CN109216711A - Utilize the method for pulsed laser deposition technique regulation crystal lattice stress preparation solid oxide fuel cell - Google Patents
Utilize the method for pulsed laser deposition technique regulation crystal lattice stress preparation solid oxide fuel cell Download PDFInfo
- Publication number
- CN109216711A CN109216711A CN201810836269.1A CN201810836269A CN109216711A CN 109216711 A CN109216711 A CN 109216711A CN 201810836269 A CN201810836269 A CN 201810836269A CN 109216711 A CN109216711 A CN 109216711A
- Authority
- CN
- China
- Prior art keywords
- nno
- target
- ysz
- laser deposition
- solid oxide
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8867—Vapour deposition
- H01M4/8871—Sputtering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physical Vapour Deposition (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses the methods using pulsed laser deposition technique regulation crystal lattice stress preparation solid oxide fuel cell；This method first prepares NNO target, then NNO target is fixed on to the Target material tray of pulse laser deposition instrument vacuum chamber；Single crystalline substrate YSZ is fixed on PLD sample carrier, is warming up to 590-610 DEG C under vacuum conditions；It is passed through pure oxygen, stablizes 0.4-0.6h in 0.8-1.2Pa oxygen pressure；PLD target NNO oxide is sputtered, metallic vapour is sequentially deposited on single crystalline substrate YSZ along laser normal direction, adjusts laser pulse number control NNO sull with a thickness of 9-50nm；Last brushing method brushing cathode slurry.The present invention is increased dramatically by the regulation to crystal lattice stress, the performance of the solid oxide fuel cell of preparation, and stability is good；The advantages such as, environmental pollution good, low in cost simultaneously with safety be few.
Description
Technical field
The present invention relates to solid oxide fuel cell, and in particular to a kind of to deposit (PLD) technology tune using pulse laser
The method for controlling crystal lattice stress preparation solid oxide fuel cell.
Background technique
Energy consumption is continuously increased the growth for reflecting a national economy.In a past century, we are main
Dependent on fossil fuel, such as: petroleum, coal, natural gas etc..However conventional fossil fuel is non-renewable, conversion ratio is low, causes serious
Energy waste, and generate a large amount of atmosphere pollution and greenhouse gases, thereby resulted in various environment and economy and ask
Topic.In order to cope with the increasingly depleted of conventional fossil fuel and its caused by the environmental problem (greenhouse effects, haze that get worse
Deng) severe challenge, to the research of new energy, exploitation, using extremely urgent.And numerous energy conversion and storage are thus derived
Memory device, solid oxide fuel cell because of the advantages such as it is high with energy conversion rate, fuel is applied widely, and pollution is few and by
To the extensive concern of researchers.The performance for improving solid oxide fuel cell thus is most important.
Model Bao'an etc. (Summarization for Preparation Methods of solid oxide fuel cell YSZ electrolytic thin-membrane, process engineering journal,
2 months 2004, the 1st phase of volume 4) it discloses and prepares electrolytic thin-membrane with using pulsed laser deposition, without regard to solid oxygen
The preparation of the anode of compound fuel cell.Especially the technology has obtained YSZ electrolytic thin-membrane on porous NiO/YSZ substrate
With a thickness of 1~2mm.The technology reduces electrolyte thickness by PLD technology, to improve the property of solid oxide fuel cell
Can, but this method is the electrolytic thin-membrane reached with a thickness of 1~2mm, needs number with the time of hour, quality of forming film is poor, production
Higher cost is unfavorable for heavy industrialization, and the stability of solid oxide fuel cell is to be improved.
Summary of the invention
The object of the present invention is to overcome the problems of the prior art, and it is short to provide a kind of film growth cycle, battery
Stability is very good, and the promotion of battery performance prepares soild oxide combustion using pulsed laser deposition technique regulation crystal lattice stress
Expect the method for battery
The present invention passes through selection monocrystalline YSZ base material and Nd2NiO4+δThe selection of anode material, can be raw by PLD
The film of long 9-50nm Nano grade and control lattice stress prepare the solid oxide fuel cell of different stress
Anode material.The present invention promotes the performance of solid oxide fuel cell by regulation crystal lattice stress, is deposited by pulse laser
Technology, preparation have the solid oxide fuel cell of different stress film, are tested by the performance to battery, table
Bright this method is more controllable, and film growth cycle is short, and the performance of solid oxide fuel cell is substantially improved.
Physical deposition methods of the present invention --- pulsed laser deposition strikes target by pulse laser, with target
There is material the material of identical stoichiometric ratio to deposit in single crystalline substrate by preferred orientation, by the frequency, the pulse that control laser
Number etc. can accuracy controlling thickness of electrode and crystal lattice stress.
The object of the invention is achieved through the following technical solutions:
Using the method for pulsed laser deposition technique regulation crystal lattice stress preparation solid oxide fuel cell, feature exists
In, comprising the following steps:
1) pulse laser deposition instrument target preparation: preparation NNO target, wherein the chemical formula of NNO oxide is Nd2NiO4+δ；
2) pulse laser deposition instrument grows anode material on electrolyte: it is true that NNO target is fixed on pulse laser deposition instrument
The Target material tray of plenum chamber；Single crystalline substrate YSZ is fixed on PLD sample carrier, is warming up to 590-610 DEG C under vacuum conditions；It is logical
Enter pure oxygen, stablizes 0.4-0.6h in 0.8-1.2Pa oxygen pressure；PLD target NNO oxide is sputtered, metallic vapour is along laser normal side
To being sequentially deposited on single crystalline substrate YSZ, laser pulse number control NNO sull is adjusted with a thickness of 9-50nm, is realized single
The lattice constant of brilliant substrate YSZ and the thin-film material NNO of growth mismatch, when compression stress~5% of the crystal lattice stress -6%
Tensile stress when, sputtering terminates, and improves oxygen pressure drop to room temperature；
3) brushing method brushing cathode slurry: the brushing of Ag-YSZ material is applied at the back side of membrane electrode as cathode material
Brush, controls the thickness of cathode material in 20~30nm.
