CN107287643B - A kind of rare earth, nickel and copper codope ceria/ceria film and preparation method thereof - Google Patents
A kind of rare earth, nickel and copper codope ceria/ceria film and preparation method thereof Download PDFInfo
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- CN107287643B CN107287643B CN201710551573.7A CN201710551573A CN107287643B CN 107287643 B CN107287643 B CN 107287643B CN 201710551573 A CN201710551573 A CN 201710551573A CN 107287643 B CN107287643 B CN 107287643B
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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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Abstract
The invention discloses a kind of rare earth, nickel and copper codope ceria/ceria films and preparation method thereof.Specific step is as follows: (1) soluble-salt, nickel salt, mantoquita, rare-earth salts, water and ethylene glycol being made into electrolyte；(2) using cerium tablet as anode, cerium tablet one side pastes adhesive tape and anode and cathode is placed in electrolyte and carries out anodic oxidation using platinized platinum or lead flake as cathode, after anodic oxidation, obtains anodic oxidation part；(3) anodic oxidation part is placed in Muffle furnace and is roasted, it is fine and close rare earth, nickel and copper codope ceria, 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, an obtained surface is below more nanometers of straight holes be fine and close rare earth, in nickel and copper codope ceria film the more nanometers of straight holes in surface a length of 18~112 μm of hole.
Description
Technical field
The present invention relates to a kind of rare earth, nickel and copper codope ceria/ceria films and preparation method thereof, belong to thin
Technical field of membrane.
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 present invention provides a kind of rare earth, nickel and copper codope ceria/titanium dioxide
Cerium film and preparation method thereof.The present invention using nickel and copper both as the dopant for improving ceria film oxygen ionic conductivity, together
When be also used as the catalyst of hydrocarbon fuel hydrogen, use anodizing and heat treating process to prepare a surface as more nanometers of straight holes
It is below fine and close rare earth, nickel and copper codope ceria film, 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, nickel and copper codope ceria/ceria film, and surface thereof is more nanometers straight
It is fine and close rare earth, nickel and copper codope ceria film, the film that another side is ceria, the hole of more nanometers of straight holes below hole
A length of 18~112 μm, the content of rare earth, nickel and rare earth in Copper-cladding Aluminum Bar ceria film, nickel and copper is distinguished by mass percentage
It is 4.8~27.1%, 1.5~20.2% and 1.1~19.5%.
The present invention also provides a kind of above-mentioned rare earth, nickel and copper codope ceria/ceria film preparation method, tools
Steps are as follows for body:
(1) soluble-salt, nickel salt, mantoquita, rare-earth salts, water and ethylene glycol are made into electrolyte；
(2) using cerium tablet as anode, cerium tablet one side pastes adhesive tape, using platinized platinum or lead flake as cathode, by anode and yin
Pole, which is placed in electrolyte, carries out anodic oxidation, after anodic oxidation, takes out, removes adhesive tape on anode, uses deionization
Water rinses only, air-dries and obtains anodic oxidation part；
(3) anodic oxidation part is placed in Muffle furnace, in 300~800 DEG C of roasting temperature, obtaining a surface is Donna
It is fine and close rare earth, nickel and copper codope ceria film, the film that another side is ceria below meter Zhi Kong.
In the present invention, in step (1), soluble-salt be selected from one of oxalates, phosphate, fluoride or carbonate or
It is two or more；Nickel salt is selected from one or more of nickel chloride, nickel nitrate or nickel sulfate；Mantoquita is selected from copper nitrate, chlorination
One or more of copper or copper sulphate；Rare-earth salts is in rare earth nitrades, rare earth sulfate or rare earth-iron-boron
One or more, rare earth in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium one
Kind is two or more.
In the present invention, in step (1), in electrolyte, in terms of 1L electrolyte, 3~50g of soluble-salt, nickel salt 0.3~
29.9g, 0.3~29.9g of mantoquita, 0.4~29.9g of rare-earth salts, 20~400g of water, remaining is ethylene glycol.
