CN114464858A - Preparation method of salt/ceramic composite electrolyte material - Google Patents
Preparation method of salt/ceramic composite electrolyte material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000003839 salts Chemical class 0.000 title claims abstract description 14
- 239000000919 ceramic Substances 0.000 title claims abstract description 13
- 239000002001 electrolyte material Substances 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 33
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 239000012693 ceria precursor Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000004321 preservation Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 abstract description 5
- 239000012792 core layer Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 238000000280 densification Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to the technical field of composite electrolyte materials, and discloses a preparation method of a salt/ceramic composite electrolyte material, aiming at solving the problem that the existing composite electrolyte material has poor performances such as density, ionic conductivity and the like, and the preparation method comprises the following steps: preparing ion-doped cerium dioxide precursor powder by using a coprecipitation method, and regulating and controlling the morphology of target powder by changing the molar ratio of a precipitator to metal ions in the preparation process of the cerium dioxide precursor powder. The invention can obtain different composite materials by changing the types of core layer and shell layer materials, and flexibly regulate and control the performances of the composite material such as density, grain size, ionic conductivity and the like by changing the parameters such as temperature, uniaxial pressure, heat preservation time and the like in the cold sintering process, and has the characteristics of simple operation, high efficiency and strong controllability.
Description
Technical Field
The invention relates to the technical field of composite electrolyte materials, in particular to a preparation method of a salt/ceramic composite electrolyte material.
Background
Solid Oxide Fuel Cells (SOFCs) are electrochemical devices that can directly convert stable chemical energy stored in substances into electrical energy, have the advantages of long service life, wide fuel selection, no need of precious metal catalysts, low power generation cost and the like, and have wide application prospects in the fields of fixed power stations, mobile power supply devices and portable electronic power supply systems. The electrolyte serves as the core component of the SOFCs, and in addition to isolating fuel gas and blocking electron conduction, the most important role is to conduct ions. CeO (CeO)2Is considered to be suitable for the advantages of simple structure, good stability, high oxygen ion conductivity and the likeAnd medium temperature (500-800 ℃) application. Its cubic fluorite structure allows for aliovalent doping by elements (e.g. Ca)2+/Gd3 +/Sm3+) External anionic cavities are formed, so that the material has good chemical stability and achieves a high ion transmission number.
However, in the case of doping with CeO2The preparation and application of (DCO) still face huge challenges. First, DCO typically requires sintering at 1600 ℃ > 1800 ℃ for tens of hours to achieve complete densification, which not only consumes much energy and is inefficient in sintering, but also thermally activated diffusion causes unwanted chemical reactions between the material and the surrounding environment. In order to lower the sintering temperature, many new sintering techniques have been developed, such as electric field assisted sintering (spark plasma sintering/flash sintering), microwave sintering, and liquid phase sintering. However, the temperature required by all the methods still exceeds 1000 ℃, and the performance of the material is not improved to a great extent, and the existing composite electrolyte material has the problems of poor performance such as compactness, ionic conductivity and the like.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a preparation method of a salt/ceramic composite electrolyte material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a salt/ceramic composite electrolyte material comprises the following steps:
preparing ion-doped cerium dioxide precursor powder by using a coprecipitation method, and regulating and controlling the morphology of target powder by changing the molar ratio of a precipitator to metal ions in the preparation process of the cerium dioxide precursor powder;
then mixing the precursor powder with a carbonate solution by a wet mixing method, drying and calcining to obtain a composite electrolyte powder with a core-shell structure;
and fully mixing the obtained composite powder with deionized water in a grinding bowl, transferring into a stainless steel mold, heating the mold to raise the temperature, simultaneously applying uniaxial pressure, preserving the heat, and cooling the mold to room temperature to obtain the salt/ceramic composite electrolyte block.
Preferably, the ions doped in the ceria precursor powder include one of Ca ions, Sm ions, and Gd ions.
Preferably, the carbonate in the carbonate solution as a shell structure includes Li2CO3、K2CO3、Na2CO3One or more of;
the carbonate solution has a mass fraction of 5-30 wt.%.
Preferably, the metal ions provided during the preparation of the ceria precursor powder by the coprecipitation method are salts that are readily soluble in water to form a clear solution.
Preferably, the metal salt for providing metal ions includes one of nitrate and chloride.
Preferably, the precipitant is a substance capable of binding the metal ions in a complex form in an aqueous solution.
Preferably, the precipitating agent comprises Na2CO3、(NH4)2CO3One kind of (1).
