CN107130283A - A kind of rare earth, calcium, the preparation method of nickel and copper codope ceria/ceria film - Google Patents
A kind of rare earth, calcium, the preparation method of nickel and copper codope ceria/ceria film Download PDFInfo
- Publication number
- CN107130283A CN107130283A CN201710551141.6A CN201710551141A CN107130283A CN 107130283 A CN107130283 A CN 107130283A CN 201710551141 A CN201710551141 A CN 201710551141A CN 107130283 A CN107130283 A CN 107130283A
- Authority
- CN
- China
- Prior art keywords
- ceria
- nickel
- calcium
- rare earth
- salt
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 49
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 28
- 239000011575 calcium Substances 0.000 title claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 26
- 239000010949 copper Substances 0.000 title claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 27
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- -1 mantoquita Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002390 adhesive tape Substances 0.000 claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000005498 polishing Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 150000003891 oxalate salts Chemical group 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 24
- 238000005507 spraying Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004452 microanalysis Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011162 ammonium carbonates Nutrition 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- TZIBOXWEBBRIBM-UHFFFAOYSA-N cerium(3+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Ce+3] TZIBOXWEBBRIBM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical class Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- YDLRCMNQRQILLP-UHFFFAOYSA-N ethane-1,2-diol;nitric acid Chemical compound OCCO.O[N+]([O-])=O YDLRCMNQRQILLP-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical class [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical class Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses the preparation method of a kind of rare earth, calcium, nickel and copper codope ceria/ceria film.The present invention's comprises the following steps that：(1) soluble-salt, calcium salt, nickel salt, mantoquita, rare-earth salts, water and ethylene glycol are mixed to get electrolyte；(2) using cerium tablet as anode, the one side bonding adhesive tape of cerium tablet, with platinized platinum or lead electrode, anode and negative electrode is put into electrolyte and carry out anodic oxidation；After anodic oxidation is finished, anodic oxidation part is obtained；(3) by anodic oxidation part in Muffle kiln roasting, it is fine and close rare earth, calcium, nickel and copper codope ceria film, the film that another side is ceria below many nanometers of straight holes to obtain a surface to be.Preparation method of the present invention is simple, and it is fine and close rare earth, calcium, nickel and copper codope ceria film, the film that another side is ceria below many nanometers of straight holes to obtain a surface to be.
Description
Technical field
The invention belongs to technical field of film preparation, specifically, it is related to a kind of rare earth, calcium, nickel and copper codope dioxy
Change the preparation method of cerium/ceria film.
Background technology
Doping cerium dioxide is due to high oxygen storage capacity and oxygen ionic conductivity, available for solid oxide fuel
The electrolyte of battery.The preparation of the anode of SOFC, it is generally that catalyst, electrolyte powder, pore creating material etc. is mixed
Close uniform, mixed powder is deposited on behind the surface of electrolyte, sintered generally more than 1000 DEG C.So high temperature is introduced and asked
Topic has：Electrode surface area reduces, growing up for electrode material granules, is accumulated so as to reduce three phase boundary；Some electrodes exist with electrolyte
Phase reaction easily occurs under high temperature；The thermal expansion coefficient difference of some anode materials and electrolyte is big, directly by electrode load in electricity
Solve in matter, the interface peel of electrode and electrolyte is easily caused in long-time operation, so as to cause the decay of battery performance.
The content of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of rare earth, calcium, nickel and copper codope two
The preparation method of cerium oxide/ceria film.Preparation method of the present invention is simple, and it below many nanometers of straight holes is cause to obtain a surface to be
Close rare earth, calcium, nickel and copper codope ceria film, another side are the film of ceria.
The present invention using calcium, nickel and copper both as raising ceria film oxygen ionic conductivity dopant, while also making
For the catalyst of hydrocarbon fuel hydrogen, anodizing and heat treating process is used to prepare a surface to be below many nanometers of straight holes
Fine and close rare earth, calcium, nickel and film that copper codope ceria film, another side are ceria.
Technical scheme is specifically described as follows.
