CN109216711B - Method for preparing solid oxide fuel cell by regulating and controlling lattice stress by using pulsed laser deposition technology - Google Patents

Method for preparing solid oxide fuel cell by regulating and controlling lattice stress by using pulsed laser deposition technology Download PDF

Info

Publication number
CN109216711B
CN109216711B CN201810836269.1A CN201810836269A CN109216711B CN 109216711 B CN109216711 B CN 109216711B CN 201810836269 A CN201810836269 A CN 201810836269A CN 109216711 B CN109216711 B CN 109216711B
Authority
CN
China
Prior art keywords
nno
ysz
fuel cell
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.)
Active
Application number
CN201810836269.1A
Other languages
Chinese (zh)
Other versions
CN109216711A (en
Inventor
陈燕
李菲
陈惠君
张亚鹏
刘江
刘美林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201810836269.1A priority Critical patent/CN109216711B/en
Publication of CN109216711A publication Critical patent/CN109216711A/en
Application granted granted Critical
Publication of CN109216711B publication Critical patent/CN109216711B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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 a method for preparing a solid oxide fuel cell by regulating and controlling lattice stress by using a pulse laser deposition technology; firstly, preparing an NNO target material, and then fixing the NNO target material on a target material support of a vacuum chamber of a pulse laser deposition instrument; fixing a single crystal substrate YSZ on a PLD sample holder, and heating to 590-610 ℃ under a vacuum condition; introducing pure oxygen, and stabilizing for 0.4-0.6 h under the oxygen pressure of 0.8-1.2 Pa; sputtering an NNO oxide of the PLD target, sequentially depositing metal vapor on a single crystal substrate YSZ along the normal direction of laser, and adjusting the number of laser pulses to control the thickness of the NNO oxide film to be 9-50 nm; and finally brushing the cathode slurry by a brushing method. By regulating and controlling the lattice stress, the performance of the prepared solid oxide fuel cell is greatly improved, and the stability is good; meanwhile, the method has the advantages of good safety, low cost, environmental protection, little pollution and the like.