To further realize the object of the invention, it is preferable that the sputtering PLD target NNO oxide is in 290-310mJ
Laser energy is sputtered under the frequency of 5Hz and 10Hz respectively under potentiostatic mode.
Preferably, the single crystalline substrate YSZ selects one of 100,110 and 111 3 kind of different crystal orientations, thickness
For 500um.
Preferably, the raising oxygen pressure drop to room temperature is that room temperature is down to from 590-610 DEG C, and cooling rate is 5-7 DEG C/min,
And the oxygen pressure during control cooling is 190-210Pa.
Preferably, the NNO target is by combustion synthesis powder, and powder is pressed into target using tablet press machine,
It is obtained after high temperature sintering.
Preferably, the NNO target is referred to by combustion synthesis powder by chemical formula Nd2NiO4+δWeigh respectively Nd,
The nitrate of Ni is added glycine and deionized water, stirs evenly；Being heated to being stirred liquid at 190-200 DEG C becomes melting
State adjusts the temperature to 490-510 DEG C, and then heating is until spontaneous combustion, obtains fluffy powder；It is then placed in Muffle furnace, air
1000-1100 DEG C of sintering 5-7h, obtains Nd under atmosphere2NiO4+δPowder；
It is preferably, described that powder is pressed into target using tablet press machine is by Nd2NiO4+δPVB wine is added in powder mull
Smart solution, then tabletting after grinding, obtain NNO piece；
The high temperature sintering is that NNO piece 1250-1300 DEG C of sintering 5-6h in air atmosphere is obtained NNO target.
Preferably, the NNO target with a thickness of 21-25mm.
Preferably, the Ag-YSZ material is to mix silver paste by the mass ratio of 7:3 with YSZ powder, and binder ball is added
Mill, obtains porous Ag-YSZ material；The number of the brushing is 2 times or more.
Preferably, the heating rate for being warming up to 590-610 DEG C under vacuum conditions is 8-10 DEG C/min.
Ag-YSZ material brushing of the present invention is used as at the back side of membrane electrode to electrode.
In various film preparing technologies, pulsed laser deposition technique is simple and has lot of advantages, can to chemistry at
Divide complicated composite materials to carry out the same plated film of congruence, is easy to guarantee the stabilization of stoichiometric ratio after plated film；It is swift in response, grows
Fastly.Usual situation can obtain 1 μm or so of film for lower hour；Easily multilayer film production and heterogeneous membrane, especially multivariant oxide is different
Matter knot, only need to be by simply changing target just；High vacuum environment can be made into high purity films to Film Contamination less.The present invention utilizes arteries and veins
Thin-film material needed for impulse light deposition technology growth, and stress is controlled, thin-skin model system is prepared, for improving electricity
Pond performance.
The present invention introduces crystal lattice stress by the mismatch of lattice constant between material.
The difference of the base material of different crystal orientations is that substrate crystal orientation is different, and NNO film is grown in his crystal orientation above
Can be different, it just will be different in the YSZ upper stress of different crystal orientations.Crystal lattice stress of the present invention is introduced by selection monocrystalline
The lattice constant mismatch introducing with the thin-film material NNO of growth of YSZ substrate.The growing film material such as in substrate, material
Expect and contacted between interface between material, if that being exactly one big if the lattice constant between two materials mismatches
It is one small, the stress that drawing force either compresses will be generated after film is grown in substrate, between film and substrate, still
If the film of growth is very thick, such as micron level would not have crystal lattice stress between film and substrate, stress will be released
It puts, will not consider further that very small crystal lattice stress.As the lattice constant of the single crystalline substrate YSZ of the invention selected isNNO
The lattice constant of film isGrowing film is removed with PLD, controls the thickness of film in 8- by adjusting laser pulse number
Between 50nm, the data of high-resolution XRD and by calculate also indicate that, hence it is evident that produce crystal lattice stress.Therefore lattice constant
It is different, cause just to will form stress between the interface of film, and stress can have an impact the characteristic of material, and then influence
The performance of battery.
Present invention discover that stress improves a lot to the stability of Solid Oxide Fuel Cells.In the system of film
Preferably pass through selection (100), YSZ (0.8% Y of (110) and (111) three kinds of different crystal orientations during standby2O3The ZrO2 of doping)
Base material controls film thickness in 9- by adjusting laser pulse number (laser energy 300mj, laser frequency 5HZ, 10HZ)
Between 50nm, always regulate and control crystal lattice stress, when crystal lattice stress is in -6% (compression stress)~5% (between tensile stress).