Preferably, the molar ratio of the precipitant to the metal ion is (1-3): 1.
preferably, the molar ratio of the precipitant to the metal ion is 1.5: 1.
preferably, the molar ratio of the precipitant to the metal ion is 2: 1.
preferably, the wet mixing method comprises the steps of: mixing ion-doped ceria precursor powder with a carbonate solution, placing the mixture on a magnetic stirrer with a heating function, stirring at a constant speed, and gradually evaporating water to obtain a mixture;
then the mixture is put into a forced air drying oven for drying treatment, and then is put into a furnace for calcining at the temperature of 600 ℃ for 0.5-2h to obtain the composite electrolyte powder with the core-shell structure.
Preferably, the mass fraction of deionized water added to the composite electrolyte powder is 0-20 wt.%.
Preferably, the heating rate of the heating temperature rise of the die is 5 ℃/min; the sintering temperature is 100-250 ℃.
Preferably, the uniaxial pressure is 200-650 MPa.
Preferably, the heat preservation time is 0-120 min.
The invention has the beneficial effects that:
1. compared with the existing preparation method utilizing the core-shell structure such as chemical surface modification, the preparation method disclosed by the invention has the advantages that complex experimental equipment and operation steps are not needed, the ceramic @ carbonate composite electrolyte powder with the core-shell structure can be synthesized directly by mixing the precursor with the carbonate solution, and the operation flow is greatly simplified.
2. Compared with the existing low-temperature ceramic sintering method such as liquid phase sintering and electric field auxiliary sintering technology, the method adopts the carbonate which is easy to realize densification through cold sintering as the shell layer, and obtains the compact composite electrolyte block under the temperature condition of not more than 250 ℃.
3. The invention can obtain different composite materials by changing the types of core layer and shell layer materials, and flexibly regulate and control the performances of the composite material such as density, grain size, ionic conductivity and the like by changing the parameters such as temperature, uniaxial pressure, heat preservation time and the like in the cold sintering process, and has the characteristics of simple operation, high efficiency and strong controllability.
Drawings
FIG. 1 shows Sm doped CeO obtained in example 1 of the present invention2A microscopic morphology graph of the sodium carbonate composite powder;
FIG. 2 shows Sm doped CeO as obtained in inventive example 12XRD pattern of the compound powder with sodium carbonate;
FIG. 3 is Sm doped CeO obtained in example 1 of the present invention2The back scattering electron image of the sample after cold sintering is taken as a raw material together with the sodium carbonate composite powder;
FIG. 4 is Sm doped CeO obtained in example 3 of the present invention2Taking the sodium carbonate composite powder as a raw material, and carrying out cold sintering on the raw material to obtain a field emission image of a sample;
FIG. 5 is Sm doped CeO obtained in example 4 of the present invention2Taking the sodium carbonate composite powder as a raw material, and carrying out cold sintering on the raw material to obtain a field emission image of the sample;
FIG. 6 is Sm doped CeO obtained in example 5 of the present invention2And (3) taking the sodium carbonate composite powder as a raw material, and carrying out cold sintering on the obtained field emission image of the sample.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Respectively weighing a certain mass of nitrate and a precipitator before experiment, dissolving the nitrate and the precipitator in deionized water, slowly dripping a nitrate solution into the precipitator solution, stirring the mixed solution for 2 hours to enable the mixed solution to fully react, standing and aging the obtained mixture at room temperature for more than 6 hours to promote full nucleation, then repeatedly washing the precipitate by using deionized water to remove impurity ions, and drying the collected precipitate at 80 ℃ for 12 hours to obtain precursor powder; then mixing the precursor powder with a carbonate solution, placing the mixture on a magnetic stirrer with a heating function, stirring at a constant speed, gradually evaporating water, then placing the mixture into a forced air drying box for drying treatment, and then placing the mixture into a furnace for calcining at 600 ℃ for 0.5-2h to obtain a composite electrolyte powder with a core-shell structure; mixing 0-20 wt.% of deionized water with the calcined composite electrolyte powder, transferring the mixture into a stainless steel mold with an inner diameter of 12mm, heating the mixture to the temperature of 100-250 ℃ at a certain heating rate under the action of uniaxial pressure of 200-650MPa, keeping the temperature for 0-120min, and naturally cooling the mixture to the room temperature to finish the sintering of the composite electrolyte material.
The invention is further illustrated with reference to the following figures and examples, but the invention is not limited to the following examples.
