CN116864763A - ScSZ electrolyte layer, preparation method thereof and battery - Google Patents
ScSZ electrolyte layer, preparation method thereof and battery Download PDFInfo
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- CN116864763A CN116864763A CN202311131912.8A CN202311131912A CN116864763A CN 116864763 A CN116864763 A CN 116864763A CN 202311131912 A CN202311131912 A CN 202311131912A CN 116864763 A CN116864763 A CN 116864763A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title abstract description 54
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 84
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 80
- 239000000843 powder Substances 0.000 claims abstract description 46
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 44
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 42
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 36
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 34
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 30
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 22
- 239000001103 potassium chloride Substances 0.000 claims abstract description 22
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 20
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 28
- 239000003153 chemical reaction reagent Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 abstract description 10
- 230000005611 electricity Effects 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 description 17
- 239000002994 raw material Substances 0.000 description 16
- 238000004070 electrodeposition Methods 0.000 description 15
- 238000007747 plating Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M8/1253—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
-
- 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
- H01M2008/1293—Fuel cells with solid oxide electrolytes
Landscapes
- 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)
- Conductive Materials (AREA)
Abstract
The invention relates to a ScSZ electrolyte layer, a preparation method thereof and a battery, relates to the technical field of solid oxide fuel cells, and aims to solve the technical problems of low stability and low conductivity of a conventional ScSZ electrolyte layer. The preparation method of the ScSZ electrolyte layer provided by the invention comprises the following steps: sodium fluoride, potassium chloride, lithium fluoride, zirconium dioxide and scandium oxide are put into a reaction kettle; heating the reaction kettle to a first preset temperature, and preserving heat for a first preset time period to generate ScSZ powder in the reaction kettle; preparing an electrolyte, wherein the electrolyte comprises sodium fluoride, potassium fluoride and lithium fluoride; the ScSZ powder was put into the electrolyte, the electrolyte was heated, and electricity was applied to the electrolyte to deposit the ScSZ electrolyte layer.
Description
Technical Field
The invention relates to the technical field of solid oxide fuel cells, in particular to a ScSZ electrolyte layer, a preparation method thereof and a cell.
Background
Related art usually adopts the sintering method to prepare the ScSZ powder, and the ScSZ powder prepared by this kind of method has great particle diameter, and stability and conductivity are relatively poor, have reduced electrolysis efficiency.
Therefore, the invention provides a preparation method of the ScSZ electrolyte layer to prepare the ScSZ electrolyte layer with high stability and high conductivity, which is a technical problem to be solved in the prior art.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a ScSZ electrolyte layer, which aims to solve the technical problems of low stability and low conductivity of the conventional ScSZ electrolyte layer.
Specifically, the invention is realized by the following technical scheme:
according to a first aspect of the present invention, there is provided a method for producing a ScSZ electrolyte layer, comprising: preparing a molten salt solvent, wherein the components of the molten salt solvent comprise sodium fluoride, potassium chloride and lithium fluoride; preparing a reaction reagent, wherein the reaction reagent comprises zirconium dioxide and scandium oxide; putting molten salt solvent and reaction reagent into a reaction kettle; heating the reaction kettle to a first preset temperature, and preserving heat for a first preset time period to generate ScSZ powder in the reaction kettle; preparing an electrolyte, wherein the electrolyte comprises sodium fluoride, potassium fluoride and lithium fluoride; the ScSZ powder was put into the electrolyte, the electrolyte was heated, and electricity was applied to the electrolyte to deposit the ScSZ electrolyte layer.
In the technical scheme, the molar ratio of sodium fluoride, potassium chloride and lithium fluoride in the components of the molten salt solvent is 1-3: 1 to 5:1 to 5.
In the technical scheme, in the components of the molten salt solvent, the molar ratio of sodium fluoride to potassium chloride to lithium fluoride is 2:3:3.
in the technical scheme, the molar ratio of scandium oxide to zirconium dioxide is greater than or equal to 4:100, and less than or equal to 5:100.
in the above technical solution, the molar ratio of scandium oxide to zirconium dioxide is equal to 4.5:100.
in the above technical scheme, the first preset temperature is greater than or equal to 950 ℃ and less than or equal to 1250 ℃.