Compared with the existing technology, the invention has the advantages that and the utility model has the advantages that
(1) present invention successfully regulates and controls crystal lattice stress promotion solid oxide fuel cell by pulsed laser deposition technique
Performance.It, can be with by the result of high-resolution XRD such as by growing the NNO film of 10nm or so in YSZ (100) substrate
Calculating learns that the lattice constant of NNO isAnd the lattice constant for being not affected by the NNO of stress state isTherefore exist
After growing NNO film in YSZ (110) substrate, stress state is tensile stress 4.05% ((4.075-3.854)/3.854)；From
The area specific resistance that the attached drawing of embodiment can see battery has 34.04 Ω cm at 600 degree2, and pass through long-time stability
It tests, in the test of 60h, area specific resistance is still maintained at 34 Ω cm2Left and right, the stability for showing battery is very good, electricity
The promotion of pond performance illustrates the tensile stress introduced by pld technology, makes a significant impact on the characteristic of material.
(2) base material is used as using monocrystalline YSZ, convenient for the base material of commercially-available different crystal orientations, as (100),
(110), (111) crystal orientation, and YSZ has excellent oxygen conduction, therefore allow to be used as solid oxide fuel cell
Electrolyte.
(3) present invention prepares thin-skin model system using pulsed laser deposition technique, and the film grown is good quality
High purity films.
(4) the features such as the method for the present invention has parameter controllable, and model is simple, repeatability is high is suitable for other electrochemistry
The electrode material design concept of energy device.
Detailed description of the invention
Fig. 1 is Nd in embodiment 1,2,32NiO4+δThe X-ray diffractogram of powder and target.
Fig. 2 is the result of NNO/YSZ (100) film X ray reflection in embodiment 1.
Fig. 3 is NNO/YSZ (100) field emission scanning electron microscope figure in embodiment 1.
Fig. 4 is NNO/YSZ (100) film high-resolution XRD spectrum in embodiment 1.
Fig. 5 is that the stability for the solid oxide fuel cell that NNO/YSZ (100) hull cell assembles in embodiment 1 is surveyed
Test result.
Fig. 6 is the result of NNO/YSZ (110) film X ray reflection in embodiment 2.
Fig. 7 is NNO/YSZ (110) field emission scanning electron microscope figure in embodiment 2.
Fig. 8 is NNO/YSZ (110) film high-resolution XRD spectrum in embodiment 2.
Fig. 9 is NNO/YSZ (111) field emission scanning electron microscope figure in embodiment 3.
Figure 10 is NNO/YSZ (111) film high-resolution XRD spectrum in embodiment 3.
Specific embodiment
For a better understanding of the invention, the present invention is further illustrated with reference to the accompanying drawings and examples, but this hair
Bright embodiment is unlimited so.
Embodiment 1
(1) it is used for pulsed laser deposition technique target Nd2NiO4+δPreparation: first by Nd (NO3)3·6H2O (Mike woods,
Analyze pure) and Ni (NO3)26H2O (Mike woods is analyzed pure) is according to Nd2NiO4+δIn stoichiometric ratio weighed, then claim
Take corresponding Nd2NiO4+δCitric acid (the C of middle cation mole half6H8O7·H2O) amount, pour into the beaker of 1000ml
In, the deionized water of 100ml is added, and beaker is placed on magnetic stirring apparatus, is heated to being stirred liquid change at 190-200 DEG C
For molten condition, 490-510 DEG C is adjusted the temperature to, then heating is until spontaneous combustion, the powder of generation is put into crucible, in high temperature
In furnace, 6h is calcined at 1050 DEG C with the heating rate of 3 DEG C/min in air, cooled to room temperature obtains black powder.It is right
The powder carries out X-ray diffraction (XRD) characterization, and gained XRD spectra is as shown in Figure 1, completely right with standard card (89-0131)
It answers, it was demonstrated that black powder Nd2NiO4+δ, without miscellaneous phase.By 5g synthesize powder is fitted into 100ml ball grinder, addition 36ml without
Water-ethanol (CH3CH2OH, Tianjin Fu Yu Fine Chemical Co., Ltd analyze pure), ball milling 10h is then placed under infrared lamp
Drying, obtained powder is poured into agate mortar, PVB- ethanol solution is added, PVB is adhesive, mass concentration 6%.
PVB adds the Nd that quality is required bonding2NiO4+δThe 3% of powder quality, grinding is up to solution evaporation to dry fine-grained powder
End.Recycling diameter is that powder is pressed into target at 10Mpa by the tabletting grinding tool of 25mm, and the target suppressed is at 1300 DEG C
6h is calcined in air.The XRD spectrum of target is shown in Fig. 1, and used test equipment is Bruker D8Advance.
(2) film is grown: being used frosted paper polishing NNO target, is removed the powder of skim-coat (about 0.1mm).It is individually fixed in
The Target material tray of pulse laser deposition instrument (PLD) (tech, D13-046 in Shenyang) vacuum chamber.By single crystalline substrate YSZ (100)
(Y2O3Adulterate ZrO2) it is fixed on PLD sample carrier, under vacuum conditions (10‐5Pa 610 DEG C) are warming up to 10 DEG C/min.It is passed through pure
Oxygen stablizes 0.6h in 1.2Pa oxygen pressure.Metallic vapour is sequentially deposited in single crystalline substrate along laser normal direction, generation and target
The consistent electrode material of stoichiometric ratio, and its thickness can be adjusted by the umber of pulse of laser, up to nanometer scale.300mJ
Laser energy sputters 120s and 100s respectively under potentiostatic mode with the frequency of 5Hz and 10Hz respectively, and it is thin that NNO oxide is made
Film, NNO sull with a thickness of 9.44nm, achieve the purpose that by umber of pulse adjust thickness.The X ray reflection of film
As a result see Fig. 2.The test result of X ray reflection can immediately arrive at the thickness of thin-film material by the fitting of software, according to quasi-
Close result NNO film with a thickness of 9.44nm.Sputtering terminates, and improves oxygen and is depressed into 200Pa, is down to room temperature with 7 DEG C/min.
