CN102005579B - Method for preparing LSM (Lanthanum Strontium Manganate) cathode of solid oxide fuel cell - Google Patents
Method for preparing LSM (Lanthanum Strontium Manganate) cathode of solid oxide fuel cell Download PDFInfo
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- CN102005579B CN102005579B CN201010515252XA CN201010515252A CN102005579B CN 102005579 B CN102005579 B CN 102005579B CN 201010515252X A CN201010515252X A CN 201010515252XA CN 201010515252 A CN201010515252 A CN 201010515252A CN 102005579 B CN102005579 B CN 102005579B
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- oxide fuel
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- 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
Abstract
The invention belongs to the technical field of preparation of solid oxide fuel cells, and in particular relates to a method for preparing an LSM (Lanthanum Strontium Manganate) cathode of the solid oxide fuel cell. The method of the invention is used for preparing the cathode of the solid oxide fuel cell by using the electron beam physical vapor deposition technology. Through establishing reasonable technical parameters, a La1-xSrxMnO3 cathode material is deposited on traditional YSZ (Yttria Stabilized Zirconia) electrolyte so that the cell can become the cell in the LSM-YSZ-Ni-YSZ structure, in addition, the proper thickness can be selected according to the concrete requirements, and coating layers are regulated by using different processes to reach the industrial use requirements. Because the tissue obtained by electron beam physical vapor deposition is in a cylindrical crystal structure, oxygen diffusion passages can be formed between the two cylindrical crystals, and a three-phase region can be formed at the root of the cylindrical crystals. Therefore, the cathode of the solid oxide fuel cell is prepared by using the electron beam vapor deposition technology, the three-phase region with better quality can be obtained, and the performance of the solid oxide fuel cell is improved.
Description
Technical field
The invention belongs to the Solid Oxide Fuel Cell preparing technical field, particularly a kind of method for preparing Solid Oxide Fuel Cell LSM negative electrode.
Background technology
The world today is faced with environment and energy crisis; people explore constantly and solve the important problem that these mankind face; the preferred approach of head it off is to adopt new technology; the energy can be utilized effectively; reduce simultaneously discharging; and Solid Oxide Fuel Cell is a kind of all solid state electrochemical generating unit that chemical energy is directly changed into electric energy because of it; have environmental friendliness, the advantage such as energy conversion efficiency is high and fuel is scalable, be a kind of new green power that countries in the world are competitively developed.Can be good at solving the human problem that faces, so Solid Oxide Fuel Cell being described as the final scheme that solves the energy and environment problem, is the environmental protection energy project of the richest exploitation and application potential.To the research and development of Solid Oxide Fuel Cell, have important economic worth and social benefit.
Solid Oxide Fuel Cell mainly contains three parts and consists of, and is respectively: negative electrode, anode and electrolyte.In this three part, negative electrode is owing to having the ability of adsorb oxygen and the performance of dissociating oxygen, so it has very important effect.In Solid Oxide Fuel Cell, LSM is considered to traditional cathode material, and it is high that it has conductivity, and catalytic activity is high, good chemical stability, the advantage such as thermal coefficient of expansion is lower, extensive use in field of solid oxide fuel.
The course of work of present cathode of solid oxide fuel cell is: oxygen molecule is dissociated absorption at negative electrode, be that elemental oxygen is at LSM electrode oxygen empty place electrochemical reduction, oxonium ion passes through the oxygen room to the interfacial migration between electrode and the electrolyte by electrode surface, and oxonium ion is transferred to electrolyte by three phase boundary.These a few step processes are generally all worked under middle hot conditions, require electrode must have porousness, thereby allow reacting gas easily to be diffused into three phase boundary, and increase catalytic reaction surface.
Electro beam physics vapour deposition is with a kind of evaporation coating method of electron beam as thermal source, with respect to other method for manufacturing thin film, its evaporation rate is high, almost can evaporate all materials, and the adhesion of the coating that obtains of deposition and matrix is very good, and what obtain is organized as columnar crystal structure.Beam power is easy to regulate, and beam spot size and position are easy to control, are conducive to accurately control thickness and uniformity.