In the above technical solution, the first preset temperature is equal to 1100 ℃.
In the above technical solution, the first preset time period is greater than or equal to 10h and less than or equal to 300h.
In the above technical solution, the first preset duration is equal to 100h.
In the technical scheme, the molar ratio of sodium fluoride, potassium fluoride and lithium fluoride in the components of the electrolyte is 1-8: 1 to 4:1 to 2.
In the above technical solution, the molar ratio of sodium fluoride, potassium fluoride and lithium fluoride in the components of the electrolyte is equal to 4:2:1.
in the technical scheme, the mass ratio of the ScSZ powder to the electrolyte is greater than or equal to 8:100, and less than or equal to 12:100.
in the technical scheme, the mass ratio of the ScSZ powder to the electrolyte is equal to 10:100.
in the technical proposal, in the step of electrifying the electrolyte, the electrifying current density is more than or equal to 0.1A/dm 2 And less than or equal to 5A/dm 2 。
In the technical proposal, in the step of electrifying the electrolyte, the electrifying current density is more than or equal to 2A/dm 2 。
In the above technical scheme, in the step of heating the electrolyte, the temperature of the electrolyte is heated to 850 ℃ or higher and 1050 ℃ or lower.
In the technical scheme, in the step of electrifying the electrolyte, the electrifying time is longer than or equal to 30s and is smaller than or equal to 30min. Further, the energization time period is equal to 10min.
In the technical scheme, the mass ratio of the reactant to the molten salt solvent is more than or equal to 5% and less than or equal to 60%.
According to a second aspect of the present invention, there is provided a ScSZ electrolyte layer, which is prepared by the preparation method of the ScSZ electrolyte layer according to any one of the aspects of the first aspect of the present invention.
According to a third aspect of the present invention there is provided a battery comprising the ScSZ electrolyte layer of the second aspect of the invention.
The technical scheme provided by the invention has at least the following beneficial effects:
the ScSZ electrolyte layer (ScSZ, scandium stabilized zirconia) prepared by the method of the invention stabilizes the zirconia by the scandium trioxide, thus improving the stability of the zirconia.
On the other hand, the solid oxide ScSZ electrolyte layer prepared by the molten salt method and the electro-deposition method has small particle size of powder particles and uniform size distribution, and greatly improves the structural stability and electrochemical performance of the solid oxide ScSZ electrolyte layer.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
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 to be used in the description of the embodiments or the related art will be briefly described below, and it will be apparent to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is one of the flow charts of the preparation method of the ScSZ electrolyte layer provided in the preparation example of the invention;
FIG. 2 is a second flowchart of a method for preparing an ScSZ electrolyte layer according to the preparation example of the present invention;
FIG. 3 is a third preparation flow chart of the preparation method of the ScSZ electrolyte layer provided in the preparation example of the invention;
FIG. 4 is a fourth flowchart of the preparation method of the ScSZ electrolyte layer provided in the preparation example of the present invention;
FIG. 5 is a fifth flowchart of the preparation method of the ScSZ electrolyte layer according to the preparation example of the present invention;
fig. 6 is an electrolytic schematic diagram in the preparation method of the ScSZ electrolyte layer provided in the embodiment of the invention;
fig. 7 is a block diagram of a battery structure according to an embodiment of the present invention.
The correspondence between the reference numerals and the component names in fig. 6 and 7 is:
1 cell, 3 plating tank, 32 electrolyte, 34ScSZ powder, 36ScSZ electrolyte layer, 4 power source, 5 anode material, 6 cathode material.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the ScSZ electrolyte layer provided by the embodiment comprises the following steps: preparing a molten salt solvent, wherein the components of the molten salt solvent comprise sodium fluoride, potassium chloride and lithium fluoride; preparing a reaction reagent, wherein the reaction reagent comprises zirconium dioxide and scandium oxide; sodium fluoride, potassium chloride, lithium fluoride, zirconium dioxide and scandium oxide are put into a reaction kettle; heating the reaction kettle to a first preset temperature, and preserving heat for a first preset time period to generate ScSZ powder in the reaction kettle; preparing an electrolyte, wherein the electrolyte comprises sodium fluoride, potassium fluoride and lithium fluoride; the ScSZ powder was put into the electrolyte, the electrolyte was heated, and electricity was applied to the electrolyte to deposit the ScSZ electrolyte layer.