Fig. 3 is the scanning electron microscope image that NNO film prepared by the present embodiment 1 is grown in YSZ (100) substrate
(SEM), 70000 times of amplification factor, from image it can be seen that material surface occurs without particle and other defects, it is seen that this implementation
Example obtains the film of surfacing good quality using PLD technology, and excellent film quality is for solid oxide fuel
Battery can work normally most important.Used test equipment is field emission scanning electron microscope.
Fig. 4 is the high-resolution XRD spectrum that NNO film prepared by embodiment 1 is grown in YSZ (100) substrate, YSZ base
The lattice constant at bottom isIt can be calculated and be learnt by the result of high-resolution XRD: (specific calculating process is as follows)
1) 2 θ=31.54 ° can be read according to the result of high-resolution XRD
2) according to formula bragg's formula 2dsin θ=n λ
3) according to formula d2=a2/2
Calculating is learntTherefore the lattice constant of NNO isAnd it is not affected by the crystalline substance of the NNO of stress state
Lattice constant isTherefore after growing NNO film in YSZ (100) substrate, stress state is tensile stress 4.05%
((4.010‐3.854)/3.854)。
(3) it prepares battery: weighing the PVB and terpinol that mass ratio is 1:9 respectively, be placed in a beaker, in 60 DEG C of baking oven
Middle dissolution is used as binder for 24 hours, for use.Mass ratio according to Ag and YSZ is that 7:3 weighs 4.38g silver paste (DAD-87, Shanghai City
80%) and 1.5g YSZ (after ball milling) synthetic resin research institute, amount containing Ag are that, then weighing quality is binder described in 5g,
It is added in agate mortar and grinds 4h, obtain evenly dispersed Ag-YSZ combination electrode slurry.It is with pigment tools pen that Ag-YSZ is electric
Pole slurry, which is uniformly brushed, to be used as at the back side of film to electrode, and area is about 0.8 square centimeter, is dried in 140 DEG C of high temperature
It is dried in case.
In the exposure mask of film surface covering hollow out, tech sputtering equipment in use, under the conditions of air pressure 6Pa, sputtering current 5mA
Sputtering gold target material 210 seconds.Film surface forms the gold of comb shape, and as electronics collector, area is 0.24 square centimeter.It takes
Two short silver wires are separately fixed on the center of Ag-YSZ electrode and the gold on membrane electrode surface by silver paste.
Then the one end for the glass tube for being 13mm in diameter with silver paste sealing-in by the battery of preparation, then take two diplopore corundum
Pipe is fixed on the two sides of glass tube, and a silver wire is respectively imported in each hole.By two silver wires of a diplopore alundum tube and NNO mono-
The anode of side is connected, and two silver wires of another diplopore alundum tube are connected with Ag-YSZ cathode.
(4) assembled hull cell performance test: is put into the heated constant temperature area of electric tube furnace in H2In rise to 600
DEG C, in H after 600 DEG C of reductase 12 h2It is middle that test electrochemical impedance test is carried out to battery using I-vium electrochemical workstation.
By the black green both threads of NNO electrode connection electrochemical workstation, the red white both threads of Ag-YSZ connection, set the amplitude of instrument as
10mV, frequency are 0.1Hz~105Hz carries out data processing with Origin software, obtains the area specific resistance spectrogram of battery, sees figure
4.The area specific resistance of impedance spectra battery has 34.04 Ω cm2 at 600 degree, and is tested by long-time stability, 60h's
In test, area specific resistance is still maintained at 34 Ω cm2 or so and sees Fig. 5, and showing battery has extraordinary stability, because
This, the present embodiment sinks to the bottom technology using pulse laser, and 300mJ laser energy is under potentiostatic mode respectively with the frequency of 5Hz and 10Hz
Rate sputters 120s and 100s respectively and grows 9.44nmNNO film, the stretching that stress state is 4.05% in YSZ (100) substrate
Stress, and be assembled into battery and tested, for battery in the stability test of 60h, area specific resistance is maintained at 34 Ω cm2Left and right,
Show that battery has extraordinary stability.There is technology for solid oxide fuel cell of the preparation with excellent stability
Property directive significance, may advantageously facilitate solid oxide fuel cell commercialization.
Embodiment 2
(1) it is used for pulsed laser deposition technique target Nd2NiO4+δPreparation: first by Nd (NO3)3·6H2O (Mike woods,
Analyze pure) and Ni (NO3)26H2O (Mike woods is analyzed pure) is according to Nd2NiO4+δIn stoichiometric ratio successively weighed,
Corresponding Nd is weighed again2NiO4+δCitric acid (the C of middle cation mole half6H8O7·H2O) amount, pour into the burning of 1000ml
In cup, 100ml deionized water is added, and beaker is placed on magnetic stirring apparatus, is heated to being stirred liquid change at 190-200 DEG C
For molten condition, 490-510 DEG C is adjusted the temperature to, then heating is until spontaneous combustion, the powder of generation is put into crucible, in high temperature
In furnace, 6h is calcined at 1050 DEG C with the heating rate of 3 DEG C/min in air, cooled to room temperature obtains black powder.It is right
The powder carries out X-ray diffraction (XRD) characterization, and gained XRD spectra (see Fig. 1) is completely corresponding with standard card (89-0131), card
Bright black powder is Nd2NiO4+δ, without miscellaneous phase.The 5g powder synthesized is fitted into 100ml ball grinder, the anhydrous second of 36ml is added
Alcohol (Tianjin Fu Yu Fine Chemical Co., Ltd analyzes pure), ball milling 10h is then placed under infrared lamp and dries, by what is obtained
Powder pours into agate mortar, PVB- ethanol solution is added, PVB is adhesive, mass concentration 6%.PVB additive amount is required
The Nd to be bonded2NiO4+δThe 3% of powder quality, grinding is up to solution evaporation to dry fine grained powder.Recycle diameter be
Powder is pressed into target at 10Mpa by the tabletting grinding tool of 25mm, and the target suppressed calcines 6h in air at 1300 DEG C.Target
The XRD spectrum of material is shown in Fig. 1, and used test equipment is Bruker D8Advance.
