CN113773076A - Fuel cell electrolyte membrane with low sintering temperature and preparation method thereof - Google Patents
Fuel cell electrolyte membrane with low sintering temperature and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of solid oxide fuel cells, and particularly relates to a fuel cell electrolyte membrane with low sintering temperature and a preparation method thereof. The invention aims to provide a fuel cell electrolyte membrane with low sintering temperature and a preparation method thereof, aiming at the problems that the sintering performance of zirconia-based electrolyte is poor, the sintering additive influences the conductivity of the electrolyte and the like in the prior art. The expression of the electrolyte material is ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89) x1‑+(ZnO) x Wherein x is the addition of the sintering aid ZnO, and x is more than 0 and less than or equal to 0.05. By using cheap ZnO as the sintering aid of SSZ, the sintering temperature of SSZ can be reduced by 150-oC, also can improve the conductivity of the SSZ by 10-25%. The invention has simple preparation process, is easy for industrialized production, and is suitable for solid oxide fuel cells and related high-performance electrochemical devices thereof.
Description
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to a fuel cell electrolyte membrane with low sintering temperature and a preparation method thereof.
Background
Solid Oxide Fuel Cells (SOFC) are important electrochemical devices that can directly and efficiently convert chemical energy into electrical energy, and can be widely used in stationary power generation and transportation. The traditionally used SOFC electrolyte material is mainly Yttria Stabilized Zirconia (YSZ), however YSZ needs to operate at high temperature of 800-. Therefore, there is an urgent need to develop a zirconia-based electrolyte material with high ionic conductivity, Sc-doped ZrO2（SSZ，(SC2O3)0.1(CeO2)0.01(ZrO2)0.89) Is considered to be one of the most promising SOFC electrolyte materials due to its high oxygen ion conductivity and good compatibility with electrodes, and is a good electrolyte separator material for electrolyte-supported cells.
However, one of the major problems with zirconia-based materials is poor sinterability ratio. To lower the sintering temperature, various physicochemical methods can be used to synthesize ultrafine zirconia-based powders, such as: sol-gel method, coprecipitation method, chemical combustion evaporation method and high-strength mechanical ball milling method. On the other hand, CuO or Al is used2O3、MnO2And sintering aids such as CoO, can also promote densification, but these additives are relatively detrimental to the electrical conductivity of the zirconia ceramic.
The invention discloses a fuel cell electrolyte membrane with low sintering temperature and a preparation method thereof, aiming at solving the problems that the sintering performance of zirconia-based electrolyte is poor, the sintering additive influences the conductivity of the electrolyte and the like in the prior art.
Disclosure of Invention
The invention aims to solve the problems that the zirconia-based electrolyte membrane in the prior art has poor sintering performance, low mechanical strength, influence of sintering aids on the conductivity of the electrolyte and the like, and provides a fuel cell electrolyte membrane with low sintering temperature and a preparation method thereofoC, also can improve the conductivity of the SSZ by 10-25%.
In order to achieve the purpose, the invention adopts the technical scheme that:
a fuel cell electrolyte membrane material with low sintering temperature, wherein the electrolyte membrane material is expressed as (SC)2O3)0.1(CeO2)0.01(ZrO2)0.89) x1-+(ZnO) x Wherein x is the addition amount of ZnO, and x is more than 0 and less than or equal to 0.05.
The invention also aims to provide a preparation method of the solid oxide fuel cell electrolyte membrane, which comprises the following steps:
(a) firstly, preparing SSZ powder, and then adding sintering aid ZnO powder into the SSZ powder;
(b) respectively weighing a certain amount of SC according to the stoichiometric ratio of SSZ2O3、CeO2And ZrO2Powder raw materials;
(c) fully mixing the powder with deionized water and balls, ball-milling the mixture on a planetary ball mill, pouring the mixture into a beaker after ball-milling, and drying the mixture in an oven;
(d) pouring the dried sample into a mortar for fully grinding and sieving;
(e) loading the sieved powder into a crucible, and putting the crucible into a muffle furnace for calcining to synthesize SSZ powder;
(f) mixing the pre-sintered SSZ powder with a proper amount of ZnO powder, and then carrying out secondary ball milling, drying, grinding and sieving to obtain a mixture of SSZ and ZnO;
(g) crushing the obtained powder, adding 5% by mass of polyvinyl alcohol (PVA) for granulation, performing dry pressing under the pressure of 150MPa to form a wafer (the diameter is about 13mm, the thickness is about 1 mm), and sintering at different temperatures respectively to obtain the required electrolyte wafer.