In the preparation method of the ScSZ electrolyte layer provided by the embodiment, in the process of preparing the ScSZ electrolyte layer, firstly, sodium fluoride, potassium chloride, lithium fluoride, zirconium dioxide and scandium oxide are placed in a reaction kettle, the reaction kettle is heated to a first preset temperature, and the first preset time is kept warm, wherein sodium fluoride, potassium chloride and lithium fluoride are used as molten salt solvents, zirconium dioxide and scandium oxide are used as reaction reagents, so that the ScSZ powder can be generated in the reaction kettle after the reaction reagents are heated, scandium oxide can be diffused into the crystal structure of zirconium dioxide in the reaction process to form the ScSZ powder, therefore, the ScSZ powder is also called scandium oxide stabilized zirconia powder or scandium stabilized zirconia powder, then, the sodium fluoride, the potassium fluoride and the lithium fluoride are used as raw materials to prepare an electrolyte, the ScSZ powder is put into the electrolyte, the electrolyte is heated, and the electrolyte is electrified, so that pure ScSZ in the ScSZ powder can be deposited, and the ScSZ electrolyte layer is obtained. The ScSZ electrolyte layer prepared by the method of the invention stabilizes the zirconium dioxide by the scandium oxide, thus improving the stability of the zirconium oxide. On the other hand, the solid oxide ScSZ electrolyte layer prepared by the molten salt method and the plasma treatment method has small particle size of powder particles and uniform size distribution, and greatly improves the structural stability and electrochemical performance of the solid oxide ScSZ electrolyte layer.
In the above examples, the molar ratio of sodium fluoride, potassium chloride and lithium fluoride in the components of the molten salt solvent was 1 to 3:1 to 5:1 to 5.
In the technical scheme, the molar ratio of sodium fluoride, potassium chloride and lithium fluoride is 1-3: 1 to 5: 1-5, namely, 1-3 parts of sodium fluoride, 1-5 parts of potassium chloride and 1-5 parts of lithium fluoride are proportioned according to the mole in the process of preparing the molten salt solvent, and the reactant can be well dissolved in the molten salt solvent by controlling the mole ratio of the sodium fluoride, the potassium chloride and the lithium fluoride, so that the reactant is fully dispersed, and the reaction rate is improved. Alternatively, the molar ratio of sodium fluoride, potassium chloride and lithium fluoride is 2:3:3.
in the above examples, the molar ratio of scandium oxide to zirconium dioxide was 4 or more: 100, and less than or equal to 5:100.
in this example, the molar ratio of scandium oxide to zirconium dioxide was 4 or more: 100, and less than or equal to 5:100, that is, the atomic ratio of scandium atoms to zirconium atoms is 8 or more: 100, and 10 or less: 100, the atomic ratio of scandium atoms to zirconium atoms can be controlled to improve the reaction rate of scandium oxide and zirconium dioxide, reduce the reaction time and improve the yield of ScSZ. Further, the molar ratio of scandium oxide to zirconium dioxide is equal to 4.5:100. that is, the atomic ratio of scandium atoms to zirconium atoms is 9:100.
in the above embodiment, the first preset temperature is greater than or equal to 950 ℃ and less than or equal to 1250 ℃.
In this embodiment, the first preset temperature is greater than or equal to 950 ℃ and less than or equal to 1250 ℃, that is, the reaction temperature of scandium oxide and zirconium dioxide is greater than or equal to 950 ℃ and less than or equal to 1250 ℃, and further, the first preset temperature is equal to 1100 ℃, so that the scandium oxide doped zirconium dioxide can be ensured to react and form scandium oxide stable zirconium oxide powder (ScSZ powder).
In the above embodiment, the first preset time period is greater than or equal to 10h and less than or equal to 300h.
In this embodiment, the first preset time period is greater than or equal to 10h and less than or equal to 300h. That is, the reaction time of the scandium oxide and the zirconium dioxide is not less than 10 hours and not more than 300 hours, so that the scandium oxide doped with the zirconium dioxide can be ensured to form stable scandium oxide stabilized zirconia powder (ScSZ powder). Further, the first preset duration is equal to 100h.
