CN111313068B - Dispersed proton conductive ceramic electrolyte film and preparation method thereof - Google Patents
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- CN111313068B CN111313068B CN201811514392.8A CN201811514392A CN111313068B CN 111313068 B CN111313068 B CN 111313068B CN 201811514392 A CN201811514392 A CN 201811514392A CN 111313068 B CN111313068 B CN 111313068B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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Abstract
The invention discloses a dispersed proton conductive ceramic electrolyte film and a preparation method thereof. The film is formed on the surface of the ceramic tube and is made of a film material SrCe1‑xYbxO3‑αAnd SrCe1‑ xErxO3‑αFormed into a dispersed film, wherein SrCe1‑xYbxO3‑αAs a main phase, SrCe1‑xErxO3‑αDispersed in the main phase. The preparation method comprises the following steps: (1) ultrasonically cleaning the surface of the ceramic tube for 15-30min, and drying; (2) simultaneously depositing SrCe on the surface of the ceramic tube by adopting a metal organic chemical vapor deposition technology1‑xYbxO3‑αAnd SrCe1‑xErxO3‑αThe metal reaction source is Yb organic reaction source and Er organic reaction source, and the carrier gas is H2(ii) a SrCe by adjusting the temperature of a reaction source and the reaction time1‑xYbxO3‑αThe phase becomes a main phase, and finally the dispersed proton conductive ceramic electrolyte film is obtained. The film of the invention has the characteristics of high bonding strength with a matrix, high compactness, uniformity, stability, excellent hydrogen resistance and the like, and can be applied to the aspects of solid oxide fuel cells, efficient preparation of hydrogen by electrolyzing water, synthesis of ammonia under normal pressure, separation and purification of hydrogen and the like.
Description
Technical Field
The invention relates to a dispersed proton conductive ceramic electrolyte film and a preparation method thereof, belonging to the field of solid oxide fuel cell electrode materials.
Background
Rare earth doped perovskite AB1-xMxO3-δThe (A ═ Sr, Ba, Ca; B ═ Ce, Zr; M ═ rare earth doping element) ceramic has high proton conductivity at medium-high temperature (600-]. The reduction of the thickness of the solid electrolyte can effectively reduce the internal resistance of the electrolyte, thereby obviously improving the proton transmission efficiency of the electrolyte and the output power of the electrochemical device. Therefore, the method has very important application significance in the research and development of the preparation technology of the compact and uniform ceramic electrolyte thin film on the electrode support.
In recent years, Metal Organic Chemical Vapor Deposition (MOCVD) has received wide attention as a new technique for producing ceramic electrolyte thin films. The metal organic chemical vapor deposition method adopts metal organic salt as a reaction source, and organic matters undergo pyrolysis reaction in a certain atmosphere and are deposited on a substrate to obtain a film. The electrolyte film prepared by MOCVD has the advantages of low preparation temperature, generally not exceeding 800 ℃, and the film preparation on the surface of a complex workpiece can be realized.
However, it is difficult to prepare a high-performance, uniform and stable proton-conducting ceramic electrolyte membrane on the surface of the ceramic tube for the fuel cell at present.
Disclosure of Invention
The invention aims to provide a dispersed proton conductive ceramic electrolyte film formed on the surface of a ceramic tube, which has good combination with a matrix, high compactness, uniformity, stability and excellent hydrogen resistance.
The invention also aims to provide a preparation method of the dispersed proton conductive ceramic electrolyte film, which is simple and low in cost, and the thickness of the prepared film is controllable.
In order to achieve the purpose, the invention adopts the following technical scheme:
a proton-dispersing electrically conductive ceramic electrolyte film is prepared from SrCe film1-xYbxO3-αAnd SrCe1-xErxO3-αFormed into a dispersed film, wherein SrCe1-xYbxO3-αAs a main phase, SrCe1-xErxO3-αAnd the dispersion is distributed in the main phase, wherein x is the doping content, and alpha is the stoichiometric ratio coefficient.