Description

Method for preparing solid oxide fuel cell by regulating and controlling lattice stress by using pulsed laser deposition technology
Technical Field
The invention relates to a solid oxide fuel cell, in particular to a method for preparing the solid oxide fuel cell by regulating and controlling lattice stress by using a Pulsed Laser Deposition (PLD) technology.
Background
The increasing consumption of energy reflects the economic growth of a country. Over the past century, we have relied primarily on fossil fuels such as: petroleum, coal, natural gas, and the like. However, conventional fossil fuels are not renewable, have low conversion rates, cause serious energy waste, and generate a large amount of atmospheric pollutants and greenhouse gases, thereby causing various environmental and economic problems. In order to meet the serious challenges of the increasing exhaustion of the traditional fossil fuel and the serious environmental problems (greenhouse effect, haze and the like), research, development and utilization of new energy resources are urgent. Therefore, a plurality of energy conversion and storage devices are derived, and the solid oxide fuel cell is widely concerned by researchers due to the advantages of high energy conversion rate, wide fuel application range, less pollution and the like. For this reason, it is important to improve the performance of the solid oxide fuel cell.
Van baoan et al (preparation method overview of YSZ electrolyte film of solid oxide fuel cell, proceedings of process engineering, 2 months 2004, vol. 4, No. 1) discloses the preparation of electrolyte film by using pulsed laser deposition method, not involving the preparation of anode of solid oxide fuel cell. Particularly, the thickness of a YSZ electrolyte film obtained on a porous NiO/YSZ substrate by the technology is 1-2 mm. The technology reduces the thickness of an electrolyte through a PLD technology so as to improve the performance of the solid oxide fuel cell, but the method needs hours to reach an electrolyte film with the thickness of 1-2 mm, the film forming quality is poor, the production cost is high, the method is not beneficial to large-scale industrialization, and the stability of the solid oxide fuel cell needs to be improved.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a method for preparing a solid oxide fuel cell by regulating and controlling lattice stress by using a pulsed laser deposition technology, which has the advantages of short film growth period, very good cell stability and improved cell performance
The invention selects single crystal YSZ substrate material and Nd2NiO4+The selection of anode materials can prepare the anode materials of the solid oxide fuel cells in different stress states by growing a film with the nanometer level of 9-50nm through PLD and controlling the lattice stress. The method improves the performance of the solid oxide fuel cell by regulating and controlling the lattice stress, prepares the solid oxide fuel cell with films in different stress states by a pulse laser deposition technology, tests the performance of the cell show that the method is more controllable, the growth period of the film is short, and the performance of the solid oxide fuel cell is greatly improvedCan be used.
The physical deposition method adopted by the invention, namely the pulse laser deposition method, strikes the target material through the pulse laser, deposits the material with the same stoichiometric ratio with the target material on the single crystal substrate according to the preferred crystal orientation, and can accurately regulate and control the thickness of the electrode and the lattice stress by controlling the frequency, the pulse number and the like of the laser.
The purpose of the invention is realized by the following technical scheme:
the method for preparing the solid oxide fuel cell by regulating and controlling the lattice stress by utilizing the pulsed laser deposition technology is characterized by comprising the following steps of:
1) preparing a target material of a pulse laser deposition instrument: preparing NNO target material, wherein the chemical formula of the NNO oxide is Nd2NiO4+；
2) Growing anode materials by a pulse laser deposition instrument on electrolyte: fixing the NNO target material on a target material support of a vacuum chamber of the pulse laser deposition instrument; fixing a single crystal substrate YSZ on a PLD sample holder, and heating to 590-610 ℃ under a vacuum condition; introducing pure oxygen, and stabilizing for 0.4-0.6 h under the oxygen pressure of 0.8-1.2 Pa; sputtering a PLD target material NNO oxide, sequentially depositing metal steam on a single crystal substrate YSZ along the normal direction of laser, adjusting the number of laser pulses to control the thickness of the NNO oxide film to be 9-50nm, realizing that the lattice constants of the single crystal substrate YSZ and a grown film material NNO are not matched, finishing sputtering when the lattice stress is-6% of compressive stress to 5% of tensile stress, and increasing the oxygen pressure drop to room temperature;
3) brushing cathode slurry by a brushing method: and coating the Ag-YSZ material on the back of the film electrode to be used as a cathode material, and controlling the thickness of the cathode material to be 20-30 nm.
To further achieve the object of the present invention, preferably, the sputtering of the NNO oxide on the PLD target is performed at frequencies of 5Hz and 10Hz respectively under the constant voltage mode with the laser energy of 290-310 mJ.
Preferably, the single crystal substrate YSZ is selected from one of three different crystal orientations of 100, 110 and 111, and has a thickness of 500 um.
Preferably, the temperature of the increased oxygen pressure drop to room temperature is decreased from 590-610 ℃ to room temperature, the temperature decrease speed is 5-7 ℃/min, and the oxygen pressure in the temperature decrease process is controlled to be 190-210 Pa.
Preferably, the NNO target is prepared by synthesizing powder by a combustion method, pressing the powder into a target by a tablet press and sintering at high temperature.
Preferably, the synthesis of the powder from the NNO target material by a combustion method is performed according to the chemical formula Nd2NiO4+Respectively weighing Nd nitrate and Ni nitrate, adding glycine and deionized water, and uniformly stirring; heating to 190-; then placing the mixture into a muffle furnace, sintering the mixture for 5 to 7 hours at the temperature of 1000 ℃ and 1100 ℃ in the air atmosphere to obtain Nd2NiO4+Powder;
preferably, the powder is pressed into the target material by a tablet press, and Nd is formed2NiO4+Grinding the powder, adding PVB alcohol solution, grinding again and tabletting to obtain an NNO tablet;
the high-temperature sintering is to sinter the NNO sheet for 5-6 h at 1250-1300 ℃ in the air atmosphere to obtain the NNO target material.
Preferably, the NNO target has a thickness of 21-25 mm.