(2) film is grown: being used frosted paper polishing NNO target, is removed the powder of skim-coat (about 0.1mm).It is individually fixed in
The Target material tray of pulse laser deposition instrument (PLD) (tech, D13-046 in Shenyang) vacuum chamber.By single crystalline substrate YSZ (110)
(Y2O3Adulterate ZrO2) it is fixed on PLD sample carrier, under vacuum conditions (10‐5Pa 610 DEG C) are warming up to 10 DEG C/min.It is passed through pure
Oxygen stablizes 0.6h in 1.2Pa oxygen pressure.Metallic vapour is sequentially deposited in single crystalline substrate along laser normal direction, generation and target
The consistent electrode material of stoichiometric ratio, and its thickness can be adjusted by the umber of pulse of laser, up to nanometer scale.300mJ
Laser energy sputters 120s and 100s respectively under potentiostatic mode with the frequency of 5Hz and 10Hz respectively, and it is thin that NNO oxide is made
Film, NNO sull with a thickness of 9nm, achieve the purpose that by umber of pulse adjust thickness.The knot of the X ray reflection of film
Fruit sees Fig. 6.The test result of X ray reflection can immediately arrive at the thickness of thin-film material by the fitting of software, according to fitting
As a result NNO film with a thickness of 9nm.Sputtering terminates, and improves oxygen and is depressed into 200Pa, is down to room temperature with 7 DEG C/min.
Fig. 7 is the scanning electron microscope image that NNO film prepared by the present embodiment 2 is grown in YSZ (100) substrate
(SEM), 70000 times of amplification factor, from image it can be seen that material surface occurs without particle and other defects, it is seen that Wo Menli
The film of surfacing good quality is obtained with PLD technology, and excellent film quality is for solid oxide fuel cell
It can work normally most important.Used test equipment is field emission scanning electron microscope.
Fig. 8 is the high-resolution XRD spectrum that NNO film prepared by embodiment 1 is grown in YSZ (100) substrate, YSZ base
The lattice constant at bottom isIt can be calculated and be learnt by the result of high-resolution XRD, the lattice constant of NNO is
And the lattice constant for being not affected by the NNO of stress state isTherefore it after growing NNO film in YSZ (100) substrate, answers
Power state is tensile stress 5.73% ((4.075-3.854)/3.854).
(3) it prepares battery: weighing the PVB and terpinol that mass ratio is 1:9 respectively, be placed in a beaker, in 60 DEG C of baking oven
Middle dissolution is used as binder for 24 hours, for use.Mass ratio according to Ag and YSZ is that 7:3 weighs 4.38g silver paste (DAD-87, Shanghai City
80%) and 1.5g YSZ (after ball milling) synthetic resin research institute, amount containing Ag are that, then weighing quality is binder described in 5g,
It is added in agate mortar and grinds 4h, obtain evenly dispersed Ag-YSZ combination electrode slurry.It is with pigment tools pen that Ag-YSZ is electric
Pole slurry, which is uniformly brushed, to be used as at the back side of film to electrode, and area is about 0.8 square centimeter, is dried in 140 DEG C of high temperature
It is dried in case.
In the exposure mask of film surface covering hollow out, tech sputtering equipment in use, under the conditions of air pressure 6Pa, sputtering current 5mA
Sputtering gold target material 210 seconds.Film surface forms the gold of comb shape, and as electronics collector, area is 0.24 square centimeter.It takes
Two short silver wires are separately fixed on the center of Ag-YSZ electrode and the gold on membrane electrode surface by silver paste.
Then the one end for the glass tube for being 13mm in diameter with silver paste sealing-in by the battery of preparation, then take two diplopore corundum
Pipe is fixed on the two sides of glass tube, and a silver wire is respectively imported in each hole.By two silver wires of a diplopore alundum tube and NNO mono-
The anode of side is connected, and two silver wires of another diplopore alundum tube are connected with Ag-YSZ cathode.
It is prepared in YSZ (110) substrate it can be seen that the present embodiment regulates and controls crystal lattice stress by pulsed laser deposition technique
The NNO film of 9nm thickness, and being learnt by characterization test, the tensile stress that the crystal lattice stress of thin-skin model is 5.73%, and by its
It is assembled into battery and has prepared solid oxide fuel cell, the performance for promoting solid oxide fuel cell has great
Meaning.
Embodiment 3
(1) it is used for pulsed laser deposition technique target Nd2NiO4+δPreparation: first by Nd (NO3)3·6H2O (Mike woods,
Analyze pure) and Ni (NO3)26H2O (Mike woods is analyzed pure) is according to Nd2NiO4+δIn stoichiometric ratio successively weighed,
Corresponding Nd is weighed again2NiO4+δCitric acid (the C of middle cation mole half6H8O7·H2O) amount, pour into the burning of 1000ml
In cup, the deionized water of 100ml is added, and beaker is placed on magnetic stirring apparatus, is heated to being stirred liquid at 190-200 DEG C
Become molten condition, adjust the temperature to 490-510 DEG C, then heating is until spontaneous combustion, the powder of generation is put into crucible, in height
In warm furnace, 6h is calcined at 1050 DEG C with the heating rate of 5 DEG C/min in air, cooled to room temperature obtains black powder.
X-ray diffraction (XRD) characterization is carried out to the powder, gained XRD spectra (Fig. 1) is completely corresponding with standard card (89-0131), card
Bright black powder is Nd2NiO4+δ, without miscellaneous phase.The 5g powder synthesized is fitted into 100ml ball grinder, the anhydrous second of 36ml is added
Alcohol (CH3CH2OH, Tianjin Fu Yu Fine Chemical Co., Ltd analyze pure), ball milling 10h is then placed under infrared lamp and dries,
Obtained powder is poured into agate mortar, PVB- ethanol solution is added, PVB is adhesive, mass concentration 6%.PVB addition
Quality is the Nd of required bonding2NiO4+δThe 3% of powder quality, grinding is up to solution evaporation to dry fine grained powder.It is sharp again
Powder is pressed into target at 10Mpa by the tabletting grinding tool for being 25mm with diameter, and the target suppressed is at 1300 DEG C in air
Calcine 6h.The XRD spectrum of target is shown in Fig. 1, and used test equipment is Bruker D8Advance.
(2) film is grown: being used frosted paper polishing NNO target, is removed the powder of skim-coat (about 0.1mm).It is individually fixed in
The Target material tray of pulse laser deposition instrument (PLD) (tech, D13-046 in Shenyang) vacuum chamber.By single crystalline substrate YSZ (111)
(Y2O3Adulterate ZrO2) it is fixed on PLD sample carrier, under vacuum conditions (10‐5Pa 610 DEG C) are warming up to 10 DEG C/min.It is passed through pure
Oxygen stablizes 0.6h in 1.2Pa oxygen pressure.Metallic vapour is sequentially deposited in single crystalline substrate along laser normal direction, generation and target
The consistent electrode material of stoichiometric ratio, and its thickness can be adjusted by the umber of pulse of laser, up to nanometer scale.300mJ
Laser energy sputters 600s and 500s respectively under potentiostatic mode with the frequency of 5Hz and 10Hz respectively, and it is thin that NNO oxide is made
Film, NNO sull with a thickness of 50nm, achieve the purpose that by umber of pulse adjust thickness.Sputtering terminates, and improves oxygen and is depressed into
200Pa is down to room temperature with 7 DEG C/min.
Fig. 9 is the scanning electron microscope image that NNO film prepared by the present embodiment 3 is grown in YSZ (111) substrate
(SEM), 70000 times of amplification factor, from image it can be seen that material surface occurs without particle and other defects, it is seen that Wo Menli
The film of surfacing good quality is obtained with PLD technology, and excellent film quality is for solid oxide fuel cell
It can work normally most important.Used test equipment is field emission scanning electron microscope.
Figure 10 is the high-resolution XRD spectrum that NNO film prepared by embodiment 3 is grown in YSZ (100) substrate, YSZ base
The lattice constant at bottom isIt can be calculated and be learnt by the result of high-resolution XRD, the lattice constant of NNO isAnd
The lattice constant for being not affected by the NNO of stress state isTherefore after growing NNO film in YSZ (100) substrate, stress
State is compression stress 3.46% ((3.854-3.721)/3.854).
(3) it prepares battery: weighing the PVB and terpinol that mass ratio is 1:9 respectively, be placed in a beaker, in 60 DEG C of baking oven
Middle dissolution is used as binder for 24 hours, for use.Mass ratio according to Ag and YSZ is that 7:3 weighs 4.38g silver paste (DAD-87, Shanghai City
80%) and 1.5g YSZ (after ball milling) synthetic resin research institute, amount containing Ag are that, then weighing quality is binder described in 5g,
It is added in agate mortar and grinds 4h, obtain evenly dispersed Ag-YSZ combination electrode slurry.It is with pigment tools pen that Ag-YSZ is electric
Pole slurry, which is uniformly brushed, to be used as at the back side of film to electrode, and area is about 0.8 square centimeter, is dried in 140 DEG C of high temperature
It is dried in case.
In the exposure mask of film surface covering hollow out, tech sputtering equipment in use, under the conditions of air pressure 6Pa, sputtering current 5mA
Sputtering gold target material 210 seconds.Film surface forms the gold of comb shape, and as electronics collector, area is 0.24 square centimeter.It takes
Two short silver wires are separately fixed on the center of Ag-YSZ electrode and the gold on membrane electrode surface by silver paste.
Then the one end for the glass tube for being 13mm in diameter with silver paste sealing-in by the battery of preparation, then take two diplopore corundum
Pipe is fixed on the two sides of glass tube, and a silver wire is respectively imported in each hole.By two silver wires of a diplopore alundum tube and NNO mono-
The anode of side is connected, and two silver wires of another diplopore alundum tube are connected with Ag-YSZ cathode.
The present embodiment regulates and controls crystal lattice stress by pulsed laser deposition technique and has prepared 50nm in YSZ (111) substrate
Thick NNO film, and being learnt by characterization test, the tensile stress that the crystal lattice stress of thin-skin model is 3.46%, and by its group
It dresses up battery and has prepared solid oxide fuel cell, the performance for promoting solid oxide fuel cell has great meaning
Justice.
Above embodiment just for the sake of clearly demonstrating examples made by the present invention is implemented to the present invention
The restriction of mode.For those of ordinary skill in the art, not similar shape can also be made on the basis of the above description
The variation or variation of formula.There is no necessity and possibility to exhaust all the enbodiments.It is all in the spirit and principles in the present invention
Within made any modifications, equivalent replacements, and improvements etc., be all contained within the scope of protection of the claims of the present invention.
Claims (10)
1. using the method for pulsed laser deposition technique regulation crystal lattice stress preparation solid oxide fuel cell, feature exists
In, comprising the following steps:
1) pulse laser deposition instrument target preparation: preparation NNO target, wherein the chemical formula of NNO oxide is Nd2NiO4+δ；
2) pulse laser deposition instrument grows anode material on electrolyte: NNO target is fixed on pulse laser deposition instrument vacuum chamber
The Target material tray of room；Single crystalline substrate YSZ is fixed on PLD sample carrier, is warming up to 590-610 DEG C under vacuum conditions；It is passed through pure
Oxygen stablizes 0.4-0.6h in 0.8-1.2Pa oxygen pressure；Sputter PLD target NNO oxide, metallic vapour along laser normal direction according to
It is secondary to be deposited on single crystalline substrate YSZ, laser pulse number control NNO sull is adjusted with a thickness of 9-50nm, realizes monocrystalline lining
The lattice constant of bottom YSZ and the thin-film material NNO of growth mismatch, when crystal lattice stress -3.46% compression stress~
When 5.73% tensile stress, sputtering terminates, and improves oxygen pressure drop to room temperature；
3) brushing method brushing cathode slurry: the brushing of Ag-YSZ material is brushed, control at the back side of membrane electrode as cathode material
The thickness of cathode material processed is in 20~30nm.
2. according to claim 1 prepare solid oxide fuel electricity using pulsed laser deposition technique regulation crystal lattice stress
The method in pond, which is characterized in that the sputtering PLD target NNO oxide is in 290-310mJ laser energy in potentiostatic mode
It is lower to be sputtered under the frequency of 5Hz and 10Hz respectively.
3. according to claim 1 prepare solid oxide fuel electricity using pulsed laser deposition technique regulation crystal lattice stress
The method in pond, which is characterized in that one in the single crystalline substrate YSZ selection 100,110 and 111 3 kind of different crystal orientations
Kind, with a thickness of 500um.
4. according to claim 1 prepare solid oxide fuel electricity using pulsed laser deposition technique regulation crystal lattice stress
The method in pond, which is characterized in that the raising oxygen pressure drop to room temperature is that room temperature is down to from 590-610 DEG C, cooling rate 5-7
DEG C/min, and controlling the oxygen pressure during cooling is 190-210Pa.
5. according to claim 1 prepare solid oxide fuel electricity using pulsed laser deposition technique regulation crystal lattice stress
The method in pond, which is characterized in that powder is pressed by the NNO target by combustion synthesis powder using tablet press machine
Target obtains after high temperature sintering.
6. according to claim 5 prepare solid oxide fuel electricity using pulsed laser deposition technique regulation crystal lattice stress
The method in pond, which is characterized in that the NNO target is referred to by combustion synthesis powder by chemical formula Nd2NiO4+δClaim respectively
The nitrate of Nd, Ni are taken, glycine and deionized water is added, stirs evenly；Being heated to being stirred liquid at 190-200 DEG C becomes
Molten condition adjusts the temperature to 490-510 DEG C, and then heating is until spontaneous combustion, obtains fluffy powder；Muffle furnace is then placed in,
1000-1100 DEG C of sintering 5-7h, obtains Nd under air atmosphere2NiO4+δPowder.
7. according to claim 5 prepare solid oxide fuel electricity using pulsed laser deposition technique regulation crystal lattice stress
The method in pond, which is characterized in that described powder is pressed into target using tablet press machine is by Nd2NiO4+δPowder mull is added
PVB alcoholic solution, then tabletting after grinding, obtain NNO piece；
The high temperature sintering is that NNO piece 1250-1300 DEG C of sintering 5-6h in air atmosphere is obtained NNO target.
8. according to claim 1 prepare solid oxide fuel electricity using pulsed laser deposition technique regulation crystal lattice stress
The method in pond, which is characterized in that the NNO target with a thickness of 21-25mm.
9. according to claim 1 prepare solid oxide fuel electricity using pulsed laser deposition technique regulation crystal lattice stress
The method in pond, which is characterized in that the Ag-YSZ material is to mix silver paste by the mass ratio of 7:3 with YSZ powder, and bonding is added
Agent ball milling obtains porous Ag-YSZ material；The number of the brushing is 2 times or more.