Wherein, SrCe is in the dispersion film1-xYbxO3-αThe mass percentage of (b) is preferably 60% to 90%. Wherein the thickness of the dispersion film is 0.1-20 μm.
Wherein the ceramic tube is made of ZrO2Or Al2O3A ceramic.
The preparation method of the dispersed proton conductive ceramic electrolyte film is characterized by comprising the following steps:
(1) ultrasonically cleaning the surface of the ceramic tube for 15-30min, and drying;
(2) simultaneously depositing SrCe on the surface of the ceramic tube by adopting a metal organic chemical vapor deposition technology1-xYbxO3-αAnd SrCe1-xErxO3-αThe metal reaction source is Yb organic reaction source and Er organic reaction source, and the carrier gas is H2(ii) a SrCe by adjusting the temperature of a reaction source and the reaction time1-xYbxO3-αPhase becomes main phase, and SrCe is finally obtained1-xYbxO3-α/SrCe1-xErxO3-αA proton conducting ceramic electrolyte membrane is dispersed.
Wherein in the step (2), the temperature of a reaction source is 50-700 ℃; the reaction time is 30-180 min; h2The carrier gas flow is 40-500 mL/min.
Preferably, in the step (2), the temperature of the Yb reaction source is 150-in; the temperature of an Er reaction source is 100-350 ℃; the reaction time is 30-60 min; carrier gas H2The flow rate is 150-200 mL/min.
The invention provides a novel dispersion film, wherein SrCe1-xYbxO3-αAnd SrCe1-xErxO3-αBoth of the two materials belong to rare earth doped perovskite type ceramic materials. The invention firstly carries out 2 dispersion preparation of the proton conductive electrolyte film, the rare earth elements between the film layers are dispersed and distributed, and the proton conductivity is improved.
The invention has the beneficial effects that:
the invention realizes SrCe on the surface of the ceramic tube for the first time1-xYbxO3-αAnd SrCe1-xErxO3-αAnd simultaneously depositing to form a dispersed proton conductive ceramic electrolyte film, wherein the film has the characteristics of high bonding strength with a matrix, high compactness, uniformity, stability, excellent hydrogen resistance and the like, and can be applied to the aspects of high-efficiency preparation of hydrogen by using solid oxide fuel cells and electrolyzed water, synthesis of ammonia at normal pressure, separation and purification of hydrogen and the like.
The invention adopts the metal organic chemical vapor deposition technology to prepare the dispersed proton conductive ceramic electrolyte film, and has the characteristics of controllable thickness and low cost.
Drawings
FIG. 1 is a schematic structural view of a dispersed proton-conducting ceramic electrolyte membrane according to the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
As shown in figure 1, which is a schematic structural diagram of a dispersed proton conductive ceramic electrolyte membrane of the present invention, the membrane 1 is formed on the surface of a ceramic tube 2 and is made of a membrane material SrCe1-xYbxO3-αAnd SrCe1-xErxO3-αFormed into a dispersed film, wherein SrCe1-xYbxO3-αAs a main phase, SrCe1-xErxO3-αIs in a dispersed phase.
Example 1
(1) ZrO 2mm in length, 15mm in outer diameter and 2mm in wall thickness2Ultrasonically cleaning the surface of the ceramic tube for 15min, and drying;
(2) simultaneously depositing SrCe on the surface of the ceramic tube by adopting a metal organic chemical vapor deposition technology1-xYbxO3-αAnd SrCe1-xErxO3-α(ii) a The reaction source adopts ytterbium acetylacetonate and erbium acetylacetonate, and the specific process parameters are as follows: the temperature of a Yb reaction source is 450 ℃; the temperature of an Er reaction source is 420 ℃, and the reaction time of an Yb reaction source is 30 min; er reaction source reaction time is 20min, and carrier gas H2The flow rate was 200 mL/min.