Preferably, the Ag-YSZ material is prepared by mixing silver paste and YSZ powder according to a mass ratio of 7:3, adding a binder, and performing ball milling to obtain a porous Ag-YSZ material; the brushing times are more than 2.
Preferably, the temperature rising speed of rising to 590-610 ℃ under the vacuum condition is 8-10 ℃/min.
The Ag-YSZ material is coated on the back of the film electrode to be used as a counter electrode.
Among various film preparation technologies, the pulsed laser deposition technology is simple and has many advantages, and can carry out congruent film coating on a composite material with complex chemical components, so that the stability of the stoichiometric ratio after film coating is easily ensured; the reaction is rapid and the growth is fast. The film with the thickness of about 1 mu m can be obtained in one hour under normal conditions; the multilayer film and the heterogeneous film are easy to manufacture, and particularly the heterojunction of the multi-component oxide can be realized only by simply changing targets; the high vacuum environment has little pollution to the film and can be made into a high-purity film. The invention utilizes the pulse laser deposition technology to grow the required film material and control the stress to prepare the film model system for improving the battery performance.
The present invention introduces lattice stress through the mismatch of lattice constants between materials.
The substrate materials of different crystal orientations differ in that the substrate crystal orientation differs, and the NNO film grown on the substrate in other crystal orientations also differs, and the stress on the YSZ of different crystal orientations differs. The introduction of lattice stress in the present invention is introduced by selecting the lattice constant mismatch of the single crystal YSZ substrate and the grown thin film material NNO. If a thin film material is grown on a substrate and the contact between the materials and the interface is between the materials, the lattice constant mismatch between the two materials is large or small, tensile or compressive stress is generated between the thin film and the substrate after the thin film is grown on the substrate, but if the grown thin film is very thick, such as micron level, no lattice stress exists between the thin film and the substrate, the stress is released, and the very small lattice stress is not considered any more. The lattice constant of the monocrystalline substrate YSZ selected according to the invention is
Figure BDA0001744558850000031
The NNO film has a lattice constant of
Figure BDA0001744558850000032
The PLD is used to grow film and the laser pulse number is regulated to control the thickness of the film in 8-50 nm, and the data of high resolution XRD and calculation show that lattice stress is obviously generated. Therefore, the difference in lattice constant causes stress to be formed between the interfaces of the thin films, and the stress affects the characteristics of the material, thereby affecting the performance of the battery.
The invention finds that the stress has great improvement on the stability of the solid oxide fuel cell material. It is preferable to select YSZ (0.8% Y) of three different crystal orientations (100), (110) and (111) during the preparation of the film2O3Doped ZrO2) base material by adjusting the number of laser pulses(laser energy 300mj, laser frequency 5HZ, 10HZ) controlling the thickness of the film between 9nm and 50nm, and regulating the lattice stress when the lattice stress is between-6% (compressive stress) and 5% (tensile stress).
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention successfully regulates and controls the lattice stress through the pulsed laser deposition technology to improve the performance of the solid oxide fuel cell. As can be calculated from the results of high resolution XRD by growing a thin film of NNO on a YSZ (100) substrate of about 10nm, the lattice constant of NNO is
Figure BDA0001744558850000041
And the lattice constant of the unstressed NNO is
Figure BDA0001744558850000042
Thus, after growing a NNO film on a YSZ (110) substrate, the stress state is 4.05% tensile stress (4.075-3.854)/3.854); from the drawings of the examples, it can be seen that the surface specific resistance of the battery at 600 degrees is 34.04. omega. cm2And the area specific resistance of the alloy still keeps 34 omega cm in 60h test through a long-time stability test2On the left and right, the stability of the battery is very good, and the improvement of the battery performance shows that the tensile stress introduced by the pld technology has a remarkable influence on the characteristics of the material.
(2) The use of single crystal YSZ as a base material facilitates commercial availability of base materials of different crystal orientations, such as (100), (110), (111), and YSZ has excellent oxygen ion conductivity, thus making it useful as an electrolyte material for solid oxide fuel cells.
(3) The invention utilizes the pulse laser deposition technology to prepare the film model system, and the grown film is a high-purity film with excellent quality.
(4) The method has the characteristics of controllable parameters, simple model, high repeatability and the like, and is suitable for the design concept of electrode materials of other electrochemical energy devices.
Drawings
FIG. 1 shows examples 1 and 2,Nd in 32NiO4+Powder and X-ray diffraction patterns of the target.
FIG. 2 is the result of X-ray reflection of the NNO/YSZ (100) film of example 1.
FIG. 3 is a scanning electron micrograph of the NNO/YSZ (100) field emission of example 1.
FIG. 4 is a high resolution XRD pattern of the NNO/YSZ (100) film of example 1.
FIG. 5 is the stability test results for the solid oxide fuel cell assembled with the NNO/YSZ (100) thin film cell of example 1.
FIG. 6 is the result of X-ray reflection of the NNO/YSZ (110) film of example 2.
FIG. 7 is a scanning electron micrograph of the NNO/YSZ (110) field emission of example 2.
FIG. 8 is a high resolution XRD pattern of the NNO/YSZ (110) thin film of example 2.
FIG. 9 is a scanning electron micrograph of the NNO/YSZ (111) field emission of example 3.
FIG. 10 is a high resolution XRD pattern of the NNO/YSZ (111) thin film of example 3.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following drawings and examples, but the present invention is not limited thereto.
Example 1
