CN118472335B - A high-temperature solid acid impregnated NiO/YSZ composite electrolyte membrane and a preparation method thereof, and a preparation method of a solid acid fuel cell - Google Patents
A high-temperature solid acid impregnated NiO/YSZ composite electrolyte membrane and a preparation method thereof, and a preparation method of a solid acid fuel cell Download PDFInfo
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- 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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Abstract
本发明公开了一种高温浸渍固体酸的NiO/YSZ复合电解质膜及其制备方法以及固体酸燃料电池的制备方法。本发明采用高温浸渍的方法，将制备的NiO/YSZ膜材料浸渍在固体酸溶液中，制备质子导体复合电解质膜材料，属于质子导体燃料电池领域。将多种不形成固溶体的氧化物共烧结，然后通过去除其中一种成分制备多孔膜材料，在多孔膜材料中浸渍固体酸材料，该方法属于燃料电池领域。采用流延成型法制备NiO/YSZ复合材料，将粉末与粘合剂和分散剂的水性浆料混合，浇铸在模具中成片状形状。将薄片煅烧，然后在一定温度的固体酸溶液中反复浸渍，该方法制备的质子导体电解质膜具有较高的质子电导率、良好热的稳定性和机械强度的性质。
The invention discloses a NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature, a preparation method thereof and a preparation method of a solid acid fuel cell. The invention adopts a high-temperature impregnation method to immerse the prepared NiO/YSZ membrane material in a solid acid solution to prepare a proton conductor composite electrolyte membrane material, belonging to the field of proton conductor fuel cells. A plurality of oxides that do not form a solid solution are co-sintered, and then a porous membrane material is prepared by removing one of the components, and a solid acid material is impregnated in the porous membrane material, and the method belongs to the field of fuel cells. The NiO/YSZ composite material is prepared by a tape casting method, and the powder is mixed with an aqueous slurry of a binder and a dispersant, and cast in a mold into a sheet shape. The thin slice is calcined, and then repeatedly immersed in a solid acid solution at a certain temperature. The proton conductor electrolyte membrane prepared by the method has the properties of high proton conductivity, good thermal stability and mechanical strength.
Description
Technical Field
The invention relates to the technical field of proton conductor fuel cells, in particular to a NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature, a preparation method thereof and a preparation method of the solid acid fuel cell, and more particularly relates to a preparation method for preparing a proton conductor composite electrolyte membrane material by impregnating a prepared NiO/YSZ membrane material in a solid acid solution by adopting a high-temperature impregnation method.
Background
A fuel cell is a device that directly converts chemical energy of fuel into electric energy. The fuel cell has the advantages of high efficiency, no pollution, light weight and the like. Fuel cells can either utilize the chemical energy of a fuel to convert it into electrical energy or can implement processes that convert electrical energy into certain gaseous fuels. For example, hydrogen and ammonia, as an ideal energy storage material, their use and synthesis in proton conductor solid oxide electrochemical devices can achieve efficient clean power generation and energy storage. Solid acids are a class of inorganic compounds that undergo an over-proton phase transition at higher temperatures and thus have good proton conductivity and phase transition characteristics. The Solid Acid Fuel Cell (SAFCs) has the characteristics of low methanol permeability, higher electrode catalytic activity and carbon monoxide poisoning resistance, and has good development prospect as a research direction in the field of fuel cells. Solid acids are electrolyte materials for fuel cells due to high proton conductivity and stability between 100 ℃ and 250 ℃.