The present invention provides the preparation method of a kind of rare earth, calcium, nickel and copper codope ceria/ceria film, specifically
Step is as follows：
(1) soluble-salt, calcium salt, nickel salt, mantoquita, rare-earth salts, water and ethylene glycol are mixed to get electrolyte；1L electrolyte
In, 2~50g of soluble-salt, 0.18~15g of calcium salt, 0.3~29.9g of nickel salt, 0.3~29.9g of mantoquita, 20~400g of water, remaining
For ethylene glycol；Wherein：Rare-earth salts is selected from more than one or both of rare earth nitrades, rare earth sulfate or rare earth-iron-boron；
Rare-earth salts is one or more dilute in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium
Earth salt；
(2) using cerium tablet as anode, the one side of cerium tablet pastes adhesive tape, using platinized platinum or lead flake as negative electrode, by anode and the moon
Pole, which is put into electrolyte, carries out anodic oxidation；The process conditions of anodic oxidation are 5~200mA/dm of current density2, oxidizing temperature 0
~25 DEG C, 100~600rpm of speed of agitator, 2~15h of oxidization time after anodic oxidation is finished, take out, remove saturating on anode
Gelatin band, it is net with deionized water rinsing, air-dry and obtain anodic oxidation part；
(3) by anodic oxidation part in Muffle kiln roasting, 0.5~2h is calcined at a temperature of 300~800 DEG C, one is obtained
It is that fine and close rare earth, calcium, nickel and copper codope ceria film, another side are ceria below many nanometers of straight holes that surface, which is,
Film.
In the present invention, the one kind or several of soluble-salt in oxalates, phosphate, fluoride, carbonate in step (1)
Kind；One or more of the calcium salt in calcium chloride, calcium nitrate or calcium acetate；Nickel salt is selected from nickel nitrate, nickel chloride or nickel sulfate
In one or more；One or more of the mantoquita in copper nitrate, copper chloride or copper sulphate.
In the present invention, in step (2), before cerium tablet is as anode, pretreatment is first passed through；Preprocess method is as follows：With anhydrous
The carborundum waterproof abrasive paper of ethanol wet is polished cerium tablet and clean with washes of absolute alcohol；It is sprayed on ceria polishing agent
On flannelette, cerium tablet is polished until being minute surface on the flannelette for having ceria polishing agent.
In the present invention, in step (3), during roasting, with 3 DEG C/min temperature programmings to 300~800 DEG C.
In the present invention, in step (3), sintering temperature is 400~600 DEG C.
Compared to the prior art, the beneficial effects of the invention are as follows：The present invention has prepared a table with simple preparation method
It is that fine and close rare earth, calcium, nickel and copper codope ceria film, another side are ceria below many nanometers of straight holes that face, which is,
Film.A length of 19~121 μm of the hole of many nanometers of straight holes in surface is determined using Fisher MPO calibrators.Using using Bruker AXS
Microanalysis GmbH energy disperse spectroscopies determine the content of rare earth, calcium, nickel, Copper-cladding Aluminum Bar ceria film middle rare earth, calcium, nickel and copper
Calculate by mass percentage is respectively 5.1~28.6%, 2.2~20.8%, 1.6~20.3% and 1.3~19.8%.
Embodiment
Technical scheme is described in detail with reference to embodiment.
Embodiment 1
20g water, 2g ammonium oxalate, 0.4984g calcium chloride, 0.6624g nickel nitrates, 0.7535g nitre are added in 1L beaker
Sour copper, 0.7018g lanthanum nitrates, plus 880mL ethylene glycol dissolve to form water-ammonium oxalate-calcium chloride-nickel nitrate-copper nitrate-nitric acid
Lanthanum-ethylene glycol mixed solution, is moved into 1L volumetric flasks, spent glycol is diluted to scale, and electrolyte is made.Soaked with absolute ethyl alcohol
Carborundum waterproof abrasive paper treat that the cerium paper tinsel of anodic oxidation is polished and dry with washes of absolute alcohol to 100mm × 100mm × 0.2mm
Only, it is sprayed on 1 μm of ceria spraying polishing agent on flannelette, by cerium tablet in the flannelette upthrow for having ceria spraying polishing agent
Light is until be minute surface.The one side of cerium paper tinsel after polishing is pasted into adhesive tape, is put into anhydrous alcohol solution and is cleaned by ultrasonic.Will be above-mentioned
Electrolyte is transferred in 2L beaker, and above-mentioned 100mm × 100mm × 0.2mm is treated into anodic oxidation cerium paper tinsel is put into electrolyte simultaneously
For anode, negative electrode is 150mm × 150mm × 0.5mm platinum sheet, and magnetic agitation, speed of agitator is 100rpm, and current density is
5mA/dm2, 0 DEG C of oxidizing temperature, oxidization time 2h, take out anodic oxidation part, remove the adhesive tape on anodic oxidation part, spend
Ionized water rinses net, air-dries, and the MPO calibrators produced using Fisher companies determine a length of 19 μ in hole of many nanometers of straight holes in surface
m.The anodic oxidation part is put into crucible, is put into Muffle furnace, with 3 DEG C/min temperature programmings to 300 DEG C, in 300 DEG C of roastings
2h.It is cooled to room temperature, takes out and obtain a surface to be being fine and close lanthanum, calcium, nickel and copper codope ceria below many nanometers of straight holes
Film, another side are the film of ceria.Using Bruker AXS Microanalysis GmbH energy disperse spectroscopies determine lanthanum, calcium, nickel and
Lanthanum in Copper-cladding Aluminum Bar ceria film, calcium, the content of nickel and copper calculate respectively 5.1% by mass percentage, 2.2%, 1.6% and
1.3%.