Preferably, the material in the step (c): ball: the mass ratio of water is 1:2:3, the rotating speed of the ball mill is 300r/min, and the ball milling time is 8 h.
Preferably, the mesh size in step (d) is 80 mesh.
Preferably, the calcination temperature in the step (e) is 1000 ℃ and the calcination time is 2 h.
Preferably, the material subjected to secondary ball milling in the step (f): ball: the mass ratio of water is 1:2:3, the rotating speed of the ball mill is 250r/min, the ball milling time is 8-16h, and the number of the screened meshes is 80-100 meshes.
Preferably, in step (g) ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89) x1-+(ZnO) x The sintering temperature of the wafer is 1100-1500 ℃, and the sintering time is 2 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) the electrolyte membrane material suitable for the solid oxide fuel cell is obtained by a simple solid-phase reaction method and by using cheap ZnO as a sintering aid of SSZ, and the preparation method is simple to operate.
(2) The sintering aid used in the invention can not only reduce the sintering temperature of SSZ by 150-oC, also can improve the conductivity of the SSZ by 10-25%.
(3) The electrolyte membrane of the solid oxide fuel cell prepared by the invention has good sintering performance and conductivity, and solves the problems of sintering performance of the SSZ electrolyte of the existing solid oxide fuel cell and use of the SSZ electrolyte in a membrane support body.
Drawings
FIG. 1 is a graph showing that a sintered material ((SC) prepared in example 1 of the present invention)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.99+(ZnO)0.01Phase of SSZ electrolyte at different sintering temperatureFor density.
FIG. 2 is a graph showing that sintered ((SC) is prepared in example 1 of the present invention2O3)0.1(CeO2)0.01(ZrO2)0.89)0.99+(ZnO)0.01SEM image of electrolyte at optimum sintering temperature (1250 ℃/2 h).
FIG. 3 is a graph showing that sintered ((SC) is prepared in example 1 of the present invention2O3)0.1(CeO2)0.01(ZrO2)0.89)0.99+(ZnO)0.01Ionic conductivity at a different test temperature than the SSZ electrolyte.
FIG. 4 is a graph showing that sintered ((SC) is prepared in example 2 of the present invention2O3)0.1(CeO2)0.01(ZrO2)0.89)0.95+(ZnO)0.05Relative density at different sintering temperatures than the SSZ electrolyte.
FIG. 5 is a graph showing that sintered ((SC) is prepared in example 2 of the present invention2O3)0.1(CeO2)0.01(ZrO2)0.89)0.95+(ZnO)0.05SEM image of electrolyte at optimal sintering temperature (1200 deg.C/2 h).
FIG. 6 is a graph showing that sintered ((SC) is prepared in example 2 of the present invention2O3)0.1(CeO2)0.01(ZrO2)0.89)0.95+(ZnO)0.05Ionic conductivity at a different test temperature than the SSZ electrolyte.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly apparent, the present invention is further described in detail with reference to the following embodiments; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention; reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
The embodiment provides a fuel cell electrolyte membrane material with low sintering temperature, and the expression is ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.99+(ZnO)0.01. Namely, the amount of the sintering aid ZnO added was 1 mol%.