Example 1
Step 1: 17.36g of Ce (NO) were weighed out separately3)3·6H2O, 4.445g of Sm (NO)3)3·6H2O and 10.6g of Na2CO3Dissolving in deionized water, slowly dropwise adding a mixed nitrate solution into a sodium carbonate solution, stirring the mixed solution for 2 hours to enable the mixed solution to fully react, standing and aging the obtained mixture at room temperature for more than 6 hours to promote full nucleation, then repeatedly washing the precipitate by using deionized water to remove impurity ions, and drying the collected precipitate at 80 ℃ for 12 hours to obtain precursor powder;
step 2: mixing the precursor powder with sodium carbonate solution to control Sm Doped Ceria (SDC) and Na2CO3Is 90:10, the mixture is placed on a magnetic stirrer with a heating function, the constant speed stirring is carried out, the water content is gradually evaporated, then the mixture is placed into a forced air drying box for drying treatment, and then the mixture is placed into a furnace for calcining at 600 ℃ for 1h to obtain the SDC @ Na with the core-shell structure2CO3A composite electrolyte powder;
and step 3: adding 5 wt.% deionized water to the calcined SDC @ Na2CO3Transferring the composite electrolyte powder into a stainless steel mold with the inner diameter of 12mm, applying uniaxial pressure of 500MPa, heating to 150 ℃ at the heating rate of 5 ℃/min, keeping for 30min, and naturally cooling to room temperature to obtain the composite electrolyte block.
And 4, step 4: the relative density of the sample tested by mass/volume method was 90.5%, and the obtained electrolyte block was subjected to conductivity test using an electrochemical workstation and the conductivity obtained at 700 ℃ was 9.89 mS/cm.
SDC @ Na obtained in example 1 of the invention2CO3The micro-morphology of the composite electrolyte powder is shown in figure 1; the XRD pattern of the composite powder is shown in figure 2, almost all diffraction peaks correspond to SDC with a cubic fluorite structure, and all Sm is shown3+Is completely doped into CeO2In the crystal structure; in addition, only a small weak peak with Na was found2CO3Related description of Na2CO3Should be present in the amorphous phase and not have any reaction with the SDC; miningThe microstructure of the sample after cold sintering using the composite powder as the raw material is shown in FIG. 3, where SDC and Na can be seen2CO3The distribution is uniform and the composite body has been sintered to near full densification.
Example 2
This example differs from example 1 in that: the composite electrolyte contains SDC and Na2CO3Is 95:5, is heated to 200 ℃ at a heating rate of 5 ℃/min during cold sintering, and has the same other parameters and steps as in example 1. SDC @ Na obtained2CO3The relative density of the composite electrolyte block is 88.3%, and the conductivity at 700 ℃ is 14 mS/cm.
Example 3
This example differs from example 1 in that: the composite electrolyte contains SDC and Na2CO3Is 100:0, the uniaxial pressure applied during cold sintering is 650MPa, and the other parameters and procedures are the same as in example 1. The fracture morphology of the obtained sample is shown in fig. 4. SDC @ Na obtained2CO3The relative density of the composite electrolyte block is 91.6%, and the conductivity at 700 ℃ is 20 mS/cm.
Example 4
This example differs from example 1 in that: the mass of the precipitant sodium carbonate is 7.95g, the set heat preservation time in the cold sintering process is 60min, and other parameters and steps are the same as those of the example 1. The fracture morphology of the obtained sample is shown in fig. 5, and it can be seen that the SDC obtained in this example is in the form of flaky particles, and a few pores exist among the particles in the sample after sintering. SDC @ Na obtained2CO3The relative density of the composite electrolyte block is 89%, and the conductivity at 700 ℃ is 12.6 mS/cm.
Example 5
This example differs from example 1 in that: the precipitant sodium carbonate is 5.3g in mass, and is heated to 180 ℃ at a heating rate of 5 ℃/min in the cold sintering process, and other parameters and steps are the same as those of the example 1. The fracture morphology of the obtained sample is shown in fig. 6, and it can be seen that the SDC obtained in this example has a thick plate shape, and due to the large and irregular particle size, the rearrangement process of the particlesIs hindered, so the sintered sample has loose particle arrangement in the fracture morphology and lower densification process. SDC @ Na obtained2CO3The relative density of the composite electrolyte block is 84.7%, and the conductivity at 700 ℃ is 9.2 mS/cm.