Solid acids have been widely studied for their high proton conductivity and high temperature phase transition behavior, and have not been considered as electrolyte membranes for fuel cells because most of them have water solubility and high temperature ductility. In 2001, solid acid CsHSO 4 is first used in fuel cells, namely Haile of the university of california and colleagues thereof, csHSO 4 is used as an electrolyte film to assemble an oxyhydrogen fuel cell, the working temperature of the cell is 150-160 ℃, the open circuit voltage reaches 1.11V, and because the working temperature of the cell exceeds 100 ℃, the performance of the solid acid electrolyte is proved not to be affected by the humidity of the working environment, so that the possibility of the solid acid as an electrolyte material is proved. Ponomareva researches on the performance of the CsHSO 4,CsH2PO4/SiO2 composite electrolyte show that the conductivity of the CsH 2PO4 can be increased to 10 -3~10-2 S/cm at 130-250 ℃ by doping different types of SiO 2. Otomo et al studied the conductivity of CsHSO 4/SiO2 composite membrane, and by impregnating CsHSO 4 solution into microporous SiO 2 membrane, the proton conductivity of CsHSO 4/SiO2 composite membrane can be made to be 60-140 ℃ lower than the phase transition temperature of the super proton conductor, Is increased by 2 orders of magnitude over pure CsHSO 4. Boysen et al prepared a composite membrane by combining CsHSO 4 with a thermoplastic polymer PVDF, which shows that the highest conductivity is obtained at a PVDF volume fraction of 20% at 100 ℃. Yang et al also prepared a CsHSO 4/PVDF composite membrane, and the results indicated that the composite membrane was suitable for use in fuel cells, but had poor stability. Replacement of SO 4 with PO 4 can improve the stability of the composite membrane. Kim and the like research the performance of the ionic liquid doped CsHSO 4 composite membrane, and the result shows that the ionic liquid/CsHSO 4 composite membrane has high conductivity at 80-180 ℃ and reaches (1-2) 10 -3 S/cm. In the medium temperature range, the ion transport mechanism in solid electrolytes is similar to that in liquids.
Because of the reversible dehydration process of the solid acid material, the gas is required to be humidified and then introduced into the electrode side of the fuel cell so as to ensure the stability of the cell under the working temperature condition. By measuring the over proton phase transition temperature of the material under the gas atmosphere of different humidity and pressure, the relative researchers can increase the ambient humidity and gas pressure to reduce the proton phase transition temperature, thereby improving the high conductivity temperature range and the thermal stability of the material. The porous oxide material is used as a supporting structure by impregnating the solid acid material into the oxide material, so that the thermal stability of the material is improved, the temperature range of the conductivity is increased, and the conductivity of the composite material at the working temperature is influenced due to the fact that the hydration characteristic of the solid acid material is influenced by the structure of the material.
Disclosure of Invention
According to the technical problems set forth above, a NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature, a method for preparing the same, and a method for preparing a solid acid fuel cell are provided. The invention adopts a high-temperature impregnation porous oxide material method, prepares a composite oxide film material by a tape casting method, removes a carbon-based material by high-temperature calcination to prepare the porous oxide film material, and prepares an inorganic composite electrolyte film by high-temperature impregnation of a solid acid solution, and jointly preparing the solid acid with high proton conductivity, nickel oxide with thermal stability and mechanical strength and a YSZ composite material.
The invention adopts the following technical means:
A preparation method of a NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature comprises the following steps: preparing slurry, ball milling, degassing, casting, calcining and drying, and specifically comprises the following steps:
preparing yttria-stabilized zirconia powder, nickel oxide, a pore-forming agent, a dispersing agent, a binder and water into slurry;
ball milling, drying and degassing the slurry, and casting the prepared slurry into a NiO/YSZ film material in a die;
Preparing a NiO/YSZ porous membrane material by sintering the cast NiO/YSZ membrane material at high temperature;
Preparing a solid acid solution: reacting metal salt with acid according to a certain mole ratio to prepare a solid acid material;
Immersing the prepared porous membrane material in a solid acid solution at a preset high temperature;
Repeatedly dipping for a certain number of times, and vacuum drying after dipping is completed to obtain the NiO/YSZ composite electrolyte membrane material.