In the present invention, in step (2), the cerium tablet as anode needs to pre-process；Pre-treatment step is as follows: being moistened with dehydrated alcohol
Wet silicon carbide waterproof abrasive paper to cerium tablet carry out polishing and with washes of absolute alcohol it is clean；Flannelette is sprayed on ceria polishing agent
On, cerium tablet is polished on the flannelette for having ceria polishing agent until for mirror surface.
In the present invention, in step (2), the process conditions of anodic oxidation are as follows: 5~200mA/dm of current density2, oxidizing temperature
0~25 DEG C, 100~600rpm of speed of agitator, 2~15h. of oxidization time
In the present invention, in step (3), maturing temperature is 400~600 DEG C；When roasting, heating rate is 2~4 DEG C/min.
Compared to the prior art, the beneficial effects of the present invention are: the present invention has prepared one with simple preparation method
It is fine and close rare earth, nickel and copper codope ceria film, the film that another side is ceria that surface, which is below more nanometers of straight holes,.
Using a length of 18~112 μm of the hole of the Fisher MPO calibrator measurement more nanometers of straight holes in surface.Using using Bruker AXS
The content of rare earth, nickel and copper presses matter in Microanalysis GmbH energy disperse spectroscopy measurement rare earth, nickel and Copper-cladding Aluminum Bar ceria film
Measuring percentages and calculating is respectively 4.8~27.1%, 1.5~20.2% and 1.1~19.5%.
Specific embodiment
Technical solution of the present invention is specifically addressed below with reference to embodiment.
Embodiment 1
20g water, 3g ammonium oxalate, 0.6624g nickel chloride, 0.7535g copper nitrate, 0.9282g nitre are added in the beaker of 1L
Sour praseodymium adds 880mL ethylene glycol to dissolve to form water-ammonium oxalate-nickel chloride-copper nitrate-praseodymium nitrate-ethylene glycol mixed solution, moves into
In 1L volumetric flask, spent glycol is diluted to scale, and electrolyte is made.The silicon carbide waterproof abrasive paper soaked with dehydrated alcohol is to 100mm
× 100mm × 0.2mm waits for that the cerium foil of anodic oxidation carries out polishing and clean with washes of absolute alcohol, is sprayed with 1 μm of ceria
Mist polishing agent 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 polishing
The one side of cerium foil afterwards pastes adhesive tape, is put into anhydrous alcohol solution and is cleaned by ultrasonic.Above-mentioned electrolyte is transferred to the beaker of 2L
In, above-mentioned 100mm × 100mm × 0.2mm is put into electrolyte to anodic oxidation cerium foil and is anode, cathode 150mm
The platinum sheet of × 150mm × 0.5mm, magnetic agitation, speed of agitator 100rpm, current density 5mA/dm2, 0 DEG C of oxidizing temperature,
Oxidization time 2h takes out anodic oxidation part, removes the adhesive tape on anodic oxidation part, is rinsed only with deionized water, air-dries, adopt
With a length of 18 μm of the hole for the MPO calibrator measurement more nanometers of straight holes in surface that Fisher company produces.The anodic oxidation part is put into
It in crucible, is put into Muffle furnace, with 3 DEG C/min temperature programming to 300 DEG C, in 300 DEG C of roasting 2h.It is cooled to room temperature, taking-up obtains
It is fine and close praseodymium, nickel and copper codope ceria film, the film that another side is ceria that one surface, which is below more nanometers of straight holes,.
Using praseodymium, nickel and copper in Bruker AXS Microanalysis GmbH energy disperse spectroscopy measurement praseodymium, nickel and Copper-cladding Aluminum Bar ceria film
Content respectively 4.8%, 1.5% and 1.1% is calculated by mass percentage.