Because what electro beam physics vapour deposition obtained is organized as columnar crystal structure, as shown in Figure 1, between two column crystals, can form the diffusion admittance of oxygen, root at column crystal can form the threephase region, therefore, adopt the electro beam physics vapour deposition technology to prepare the negative electrode of Solid Oxide Fuel Cell, can obtain preferably threephase region of quality, to opening up the preparation method of Solid Oxide Fuel Cell, and improve the performance of Solid Oxide Fuel Cell.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the electro beam physics vapour deposition technology to prepare Solid Oxide Fuel Cell LSM negative electrode.
Processing step of the present invention is:
(1) with La
1-xSr
xMnO
3, x=0.1-0.3 powder wherein by pressure forming machine, is made and is of a size of: the charge bar of diameter 60-80mm, long 60-120mm; The pressing process of described charge bar is: pressure 3-5MPa, hold time 1-2 minute;
(2) with compressing charge bar at 1200-1300 ℃ of lower sintering 3-6 hour, and with stove cooling, obtain the charge bar that uses as electro beam physics vapour deposition;
(3) in the electro beam physics vapour deposition process, depositing operation is: deposition rate is: 1-0.5 μ m/min, vacuum degree is 1.0 * (10
-1-10
-3) Pa, substrate temperature is: 800-1000 ℃, deposit thickness is 30-60 μ m;
(4) the made sample of getting ready is cooled down after, put into stove and process, its treatment process is: heating rate is 3 ℃/min, and 800-1200 ℃ is incubated 2-5 hour down, after the stove cooling, namely make described Solid Oxide Fuel Cell LSM negative electrode.
Advantage of the present invention is: because the coating structure that electro beam physics vapour deposition obtains is columnar crystal structure, between two column crystals, can form the diffusion admittance of oxygen, root at column crystal can form the threephase region, therefore, adopt the electro beam physics vapour deposition technology to prepare the negative electrode of Solid Oxide Fuel Cell, can obtain preferably threephase region of quality, improve the performance of Solid Oxide Fuel Cell, the negative electrode of the method preparation has good effect.
It is extensive that the present invention also has the raw material of use, easy to process, the serviceability temperature scope is wide, shock-resistant, the intensity high, and cost is lower, mechanical performance is higher and better, extensively be suitable for the preparation of fuel battery negative pole, have great importance for the extensive use of Solid Oxide Fuel Cell.
Description of drawings
Fig. 1 is coating microstructure's shape appearance figure (non-LSM coating) that electro beam physics vapour deposition obtains.
Embodiment
The invention provides a kind of method for preparing cathode of solid oxide fuel cell, below in conjunction with embodiment technical scheme of the present invention be described further:
Embodiment 1:
Be La with composition
0.8Sr
0.2MnO
3(LSM) powder is made by pressure forming machine and to be of a size of diameter 60mm, longly is the charge bar of 80mm, pressing process is: pressure 3MPa, and hold time is 1 minute, puts it in the high temperature furnace, with the rate of heat addition of 3 ℃/min., be heated to 1250 ℃, be incubated and cool off with stove after 4 hours.Prepared charge bar is put into the electro beam physics vapour deposition vacuum chamber, with the vacuum degree control of vacuum chamber 2 * 10
-2Pa, speed with 0.5 μ m/min. deposits, in order to obtain better bond strength and coating structure pattern, the deposition time substrate temperature is controlled at about 850 ℃, and coating layer thickness is controlled at about 40 μ m, after the made sample of getting ready cooled down, put into stove and heat-treat, its treatment process is: heating rate is 3 ℃/min., and 850 ℃ are incubated 3 hours down, after the stove cooling, namely can be made into needed Solid Oxide Fuel Cell LSM negative electrode.