Further, the slurry is calculated according to the mass ratio, the yttrium oxide stabilized zirconia powder, nickel oxide, pore-forming agent, dispersing agent and binder have the following proportion: 34.9-38.8%, 11.6-19.4%, 14.1-17.4%, 1.7-2.4%, 4.7-5.8% and the balance water.
Further, the concrete steps of slurry preparation are as follows: the slurry is prepared by mixing NiO and YSZ powder with a pore-forming agent in distilled water and a dispersing agent, the binder is added to the slurry after the stirred mixture is left for a period of time, and then stirring is performed for 9-12 hours.
Further, the mass range of the yttria-stabilized zirconia, the nickel oxide, the dispersing agent, the binder, the graphite or the starch used for preparing the NiO/YSZ film material is 30-40 g, 10-20 g, 10.5-14.5 g, 1.5-2.5 g and 4-6 g.
Further, the prepared slurry is cast into a NiO/YSZ film material in a mould, specifically: and vacuumizing the slurry, forming on a casting machine, and demolding, wherein the thickness of the ceramic sheet is 0.4-0.6 mm.
Further, the preparation of the NiO/YSZ porous membrane material comprises the following specific steps: the high-temperature sintering is programmed heating and firing, when the NiO/YSZ film is programmed heating and firing, the heating rate from room temperature to 400+/-10 ℃ is 1-2 ℃/min, the heating rate from 400+/-10 ℃ to 1300-1600 ℃ is 1-3 ℃/min after the constant temperature of 400+/-10 ℃ is 2+/-0.5 h, the constant temperature of 1300-1600 ℃ is 4+/-0.5 h, and finally the temperature is reduced to room temperature at 1-2 ℃/min.
Further, the sintered NiO/YSZ film is immersed in a solid acid solution at the temperature of 150-200 ℃ for 4-6 hours.
Further, the solid acid is one or more combinations of MH xXO4, where M is Cs, rb, K or NH 4 and X is S or P. H x corresponds based on the particular element.
Further, the molar ratio of the nickel oxide, the yttria-stabilized zirconia and the solid acid material is calculated according to the actual weighing mass, and the content of the solid acid material in the composite material is calculated.
The invention also claims a NiO/YSZ composite electrolyte membrane which is prepared based on the method and is impregnated with solid acid at high temperature.
The invention also discloses a preparation method of the solid acid fuel cell based on the NiO/YSZ composite electrolyte membrane impregnated with the solid acid at high temperature, which comprises the following steps:
And laminating the Pt/C thin sheet and the impregnated composite electrolyte film, and preparing the solid acid fuel cell under the constant temperature and constant pressure conditions of 80+/-5 ℃ and 15+/-1 Mpa for 30+/-5 minutes.
Compared with the prior art, the invention has the following advantages:
1. The casting method has simple process, low cost and no pollution, and the porosity of the material can be regulated by changing the content of the pore-forming agent in the slurry, so that the doping amount of the solid acid material is further improved;
2. compared with pure solid acid electrolyte, the inorganic composite electrolyte membrane not only improves the temperature interval of proton conductivity, but also improves the thermal stability and mechanical strength of the material;
3. the invention provides a preparation method of a medium-temperature fuel cell composite electrolyte membrane, which has low production cost, simple process and strong operability, and can be suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to the drawings without inventive effort to a person skilled in the art.
FIG. 1 is a graph showing the relationship between the conductivity and the temperature of electrolyte materials of examples 1 to 3 and 3 different solid acid material doping amounts.
FIG. 2 is a graph showing the voltage and power density change at a water partial pressure of 0.3atm for a battery prepared from the electrolyte material and the Pt/C electrode of 30% doping amount of example 4.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept.