Embodiment 2
Added in 1L beaker 400g water, 20g ammonium phosphate, 30g ammonium fluorides, 61.41g calcium nitrate, 93.08g nickel chlorides,
63.26g copper chlorides, 66.80g samaric nitrates, plus 500mL ethylene glycol dissolve to form water-ammonium phosphate-ammonium fluoride-calcium nitrate-chlorination
Nickel-copper chloride-samaric nitrate-ethylene glycol mixed solution, is moved into 1L volumetric flasks, spent glycol is diluted to scale, and electrolyte is made.
The carborundum waterproof abrasive paper soaked with absolute ethyl alcohol is treated that the cerium paper tinsel of anodic oxidation is polished to 100mm × 100mm × 0.2mm and is used in combination
Washes of absolute alcohol is clean, is sprayed on 1 μm of ceria spraying polishing agent on flannelette, and cerium tablet is being had into ceria spraying throwing
Polishing on the flannelette of photo etching is until be minute surface.The one side of cerium paper tinsel after polishing is pasted into adhesive tape, is put into anhydrous alcohol solution
It is cleaned by ultrasonic.Above-mentioned electrolyte is transferred in 2L beaker, above-mentioned 100mm × 100mm × 0.2mm is treated into anodic oxidation cerium paper tinsel
It is put into electrolyte and for anode, negative electrode is 150mm × 150mm × 0.5mm stereotype, magnetic agitation, speed of agitator is
600rpm, current density is 200mA/dm2, 25 DEG C of oxidizing temperature, oxidization time 15h, take out anodic oxidation part, remove anodic oxygen
Change the adhesive tape on part, it is net with deionized water rinsing, air-dry, the MPO calibrators produced using Fisher companies determine surface
A length of 121 μm of the hole of many nanometers of straight holes.The anodic oxidation part is put into crucible, is put into Muffle furnace, with 3 DEG C/min program liters
Temperature is calcined 0.5h to 800 DEG C at 800 DEG C.Be cooled to room temperature, take out obtain a surface and be below many nanometers of straight holes fine and close samarium,
Calcium, nickel and copper codope ceria film, another side are the film of ceria.Using using BrukerAXS
The content that Microanalysis GmbH energy disperse spectroscopies determine samarium in samarium, calcium, nickel and Copper-cladding Aluminum Bar ceria film, calcium, nickel and copper is pressed
It is respectively 28.6%, 20.8%, 20.3% and 19.8% that mass percent, which is calculated,.
Embodiment 3
200g water, 25g ammonium carbonates, 20.47g calcium nitrate, 10.23g calcium acetates, 39.55g sulfuric acid are added in 1L beaker
Nickel, 29.51g copper nitrates, 12.56g copper sulphate, 3.35g terbium chlorides, 16.36g erbium chlorides, plus 700mL ethylene glycol dissolve to be formed
Water-ammonium carbonate-calcium nitrate-calcium acetate-nickel sulfate-copper nitrate-copper sulphate-terbium chloride-erbium chloride-ethylene glycol mixed solution, is moved
Enter in 1L volumetric flasks, spent glycol is diluted to scale, electrolyte is made.The carborundum waterproof abrasive paper pair soaked with absolute ethyl alcohol
100mm × 100mm × 0.2mm treats that the cerium paper tinsel of anodic oxidation is polished and clean with washes of absolute alcohol, with 1 μm of titanium dioxide
Cerium spraying polishing agent is sprayed on flannelette, cerium tablet is polished on the flannelette for having ceria to spray polishing agent until being minute surface.Will
The one side of cerium paper tinsel after polishing pastes adhesive tape, is put into anhydrous alcohol solution and is cleaned by ultrasonic.Above-mentioned electrolyte is transferred to 2L's
In beaker, above-mentioned 100mm × 100mm × 0.2mm is treated that anodic oxidation cerium paper tinsel is put into electrolyte and for anode, negative electrode is
150mm × 150mm × 0.5mm platinum sheet, magnetic agitation, speed of agitator is 350rpm, and current density is 100mA/dm2, oxidation
12.5 DEG C of temperature, oxidization time 8.5h takes out anodic oxidation part, removes the adhesive tape on anodic oxidation part, use deionized water
Rinse net, air-dry, the MPO calibrators produced using Fisher companies determine a length of 82 μm of the hole of many nanometers of straight holes in surface.Should
Anodic oxidation part is put into crucible, is put into Muffle furnace, with 3 DEG C/min temperature programmings to 550 DEG C, and 1h is calcined at 550 DEG C.It is cooled to
Room temperature, it is fine and close terbium, erbium, calcium, nickel and copper codope ceria film below many nanometers of straight holes that taking-up, which obtains a surface to be, another
It is simultaneously the film of ceria.Terbium, erbium, calcium, nickel and copper are determined using Bruker AXS Microanalysis GmbH energy disperse spectroscopies
Terbium in doping cerium dioxide film, erbium, calcium, the content of nickel and copper calculate respectively 6.6% by mass percentage, 15.6%,
17.2%th, 17.8% and 15.9%.