Embodiment 2
In the beaker of 1L be added 400g water, 25g ammonium phosphate, 25g ammonium fluoride, 49.84g nickel sulfate, 75.10g copper sulphate,
61.14g dysprosium nitrate adds 500mL ethylene glycol to dissolve to form water-ammonium phosphate-ammonium fluoride-nickel sulfate-copper sulphate-dysprosium nitrate-second two
Mixed alkoxide solution moves into 1L volumetric flask, and spent glycol is diluted to scale, and electrolyte is made.The carbonization soaked with dehydrated alcohol
Silicon 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 clean, with 1
μm ceria be sprayed polishing agent and be sprayed on flannelette, cerium tablet is polished on the flannelette for having ceria to be sprayed polishing agent until
For 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.By above-mentioned electrolyte
It is transferred in the beaker of 2L, above-mentioned 100mm × 100mm × 0.2mm is put into electrolyte to anodic oxidation cerium foil and is anode,
Cathode is 150mm × 150mm × 0.5mm stereotype, magnetic agitation, speed of agitator 600rpm, current density 200mA/
dm2, 25 DEG C of oxidizing temperature, oxidization time 15h, take out anodic oxidation part, remove the adhesive tape on anodic oxidation part, spend from
Sub- water rinses only, air-dries, and MPO calibrator measurement more nanometers of the surface straight hole produced using Fisher company is respectively 112 μm.
The anodic oxidation part is put into crucible, is put into Muffle furnace, with 3 DEG C/min temperature programming to 800 DEG C, is roasted at 800 DEG C
0.5h.It is cooled to room temperature, taking out and obtaining a surface be below more nanometers of straight holes is fine and close dysprosium, nickel and copper codope ceria
Film, the film that another side is ceria.Using Bruker AXS Microanalysis GmbH energy disperse spectroscopy measurement dysprosium, nickel and copper
Respectively 27.1%, 20.2% and 19.5% is calculated by mass percentage in the content of dysprosium, nickel and copper in doping cerium dioxide film.
Embodiment 3
200g water, 25g ammonium carbonate, 24.90g nickel nitrate, 15.45g nickel chloride, 23.61 nitric acid are added in the beaker of 1L
Copper, 14.81g copper chloride, 17.79g europium nitrate, 14.77g erbium nitrate add 700mL ethylene glycol to dissolve to form water-ammonium carbonate-nitric acid
Nickel-nickel chloride-copper nitrate-copper chloride-europium nitrate-erbium nitrate-ethylene glycol mixed solution moves into 1L volumetric flask, spent glycol
It is diluted to scale, electrolyte is made.Anode is waited for 100mm × 100mm × 0.2mm with the silicon carbide waterproof abrasive paper that dehydrated alcohol soaks
The cerium foil of oxidation carry out polishing and it is clean with washes of absolute alcohol, be sprayed polishing agent with 1 μm of ceria and be sprayed on flannelette, general
Cerium tablet is polished on the flannelette for having ceria to be sprayed polishing agent until for mirror surface.The one side of cerium foil after polishing is pasted transparent
Adhesive tape is put into anhydrous alcohol solution and is cleaned by ultrasonic.Above-mentioned electrolyte is transferred in the beaker of 2L, by above-mentioned 100mm × 100mm ×
0.2mm's is put into electrolyte to anodic oxidation cerium foil and is anode, and cathode is 150mm × 150mm × 0.5mm platinum sheet, magnetic
Power stirring, speed of agitator 350rpm, current density 100mA/dm2, 12.5 DEG C of oxidizing temperature, oxidization time 8.5h, take out
Anodic oxidation part removes the adhesive tape on anodic oxidation part, is rinsed only, is air-dried with deionized water, raw using Fisher company
A length of 81 μm of the hole of the MPO calibrator measurement more nanometers of straight holes in surface of production.The anodic oxidation part is put into crucible, Muffle is put into
In furnace, with 3 DEG C/min temperature programming to 600 DEG C, in 600 DEG C of roasting 1h.It is cooled to room temperature, it is more nanometers straight that taking-up, which obtains a surface,
It is fine and close europium, erbium, nickel and copper codope ceria film, the film that another side is ceria below hole.Using Bruker
AXS Microanalysis GmbH energy disperse spectroscopy measures europium, erbium, europium in nickel and copper codope ceria film, erbium, nickel and copper
Respectively 10.3%, 8.9%, 12.7% and 11.8% is calculated by mass percentage in content.