In the above examples, the molar ratio of sodium fluoride, potassium fluoride and lithium fluoride in the components of the electrolyte was 1 to 8:1 to 4:1 to 2.
In the embodiment, the molar ratio of sodium fluoride, potassium fluoride and lithium fluoride in the components of the electrolyte is 1-8: 1-4: 1-2, namely, in the process of preparing electrolyte, the electrolyte is prepared according to the mole ratio, 1-8 parts of sodium fluoride, 1-4 parts of potassium fluoride and 1-2 parts of lithium fluoride, and further, the mole ratio of sodium fluoride, potassium fluoride and lithium fluoride is 4:2:1, thus the electrolysis efficiency can be ensured.
In the above embodiment, the mass ratio of the ScSZ powder to the electrolyte is 8 or more: 100, and less than or equal to 12:100.
in this embodiment, the mass ratio of the ScSZ powder to the electrolyte is 8 or more: 100, and less than or equal to 12:100, further, the mass ratio of the ScSZ powder to the electrolyte is equal to 10:100, so that the ScSZ powder is fully dissolved, and the adsorption efficiency of the ScSZ is improved.
In the above embodiment, in the step of supplying electricity to the electrolytic solution, the current density is 0.1A/dm or more 2 And less than or equal to 5A/dm 2 . Further, the current density is equal to 2A/dm 2 。
In the above embodiment, in the step of heating the electrolyte, the temperature of the electrolyte is heated to 850 ℃ or higher and 1050 ℃ or lower.
In the above embodiment, in the step of energizing the electrolyte, the energizing time period is 30s or longer and 30min or shorter.
In the above examples, the mass ratio of the reactive agent to the molten salt solvent was 5% or more and 60% or less.
According to a second aspect of the present invention, there is provided a ScSZ electrolyte layer, which is prepared according to the method for preparing a ScSZ electrolyte layer according to any one of the first aspect of the present invention.
Referring to fig. 7, an embodiment of the third aspect of the present invention provides a battery 1, the battery 1 provided by the present invention comprising the ScSZ electrolyte layer 36 of the embodiment of the second aspect of the present invention. Further, the battery of the present invention is a solid oxide cell, i.e., a SOEC cell.
Preparation example one
Referring to fig. 1, the present preparation example provides a preparation method of a ScSZ electrolyte layer of a battery, comprising the steps of:
s101: preparing raw materials of 1mol of sodium fluoride, 1mol of potassium chloride and 1mol of lithium fluoride as molten salt solvents;
s102: preparing raw materials of 1mol of zirconium dioxide and 0.04mol of scandium oxide as reaction reagents;
s103: the preparation method comprises the steps of (1) placing a reaction reagent and a molten salt solvent in a sintering container for sintering treatment, wherein the sintering temperature is 950 ℃, preserving heat for 10 hours, and then cleaning and drying to prepare ScSZ powder;
s104: preparing raw materials of 1mol of sodium fluoride, 2mol of potassium fluoride and 1mol of lithium fluoride as electrolyte, mixing 8g of ScSZ powder with 100g of electrolyte, placing the mixed solution in a plating bath and connecting with an anode of a power supply, and placing the other end of the power supply, which is connected with a graphite plate, in the plating bath for electrodeposition to deposit a ScSZ electrolyte layer; wherein, electrodeposition process sets up: current density 0.1A/dm 2 The temperature was set at 850℃and the deposition time was 30s.
Preparation example two
Referring to fig. 2, the present preparation example provides a preparation method of a ScSZ electrolyte layer of a battery, comprising the steps of:
s201: preparing raw materials of 1mol of sodium fluoride, 2mol of potassium chloride and 1mol of lithium fluoride as molten salt solvents;
s202: preparing raw materials of 1mol of zirconium dioxide and 0.045mol of scandium oxide as reaction reagents;
s203: the preparation method comprises the steps of (1) placing a reaction reagent and a molten salt solvent in a sintering container for sintering treatment, wherein the sintering temperature is 1000 ℃, preserving heat for 50 hours, and then cleaning and drying to prepare ScSZ powder;
s204: preparing raw materials of 1mol of sodium fluoride, 4mol of potassium fluoride and 2mol of lithium fluoride as electrolyte, mixing 9g of ScSZ powder with 100g of electrolyte, placing the mixed solution in a plating bath and connecting with an anode of a power supply, and placing the other end of the power supply, which is connected with a graphite plate, in the plating bath for electrodeposition to deposit a ScSZ electrolyte layer; wherein, electrodeposition process sets up: current density 1A/dm 2 Setting the temperature to 900 ℃ and depositing for 1min.