A preparation method of a NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature comprises the following steps: preparing slurry, ball milling, degassing, casting, calcining and drying, and specifically comprises the following steps:
preparing yttria-stabilized zirconia powder, nickel oxide, a pore-forming agent, a dispersing agent, a binder and water into slurry;
The slurry is prepared from yttria-stabilized zirconia powder, nickel oxide, a pore-forming agent, a dispersing agent and a binding agent according to the mass ratio: 34.9-38.8%, 11.6-19.4%, 14.1-17.4%, 1.7-2.4%, 4.7-5.8%, and the balance water, specifically 34.9-38.8%.
Further, as a specific embodiment, the mass range of the yttria-stabilized zirconia, the nickel oxide, the dispersing agent, the binder, the graphite or the starch used for preparing the NiO/YSZ film material is 30-40 g, 10-20 g, 10.5-14.5 g, 1.5-2.5 g and 4-6 g.
The concrete steps of the slurry preparation are as follows: the slurry is prepared by mixing NiO and YSZ powder with a pore-forming agent in distilled water and a dispersing agent, the binder is added to the slurry after the stirred mixture is left for a period of time, and then stirring is performed for 9-12 hours. In this embodiment, the time of placement is about one day, i.e., 24±5 hours.
Ball milling, drying and degassing the slurry, and casting the prepared slurry into a NiO/YSZ film material in a die;
further, the prepared slurry is cast into a NiO/YSZ film material in a mould, specifically: and vacuumizing the slurry, forming on a casting machine, and demolding, wherein the thickness of the ceramic sheet is 0.4-0.6 mm.
Preparing a NiO/YSZ porous membrane material by sintering the cast NiO/YSZ membrane material at high temperature;
Further, the preparation of the NiO/YSZ porous membrane material comprises the following specific steps: the high-temperature sintering is programmed heating and firing, when the NiO/YSZ film is programmed heating and firing, the heating rate from room temperature to 400 ℃ is 1-2 ℃/min, the heating rate from 400 ℃ to 1300-1600 ℃ is 1-3 ℃/min after the constant temperature is kept at 400 ℃ for 2 hours, the constant temperature is kept at 1300-1600 ℃ for 4 hours, and finally the temperature is reduced to room temperature at 1-2 ℃/min.
Preparing a solid acid solution: reacting metal salt with acid according to a certain mole ratio to prepare a solid acid material;
further, the solid acid is one or more combinations of MH xXO4, where M is Cs, rb, K or NH 4 and X is S or P.
The solid acid can be self-prepared. Specifically, one or more of CsH2PO4、RbH2PO4、K2HPO4、NH4H2PO4、CsHSO4、RbHSO4、KHSO4、NH4HSO4 may be combined.
The mass of the solid acid is 40-50 g corresponding to the mass of the slurry.
Further, the sintered NiO/YSZ film is immersed in a solid acid solution at the temperature of 150-200 ℃ for 4-6 hours.
Immersing the prepared porous membrane material in a solid acid solution at a preset high temperature;
Repeatedly dipping for a certain number of times, and vacuum drying after dipping is completed to obtain the NiO/YSZ composite electrolyte membrane material.
Further, the molar ratio of the nickel oxide, the yttria-stabilized zirconia and the solid acid material is calculated according to the actual weighing mass, and the content of the solid acid material in the composite material is calculated. Can be adjusted according to the actual situation.