(1) Target material Nd for pulsed laser deposition technology2NiO4+The preparation of (1): first Nd (NO)3)3·6H2O (Meclin, analytical pure) and Ni (NO)3)26H2O (Michelin, analytical purity) according to Nd2NiO4+The stoichiometric ratio in (1) is weighed, and then the corresponding Nd is weighed2NiO4+Citric acid (C) with half of the molar amount of the middle cation6H8O7·H2O,) is poured into a 1000ml beaker, 100ml of deionized water is added, the beaker is placed on a magnetic stirrer, the mixed solution is stirred to be in a molten state under the temperature of 190 ℃ and 200 ℃, the temperature is adjusted to 490 ℃ and 510 ℃, then the mixed solution is heated until spontaneous combustion, the generated powder is placed into a crucible, and in a high temperature furnace, the temperature rise rate is 3 ℃/minCalcining in air at 1050 ℃ for 6h, and naturally cooling to room temperature to obtain black powder. The powder was subjected to X-ray diffraction (XRD) characterization, and the obtained XRD spectrum is shown in FIG. 1, and completely corresponds to a standard card (89-0131), and it was confirmed that the black powder was Nd2NiO4+There is no impurity phase. 5g of the synthesized powder was charged into a 100ml ball mill jar, and 36ml of anhydrous ethanol (CH) was added3CH2OH, Fuyu fine chemical industry Co., Ltd, Tianjin), ball milling for 10h, placing under an infrared lamp for drying, pouring the obtained powder into an agate mortar, adding PVB-ethanol solution, wherein PVB is a binder and has the mass concentration of 6%. With PVB added in an amount of Nd required for adhesion2NiO4+3% of the mass of the powder, grinding until the solution is evaporated to a dry fine-grained powder. Pressing the powder into a target material under 10Mpa by using a tabletting grinding tool with the diameter of 25mm, and calcining the pressed target material in air at 1300 ℃ for 6 h. The XRD pattern of the target is shown in FIG. 1, and the test equipment used is Bruker D8 Advance.
(2) Growing a film: the NNO target was polished using sandpaper to remove the surface (approximately 0.1mm) powder. Respectively fixed to vacuum chambers of a pulse laser deposition device (PLD) (Shenyang Zhongke device, D13-046). Subjecting a single crystal substrate YSZ (100) (Y)2O3Doped ZrO2) Fixed on a PLD sample holder under vacuum (10)‐5Pa) was raised to 610 ℃ at 10 ℃/min. Pure oxygen is introduced, and the mixture is stabilized for 0.6h under the oxygen pressure of 1.2 Pa. The metal vapor is deposited on the single crystal substrate along the normal direction of the laser in sequence to generate the electrode material which is consistent with the stoichiometric ratio of the target material, and the thickness of the electrode material can be adjusted by the pulse number of the laser and can reach the nanometer level. 300mJ laser energy is respectively sputtered for 120s and 100s at the frequencies of 5Hz and 10Hz in a voltage stabilizing mode to prepare the NNO oxide film, the thickness of the NNO oxide film is 9.44nm, and the purpose of adjusting the thickness through the pulse number is achieved. The results of the X-ray reflection of the film are shown in figure 2. The thickness of the film material can be directly obtained through the fitting of software according to the test result of X-ray reflection, and the thickness of the NNO film is 9.44nm according to the fitting result. After the sputtering is finished, the oxygen pressure is increased to 200Pa, and the temperature is reduced to the room temperature at the speed of 7 ℃/min.
Fig. 3 is a scanning electron microscope image (SEM) of the NNO film prepared in this example 1 grown on a YSZ (100) substrate at a magnification of 70000 times, from which it can be seen that no particles and other defects appear on the surface of the material, and it can be seen that this example obtained a film with excellent surface flatness quality using PLD technique, and that excellent film quality is critical for the proper operation of the solid oxide fuel cell. The test equipment used was a field emission scanning electron microscope.
FIG. 4 is a high resolution XRD pattern of the NNO film prepared in example 1 grown on a YSZ (100) substrate having a lattice constant of
Figure BDA0001744558850000065
From the results of high resolution XRD it can be calculated: (the specific calculation procedure is as follows)
1) From the results of high resolution XRD, it can be read that 2 θ is 31.54 °
2) According to the formula Bragg formula 2dsin theta-n lambda
Figure BDA0001744558850000061
3) According to formula d2＝a2/2
Is calculated to know
Figure BDA0001744558850000062
Thus the lattice constant of NNO is
Figure BDA0001744558850000063
And the lattice constant of the unstressed NNO is
Figure BDA0001744558850000064
Thus, after the NNO film is grown on a YSZ (100) substrate, the stress state is 4.05% tensile stress (4.010-3.854)/3.854).
(3) Preparing a battery: PVB and terpineol in a mass ratio of 1:9 are respectively weighed and placed in a beaker, and are dissolved in an oven at 60 ℃ for 24 hours to serve as binders for standby. Weighing 4.38g of silver paste (DAD-87, 80% of Ag content in research institute of synthetic resin in Shanghai) and 1.5g of YSZ (after ball milling) according to the mass ratio of Ag to YSZ of 7:3, then weighing 5g of the binder, adding the binder into an agate mortar, and grinding for 4 hours to obtain the uniformly dispersed Ag-YSZ composite electrode slurry. And uniformly coating the Ag-YSZ electrode slurry on the back surface of the film as a counter electrode by using a water powder tool pen, wherein the area of the counter electrode is about 0.8 square centimeter, and drying in a high-temperature oven at 140 ℃.
And covering a hollow mask on the surface of the film, and sputtering the gold target for 210 seconds by using a sputtering device of a clinical instrument under the conditions of 6Pa of air pressure and 5mA of sputtering current. The surface of the film is formed with comb-shaped gold as an electron collector, and the area of the gold is 0.24 square centimeter. Two short silver wires are taken and fixed on the center of the Ag-YSZ electrode and the gold on the surface of the film electrode respectively through silver paste.
And then sealing the prepared battery at one end of a glass tube with the diameter of 13mm by using silver paste, fixing two double-hole corundum tubes at two sides of the glass tube, and respectively introducing a silver wire into each hole. Two silver wires of one double-hole corundum tube are connected with the anode on one side of NNO, and two silver wires of the other double-hole corundum tube are connected with the Ag-YSZ cathode.
(4) And (3) performance testing: putting the assembled thin-film battery into a heating constant-temperature area of a tubular electric furnace at H2Raised to 600 ℃ and reduced at 600 ℃ for 2H before being added to H2The battery is tested for electrochemical impedance by using an I-vium electrochemical workstation. Connecting the NNO electrode with a black wire and a green wire of an electrochemical workstation, connecting the Ag-YSZ with a red wire and a white wire, setting the amplitude of the instrument to be 10mV and the frequency to be 0.1 Hz-105Hz, and data processing is carried out by Origin software, and an area specific resistance spectrogram of the battery is obtained and is shown in figure 4. The specific surface resistance of the impedance spectrogram cell is 34.04 omega cm2 at 600 ℃, and through a long-time stability test, the specific surface resistance of the impedance spectrogram cell is still maintained to be about 34 omega cm2 in a 60h test as shown in FIG. 5, which shows that the cell has very good stability, therefore, the embodiment adopts a pulse laser bottoming technology, 300mJ laser energy is respectively sputtered to grow 9.44nmNNO films on a YSZ (100) substrate at frequencies of 5Hz and 10Hz in a voltage stabilizing mode for 120s and 100s respectively, the tensile stress is 4.05 percent in a stress state, and the cell is assembled to be tested, and the specific surface resistance of the cell is maintained to be 34 omega cm in a 60h stability test2And the battery has very good stability. The method has technical guidance significance for preparing the solid oxide fuel cell with excellent stability, and is beneficial to promoting the commercialization of the solid oxide fuel cell.