Preparation example three
Referring to fig. 3, the present preparation example provides a preparation method of a ScSZ electrolyte layer of a battery, comprising the steps of:
s301: preparing raw materials of 1mol of sodium fluoride, 3mol of potassium chloride and 3mol of lithium fluoride as molten salt solvents;
s302: preparing raw materials of 1mol of zirconium dioxide and 0.045mol of scandium oxide as reaction reagents;
s303: the preparation method comprises the steps of (1) placing a reaction reagent and a molten salt solvent in a sintering container for sintering treatment, wherein the sintering temperature is 1050 ℃, preserving heat for 100 hours, and then cleaning and drying to prepare ScSZ powder;
s204: preparing raw materials of 5mol of sodium fluoride, 3mol of potassium fluoride and 1mol of lithium fluoride as electrolyte, mixing 10g of ScSZ powder with 100g of electrolyte, placing the mixed solution in a plating bath and connecting with an anode of a power supply, and placing the other end of the power supply, which is connected with a graphite plate, in the plating bath for electrodeposition to deposit a ScSZ electrolyte layer; wherein, electrodeposition process sets up: current density 2A/dm 2 Setting the temperature to 1000 ℃ and depositing for 5min.
Preparation example IV
Referring to fig. 4, the present preparation example provides a preparation method of a ScSZ electrolyte layer of a battery, comprising the steps of:
s401: preparing raw materials of 2mol of sodium fluoride, 2mol of potassium chloride and 5mol of lithium fluoride as molten salt solvents;
s402: preparing raw materials of 1mol of zirconium dioxide and 0.05 mol of scandium oxide as reaction reagents;
s403: the preparation method comprises the steps of (1) placing a reaction reagent and a molten salt solvent in a sintering container for sintering treatment, wherein the sintering temperature is 1100 ℃, preserving heat for 200 hours, and then cleaning and drying to prepare ScSZ powder;
s404: preparing raw materials of 8mol of sodium fluoride, 3mol of potassium fluoride and 2mol of lithium fluoride as electrolyte, mixing 11g of ScSZ powder with 100g of electrolyte, placing the mixed solution in a plating bath and connecting with an anode of a power supply, placing the other end of the power supply in the plating bath to be connected with a graphite plate for electrodeposition so as to deposit a ScSZ electrolyte layer; wherein, electrodeposition process sets up: current density 3A/dm 2 Setting the temperature at 1025 ℃ and depositing for 10min.
Preparation example five
Referring to fig. 5, the present preparation example provides a preparation method of a ScSZ electrolyte layer of a battery, comprising the steps of:
s501: preparing raw materials of 1mol of sodium fluoride, 3mol of potassium chloride and 5mol of lithium fluoride as molten salt solvents;
s502: preparing raw materials of 1mol of zirconium dioxide and 0.045mol of scandium oxide as reaction reagents;
s503: the preparation method comprises the steps of (1) placing a reaction reagent and a molten salt solvent in a sintering container for sintering treatment, wherein the sintering temperature is 1250 ℃, preserving heat for 300 hours, and then cleaning and drying to finish the preparation of ScSZ powder;
s504: preparing raw materials of 8mol of sodium fluoride, 1mol of potassium fluoride and 1mol of lithium fluoride as electrolyte, mixing 12g of ScSZ powder with 100g of electrolyte, placing the mixed solution in a plating bath and connecting with an anode of a power supply, and placing the other end of the power supply, which is connected with a graphite plate, in the plating bath for electrodeposition to deposit a ScSZ electrolyte layer; wherein, electrodeposition process sets up: current density 5A/dm 2 Setting 1050 ℃ for 30min.