Claims (6)
1. a kind of rare earth, calcium, the preparation method of nickel and copper codope ceria/ceria film, it is characterised in that specific step
It is rapid as follows：
(1) soluble-salt, calcium salt, nickel salt, mantoquita, rare-earth salts, water and ethylene glycol are mixed to get electrolyte；In 1L electrolyte,
2~50g of soluble-salt, 0.18~15g of calcium salt, 0.3~29.9g of nickel salt, 0.3~29.9g of mantoquita, 20~400g of water, remaining is
Ethylene glycol；Wherein：Rare-earth salts is selected from more than one or both of rare earth nitrades, rare earth sulfate, rare earth-iron-boron；Rare earth
One or more rare-earth salts of the salt in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium；
(2) using cerium tablet as anode, the one side of cerium tablet pastes adhesive tape, and using platinized platinum or lead flake as negative electrode, anode and negative electrode are put
Enter and anodic oxidation is carried out in electrolyte；The process conditions of anodic oxidation are 5~200mA/dm of current density2, oxidizing temperature 0~25
DEG C, 100~600rpm of speed of agitator, 2~15h of oxidization time, the transparent adhesive tape for after anodic oxidation is finished, taking out, removing on anode
Band, it is net with deionized water rinsing, air-dry and obtain anodic oxidation part；
(3) by anodic oxidation part in Muffle kiln roasting, 0.5~2h is calcined at a temperature of 300~800 DEG C, a surface is obtained
To be fine and close rare earth, calcium, nickel and copper codope ceria film, the film that another side is ceria below many nanometers of straight holes.
2. preparation method according to claim 1, it is characterised in that in step (1), soluble-salt is selected from oxalates, phosphorus
One or more in hydrochlorate, fluoride, carbonate；One or more of the calcium salt in calcium chloride, calcium nitrate or calcium acetate；
One or more of the nickel salt in nickel nitrate, nickel chloride or nickel sulfate；Mantoquita is in copper nitrate, copper chloride or copper sulphate
It is one or more of.
3. preparation method according to claim 1, it is characterised in that in step (2), before cerium tablet is as anode, first pass through
Pretreatment；Preprocess method is as follows：The carborundum waterproof abrasive paper soaked with absolute ethyl alcohol is polished cerium tablet and uses absolute ethyl alcohol
Clean up；Be sprayed on ceria polishing agent on flannelette, cerium tablet is polished on the flannelette for having ceria polishing agent until
For minute surface.
4. preparation method according to claim 1, it is characterised in that in step (3), during roasting, with 2~4 DEG C/min journeys
Sequence is warming up to 300~800 DEG C.
5. preparation method according to claim 1, it is characterised in that in step (3), sintering temperature is 400~600 DEG C.
6. preparation method according to claim 1, it is characterised in that it is fine and close below many nanometers of straight holes to obtain a surface to be
Rare earth, calcium, the film that nickel and copper codope ceria film, another side are ceria, the hole of many nanometers of straight holes on surface is long
For 19~121 μm, rare earth, calcium, the content of nickel and copper are respectively 5.1~28.6%, 2.2~20.8%, 1.6 by mass percentage
~20.3% and 1.3~19.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710551141.6A CN107130283B (en) | 2017-07-07 | 2017-07-07 | A kind of rare earth, calcium, nickel and copper codope ceria/ceria film preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710551141.6A CN107130283B (en) | 2017-07-07 | 2017-07-07 | A kind of rare earth, calcium, nickel and copper codope ceria/ceria film preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107130283A true CN107130283A (en) | 2017-09-05 |
| CN107130283B CN107130283B (en) | 2019-12-03 |
Family
ID=59737976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710551141.6A Expired - Fee Related CN107130283B (en) | 2017-07-07 | 2017-07-07 | A kind of rare earth, calcium, nickel and copper codope ceria/ceria film preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107130283B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1633726A (en) * | 2002-02-14 | 2005-06-29 | 阿尔伯达研究理事会股份公司 | Tubular solid oxide fuel cell stack |
| CN1685554A (en) * | 2002-05-23 | 2005-10-19 | 阿尔伯达研究理事会股份公司 | Solid oxide fuel cell system |
| CN102881930A (en) * | 2012-10-26 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | Method for preparing flat-plate type metal-support solid oxide fuel cell |
| CN105088317A (en) * | 2015-08-17 | 2015-11-25 | 上海应用技术学院 | Preparation method of ceria film |
| CN105088316A (en) * | 2015-08-17 | 2015-11-25 | 上海应用技术学院 | Preparation method of rare earth doped ceria membrane |
-
2017
- 2017-07-07 CN CN201710551141.6A patent/CN107130283B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1633726A (en) * | 2002-02-14 | 2005-06-29 | 阿尔伯达研究理事会股份公司 | Tubular solid oxide fuel cell stack |
| CN1685554A (en) * | 2002-05-23 | 2005-10-19 | 阿尔伯达研究理事会股份公司 | Solid oxide fuel cell system |
| CN102881930A (en) * | 2012-10-26 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | Method for preparing flat-plate type metal-support solid oxide fuel cell |
| CN105088317A (en) * | 2015-08-17 | 2015-11-25 | 上海应用技术学院 | Preparation method of ceria film |
| CN105088316A (en) * | 2015-08-17 | 2015-11-25 | 上海应用技术学院 | Preparation method of rare earth doped ceria membrane |
Non-Patent Citations (2)
| Title |
|---|
| 仙存妮 等: ""Ni掺杂对纳米结构牡丹花状CeO2材料催化特性的影响"", 《催化学报》 * |
| 张建强 等: ""直接甲烷SOFCNiCu-CeO2阳极的制备与性能"", 《电源技术》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107130283B (en) | 2019-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103046088B (en) | A kind of micro-nano compound porous copper surface tissue and preparation method thereof and device | |
| CN105088316B (en) | A kind of preparation method of rear-earth-doped ceria film | |
| CN106340638A (en) | High multiplying power lithium-enriched manganese-based anode material with double-layer hollow structure and preparation method thereof | |
| CN108682795B (en) | Surface pickling coating TiO of ternary anode material of lithium ion battery2Method (2) | |
| CN102931388A (en) | Rare earth oxide clad lithium titanate anode material, preparation method thereof and lithium ion battery | |
| CN103441240A (en) | Single-step preparation method of surface coating and chemical activation lithium-rich solid solution anode material | |
| CN104051725A (en) | Preparation method for high-voltage nickel-cobalt-manganese-lithium oxide positive electrode material | |
| 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 | |
| CN104818503A (en) | Preparation method of porous copper full-impregnated film of three-dimensional network structure | |
| JP2011076748A (en) | Separator for non-aqueous electrolyte secondary cell, method for manufacturing the same, and the non-aqueous electrolyte secondary cell | |
| CN113186535B (en) | Solid electrolyte, preparation method thereof and cathode protection system | |
| CN107287643B (en) | A kind of rare earth, nickel and copper codope ceria/ceria film and preparation method thereof | |
| 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 | |
| CN108461740A (en) | A kind of LiVOPO4Nickelic tertiary cathode material of lithium ion battery of cladding and its preparation method and application | |
| CN108163932A (en) | A kind of PbO of the three-dimensional macroporous structure of doped metal ion2The preparation method of electrode | |
| CN107331849A (en) | A kind of nickel cobalt lithium aluminate@metal oxide/carbon nano-tube composite positive poles and preparation method and application | |
| CN105088317B (en) | A kind of preparation method of ceria film | |
| CN1276528C (en) | Method for preparing active material of positive electrode of alkali accumulator and nickle and electrode and alkali accumulator | |
| CN113555559B (en) | Lithium-rich manganese-based positive electrode material, and preparation method and application thereof | |
| CN107130284A (en) | A kind of preparation method of rare earth, calcium and nickel co-doped ceria/ceria film | |
| CN108217640B (en) | Preparation method of negative electrode of lithium ion battery capable of being used for quick charging | |
| CN106159319B (en) | A kind of preparation method of LiBaLaZrAlREWO lithium ion solid electrolytes | |
| CN106801242B (en) | The quickly method of the preparation big pitch of holes porous anodic alumina films of large area high-sequential |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for 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: 20191203 |