(3) SrCe with the thickness of about 0.5 mu m is finally obtained1-xYbxO3-a/SrCe1-xErxO3-αDispersed film of the main phase SrCe1-xYbxO3-αThe content is about 70 percent, the film layer is uniform and compact, and the bonding force with the matrix is good;
measurement of SrCe by AC impedance method1-xYbxO3-α/SrCe1-xErxO3-αThe proton conductivity of the dispersed film at 650 ℃ is 5.3X 10-3S/cm。
Example 2
(1) ZrO 2mm in length, 15mm in outer diameter and 2mm in wall thickness2Ultrasonically cleaning the surface of the ceramic tube for 15min, and drying;
(2) simultaneously depositing SrCe on the surface of the ceramic tube by adopting a metal organic chemical vapor deposition technology1-xYbxO3-αAnd SrCe1-xErxO3-α(ii) a The reaction source adopts ytterbium acetylacetonate and erbium acetylacetonate, and the specific process parameters are as follows: the temperature of a Yb reaction source is 350 ℃; the temperature of the Er reaction source is 320 ℃, and the reaction time of the Yb reaction source is 30 min; er reaction source reaction time is 20min, and carrier gas H2The flow rate was 100 mL/min.
(3) SrCe with the thickness of about 1.5 mu m is finally obtained1-xYbxO3-a/SrCe1-xErxO3-αDispersed film of the main phase SrCe1-xYbxO3-αThe content is about 70 percent, the film layer is uniform and compact, and the bonding force with the matrix is good;
measurement of SrCe by AC impedance method1-xYbxO3-α/SrCe1-xErxO3-αThe proton conductivity of the dispersed film at 650 ℃ is 9.3 multiplied by 10-3S/cm。
Example 3
(1) ZrO 2mm in length, 15mm in outer diameter and 2mm in wall thickness2Ultrasonically cleaning the surface of the ceramic tube for 15min, and drying;
(2) simultaneously depositing SrCe on the surface of the ceramic tube by adopting a metal organic chemical vapor deposition technology1-xYbxO3-αAnd SrCe1-xErxO3-α(ii) a The reaction source adopts ytterbium acetylacetonate and erbium acetylacetonate, and the specific process parameters are as follows: the temperature of a Yb reaction source is 650 ℃; the temperature of an Er reaction source is 620 ℃, and the reaction time of a Yb reaction source is 30 min; er reaction source reaction time is 20min, and carrier gas H2The flow rate was 400 mL/min.
(3) SrCe with the thickness of about 8.5 mu m is finally obtained1-xYbxO3-a/SrCe1-xErxO3-αDispersed film of the main phase SrCe1-xYbxO3-αThe content is about 80 percent, the film layer is uniform and compact, and the bonding force with the matrix is good;
measurement of SrCe by AC impedance method1-xYbxO3-α/SrCe1-xErxO3-αThe proton conductivity of the dispersed film at 650 ℃ is 3X 10-2S/cm。
SrCe of the invention1-xYbxO3-a/SrCe1-xErxO3-αThe dispersion film is prepared by metal organic chemical vapor deposition method through simultaneous SrCe deposition1-xYbxO3-αAnd SrCe1-xErxO3-αA thin film formed of SrCe on the surface of the ceramic tube1-xYbxO3-αAs a main phase, SrCe1-xErxO3-αA proton-conducting ceramic electrolyte membrane dispersed in the main phase. SrCe with the thickness of about x-20 mu m can be obtained by adopting the method1-xYbxO3-a/SrCe1-xErxO3-αA proton conducting ceramic electrolyte membrane is dispersed. The proton conductive ceramic electrolyte film has high bonding strength with a matrix, simple preparation process and low cost, and the proton conductivity is not less than 10-4S/cm。
Claims (7)
1. A proton-dispersed conductive ceramic electrolyte film is characterized in that the film is formed on the surface of a ceramic tube and is made of a film material SrCe1-xYbxO3-αAnd SrCe1-xErxO3-αFormed into a dispersed film, wherein SrCe1-xYbxO3-αAs a main phase, SrCe1- xErxO3-αAnd the dispersion is distributed in the main phase, wherein x is the doping content, and alpha is the stoichiometric ratio coefficient.