Example 1
The embodiment relates to a preparation method of a NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature, wherein in the composite electrolyte membrane, the mass ratio of yttria-stabilized zirconia, nickel oxide and solid acid materials is 5:3:3, a step of; the method specifically comprises the following steps:
step 1: preparing nickel oxide, yttria-stabilized zirconia oxide, a pore-forming agent, a dispersing agent and water into slurry; in the embodiment, 30g of zirconia powder, 18g of nickel oxide, 10.5g of dispersing agent, 1.5g of binder and 5g of pore-forming agent selected from graphite or starch;
step 2: ball milling the mixed slurry for 24 hours, adding a binder, stirring, and ball milling for 9 hours;
Step 3: drying and degassing the slurry, forming on a casting machine, and demolding to prepare a NiO/YSZ film with the thickness of 0.42mm;
Step 4: the NiO/YSZ film is sintered at a high temperature, the sintering at the high temperature is programmed to be heated, when the NiO/YSZ film is programmed to be heated, the heating rate from room temperature to 400 ℃ is 2 ℃/min, after the constant temperature is kept at 400 ℃ for 2 hours, the heating rate from 400 ℃ to 1400 ℃ is 2 ℃/min, the constant temperature is kept at 1400 ℃ for 4 hours, and finally the temperature is reduced to room temperature at 2 ℃/min, so that the NiO/YSZ porous film is prepared;
step 5: mixing 40g of the prepared solid acid CsH 2PO4 material with a small amount of distilled water, and heating the solution to 200 ℃;
Step 6: vacuumizing the NiO/YSZ porous film to remove air in the pore canal, putting the porous film into a solid acid solution which is configured with heating, soaking for 4 hours at constant temperature, repeating the process for 8-10 times, drying at room temperature, and weighing 0.116g;
step 7: the impregnated composite electrolyte membrane material was taken out and heat treated at 150℃under steam conditions, and dried at room temperature, and then weighed 0.145g.
Example 2
The embodiment relates to a preparation method of a NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature, wherein in the composite electrolyte membrane, the total mass ratio of yttria-stabilized zirconia, nickel oxide and solid acid materials is 6:3:1, a step of; the method specifically comprises the following steps:
step 1: preparing yttria-stabilized zirconia oxide, nickel oxide, a pore-forming agent, a dispersing agent and water into slurry; in the embodiment, 32g of zirconia powder, 16g of nickel oxide, 11g of dispersing agent, 2g of binder and 6g of pore-forming agent selected from graphite or starch pore-forming agent;
step 2: ball milling the mixed slurry for 12 hours, adding a binder, stirring and ball milling for 9 hours;
step 3: drying and degassing the slurry, forming on a casting machine, and demolding to prepare a NiO/YSZ film with the thickness of 0.6mm;
Step 4: the NiO/YSZ film is sintered at a high temperature, the sintering at the high temperature is programmed to be heated, when the NiO/YSZ film is programmed to be heated, the heating rate from room temperature to 405 ℃ is 2 ℃/min, after the constant temperature is kept at 405 ℃ for 2 hours, the heating rate from 405 ℃ to 1500 ℃ is 3 ℃/min, the constant temperature is kept at 1500 ℃ for 4 hours, and finally the temperature is reduced to the room temperature at 2 ℃/min, so that the NiO/YSZ porous film is prepared;
Step 5: 45g of the prepared solid acid CsH 2PO4、RbH2PO4 mixture was mixed with a small amount of distilled water, and the solution was heated to 200 ℃;
step 6: vacuumizing the NiO/YSZ porous film to remove air in the pore canal, putting the porous film into a solid acid solution which is configured with heating, soaking for 4 hours at constant temperature, repeating the process for 8-10 times, drying at room temperature, and weighing 0.12g;
Step 7: the impregnated composite electrolyte membrane material was taken out and heat-treated at 150℃under steam conditions, and dried at room temperature, and then weighed 0.133g.