Example 2
(1) Target material Nd for pulsed laser deposition technology2NiO4+First Nd (NO)3)3·6H2O (Meclin, analytical pure) and Ni (NO)3)26H2O (Michelin, analytical purity) according to Nd2NiO4+The stoichiometric ratio in the process is sequentially weighed, and then the corresponding Nd is weighed2NiO4+Citric acid (C) with half of the molar amount of the middle cation6H8O7·H2O,) is poured into a 1000ml beaker, 100ml deionized water is added, the beaker is placed on a magnetic stirrer, the mixed solution is stirred to be in a molten state when the temperature is increased to 190-200 ℃, the temperature is adjusted to 490-510 ℃, then the mixed solution is heated until spontaneous combustion, the generated powder is placed into a crucible, the mixed solution is calcined in air at 1050 ℃ for 6h at the heating rate of 3 ℃/min in a high-temperature furnace, and the mixed solution is naturally cooled to room temperature, so that black powder is obtained. The powder was characterized by X-ray diffraction (XRD), and the obtained XRD spectrum (see FIG. 1) corresponded well to that of standard card (89-0131), thus proving that the black powder was Nd2NiO4+There is no impurity phase. 5g of the synthesized powder is put into a 100ml ball milling tank, 36ml of absolute ethyl alcohol (analytical purity, Fuyu fine chemical Co., Ltd., Tianjin) is added, ball milling is carried out for 10 hours, then the ball milling tank is placed under an infrared lamp for drying, the obtained powder is poured into an agate mortar, and PVB-ethanol solution is added, wherein PVB is an adhesive, and the mass concentration is 6%. The PVB is added in the amount of Nd required to be bonded2 NiO 4+3% of the mass of the powder, grinding until the solution is evaporated to a dry fine-grained powder. Pressing the powder into a target material under 10Mpa by using a tabletting grinding tool with the diameter of 25mm, and calcining the pressed target material in air at 1300 ℃ for 6 h. The XRD pattern of the target is shown in FIG. 1, and the test equipment used is Bruker D8 Advance.
(2) Growing a film: the NNO target was polished using sandpaper to remove the surface (approximately 0.1mm) powder. Respectively fixed on the pulse laser sinkDeposition apparatus (PLD) (Shenyang Zhongke apparatus, D13-046) a target holder of a vacuum chamber. Subjecting a single crystal substrate YSZ (110) (Y)2O3Doped ZrO2) Fixed on a PLD sample holder under vacuum (10)‐5Pa) was raised to 610 ℃ at 10 ℃/min. Pure oxygen is introduced, and the mixture is stabilized for 0.6h under the oxygen pressure of 1.2 Pa. The metal vapor is deposited on the single crystal substrate along the normal direction of the laser in sequence to generate the electrode material which is consistent with the stoichiometric ratio of the target material, and the thickness of the electrode material can be adjusted by the pulse number of the laser and can reach the nanometer level. 300mJ laser energy is respectively sputtered for 120s and 100s at the frequencies of 5Hz and 10Hz in a voltage stabilizing mode to prepare the NNO oxide film, the thickness of the NNO oxide film is 9nm, and the purpose of adjusting the thickness through the pulse number is achieved. The results of the X-ray reflection of the film are shown in figure 6. The thickness of the film material can be directly obtained through the fitting of software according to the test result of X-ray reflection, and the thickness of the NNO film is 9nm according to the fitting result. After the sputtering is finished, the oxygen pressure is increased to 200Pa, and the temperature is reduced to the room temperature at the speed of 7 ℃/min.
Fig. 7 is a scanning electron microscope image (SEM) of the NNO film prepared in example 2 grown on a YSZ (100) substrate at a magnification of 70000 times, from which it can be seen that no particles and other defects appear on the surface of the material, and we can see that we obtained a film with excellent surface flatness quality using PLD technique, and that excellent film quality is critical for the proper operation of the solid oxide fuel cell. The test equipment used was a field emission scanning electron microscope.
FIG. 8 is a high resolution XRD pattern of the NNO film prepared in example 1 grown on a YSZ (100) substrate having a lattice constant of
Figure BDA0001744558850000081
From the results of high resolution XRD, it can be calculated that the lattice constant of NNO is
Figure BDA0001744558850000082
And the lattice constant of the unstressed NNO is
Figure BDA0001744558850000083
Thus growing on a YSZ (100) substrateThe stress state after the NNO film was 5.73% tensile stress (4.075-3.854)/3.854).
(3) Preparing a battery: PVB and terpineol in a mass ratio of 1:9 are respectively weighed and placed in a beaker, and are dissolved in an oven at 60 ℃ for 24 hours to serve as binders for standby. Weighing 4.38g of silver paste (DAD-87, 80% of Ag content in research institute of synthetic resin in Shanghai) and 1.5g of YSZ (after ball milling) according to the mass ratio of Ag to YSZ of 7:3, then weighing 5g of the binder, adding the binder into an agate mortar, and grinding for 4 hours to obtain the uniformly dispersed Ag-YSZ composite electrode slurry. And uniformly coating the Ag-YSZ electrode slurry on the back surface of the film as a counter electrode by using a water powder tool pen, wherein the area of the counter electrode is about 0.8 square centimeter, and drying in a high-temperature oven at 140 ℃.
And covering a hollow mask on the surface of the film, and sputtering the gold target for 210 seconds by using a sputtering device of a clinical instrument under the conditions of 6Pa of air pressure and 5mA of sputtering current. The surface of the film is formed with comb-shaped gold as an electron collector, and the area of the gold is 0.24 square centimeter. Two short silver wires are taken and fixed on the center of the Ag-YSZ electrode and the gold on the surface of the film electrode respectively through silver paste.
And then sealing the prepared battery at one end of a glass tube with the diameter of 13mm by using silver paste, fixing two double-hole corundum tubes at two sides of the glass tube, and respectively introducing a silver wire into each hole. Two silver wires of one double-hole corundum tube are connected with the anode on one side of NNO, and two silver wires of the other double-hole corundum tube are connected with the Ag-YSZ cathode.