In this example ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.99+(ZnO)0.01The preparation method of the solid oxide fuel cell electrolyte membrane comprises the following steps:
(a) 1.37g of SC were weighed out in accordance with the SSZ stoichiometric ratio2O3、0.31g CeO2And 18.7g ZrO2Powder raw materials;
(b) fully mixing the powder with deionized water and balls, and mixing: ball: putting the mixture on a planetary ball mill for ball milling at the rotating speed of 300r/min for 8 hours, pouring the mixture into a beaker after ball milling, and putting the beaker into an oven for drying, wherein the mass ratio of water is 1:2: 3;
(c) pouring the dried sample into a mortar for fully grinding and sieving by a 80-mesh sieve;
(d) placing the sieved powder into a crucible, and placing the crucible into a muffle furnace for calcination at the calcination temperature of 1000 ℃ for 2 hours to synthesize SSZ powder;
(e) mixing the pre-sintered SSZ powder with 0.08g ZnO powder, and then carrying out secondary ball milling, drying, grinding and sieving, wherein the weight ratio of the materials: ball: the mass ratio of water is 1:2:3, the rotating speed of the ball mill is 250r/min, the ball milling time is 8h, and the screening mesh number is 80 meshes, so that a mixture of SSZ and ZnO is obtained;
(f) crushing the obtained powder, adding 5% of PVA by mass for granulation, performing dry pressing under the pressure of 150MPa to form wafers (the diameter is about 13mm, the thickness is about 1 mm), and sintering at different temperatures (the sintering temperature is 1100-1450 ℃, and the sintering time is 2 h) respectively to obtain the required electrolyte wafers.
Prepared for this example ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.99+(ZnO)0.01The electrolyte separator was subjected to a sintering property test, and the results are shown in FIG. 1, which is a graph of FIG. 1As a result, SSZ requires sintering at 1450 ℃ to achieve densification, whereas ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.99+(ZnO)0.01Densification was achieved by sintering at 1250 ℃ for 2 hours, indicating that 1mol% ZnO addition reduced the SSZ sintering temperature by 200oC。
Obtained at the optimum sintering temperature (1250 ℃/2 h) for the preparation of this example ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.99+(ZnO)0.01The electrolyte was characterized by Scanning Electron Microscopy (SEM), and the results are shown in fig. 2, and it is understood from the results in fig. 2 that the electrolyte sintered under these conditions was very dense.
Prepared for this example ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.99+(ZnO)0.01The results of the conductivity test of the electrolyte are shown in FIG. 3, and 800 is shown in FIG. 3oC is (((SC))2O3)0.1(CeO2)0.01(ZrO2)0.89)0.99+(ZnO)0.01Is 24% higher than the conductivity of SSZ.
The above results show that the addition of 1mol% ZnO sintering aid not only reduces the sintering temperature of SSZ by 200oC, also increased the electrical conductivity of SSZ by 24%.
Example 2
The embodiment provides a fuel cell electrolyte membrane material with low sintering temperature, and the expression is ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.95+(ZnO)0.05. Namely, the amount of ZnO as a sintering aid added was 5 mol%.
In this example ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.95+(ZnO)0.05The preparation method of the solid oxide fuel cell electrolyte membrane comprises the following steps:
(a) 1.31g of SC were weighed in accordance with the stoichiometric ratio of SSZ2O3、0.3g CeO2And 18.1g ZrO2Powder raw materials;
(b) fully mixing the powder with deionized water and balls, and mixing: ball: putting the mixture on a planetary ball mill for ball milling at the rotating speed of 300r/min for 8 hours, pouring the mixture into a beaker after ball milling, and putting the beaker into an oven for drying, wherein the mass ratio of water is 1:2: 3;
(c) pouring the dried sample into a mortar for fully grinding and sieving by a 80-mesh sieve;
(d) placing the sieved powder into a crucible, and placing the crucible into a muffle furnace for calcination at the calcination temperature of 1000 ℃ for 2 hours to synthesize SSZ powder;
(e) mixing the pre-sintered SSZ powder with 0.4g ZnO powder, and then carrying out secondary ball milling, drying, grinding and sieving, wherein the weight ratio of the materials: ball: the mass ratio of water is 1:2:3, the rotating speed of the ball mill is 250r/min, the ball milling time is 8h, and the screening mesh number is 80 meshes, so that a mixture of SSZ and ZnO is obtained;
(f) crushing the obtained powder, adding 5% of PVA by mass for granulation, performing dry pressing under the pressure of 150MPa to form wafers (the diameter is about 13mm, the thickness is about 1 mm), and sintering at different temperatures (the sintering temperature is 1100-1450 ℃, and the sintering time is 2 h) respectively to obtain the required electrolyte wafers.