Claims (6)
1. a kind of rare earth, nickel and copper codope ceria/ceria film preparation method, which is characterized in that surface thereof
For the rare earth, nickel and copper codope ceria film, the film that another side is ceria for below more nanometers of straight holes being densification, Donna
The content in a length of 18~112 μm of the hole of meter Zhi Kong, rare earth, nickel and rare earth in Copper-cladding Aluminum Bar ceria film, nickel and copper presses quality
Percentage is respectively 4.8~27.1%, 1.5~20.2% and 1.1~19.5%；Specific step is as follows:
(1) soluble-salt, nickel salt, mantoquita, rare-earth salts, water and ethylene glycol are made into electrolyte；
(2) using cerium tablet as anode, cerium tablet one side is pasted adhesive tape and is set anode and cathode using platinized platinum or lead flake as cathode
Anodic oxidation is carried out in electrolyte, after anodic oxidation, is taken out, is removed adhesive tape on anode, is rushed with deionized water
It cleans, air-dries and obtain anodic oxidation part；
(3) anodic oxidation part is placed in Muffle furnace, in 300~800 DEG C of roasting temperature, obtaining a surface is more nanometers straight
It is fine and close rare earth, nickel and copper codope ceria film, the film that another side is ceria below hole.
2. preparation method according to claim 1, which is characterized in that in step (1), soluble-salt is selected from oxalates, phosphorus
One or more of hydrochlorate, fluoride or carbonate；Nickel salt be selected from one of nickel chloride, nickel nitrate or nickel sulfate or
It is two or more；Mantoquita is selected from one or more of copper nitrate, copper chloride or copper sulphate；Rare-earth salts is selected from rare earth nitric acid
One or more of salt, rare earth sulfate or rare earth-iron-boron, rare earth be selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium,
One or more of dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium.
3. preparation method according to claim 1, which is characterized in that in step (1), in electrolyte, in terms of 1L electrolyte,
3~50g of soluble-salt, 0.3~29.9g of nickel salt, 0.3~29.9g of mantoquita, 0.4~29.9g of rare-earth salts, 20~400g of water, remaining
For ethylene glycol.
4. preparation method according to claim 1, which is characterized in that in step (2), the cerium tablet as anode need to be located in advance
Reason；Pre-treatment step is as follows: being polished with the silicon carbide waterproof abrasive paper that dehydrated alcohol soaks cerium tablet and uses washes of absolute alcohol
Completely；It is sprayed on flannelette, cerium tablet is polished on the flannelette for having ceria polishing agent until for mirror with ceria polishing agent
Face.
5. preparation method according to claim 1, which is characterized in that in step (2), the process conditions of anodic oxidation are electricity
5~200mA/dm of current density2, 0~25 DEG C of oxidizing temperature, 100~600rpm of speed of agitator, 2~15h of oxidization time.
6. preparation method according to claim 1, which is characterized in that in step (3), maturing temperature is 400~600 DEG C；
When roasting, heating rate is 2~4 DEG C/min.
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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 |
| CN103055875A (en) * | 2012-11-05 | 2013-04-24 | 昆明理工大学 | Preparation method of catalytic material mixed by copper and cerium oxide |
| CN106431845B (en) * | 2015-08-11 | 2019-04-16 | 中国科学院大连化学物理研究所 | A kind of method that doping type ceria catalysis acetone prepares phenolic compound |
| CN105088315B (en) * | 2015-08-17 | 2017-06-23 | 上海应用技术学院 | A kind of method that use two-step anodization prepares rear-earth-doped ceria film |
| CN105088317B (en) * | 2015-08-17 | 2017-05-31 | 上海应用技术学院 | A kind of preparation method of ceria film |
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