10. according to claim 1 prepare solid oxide fuel using pulsed laser deposition technique regulation crystal lattice stress
The method of battery, which is characterized in that the heating rate for being warming up to 590-610 DEG C under vacuum conditions be 8-10 DEG C/
min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810836269.1A CN109216711B (en) | 2018-07-26 | 2018-07-26 | Method for preparing solid oxide fuel cell by regulating and controlling lattice stress by using pulsed laser deposition technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810836269.1A CN109216711B (en) | 2018-07-26 | 2018-07-26 | Method for preparing solid oxide fuel cell by regulating and controlling lattice stress by using pulsed laser deposition technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109216711A true CN109216711A (en) | 2019-01-15 |
| CN109216711B CN109216711B (en) | 2020-12-22 |
Family
ID=64990715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810836269.1A Active CN109216711B (en) | 2018-07-26 | 2018-07-26 | Method for preparing solid oxide fuel cell by regulating and controlling lattice stress by using pulsed laser deposition technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109216711B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144600A (en) * | 2019-05-21 | 2019-08-20 | 华南理工大学 | A kind of flat high performance thin film electro-catalysis working electrode and preparation and application |
| CN110144599A (en) * | 2019-05-21 | 2019-08-20 | 华南理工大学 | Membrane electrode and its preparation method and application is precipitated in a kind of efficient oxygen |
| CN110804761A (en) * | 2019-12-09 | 2020-02-18 | 湘潭大学 | Preparation method of different-orientation single-variant yttria-stabilized zirconia epitaxial film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752585A (en) * | 2010-01-21 | 2010-06-23 | 南京工业大学 | Solid oxide fuel battery system and preparation method thereof |
| EP2886678A1 (en) * | 2013-12-18 | 2015-06-24 | EDISON S.p.A. | Method for the deposition of films of mixed oxides on composite material substrates |
-
2018
- 2018-07-26 CN CN201810836269.1A patent/CN109216711B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752585A (en) * | 2010-01-21 | 2010-06-23 | 南京工业大学 | Solid oxide fuel battery system and preparation method thereof |
| EP2886678A1 (en) * | 2013-12-18 | 2015-06-24 | EDISON S.p.A. | Method for the deposition of films of mixed oxides on composite material substrates |
Non-Patent Citations (2)
| Title |
|---|
| ATSUO YAMADA,ET AL.: ""Anisotropic catalytic activity of the orientation controlled Nd2NiO4 + δ/YSZ hetero-epitaxial system for SOFC cathode"", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
| ATSUO YAMADA,ET AL.: ""Ruddlesden-Popper-Type Epitaxial Film as OxygenElectrode for Solid-Oxide Fuel Cells"", 《ADVANCED MATERIALS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144600A (en) * | 2019-05-21 | 2019-08-20 | 华南理工大学 | A kind of flat high performance thin film electro-catalysis working electrode and preparation and application |
| CN110144599A (en) * | 2019-05-21 | 2019-08-20 | 华南理工大学 | Membrane electrode and its preparation method and application is precipitated in a kind of efficient oxygen |
| CN110804761A (en) * | 2019-12-09 | 2020-02-18 | 湘潭大学 | Preparation method of different-orientation single-variant yttria-stabilized zirconia epitaxial film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109216711B (en) | 2020-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103811772B (en) | Composite containing perovskite structure oxide and its production and use | |
| WO2017130622A1 (en) | Solid electrolyte material and all solid lithium ion secondary battery | |
| CN109216711A (en) | Utilize the method for pulsed laser deposition technique regulation crystal lattice stress preparation solid oxide fuel cell | |
| CN104388972B (en) | Cathode material and its application for electrolytic tank of solid oxide | |
| CN109037759A (en) | Prepare the sintering method of fine and close carbuncle type lithium ion solid electrolyte | |
| CN102683667A (en) | Lithium-manganese-aluminum oxygen anode material and preparation method thereof | |
| CN108390071A (en) | A kind of cathode of solid oxide fuel cell surface modification method | |
| CN101114719B (en) | Process for producing gradient structure film supporting with porous substrate material | |
| CN103872367A (en) | Zirconia based electrolyte film of solid oxide fuel cell | |
| CN115810743B (en) | Single crystal layered oxide positive electrode material, preparation method and application thereof in sodium ion battery | |
| CN101362205A (en) | Preparation method of solid oxide electrolytic cell NiO-YSZ hydrogen electrode powder | |
| CN103224394A (en) | Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof | |
| CN101307461B (en) | Method for preparing YSZ-LSM oxygen electrode powder of solid oxidate electrolytic cell | |
| CN107195938A (en) | A kind of simple SOFC preparation method | |
| CN110882707A (en) | CoP/Si hydrogen evolution catalytic material and preparation method thereof | |
| CN100391033C (en) | Lithium-ion film cell negative pole and preparing method | |
| CN107658145B (en) | A kind of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide and the preparation method and application thereof | |
| Xin et al. | Fabrication of dense YSZ electrolyte membranes by a modified dry-pressing using nanocrystalline powders | |
| Yang et al. | A novel preparation method for NiCo 2 O 4 electrodes stacked with hexagonal nanosheets for water electrolysis | |
| CN106299301A (en) | A kind of Li with excellent storage lithium performance3vO4the pattern of nano wire regulates and controls method mutually with thing | |
| CN103165903A (en) | Anti-carbon-deposition, high-performance and functionally-graded anode composite film of solid oxide fuel cells and preparation method thereof | |
| CN108417824A (en) | A kind of preparation method of high-performance lithium battery negative material carbon cladding lithium titanate | |
| CN108666589A (en) | There is one kind low thermal coefficient of expansion solid oxide fuel cell cobalt-based cathode material to prepare and its apply | |
| CN103831097A (en) | Nano-catalyst-lanthanum strontium manganese oxygen material, and preparation method and application of nano-catalyst-lanthanum strontium manganese oxygen material | |
| CN103367763B (en) | Method for preparing solid oxide fuel cell nanometer thin film cathode by magnetron sputtering method |
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 |