Prepared for this example ((SC)2O3)0.1(CeO2)0.05(ZrO2)0.89)0.99+(ZnO)0.05The results of the sintering property test of the electrolyte separator are shown in fig. 4, and it can be seen from the results in fig. 4 that the SSZ requires sintering at 1450 temperature to achieve densification, and ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.95+(ZnO)0.05Densification was achieved by sintering at 1200 ℃ for 2 hours, indicating that 1mol% ZnO addition reduced the SSZ sintering temperature by 250oC。
Obtained at the optimum sintering temperature (1200 ℃/2 h) for the preparation of this example ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.95+(ZnO)0.05The electrolyte was subjected to SEM characterization, and the results are shown in fig. 5, and it is understood from the results in fig. 5 that the electrolyte sintered under these conditions was very dense.
Prepared for this example ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89)0.95+(ZnO)0.05The results of the conductivity test of the electrolyte are shown in FIG. 6, and 800 is shown in FIG. 6oC is (((SC))2O3)0.1(CeO2)0.01(ZrO2)0.89)0.95+(ZnO)0.05The conductivity of (a) was 16.3% higher than that of SSZ.
The above results show that the addition of 5mol% ZnO sintering aid not only reduces the SSZ sintering temperature by 250oC, also increased the electrical conductivity of SSZ by 16.3%.
The above embodiments are described in detail to explain the technical solutions and advantages of the present invention, and it should be understood that the above embodiments are only specific examples of the present invention and are not intended to limit the present invention, and any modifications and improvements made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A fuel cell electrolyte membrane with low sintering temperature is characterized in that the electrolyte material is of a fluorite structure and has an expression of ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89) x1-+(ZnO) x Wherein x is the addition of the sintering aid ZnO, and x is more than 0 and less than or equal to 0.05.
2. A method of making a low sintering temperature fuel cell electrolyte membrane according to claim 1, comprising the steps of:
(a) firstly, preparing SSZ powder, and then adding sintering aid ZnO powder into the SSZ powder;
(b) respectively weighing a certain amount of SC according to the stoichiometric ratio of SSZ2O3、CeO2And ZrO2Powder raw materials;
(c) fully mixing the powder with deionized water and balls, ball-milling the mixture on a planetary ball mill, pouring the mixture into a beaker after ball-milling, and drying the mixture in an oven;
(d) pouring the dried sample into a mortar for fully grinding and sieving;
(e) loading the sieved powder into a crucible, and putting the crucible into a muffle furnace for calcining to synthesize SSZ powder;
(f) mixing the pre-sintered SSZ powder with a proper amount of ZnO powder, and then carrying out secondary ball milling, drying, grinding and sieving to obtain a mixture of SSZ and ZnO;
(g) crushing the obtained powder, adding 5% by mass of polyvinyl alcohol (PVA) for granulation, performing dry pressing under the pressure of 150MPa to form a wafer (the diameter is about 13mm, the thickness is about 1 mm), and sintering at different temperatures respectively to obtain the required electrolyte wafer.
3. The method for preparing a fuel cell electrolyte membrane with low sintering temperature according to claim 2, wherein the material in the step (c): ball: the mass ratio of water is 1:2:3, the rotating speed of the ball mill is 300r/min, and the ball milling time is 8 h.
4. The method for preparing a fuel cell electrolyte membrane with a low sintering temperature according to claim 2, wherein the number of the sieving meshes in the step (d) is 80 meshes.
5. The method for preparing a fuel cell electrolyte membrane with low sintering temperature according to claim 2, wherein the calcining temperature in the step (e) is 1000 ℃ and the calcining time is 2 h.
6. The method for preparing a fuel cell electrolyte membrane with low sintering temperature according to claim 2, wherein the material of the secondary ball milling in the step (f): ball: the mass ratio of water is 1:2:3, the rotating speed of the ball mill is 250r/min, the ball milling time is 8-16h, and the number of the screened meshes is 80-100 meshes.
7. The method for preparing a fuel cell electrolyte membrane with low sintering temperature according to claim 2, wherein in the step (g) ((SC)2O3)0.1(CeO2)0.01(ZrO2)0.89) x1-+(ZnO) x The sintering temperature of the wafer is 1100-1500 ℃, and the sintering time is 2 h.
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