It can be seen that in this embodiment, an NNO thin film with a thickness of 9nm is prepared on a YSZ (110) substrate by adjusting and controlling lattice stress through a pulsed laser deposition technique, and characterization tests show that the lattice stress of a thin film model is 5.73% of tensile stress, and the thin film model is assembled into a cell to prepare a solid oxide fuel cell, which has great significance for improving the performance of the solid oxide fuel cell.
Example 3
(1) Target material Nd for pulsed laser deposition technology2NiO4+First Nd (NO)3)3·6H2O (Meclin, analytical pure) and Ni (NO)3)26H2O (Mecany,analytically pure) according to Nd2NiO4+The stoichiometric ratio in the process is sequentially weighed, and then the corresponding Nd is weighed2NiO4+Citric acid (C) with half of the molar amount of the middle cation6H8O7·H2O,) is poured into a 1000ml beaker, 100ml of deionized water is added, the beaker is placed on a magnetic stirrer, the mixed solution is stirred to be in a molten state when the temperature is increased to 190-200 ℃, the temperature is adjusted to 490-510 ℃, then the mixed solution is heated until spontaneous combustion, the generated powder is placed into a crucible, the mixed solution is calcined in air at 1050 ℃ for 6h at the heating rate of 5 ℃/min in a high-temperature furnace, and the mixed solution is naturally cooled to room temperature, so that black powder is obtained. The powder is characterized by X-ray diffraction (XRD), the obtained XRD spectrum (figure 1) completely corresponds to a standard card (89-0131), and the black powder is proved to be Nd2NiO4+There is no impurity phase. 5g of the synthesized powder was charged into a 100ml ball mill jar, and 36ml of anhydrous ethanol (CH) was added3CH2OH, Fuyu fine chemical industry Co., Ltd, Tianjin), ball milling for 10h, placing under an infrared lamp for drying, pouring the obtained powder into an agate mortar, adding PVB-ethanol solution, wherein PVB is a binder and has the mass concentration of 6%. With PVB added in an amount of Nd required for adhesion2NiO4+3% of the mass of the powder, grinding until the solution is evaporated to a dry fine-grained powder. Pressing the powder into a target material under 10Mpa by using a tabletting grinding tool with the diameter of 25mm, and calcining the pressed target material in air at 1300 ℃ for 6 h. The XRD pattern of the target is shown in FIG. 1, and the test equipment used is Bruker D8 Advance.
(2) Growing a film: the NNO target was polished using sandpaper to remove the surface (approximately 0.1mm) powder. Respectively fixed to vacuum chambers of a pulse laser deposition device (PLD) (Shenyang Zhongke device, D13-046). Subjecting a single crystal substrate YSZ (111) (Y)2O3Doped ZrO2) Fixed on a PLD sample holder under vacuum (10)‐5Pa) was raised to 610 ℃ at 10 ℃/min. Pure oxygen is introduced, and the mixture is stabilized for 0.6h under the oxygen pressure of 1.2 Pa. The metal vapor is deposited on the single crystal substrate along the normal direction of the laser to generate the electrode material with the stoichiometric ratio consistent with that of the target material, and the thickness of the electrode material can be adjusted by the pulse number of the laser to reach the nanometer quantityAnd (4) stages. 300mJ laser energy is respectively sputtered for 600s and 500s at the frequencies of 5Hz and 10Hz in a voltage stabilizing mode to prepare the NNO oxide film, the thickness of the NNO oxide film is 50nm, and the purpose of adjusting the thickness through the pulse number is achieved. After the sputtering is finished, the oxygen pressure is increased to 200Pa, and the temperature is reduced to the room temperature at the speed of 7 ℃/min.
Fig. 9 is a scanning electron microscope image (SEM) of the NNO film prepared in this example 3 grown on a YSZ (111) substrate at a magnification of 70000 times, from which it can be seen that no particles and other defects appear on the surface of the material, and we can see that we obtained a film with excellent surface flatness quality using PLD technique, and that excellent film quality is critical for the proper operation of the solid oxide fuel cell. The test equipment used was a field emission scanning electron microscope.
FIG. 10 is a high resolution XRD pattern of the NNO film prepared in example 3 grown on a YSZ (100) substrate having a lattice constant of
Figure BDA0001744558850000091
From the results of high resolution XRD, it can be calculated that the lattice constant of NNO is
Figure BDA0001744558850000092
And the lattice constant of the unstressed NNO is
Figure BDA0001744558850000093
Thus, after the NNO film was grown on a YSZ (100) substrate, the stress state was 3.46% compressive stress (3.854-3.721)/3.854).
(3) Preparing a battery: PVB and terpineol in a mass ratio of 1:9 are respectively weighed and placed in a beaker, and are dissolved in an oven at 60 ℃ for 24 hours to serve as binders for standby. Weighing 4.38g of silver paste (DAD-87, 80% of Ag content in research institute of synthetic resin in Shanghai) and 1.5g of YSZ (after ball milling) according to the mass ratio of Ag to YSZ of 7:3, then weighing 5g of the binder, adding the binder into an agate mortar, and grinding for 4 hours to obtain the uniformly dispersed Ag-YSZ composite electrode slurry. And uniformly coating the Ag-YSZ electrode slurry on the back surface of the film as a counter electrode by using a water powder tool pen, wherein the area of the counter electrode is about 0.8 square centimeter, and drying in a high-temperature oven at 140 ℃.
And covering a hollow mask on the surface of the film, and sputtering the gold target for 210 seconds by using a sputtering device of a clinical instrument under the conditions of 6Pa of air pressure and 5mA of sputtering current. The surface of the film is formed with comb-shaped gold as an electron collector, and the area of the gold is 0.24 square centimeter. Two short silver wires are taken and fixed on the center of the Ag-YSZ electrode and the gold on the surface of the film electrode respectively through silver paste.
And then sealing the prepared battery at one end of a glass tube with the diameter of 13mm by using silver paste, fixing two double-hole corundum tubes at two sides of the glass tube, and respectively introducing a silver wire into each hole. Two silver wires of one double-hole corundum tube are connected with the anode on one side of NNO, and two silver wires of the other double-hole corundum tube are connected with the Ag-YSZ cathode.
In the embodiment, a 50 nm-thick NNO film is prepared on a YSZ (111) substrate by regulating and controlling lattice stress through a pulse laser deposition technology, and a characterization test shows that the lattice stress of a film model is 3.46% of tensile stress, and the film model is assembled into a cell to prepare the solid oxide fuel cell, which has great significance for improving the performance of the solid oxide fuel cell.
The above embodiments are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Variations or modifications in different forms may occur to those skilled in the art upon reading the foregoing description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention are included in the protection scope of the claims of the present invention.

