth-doped ceria film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105088316A true CN105088316A (en) | 2015-11-25 |
| CN105088316B CN105088316B (en) | 2017-05-31 |
Family
ID=54569614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510503083.0A Expired - Fee Related CN105088316B (en) | 2015-08-17 | 2015-08-17 | A kind of preparation method of rear-earth-doped ceria film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105088316B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107130284A (en) * | 2017-07-07 | 2017-09-05 | 上海应用技术大学 | A kind of preparation method of rare earth, calcium and nickel co-doped ceria/ceria film |
| CN107130283A (en) * | 2017-07-07 | 2017-09-05 | 上海应用技术大学 | A kind of rare earth, calcium, the preparation method of nickel and copper codope ceria/ceria film |
| CN107130282A (en) * | 2017-07-07 | 2017-09-05 | 上海应用技术大学 | A kind of preparation method of rare earth and nickel co-doped ceria/ceria film |
| CN107287643A (en) * | 2017-07-07 | 2017-10-24 | 上海应用技术大学 | A kind of rare earth, nickel and copper codope ceria/ceria film and preparation method thereof |
| CN112158883A (en) * | 2020-10-16 | 2021-01-01 | 成都先进金属材料产业技术研究院有限公司 | Process for preparing vanadium dioxide nano powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995480A (en) * | 2006-12-18 | 2007-07-11 | 天津理工大学 | Preparation process for obtaining highly ordered alumina mold |
-
2015
- 2015-08-17 CN CN201510503083.0A patent/CN105088316B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995480A (en) * | 2006-12-18 | 2007-07-11 | 天津理工大学 | Preparation process for obtaining highly ordered alumina mold |
Non-Patent Citations (3)
| Title |
|---|
| HUI WANG: "Synergistic effect of rare earth salt and organic acid in the anodization of aluminum in phosphoric acid", 《J MATER SCI》 * |
| NEIL J. LAWRENCE ET AL: "Formation of a porous cerium oxide membrane by anodization", 《CHEM. COMMUN.》 * |
| SOVANNARY PHOK ET AL: "Effect of samarium doping on electrodeposited CeO2 thin film", 《PHYS. STAT. SOL. (A)》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107130284A (en) * | 2017-07-07 | 2017-09-05 | 上海应用技术大学 | A kind of preparation method of rare earth, calcium and nickel co-doped ceria/ceria film |
| CN107130283A (en) * | 2017-07-07 | 2017-09-05 | 上海应用技术大学 | A kind of rare earth, calcium, the preparation method of nickel and copper codope ceria/ceria film |
| CN107130282A (en) * | 2017-07-07 | 2017-09-05 | 上海应用技术大学 | A kind of preparation method of rare earth and nickel co-doped ceria/ceria film |
| CN107287643A (en) * | 2017-07-07 | 2017-10-24 | 上海应用技术大学 | A kind of rare earth, nickel and copper codope ceria/ceria film and preparation method thereof |
| CN107130283B (en) * | 2017-07-07 | 2019-12-03 | 上海应用技术大学 | A kind of rare earth, calcium, nickel and copper codope ceria/ceria film preparation method |
| CN112158883A (en) * | 2020-10-16 | 2021-01-01 | 成都先进金属材料产业技术研究院有限公司 | Process for preparing vanadium dioxide nano powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105088316B (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105088316A (en) | Preparation method of rare earth doped ceria membrane | |
| CN104087970B (en) | A kind of rich surface cupric oxide doped iridium dioxide Ni-Ti anode containing iridium dioxide and preparation method thereof | |
| CN106602053B (en) | A kind of preparation method of the lithium titanate composite anode material of salic doping | |
| CN104710302A (en) | Gradient-doped manganese iron oxalate precursor and preparation method thereof | |
| CN106058243B (en) | The nickel cobalt lithium aluminate cathode material of nickel cobalt aluminium presoma of Fluorin doped and preparation method thereof and the Fluorin doped prepared | |
| CN103441240A (en) | Single-step preparation method of surface coating and chemical activation lithium-rich solid solution anode material | |
| CN108682795A (en) | Surface pickling coating TiO of ternary anode material of lithium ion battery2Method (2) | |
| CN104294311B (en) | Making method of platinum iridium oxide alloy electrode | |
| CN108110258A (en) | A kind of building method of copper foil surface three-dimensional structure | |
| CN109659519A (en) | TiO2The ternary cathode material of lithium ion battery preparation method and product of nano fiber coated | |
| CN109616658B (en) | Selenium and sulfate radical co-doped high-nickel cathode material and preparation method and application thereof | |
| CN113896244B (en) | Porous disc-shaped lithium manganate electrode for extracting lithium from salt lake and preparation method thereof | |
| CN107316998A (en) | A kind of long-life LiMn2O4 base anode material of specific composition and shape characteristic and preparation method thereof | |
| CN105088315B (en) | A kind of method that use two-step anodization prepares rear-earth-doped ceria film | |
| CN105088317B (en) | A kind of preparation method of ceria film | |
| CN108461740A (en) | A kind of LiVOPO4Nickelic tertiary cathode material of lithium ion battery of cladding and its preparation method and application | |
| CN109244415A (en) | A kind of preparation method of spherical shape carbon coating titanate composite negative pole material | |
| CN107287643B (en) | A kind of rare earth, nickel and copper codope ceria/ceria film and preparation method thereof | |
| CN105271443A (en) | Method for preparing flaky nano CoO or Co3O4 through assistant microwave heating | |
| CN105040073B (en) | A kind of method that use two-step anodization prepares ceria film | |
| CN107130282B (en) | A kind of rare earth and nickel co-doped ceria/ceria film preparation method | |
| CN107130283B (en) | A kind of rare earth, calcium, nickel and copper codope ceria/ceria film preparation method | |
| CN106801242B (en) | The quickly method of the preparation big pitch of holes porous anodic alumina films of large area high-sequential | |
| CN112624201B (en) | Preparation method of lithium-rich cathode material | |
| CN106350835B (en) | A kind of production method of electrolytic manganese electrowinning process middle rare earth positive plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170531 Termination date: 20200817 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |