CN107130283B - A kind of rare earth, calcium, nickel and copper codope ceria/ceria film preparation method - Google Patents
A kind of rare earth, calcium, nickel and copper codope ceria/ceria film preparation method Download PDFInfo
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- CN107130283B CN107130283B CN201710551141.6A CN201710551141A CN107130283B CN 107130283 B CN107130283 B CN 107130283B CN 201710551141 A CN201710551141 A CN 201710551141A CN 107130283 B CN107130283 B CN 107130283B
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- 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
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- 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
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- 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
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Abstract
The invention discloses a kind of rare earth, calcium, nickel and copper codope ceria/ceria film preparation methods.The specific steps of the present invention are as follows: (1) soluble-salt, calcium salt, nickel salt, mantoquita, rare-earth salts, water and ethylene glycol being mixed to get electrolyte；(2) using cerium tablet as anode, anode and cathode is put into electrolyte with platinized platinum or lead electrode and is carried out anodic oxidation by the one side bonding adhesive tape of cerium tablet；After anodic oxidation, 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 that obtain a surface, which be below more nanometers of straight holes,.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 that obtain a surface, which be below more nanometers of straight holes,.
Description
Technical field
The invention belongs to technical field of film preparation, specifically, being related to a kind of rare earth, calcium, nickel and copper codope dioxy
Change cerium/ceria film preparation method.
Background technique
Doping cerium dioxide is due to can be used for solid oxide fuel with high oxygen storage capacity and oxygen ionic conductivity
The electrolyte of battery.The preparation of the anode of solid oxide fuel cell, it is usually that catalyst, electrolyte powder, pore creating material etc. is mixed
It closes uniformly, after mixed powder to be deposited on to the surface of electrolyte, is usually sintered at 1000 DEG C or more.So high temperature introducing is asked
Topic has: electrode surface area reduces, and electrode material granules are grown up, to reduce three phase boundary product；Certain electrodes and electrolyte exist
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
It solves in matter, the interface peel of electrode and electrolyte is be easy to cause in long-time operation, to cause the decaying of battery performance.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of rare earth, calcium, nickel and copper codopes two
Cerium oxide/ceria film preparation method.Preparation method of the present invention is simple, and it is cause that obtain a surface, which be below more nanometers of straight holes,
Close rare earth, calcium, nickel and copper codope ceria film, the film that another side is ceria.
The present invention both as the dopant for improving ceria film oxygen ionic conductivity, while also making calcium, nickel and copper
For the catalyst of hydrocarbon fuel hydrogen, anodizing and heat treating process is used to prepare a surface to be below more nanometers of straight holes
Rare earth, calcium, nickel and the copper codope ceria film of densification, the film that another side is ceria.
Technical solution of the present invention is specifically described as follows.
The present invention provides a kind of rare earth, calcium, nickel and copper codope ceria/ceria film preparation method, specifically
Steps are 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 one or more of rare earth nitrades, rare earth sulfate or rare earth-iron-boron；
Rare-earth salts is selected from one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium or a variety of dilute
Earth salt；
(2) using cerium tablet as anode, the one side of cerium tablet pastes adhesive tape, using platinized platinum or lead flake as cathode, by anode and yin
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, take out, remove it is saturating on anode
Gelatin band is rinsed only with deionized water, air-dries and obtain anodic oxidation part；
(3) anodic oxidation part is obtained one in 300~800 DEG C of 0.5~2h of roasting temperature in Muffle kiln roasting
It is fine and close rare earth, calcium, nickel and copper codope ceria film, another side is ceria that surface, which is below more nanometers of straight holes,
Film.
In the present invention, soluble-salt is selected from one of oxalates, phosphate, fluoride, carbonate or several in step (1)
Kind；Calcium salt is selected from one or more of calcium chloride, calcium nitrate or calcium acetate；Nickel salt is selected from nickel nitrate, nickel chloride or nickel sulfate
One or more of；Mantoquita is selected from one or more of 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 silicon carbide waterproof abrasive paper of ethanol wet to cerium tablet carry out polishing and with washes of absolute alcohol it is clean；It is sprayed on ceria polishing agent
On flannelette, cerium tablet is polished on the flannelette for having ceria polishing agent until for mirror surface.
In the present invention, in step (3), when roasting, with 3 DEG C/min temperature programming to 300~800 DEG C.
In the present invention, in step (3), maturing temperature is 400~600 DEG C.
Compared to the prior art, the beneficial effects of the present invention are: the present invention has prepared a table with simple preparation method
It is fine and close rare earth, calcium, nickel and copper codope ceria film, another side is ceria that face, which is below more nanometers of straight holes,
Film.Using a length of 19~121 μm of the hole of the Fisher MPO calibrator measurement more nanometers of straight holes in surface.Using using Bruker AXS
Microanalysis GmbH energy disperse spectroscopy measure rare earth, calcium, nickel, in Copper-cladding Aluminum Bar ceria film rare earth, calcium, nickel and copper content
Respectively 5.1~28.6%, 2.2~20.8%, 1.6~20.3% and 1.3~19.8% are calculated by mass percentage.
Specific embodiment
It describes in detail below with reference to embodiment to technical solution of the present invention.
Embodiment 1
20g water, 2g ammonium oxalate, 0.4984g calcium chloride, 0.6624g nickel nitrate, 0.7535g nitre are added in the beaker of 1L
Sour copper, 0.7018g lanthanum nitrate add 880mL ethylene glycol to dissolve to form water-ammonium oxalate-calcium chloride-nickel nitrate-copper nitrate-nitric acid
Lanthanum-ethylene glycol mixed solution moves into 1L volumetric flask, and spent glycol is diluted to scale, and electrolyte is made.It is soaked with dehydrated alcohol
Silicon carbide waterproof abrasive paper to 100mm × 100mm × 0.2mm wait for anodic oxidation cerium foil carry out polishing and with washes of absolute alcohol it is dry
Only, it is sprayed polishing agent with 1 μm of ceria to be sprayed on flannelette, by cerium tablet in the flannelette upthrow for thering is ceria to be sprayed polishing agent
Light is until be mirror surface.The one side of cerium foil after polishing is pasted into adhesive tape, is put into anhydrous alcohol solution and is cleaned by ultrasonic.It will be above-mentioned
Electrolyte is transferred in the beaker of 2L, and above-mentioned 100mm × 100mm × 0.2mm is put into electrolyte simultaneously to anodic oxidation cerium foil
For anode, cathode is 150mm × 150mm × 0.5mm platinum sheet, magnetic agitation, speed of agitator 100rpm, and current density is
5mA/dm2, 0 DEG C of oxidizing temperature, oxidization time 2h, anodic oxidation part is taken out, removes the adhesive tape on anodic oxidation part, spends
Ionized water rinses only, air-dries, using a length of 19 μ in hole of the MPO calibrator measurement more nanometers of straight holes in surface of Fisher company production
m.The anodic oxidation part is put into crucible, is put into Muffle furnace, with 3 DEG C/min temperature programming to 300 DEG C, is roasted at 300 DEG C
2h.It is cooled to room temperature, taking out and obtaining a surface be below more nanometers of straight holes is fine and close lanthanum, calcium, nickel and copper codope ceria
Film, the film that another side is ceria.Using Bruker AXS Microanalysis GmbH energy disperse spectroscopy measurement lanthanum, calcium, nickel and
Lanthanum in Copper-cladding Aluminum Bar ceria film, calcium, nickel and copper content respectively 5.1%, 2.2%, 1.6% and is calculated by mass percentage
1.3%.
Embodiment 2
In the beaker of 1L be added 400g water, 20g ammonium phosphate, 30g ammonium fluoride, 61.41g calcium nitrate, 93.08g nickel chloride,
63.26g copper chloride, 66.80g samaric nitrate add 500mL ethylene glycol to dissolve to form water-ammonium phosphate-ammonium fluoride-calcium nitrate-chlorination
Nickel-copper chloride-samaric nitrate-ethylene glycol mixed solution moves into 1L volumetric flask, and spent glycol is diluted to scale, and electrolyte is made.
It waits for that the cerium foil of anodic oxidation is polished to 100mm × 100mm × 0.2mm with the silicon carbide waterproof abrasive paper that dehydrated alcohol soaks to be used in combination
Washes of absolute alcohol is clean, is sprayed polishing agent with 1 μm of ceria and is sprayed on flannelette, is having ceria to throw by spraying cerium tablet
Polishing on the flannelette of photo etching is until be mirror surface.The one side of cerium foil after polishing is pasted into adhesive tape, is put into anhydrous alcohol solution
Ultrasonic cleaning.Above-mentioned electrolyte is transferred in the beaker of 2L, by above-mentioned 100mm × 100mm × 0.2mm to anodic oxidation cerium foil
It is put into electrolyte and for anode, cathode is 150mm × 150mm × 0.5mm stereotype, magnetic agitation, and speed of agitator is
600rpm, current density 200mA/dm2, 25 DEG C of oxidizing temperature, oxidization time 15h, anodic oxidation part is taken out, anodic oxygen is removed
Change the adhesive tape on part, rinsed only, air-dried with deionized water, surface is measured using the MPO calibrator of Fisher company production
A length of 121 μm of the hole of more nanometers of straight holes.The anodic oxidation part is put into crucible, is put into Muffle furnace, with 3 DEG C/min program liter
Temperature is to 800 DEG C, in 800 DEG C of roasting 0.5h.Be cooled to room temperature, take out and obtain a surface to be below more nanometers of straight holes be fine and close samarium,
Calcium, nickel and copper codope ceria film, the film that another side is ceria.Using using BrukerAXS
Microanalysis GmbH energy disperse spectroscopy measurement samarium, calcium, samarium in nickel and Copper-cladding Aluminum Bar ceria film, calcium, nickel and copper content press
It is respectively 28.6%, 20.8%, 20.3% and 19.8% that mass percent, which calculates,.
Embodiment 3
200g water, 25g ammonium carbonate, 20.47g calcium nitrate, 10.23g calcium acetate, 39.55g sulfuric acid are added in the beaker of 1L
Nickel, 29.51g copper nitrate, 12.56g copper sulphate, 3.35g terbium chloride, 16.36g erbium chloride, add 700mL ethylene glycol to 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 moves
Enter in 1L volumetric flask, spent glycol is diluted to scale, and electrolyte is made.The silicon carbide waterproof abrasive paper pair soaked with dehydrated alcohol
100mm × 100mm × 0.2mm wait for the cerium foil of anodic oxidation carry out polishing and it is clean with washes of absolute alcohol, with 1 μm of titanium dioxide
Cerium is sprayed polishing agent and is sprayed on flannelette, cerium tablet is polished on the flannelette for having ceria to be sprayed polishing agent until for mirror surface.It will
The one side of cerium foil 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 put into electrolyte to anodic oxidation cerium foil and is anode, cathode is
150mm × 150mm × 0.5mm platinum sheet, magnetic agitation, speed of agitator 350rpm, current density 100mA/dm2, oxidation
12.5 DEG C of temperature, oxidization time 8.5h, anodic oxidation part is taken out, removes the adhesive tape on anodic oxidation part, uses deionized water
It rinses only, air-dries, using a length of 82 μm of the hole of the MPO calibrator measurement more nanometers of straight holes in surface of Fisher company production.It should
Anodic oxidation part is put into crucible, is put into Muffle furnace, with 3 DEG C/min temperature programming to 550 DEG C, in 550 DEG C of roasting 1h.It is cooled to
Room temperature, to take out that obtain a surface be below more nanometers of straight holes be fine and close terbium, erbium, calcium, nickel and copper codope ceria film, another
It is on one side the film of ceria.Using Bruker AXS Microanalysis GmbH energy disperse spectroscopy measurement terbium, erbium, calcium, nickel and copper
Terbium in doping cerium dioxide film, erbium, calcium, nickel and copper content be calculated by mass percentage respectively 6.6%, 15.6%,
17.2%, 17.8% and 15.9%.
Claims (5)
1. a kind of rare earth, calcium, nickel and copper codope ceria/ceria film preparation method, which is characterized 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 one or more of rare earth nitrades, rare earth sulfate, rare earth-iron-boron；Rare earth
Salt is selected from one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium or a variety of rare-earth salts；
(2) using cerium tablet as anode, the one side stickup adhesive tape of cerium tablet puts anode and cathode using platinized platinum or lead flake as cathode
Enter and carries out anodic oxidation 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, after anodic oxidation, take out anodic oxidation part, remove anode
On adhesive tape, rinsed with deionized water net, air-dry and obtain anodic oxidation part；
(3) anodic oxidation part is obtained into a surface in 300~800 DEG C of 0.5~2h of roasting temperature in Muffle kiln roasting
For rare earth, calcium, nickel and the copper codope ceria film, the film that another side is ceria for below more nanometers of straight holes being densification；
In step (1), soluble-salt is selected from one or more of oxalates, phosphate, fluoride, carbonate；Calcium salt is selected from
One or more of calcium chloride, calcium nitrate or calcium acetate；Nickel salt is selected from one of nickel nitrate, nickel chloride or nickel sulfate or several
Kind；Mantoquita is selected from one or more of copper nitrate, copper chloride or copper sulphate.
2. preparation method according to claim 1, which is characterized in that in step (2), before cerium tablet is as anode, first pass through
Pretreatment；Preprocess method is as follows: being polished with the silicon carbide waterproof abrasive paper that dehydrated alcohol soaks cerium tablet and uses dehydrated alcohol
It cleans up；Be sprayed on flannelette with ceria polishing agent, cerium tablet is polished on the flannelette for having ceria polishing agent until
For mirror surface.
3. preparation method according to claim 1, which is characterized in that in step (3), when roasting, with 2~4 DEG C/min journey
Sequence is warming up to 300~800 DEG C.
4. preparation method according to claim 1, which is characterized in that in step (3), maturing temperature is 400~600 DEG C.
5. preparation method according to claim 1, which is characterized in that it is fine and close that obtain a surface, which be below more nanometers of straight holes,
Rare earth, calcium, nickel and copper codope ceria film, the film that another side is ceria, the hole of the more nanometers of straight holes on surface is long
Be 19~121 μm, rare earth, calcium, nickel and copper content be by mass percentage respectively 5.1~28.6%, 2.2~20.8%, 1.6
~20.3% and 1.3~19.8%.
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| 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 |
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2017
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| 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 |
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| 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 |
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