2. The dispersed proton conducting ceramic electrolyte membrane of claim 1, wherein the dispersed membrane comprises SrCe1-xYbxO3-αThe mass percentage of the component (A) is 60-90%.
3. The dispersed proton conducting ceramic electrolyte membrane according to claim 1, wherein the thickness of the dispersed membrane is 0.1 to 20 μm.
4. The dispersed proton conducting ceramic electrolyte membrane according to claim 1, wherein the ceramic tube is made of ZrO2Or Al2O3A ceramic.
5. A method of preparing a dispersed proton-conducting ceramic electrolyte membrane according to claim 1, comprising the steps of:
(1) ultrasonically cleaning the surface of the ceramic tube for 15-30min, and drying;
(2) simultaneously depositing SrCe on the surface of the ceramic tube by adopting a metal organic chemical vapor deposition technology1-xYbxO3-αAnd SrCe1- xErxO3-αThe metal reaction source is Yb organic respectivelyA reaction source and an organic Er reaction source, the carrier gas is H2(ii) a SrCe is prepared by adjusting reaction temperature and reaction time1-xYbxO3-αThe phase is a main phase, wherein the temperature of a Yb reaction source is 350 ℃, and the reaction time is 30 min; the temperature of an Er reaction source is 320 ℃, and the reaction time is 20 min; or the temperature of the Yb reaction source is 450 ℃, and the reaction time is 30 min; the temperature of an Er reaction source is 420 ℃, and the reaction time is 20 min; or the temperature of the Yb reaction source is 650 ℃, and the reaction time is 30 min; the temperature of an Er reaction source is 620 ℃, and the reaction time is 20 min; finally obtaining SrCe1-xYbxO3-α/SrCe1-xErxO3-αA proton conducting ceramic electrolyte membrane is dispersed.
6. The method for producing a dispersed proton-conducting ceramic electrolyte membrane according to claim 5, wherein H in the step (2)2The carrier gas flow is 40-500 mL/min.
7. The method for producing a dispersed proton-conducting ceramic electrolyte membrane according to claim 6, wherein, in the step (2), the carrier gas H is2The flow rate is 150-200 mL/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015114684A1 (en) * | 2014-01-31 | 2015-08-06 | パナソニックＩｐマネジメント株式会社 | Proton conductor |
| GB201410092D0 (en) * | 2014-06-06 | 2014-07-23 | Cambridge Entpr Ltd | Electrolyte membrane |
| JP6578970B2 (en) * | 2016-01-29 | 2019-09-25 | 住友電気工業株式会社 | Solid oxide fuel cell |
| CN107591541A (en) * | 2016-07-06 | 2018-01-16 | 阜阳师范学院 | A kind of ytterbium doping strontium cerate alkali metal salt congruent melting nanocrystal composition and preparation method thereof |
| CN107591553A (en) * | 2016-07-06 | 2018-01-16 | 阜阳师范学院 | A kind of Er ions strontium cerate hydrochloride congruent melting nanocrystal composition and preparation method thereof |
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Non-Patent Citations (2)
| Title |
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| Synthesis and characterization of proton conducting Sr(Ce1-xZrx)0.95Yb0.05O3-δ by the citrate method;Jingchao Zhang等;《Journal of Alloys and Compounds》;20061019;第440卷(第1-2期);第270-275页 * |
| 碱土金属双掺杂的Ce0.9Ca0.1-xSrxO1.9中温固体电解质的性能与应用;吕喆，等;《中国稀土学报》;20001231;第18卷(第4期);第313-316页 * |
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