Further, in the preparation method of the ScSZ electrolyte layer of the battery of each preparation example, the electrolysis principle is shown in fig. 6, the electrolyte 32 composed of NaF, KF and LiF and the ScSZ powder 34 are in the electroplating tank 3, the anode of the power source 4 is penetrated into the electrolyte 32 through the anode material 5, the cathode of the power source 4 is penetrated into the electrolyte 32 through the cathode material 6, the cathode material 6 may be a graphite plate, after the power source 4 is electrified, the ScSZ powder 34 in the electrolyte 32 moves to the anode of the power source, adheres to the surface of the anode material 5 to form the ScSZ electrolyte layer 36, and finally the ScSZ electrolyte layer 36 adsorbed on the surface of the anode material 5 is separated to obtain the pure ScSZ electrolyte layer 36, the stability and the stability of the ScSZ electrolyte layer obtained by the preparation method of the ScSZ electrolyte layer of each preparation example are higher than the industry standard, and the technological conditions and the corresponding performances of the preparation examples are shown in table one:
table 1 process conditions and corresponding properties for preparation one to preparation five
| Preparation example one | Preparation example two | Preparation example three | Preparation example IV | Preparation example five | |
| NaF: KCl: liF (molar ratio) | 1：1：1 | 1：2：1 | 1：3：3 | 2：2：5 | 1：3：5 |
| ZrO2: sc2O3 (atomic ratio of zirconium and scandium) | 100：8 | 100：9 | 100：9 | 100：10 | 100：9 |
| Sintering temperature (. Degree. C.) | 950 | 1000 | 1050 | 1100 | 1250 |
| Time of thermal insulation (h) | 10 | 50 | 100 | 200 | 300 |
| NaF: KF: liF (molar ratio) | 1：2：1 | 1：4：2 | 5：3：1 | 8：3：2 | 8：1：1 |
| ScSZ powder A: electrolyte B (mass ratio) | 8：100 | 9：100 | 10：100 | 11：100 | 12：100 |
| Electrodeposition process current density (A/dm 2) | 0.1 | 1 | 2 | 3 | 5 |
| Electrodeposition process temperature (. Degree. C.) | 850 | 900 | 1000 | 1025 | 1050 |
| Electrodeposition processDeposition time | 30s | 1 min | 5 min | 10 min | 30 min |
| Electrochemical Properties (W/cm 2) | 0.83 | 0.75 | 0.81 | 0.82 | 0.78 |
| Stability (decay rate/kilohour) | 6.8% | 5.8% | 6.5% | 6.7% | 6.3% |
List one
In the prior art, the electrochemical performance power density of a typical solid oxide cell, such as an electrolyte supported version of the SOFCMAN manufacturer, is about 0.9W/cm 2; the stability decay rate was about 5.1%/kilohour.
The invention has the following beneficial effects:
the invention stabilizes the zirconium dioxide by scandium trioxide, thus improving the stability of the zirconium dioxide. On the other hand, the solid oxide ScSZ electrolyte layer prepared by the molten salt method and the electro-deposition method has small particle size of powder particles and uniform size distribution, and greatly improves the structural stability and electrochemical performance of the solid oxide ScSZ electrolyte layer.
While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any invention or of what may be claimed, but rather as descriptions of features of specific embodiments of particular inventions. Certain features that are described in this specification in the context of separate embodiments can also be implemented in combination in a single embodiment. On the other hand, the various features described in the individual embodiments may also be implemented separately in the various embodiments or in any suitable subcombination. Furthermore, although features may be acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination.
Similarly, although operations are depicted in the drawings in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be performed, to achieve desirable results. In some cases, multitasking and parallel processing may be advantageous. Moreover, the separation of various system modules and components in the embodiments described above should not be understood as requiring such separation in all embodiments, and it should be understood that the described program components and systems can generally be integrated together in a single software product or packaged into multiple software products.