Example 3
The embodiment relates to a preparation method of a NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature, wherein in the composite electrolyte membrane, the total mass ratio of yttria-stabilized zirconia oxide, nickel oxide and solid acid material is 6:2:2; the method specifically comprises the following steps:
Step 1: preparing nickel oxide, yttria-stabilized zirconia oxide, a pore-forming agent, a dispersing agent and water into slurry; in the embodiment, 30g of zirconia powder, 10g of nickel oxide, 10.5g of dispersing agent, 1.5g of binder and 5g of pore-forming agent selected from graphite or starch;
step 2: ball milling the mixed slurry for 12 hours, adding a binder, stirring and ball milling for 9 hours;
Step 3: drying and degassing the slurry, forming on a casting machine, and demolding to prepare a NiO/YSZ film with the thickness of 0.5mm;
step 4: the NiO/YSZ film is sintered at a high temperature, the sintering at the high temperature is programmed to be heated, when the NiO/YSZ film is programmed to be heated, the heating rate from room temperature to 400 ℃ is 1 ℃/min, after the constant temperature is kept at 400 ℃ for 2 hours, the heating rate from 400 ℃ to 1600 ℃ is 2 ℃/min, the constant temperature is kept at 1600 ℃ for 4 hours, and finally the temperature is reduced to the room temperature at 2 ℃/min, so that the NiO/YSZ porous film is prepared;
step 5: after 50g of the prepared solid acid CsHSO 4、KHSO4 mixture was mixed with a small amount of distilled water again, the solution was heated to 150 ℃;
Step 6: vacuumizing the NiO/YSZ porous film to remove air in the pore canal, putting the porous film into a solid acid solution which is configured with heating, soaking for 6 hours at constant temperature, repeating the above process for 8-10 times, drying at room temperature, and weighing 0.118g;
step 7: the impregnated composite electrolyte membrane material was taken out and heat treated at 150℃under steam conditions, and dried at room temperature, and then weighed 0.147g.
Example 4
The embodiment relates to a preparation method of a solid acid fuel cell, which adopts Pt/C as an electrode material and adopts the NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature as a composite electrolyte film, wherein the composite electrolyte film comprises nickel oxide, yttria-stabilized zirconia oxide and solid acid material with the total mass ratio of 5:3:3, a step of; the method specifically comprises the following steps:
Step 1: preparing nickel oxide, yttria-stabilized zirconia oxide, a pore-forming agent, a dispersing agent and water into slurry; 30g of zirconia powder, 18g of nickel oxide, 10.5g of dispersing agent, 1.5g of binder and 5g of pore-forming agent selected from graphite or starch pore-forming agent;
Step 2: ball milling the mixed slurry for 24 hours, adding a binder, stirring and ball milling for 9 hours;
Step 3: drying and degassing the slurry, forming on a casting machine, and demolding to prepare a NiO/YSZ film with the thickness of 0.42mm;
Step 4: the NiO/YSZ film is sintered at a high temperature, the sintering at the high temperature is programmed to be heated, when the NiO/YSZ film is programmed to be heated, the heating rate from room temperature to 400 ℃ is 2 ℃/min, after the constant temperature of 400 ℃ is kept for 1.85h, the heating rate from 400 ℃ to 1300 ℃ is 2 ℃/min, the constant temperature of 1300 ℃ is kept for 4.25h, and finally the temperature is reduced to room temperature at 1.5 ℃/min, so that the NiO/YSZ porous film is prepared;
Step 5: mixing 40g of solid acid CsH 2PO4 or K 2HPO4 and other materials with distilled water, and heating the solution to 200 ℃;
Step 6: vacuumizing the NiO/YSZ porous film to remove air in the pore canal, putting the porous film into a solid acid solution which is configured with heating, soaking for 4 hours at constant temperature, repeating the process for 8-10 times, drying at room temperature, and weighing 0.116g;
Step 7: taking out the impregnated composite electrolyte film material, performing heat treatment under the water vapor condition of 150 ℃, drying at room temperature, and weighing 0.145g;
step 8: and laminating the Pt/C thin sheet and the impregnated composite electrolyte film, and preparing the solid acid fuel cell under the conditions of 80 ℃ and 15Mpa pressure and constant temperature for 30min.