Example 6
This example differs from example 1 in that: 5 wt.% of deionized water was added to the composite electrolyte powder as a liquid phase before the cold sintering, and the uniaxial pressure applied was 350MPa, and other parameters and procedures were the same as in example 1. SDC @ Na obtained2CO3The relative density of the composite electrolyte block is 92%, and the conductivity at 700 ℃ is 9.89 mS/cm.
Example 7
This example differs from example 1 in that: before sintering, 20 wt.% of deionized water is added into the composite electrolyte powder as a liquid phase, and the composite electrolyte powder is heated to 250 ℃ at a heating rate of 5 ℃/min, and other parameters and steps are the same as those of the example 1. SDC @ Na obtained2CO3The relative density of the composite electrolyte block is 92.8%, and the conductivity at 700 ℃ is 11.6 mS/cm.
Example 8
This example differs from example 1 in that: the sintering temperature is 200 ℃, the uniaxial pressure is 600MPa, the heat preservation time is 120min, and other parameters and steps are the same as those of the example 1. SDC @ Na obtained2CO3The relative density of the composite electrolyte block is 94.6%, and the conductivity at 700 ℃ is 4.1 mS/cm.
The invention can synthesize the ceramic @ carbonate composite electrolyte powder with the core-shell structure directly by mixing the precursor with the carbonate solution without complex experimental equipment and operation steps, thereby greatly simplifying the operation flow.
The method adopts the carbonate which is easy to realize densification through cold sintering as a shell layer, and obtains the compact composite electrolyte block under the temperature condition of not more than 250 ℃, so that the method is not only suitable for wider material systems, but also greatly shortens the period of ceramic preparation, reduces energy consumption and has extremely high industrial value.
The invention can obtain different composite materials by changing the types of core layer and shell layer materials, and flexibly regulate and control the performances of the composite material such as density, grain size, ionic conductivity and the like by changing the parameters such as temperature, uniaxial pressure, heat preservation time and the like in the cold sintering process, and has the characteristics of simple operation, high efficiency and strong controllability.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of a salt/ceramic composite electrolyte material is characterized by comprising the following steps:
preparing cerium dioxide precursor powder doped with ions by using a coprecipitation method, and regulating and controlling the morphology of target powder by changing the molar ratio of a precipitator to metal ions in the preparation process of the cerium dioxide precursor powder;
then mixing the precursor powder with a carbonate solution by a wet mixing method, drying and calcining to obtain a composite electrolyte powder with a core-shell structure;
and fully mixing the obtained composite powder with deionized water in a grinding bowl, transferring into a stainless steel mold, heating the mold to raise the temperature, simultaneously applying uniaxial pressure, preserving the heat, and cooling the mold to room temperature to obtain the salt/ceramic composite electrolyte block.
2. The method of claim 1, wherein the ions doped in the ceria precursor powder include one of Ca ions, Sm ions, and Gd ions.
3. The method according to claim 1, wherein the shell is formed by a method of forming a salt/ceramic composite electrolyte materialThe carbonate in the structured carbonate solution comprises Li2CO3、K2CO3、Na2CO3One or more of;
the carbonate solution has a mass fraction of 5-30 wt.%.
4. The method of claim 1, wherein the metal ions provided during the co-precipitation process for preparing the ceria precursor powder are salts that are readily soluble in water to form a clear solution;
the precipitant is a substance capable of binding metal ions in a complex form in an aqueous solution.
5. The method according to claim 1, wherein the molar ratio of the precipitant to the metal ion is (1-3): 1.
6. the method of claim 1, wherein the wet mixing process comprises the steps of: mixing ion-doped ceria precursor powder with a carbonate solution, placing the mixture on a magnetic stirrer with a heating function, stirring at a constant speed, and gradually evaporating water to obtain a mixture;
then the mixture is put into a forced air drying oven for drying treatment, and then is put into a furnace for calcining at the temperature of 600 ℃ for 0.5-2h to obtain the composite electrolyte powder with the core-shell structure.
7. The method of claim 1, wherein the mass fraction of deionized water added to the composite electrolyte powder is 0-20 wt.%.
8. The method for preparing a salt/ceramic composite electrolyte material according to claim 1, wherein the heating rate of the mold for heating is 5 ℃/min; the sintering temperature is 100-250 ℃.
9. The method as claimed in claim 1, wherein the uniaxial pressure is 650MPa and 200 MPa.
10. The method according to claim 1, wherein the holding time is 0 to 120 min.
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