Embodiment 2:
Be La with composition
0.7Sr
0.3MnO
3(LSM) powder is made by pressure forming machine and to be of a size of diameter 60mm, longly is the charge bar of 80mm, pressing process is: pressure 4MPa, and hold time is 1 minute, puts it in the high temperature furnace, with the rate of heat addition of 3 ℃/min., be heated to 1200 ℃, be incubated and cool off with stove after 5 hours.Prepared charge bar is put into the electro beam physics vapour deposition vacuum chamber, with the vacuum degree control of vacuum chamber 2 * 10
-2Pa, speed with 0.5 μ m/min. deposits, in order to obtain better bond strength and coating structure pattern, the deposition time substrate temperature is controlled at about 850 ℃, and coating layer thickness is controlled at about 30 μ m, after the made sample of getting ready cooled down, put into stove and heat-treat, its treatment process is: heating rate is 3 ℃/min., and 800 ℃ are incubated 4 hours down, after the stove cooling, namely can be made into needed Solid Oxide Fuel Cell LSM negative electrode.
Embodiment 3:
Be La with composition
0.85Sr
0.15MnO
3(LSM) powder is made by pressure forming machine and to be of a size of diameter 60mm, longly is the charge bar of 80mm, pressing process is: pressure 3MPa, and hold time is 1 minute, puts it in the high temperature furnace, with the rate of heat addition of 3 ℃/min., be heated to 1300 ℃, be incubated and cool off with stove after 3 hours.Prepared charge bar is put into the electro beam physics vapour deposition vacuum chamber, with the vacuum degree control of vacuum chamber 5 * 10
-2Pa, speed with 1 μ m/min. deposits, in order to obtain better bond strength and coating structure pattern, the deposition time substrate temperature is controlled at about 900 ℃, and coating layer thickness is controlled at about 35 μ m, after the made sample of getting ready cooled down, put into stove and heat-treat, its treatment process is: heating rate is 3 ℃/min., and 900 ℃ are incubated 3 hours down, after the stove cooling, namely can be made into needed Solid Oxide Fuel Cell LSM negative electrode.
Claims (1)
1. a method for preparing Solid Oxide Fuel Cell LSM negative electrode is characterized in that, described method is carried out as follows:
(1) with La
1-xSr
xMnO
3, x=0.1-0.3 powder wherein by pressure forming machine, is made and is of a size of: the charge bar of diameter 60-80mm, long 60-120mm; The pressing process of described charge bar is: pressure 3-5MPa, hold time 1-2 minute;
(2) with compressing charge bar at 1200-1300 ℃ of lower sintering 3-6 hour, and with stove cooling, obtain the charge bar that uses as electro beam physics vapour deposition;
(3) in the electro beam physics vapour deposition process, depositing operation is: deposition rate is: 1-0.5 μ m/min, vacuum degree is 1.0 * 10
-3-1.0 * 10
-1Pa, substrate temperature is: 800-1000 ℃, deposit thickness is 30-60 μ m;
(4) the made sample of getting ready is cooled down after, put into stove and process, its treatment process is: heating rate is 3 ℃/min, and 800-1200 ℃ is incubated 2-5 hour down, after the stove cooling, namely make described Solid Oxide Fuel Cell LSM negative electrode.
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|---|---|---|---|
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| CN201010515252XA CN102005579B (en) | 2010-10-14 | 2010-10-14 | Method for preparing LSM (Lanthanum Strontium Manganate) cathode of solid oxide fuel cell |
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| CN101599546A (en) * | 2008-06-06 | 2009-12-09 | 中国科学院大连化学物理研究所 | A kind of cathode material for solid-oxide fuel cell and application |
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| FR2879825A1 (en) * | 2004-12-20 | 2006-06-23 | Commissariat Energie Atomique | METHOD OF MANUFACTURING A SOLID OXIDE FUEL CELL IN THE FORM OF THIN LAYERS |
| US8163434B2 (en) * | 2008-08-28 | 2012-04-24 | General Electric Company | Barrier coatings for interconnects; related devices, and methods of forming |
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