Example 5
The present example relates to a method for preparing a solid acid fuel cell, which uses Pt/C as an electrode material and uses the NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature as a composite electrolyte membrane, wherein the total mass ratio of nickel oxide, yttria-stabilized zirconia oxide, and solid acid material is 6:3:1, a step of; the method specifically comprises the following steps:
Step 1: preparing nickel oxide, yttria-stabilized zirconia oxide, a pore-forming agent, a dispersing agent and water into slurry; in the embodiment, 32g of zirconia powder, 16g of nickel oxide, 11g of dispersing agent, 2g of binder and 6g of pore-forming agent selected from graphite or starch pore-forming agent;
step 2: ball milling the mixed slurry for 24 hours, adding a binder, stirring and ball milling for 12 hours;
step 3: drying and degassing the slurry, forming on a casting machine, and demolding to prepare a NiO/YSZ film with the thickness of 0.6mm;
Step 4: the NiO/YSZ film is sintered at a high temperature, the sintering at the high temperature is programmed to be heated, when the NiO/YSZ film is programmed to be heated, the heating rate from room temperature to 400 ℃ is 2 ℃/min, after the constant temperature is kept at 400 ℃ for 2 hours, the heating rate from 400 ℃ to 1500 ℃ is 1 ℃/min, the constant temperature is kept at 1500 ℃ for 4 hours, and finally the temperature is reduced to room temperature at 1 ℃/min, so that the NiO/YSZ porous film is prepared;
Step 5: mixing 45g of solid acid CsH 2PO4 or RbH 2PO4 and other materials with distilled water, and heating the solution to 200 ℃;
step 6: vacuumizing the NiO/YSZ porous film to remove air in the pore canal, putting the porous film into a solid acid solution which is configured with heating, soaking for 4 hours at constant temperature, repeating the process for 8-10 times, drying at room temperature, and weighing 0.12g;
Step 7: taking out the impregnated composite electrolyte film material, performing heat treatment under the water vapor condition of 150 ℃, drying at room temperature, and weighing 0.133g;
step 8: and laminating the Pt/C thin sheet and the impregnated composite electrolyte film, and keeping the temperature and the pressure at 85 ℃ and 16Mpa for 30min to prepare the solid acid fuel cell.
Example 6
The present example relates to a method for preparing a solid acid fuel cell, which uses Pt/C as an electrode material and uses the NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature as a composite electrolyte membrane, wherein the total mass ratio of nickel oxide, yttria-stabilized zirconia oxide, and solid acid material is 6:2:2; the method specifically comprises the following steps:
Step 1: preparing nickel oxide, yttria-stabilized zirconia oxide, a pore-forming agent, a dispersing agent and water into slurry; in the embodiment, 30g of zirconia powder, 10g of nickel oxide, 10.5g of dispersing agent, 1.5g of binder and 5g of pore-forming agent selected from graphite or starch;
step 2: ball milling the mixed slurry for 24 hours, adding a binder, stirring and ball milling for 12 hours;
Step 3: drying and degassing the slurry, forming on a casting machine, and demolding to prepare a NiO/YSZ film with the thickness of 0.5mm;
Step 4: the NiO/YSZ film is sintered at a high temperature, the sintering at the high temperature is programmed to be heated, when the NiO/YSZ film is programmed to be heated, the heating rate from room temperature to 400 ℃ is 2 ℃/min, after the constant temperature is kept at 400 ℃ for 2 hours, the heating rate from 400 ℃ to 1600 ℃ is 2 ℃/min, the constant temperature is kept at 1600 ℃ for 4 hours, and finally the temperature is reduced to the room temperature at 2 ℃/min, so that the NiO/YSZ porous film is prepared;
step 5: distilled water is added into 50g of solid acid CsHSO 4 or KHSO 4, and the solution is heated to 200 ℃;
step 6: vacuumizing the NiO/YSZ porous film to remove air in the pore canal, putting the porous film into a solid acid solution which is configured with heating, soaking for 4 hours at constant temperature, repeating the above process for 8-10 times, drying at room temperature, and weighing 0.118g;