Claims (9)

1. The method for preparing the solid oxide fuel cell by regulating and controlling the lattice stress by utilizing the pulsed laser deposition technology is characterized by comprising the following steps of:
1) preparing a target material of a pulse laser deposition instrument: preparing NNO target material, wherein the chemical formula of the NNO oxide is Nd2NiO4+；
2) Growing anode materials by a pulse laser deposition instrument on electrolyte: fixing the NNO target material on a target material support of a vacuum chamber of the pulse laser deposition instrument; fixing a single crystal substrate YSZ on a PLD sample holder, and heating to 590-610 ℃ under a vacuum condition; introducing pure oxygen, and stabilizing for 0.4-0.6 h under the oxygen pressure of 0.8-1.2 Pa; sputtering a PLD target NNO oxide, sequentially depositing metal steam on a single crystal substrate YSZ along the normal direction of laser, adjusting the number of laser pulses to control the thickness of the NNO oxide film to be 9-50nm, realizing that the lattice constant of the single crystal substrate YSZ is not matched with that of a grown film material NNO, finishing sputtering when the lattice stress is-3.46% of compressive stress to 5.73% of tensile stress, and increasing the oxygen pressure drop to room temperature; the temperature of the oxygen pressure is increased to the room temperature from 590-610 ℃, the temperature reduction speed is 5-7 ℃/min, and the oxygen pressure in the temperature reduction process is controlled to be 190-210 Pa;
3) brushing cathode slurry by a brushing method: and coating the Ag-YSZ material on the back of the film electrode to be used as a cathode material, and controlling the thickness of the cathode material to be 20-30 nm.
2. The method as claimed in claim 1, wherein the sputtering of the PLD target NNO oxide is performed at 5Hz and 10Hz respectively in a voltage-stabilized mode with 290-310mJ laser energy.
3. The method for preparing the solid oxide fuel cell by regulating and controlling the lattice stress by using the pulsed laser deposition technology as claimed in claim 1, wherein the single crystal substrate YSZ is one of three different crystal orientations of 100, 110 and 111, and has a thickness of 500 μm.
4. The method for preparing the solid oxide fuel cell by using the pulsed laser deposition technology to regulate and control the lattice stress as claimed in claim 1, wherein the NNO target is prepared by synthesizing powder by a combustion method, pressing the powder into the target by using a tablet press and sintering the target at a high temperature.
5. The method of claim 4The method for preparing the solid oxide fuel cell by regulating and controlling the lattice stress by utilizing the pulse laser deposition technology is characterized in that the powder synthesized by the NNO target material through the combustion method is the powder according to the chemical formula Nd2NiO4+Respectively weighing Nd nitrate and Ni nitrate, adding glycine and deionized water, and uniformly stirring; heating to 190-; then placing the mixture into a muffle furnace, sintering the mixture for 5 to 7 hours at the temperature of 1000 ℃ and 1100 ℃ in the air atmosphere to obtain Nd2NiO4+And (3) powder.
6. The method for preparing a solid oxide fuel cell by using a pulsed laser deposition technology to regulate and control lattice stress as claimed in claim 4, wherein the step of pressing the powder into the target material by using a tablet press is to use Nd2NiO4+Grinding the powder, adding PVB alcohol solution, grinding again and tabletting to obtain an NNO tablet;
the high-temperature sintering is to sinter the NNO sheet for 5-6 h at 1250-1300 ℃ in the air atmosphere to obtain the NNO target material.
7. The method for manufacturing a solid oxide fuel cell by using the pulsed laser deposition technology to regulate the lattice stress as recited in claim 1, wherein the NNO target has a thickness of 21-25 mm.
8. The method for preparing the solid oxide fuel cell by utilizing the pulse laser deposition technology to regulate and control the lattice stress is characterized in that the Ag-YSZ material is prepared by mixing silver paste and YSZ powder according to the mass ratio of 7:3, adding a binder and carrying out ball milling on the mixture to obtain a porous Ag-YSZ material; the brushing times are more than 2.
9. The method for preparing a solid oxide fuel cell using a pulsed laser deposition technique to control lattice stress as claimed in claim 1, wherein the temperature-raising rate of the temperature-raising to 590-610 ℃ under vacuum is 8-10 ℃/min.
CN201810836269.1A 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 Active CN109216711B (en)