Thus, particular embodiments of the subject matter have been described. Other embodiments are within the scope of the following claims. In some cases, the actions recited in the claims can be performed in a different order and still achieve desirable results. Furthermore, the processes depicted in the accompanying drawings are not necessarily required to be in the particular order shown, or sequential order, to achieve desirable results. In some implementations, multitasking and parallel processing may be advantageous.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. The present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (20)
1. A method for preparing a ScSZ electrolyte layer, comprising:
preparing a molten salt solvent, wherein the components of the molten salt solvent comprise sodium fluoride, potassium chloride and lithium fluoride;
preparing a reactant, wherein the reactant comprises zirconium dioxide and scandium oxide;
placing the molten salt solvent and the reaction reagent in a reaction kettle;
heating the reaction kettle to a first preset temperature, and preserving heat for a first preset time period to generate ScSZ powder in the reaction kettle;
preparing an electrolyte, wherein the electrolyte comprises sodium fluoride, potassium fluoride and lithium fluoride;
and putting the ScSZ powder into the electrolyte, heating the electrolyte, and electrifying the electrolyte to deposit the ScSZ electrolyte layer.
2. The method for producing a ScSZ electrolyte layer according to claim 1, wherein the molar ratio of the sodium fluoride, the potassium chloride, and the lithium fluoride in the component of the molten salt solvent is 1 to 3:1 to 5:1 to 5.
3. The method for producing a ScSZ electrolyte layer according to claim 2, wherein,
in the components of the molten salt solvent, the molar ratio of the sodium fluoride to the potassium chloride to the lithium fluoride is 2:3:3.
4. the method for producing a ScSZ electrolyte layer according to claim 1, wherein,
the molar ratio of the scandium oxide to the zirconium dioxide is greater than or equal to 4:100, and less than or equal to 5:100.
5. the method for producing a ScSZ electrolyte layer according to claim 4, wherein,
the molar ratio of scandium oxide to zirconium dioxide is equal to 4.5:100.
6. the method for producing a ScSZ electrolyte layer according to claim 1, wherein,
the first preset temperature is greater than or equal to 950 ℃ and less than or equal to 1250 ℃.
7. The method for producing a ScSZ electrolyte layer according to claim 6, wherein,
the first preset temperature is equal to 1100 ℃.
8. The method for producing a ScSZ electrolyte layer according to claim 1, wherein,
the first preset time length is greater than or equal to 10h and less than or equal to 300h.
9. The method for producing a ScSZ electrolyte layer according to claim 8, wherein,
the first preset duration is equal to 100h.
10. The method for producing a ScSZ electrolyte layer according to claim 1, wherein the molar ratio of the sodium fluoride, the potassium fluoride, and the lithium fluoride in the components of the electrolyte is 1 to 8:1 to 4:1 to 2.
11. The method for producing a ScSZ electrolyte layer according to claim 10, wherein,
in the components of the electrolyte, the molar ratio of the sodium fluoride, the potassium fluoride and the lithium fluoride is equal to 4:2:1.
12. the method for producing a ScSZ electrolyte layer according to claim 1, wherein,
the mass ratio of the ScSZ powder to the electrolyte is greater than or equal to 8:100, and less than or equal to 12:100.
13. the method for producing a ScSZ electrolyte layer according to claim 12, wherein,
the mass ratio of the ScSZ powder to the electrolyte is equal to 10:100.
14. the method for producing a ScSZ electrolyte layer according to claim 1, wherein in the step of applying current to the electrolyte solution, the current density is 0.1A/dm or more 2 And less than or equal to 5A/dm 2 。
15. The method for producing a ScSZ electrolyte layer according to claim 14, wherein in the step of energizing the electrolyte, an energizing current density is equal to 2A/dm 2 。
16. The method according to claim 1, wherein in the step of heating the electrolyte solution, the temperature of the electrolyte solution is heated to 850 ℃ or higher and 1050 ℃ or lower.
17. The method according to claim 1, wherein in the step of supplying current to the electrolyte solution, the current is supplied for 30s or longer and 30min or shorter.
18. The method for producing a ScSZ electrolyte layer according to claim 17, wherein in the step of energizing the electrolyte solution, the energizing time period is equal to 10min.
19. A ScSZ electrolyte layer, characterized in that it is prepared by a process for preparing a ScSZ electrolyte layer according to any one of claims 1 to 18.
20. A battery comprising the ScSZ electrolyte layer of claim 19.
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