step 7: taking out the impregnated composite electrolyte film material, performing heat treatment under the water vapor condition of 150 ℃, drying at room temperature, and weighing 0.147g;
step 8: and laminating the Pt/C thin sheet and the impregnated composite electrolyte film, and preparing the solid acid fuel cell under the conditions of 80 ℃ and 15Mpa pressure and constant temperature for 30min.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. The preparation method of the NiO/YSZ composite electrolyte membrane impregnated with the solid acid at high temperature is characterized by comprising the following steps: preparing slurry, ball milling, degassing, casting, calcining and drying, and specifically comprises the following steps:
preparing yttria-stabilized zirconia powder, nickel oxide, a pore-forming agent, a dispersing agent, a binder and water into slurry, wherein the slurry comprises the following components in percentage by mass: 34.9-38.8%, 11.6-19.4%, 14.1-17.4%, 1.7-2.4%, 4.7-5.8% and the balance water;
ball milling, drying and degassing the slurry, and casting the prepared slurry into a NiO/YSZ film material in a die;
Preparing a NiO/YSZ porous membrane material by sintering the cast NiO/YSZ membrane material at high temperature;
obtaining a solid acid solution;
soaking the prepared porous membrane material in a solid acid solution at 150-200 ℃ for 4-6 hours;
repeatedly dipping for 8-10 times, and vacuum drying after the dipping is finished to obtain the NiO/YSZ composite electrolyte membrane material.
2. The method according to claim 1, wherein the specific steps of slurry configuration are: the slurry is prepared by mixing NiO and YSZ powder with a pore-forming agent in distilled water and a dispersing agent, the binder is added to the slurry after the stirred mixture is left for a period of time, and then stirring is performed for 9-12 hours.
3. The method according to claim 1, wherein the prepared slurry is cast into NiO/YSZ film material in a die specifically: and vacuumizing the slurry, forming on a casting machine, and demolding, wherein the thickness of the ceramic sheet is 0.4-0.6 mm.
4. The method according to claim 1, wherein the preparation of NiO/YSZ porous membrane material is specifically: the high-temperature sintering is programmed heating and firing, when the NiO/YSZ film is programmed heating and firing, the heating rate from room temperature to 400+/-10 ℃ is 1-2 ℃/min, the heating rate from 400+/-10 ℃ to 1300-1600 ℃ is 1-3 ℃/min after the constant temperature of 400+/-10 ℃ is 2+/-0.5 h, the constant temperature of 1300-1600 ℃ is 4+/-0.5 h, and finally the temperature is reduced to room temperature at 1-2 ℃/min.
5. The method of claim 1, wherein the solid acid is one or more combinations of MH xXO4, wherein M is Cs, rb, K or NH 4 and X is S or P.
6. The method according to claim 1, wherein the molar ratio of nickel oxide, yttria stabilized zirconia, solid acid material, and the content of solid acid material in the composite is calculated as the actual weight.
7. A NiO/YSZ composite electrolyte membrane impregnated with solid acid at high temperature prepared based on the method of any one of claims 1 to 6.
8. A method for preparing a solid acid fuel cell, which is characterized in that a high-temperature solid acid-impregnated NiO/YSZ composite electrolyte membrane prepared by the method according to any one of claims 1-6 is used for preparing the solid acid fuel cell by laminating a Pt/C sheet and an impregnated composite electrolyte film, and keeping the temperature and the pressure constant for 30+/-5 min at 80+/-5 ℃ and 15+/-1 Mpa.
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| JP2005158269A (en) * | 2003-11-20 | 2005-06-16 | Nippon Telegr & Teleph Corp <Ntt> | Method for producing solid oxide fuel cell |
| CN101015079A (en) * | 2004-06-10 | 2007-08-08 | 加利福尼亚技术学院 | Processing techniques for the fabrication of solid acid fuel cell membrane electrode assemblies |
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| CN101015079A (en) * | 2004-06-10 | 2007-08-08 | 加利福尼亚技术学院 | Processing techniques for the fabrication of solid acid fuel cell membrane electrode assemblies |
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