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 CN109216711A (en) 2019-01-15
CN109216711B true 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)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN110804761B (en) * 2019-12-09 2020-11-27 湘潭大学 Preparation method of different-orientation single-variant yttria-stabilized zirconia epitaxial film

Citations (2)

* Cited by examiner, † Cited by third party
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 cell 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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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 cell 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)

* Cited by examiner, † Cited by third party
Title
"Anisotropic catalytic activity of the orientation controlled Nd2NiO4 + δ/YSZ hetero-epitaxial system for SOFC cathode";Atsuo Yamada,et al.;《Electrochemistry Communications》;20101020;第12卷(第12期);第1690-1693页 *
"Ruddlesden-Popper-Type Epitaxial Film as OxygenElectrode for Solid-Oxide Fuel Cells";Atsuo Yamada,et al.;《Advanced materials》;20081007;第20卷(第21期);第4124-4128页 *

Also Published As

Publication number Publication date
CN109216711A (en) 2019-01-15

Similar Documents

Publication Publication Date Title
CN111477881B (en) NiFe alloy nanoparticle coated Pr0.8Sr1.2(FeNi)O4-δMaterial and method for producing the same
CN109216711B (en) Method for preparing solid oxide fuel cell by regulating and controlling lattice stress by using pulsed laser deposition technology
CN111430734B (en) (Pr0.5Sr0.5)xFe1-yRuyO3-δPerovskite material and preparation method and application thereof
CN108390071B (en) Method for modifying surface of cathode of solid oxide fuel cell
Wang et al. Desirable performance of intermediate-temperature solid oxide fuel cell with an anode-supported La0. 9Sr0. 1Ga0. 8Mg0. 2O3− δ electrolyte membrane
CN111883789A (en) Electrode material of solid oxide fuel cell and preparation method and application thereof
CN108242554B (en) Barium cerate-based electrolyte material and preparation method and application thereof
CN101307461B (en) Method for preparing YSZ-LSM oxygen electrode powder of solid oxidate electrolytic cell
CN103224394A (en) Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof
CN112408490B (en) Hydrothermal synthesis of Ba doped Sr2Fe1.5Mo0.5O6Method for preparing double perovskite nano material
CN113745548A (en) High-entropy ceramic material based on spinel structure and preparation method and application thereof
CN113745540A (en) Direct alcohol fuel cell anode reforming layer and preparation method and application thereof
CN111908512A (en) O-site halogen element doped perovskite oxide and application thereof in symmetric battery
CN113258086B (en) Three-phase conductor proton conductor composite cathode material and preparation method thereof
CN115101761B (en) Proton ceramic fuel cell cathode material and preparation method and application thereof
CN110890557A (en) Perovskite type catalyst for oxygen reduction reaction, preparation method and application
CN114657579A (en) Binary alloy nanoparticle modified solid oxide electrolytic cell working electrode and preparation method and application thereof
CN114635150A (en) Novel solid oxide electrolytic cell oxygen electrode and preparation method thereof
CN108123156B (en) Preparation method of composite membrane electrode of fuel cell
Rabo et al. Fabrication of Solid Oxide Electrolysis Single Cell Using NiO-YSZ/YSZ/LSM-YSZ via Drop-Coating Method
CN100534950C (en) Method for producing LaGaO* group solid electrolyte target material
CN115745008B (en) Bismuth ferrite doped perovskite material and preparation method and application thereof
CN115180937B (en) Gadolinium and copper co-doped barium ferrite perovskite structure anode material and preparation method thereof
CN117855499B (en) Solid oxide fuel cell anode material and preparation method and application thereof
CN114920302B (en) Mesoporous multilayer cake-shaped bimetallic oxygen evolution electrocatalyst and preparation method and application thereof

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