Preparation method of electrolyte sheet, electrolyte sheet and battery

Abstract

The invention relates to the technical field of batteries, and provides a preparation method of an electrolyte sheet, the electrolyte sheet and a battery, and the preparation method of the electrolyte sheet comprises the following steps: weighing metal nitrate according to a stoichiometric ratio BaxCeO3; dissolving metal nitrate in deionized water to obtain a metal nitrate solution; adding ethylenediamine tetraacetic acid and citric acid into the metal nitrate solution to obtain a first solution; adjusting the first solution to be alkaline to obtain a second solution; stirring the second solution to obtain colloid; drying the colloid to obtain precursor powder; the precursor powder is sintered, and target powder conforming to the stoichiometric ratio BaxCeO3 is obtained; sequentially carrying out ball-milling treatment, grinding treatment, dry-pressing molding treatment and calcination treatment on the target powder to obtain an electrolyte sheet; wherein the value range of x is as follows: x is greater than 1, and x is less than 1.09.

Description

Technical Field

[0001] The present invention relates to the technical field of batteries, and in particular to a preparation method of an electrolyte sheet, an electrolyte sheet and a battery. Background Art

[0002] In related technologies, the BaCeO3-based proton conductor electrolyte undergoes structural changes during the battery sintering process (>1400 °C), resulting in electrolyte instability; the structural instability causes the electrolyte film to have a porous structure and cracks, reducing proton conduction and battery stability.

[0003] Therefore, how to overcome the above technical defects has become a technical problem to be urgently solved. Summary of the Invention

[0004] In view of this, the present invention provides a preparation method of an electrolyte sheet, an electrolyte sheet and a battery.

[0005] Specifically, the present invention is implemented through the following technical solutions:

[0006] According to a first aspect of the present invention, there is provided a preparation method of an electrolyte sheet, the preparation method comprising: weighing metal nitrates according to the stoichiometric ratio Ba x CeO3; dissolving the metal nitrates in deionized water to obtain a metal nitrate solution; adding ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution to obtain a first solution; adjusting the first solution to be alkaline to obtain a second solution; stirring the second solution to obtain a colloid; drying the colloid to obtain a precursor powder; sintering the precursor powder to obtain a target powder conforming to the stoichiometric ratio Ba x CeO3; successively performing ball milling treatment, grinding treatment, dry pressing molding treatment and calcination treatment on the target powder to obtain an electrolyte sheet; wherein, the value range of x is: x is greater than 1 and x is less than 1.09.

[0007] The preparation method of the electrolyte sheet provided by the present application includes, according to the stoichiometric ratio Ba xWeigh metal nitrates, where the metal nitrates include metal barium ions and metal cerium ions, and the value range of x is: x > 1 and x < 1.09. Since barium is prone to evaporation at high temperatures, during the densification sintering process of the electrolyte, the temperature is usually higher than 1400 °C, and the evaporation loss of barium cannot be ignored. The evaporation loss of barium has a negative impact on the sintering and conductivity of the electrolyte. By using an excessive amount of barium, the barium loss caused by evaporation can be compensated. Dissolve the metal nitrates in deionized water to obtain a metal nitrate solution. Using deionized water as the solvent can avoid the influence of ions in the water on the composition of the solution. Add ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution to obtain a first solution. Adding ethylenediaminetetraacetic acid and citric acid helps improve the performance of the battery and protects the battery from corrosion. It can also provide good conductivity and has high chemical stability. Adjust the first solution to be alkaline to obtain a second solution, which can improve ion conductivity, improve chemical properties, and increase the energy density. Stir the second solution to obtain a colloid; dry the colloid to obtain a precursor powder. The properties and composition of the precursor powder have an important impact on the performance of the final product. Sinter the precursor powder to obtain a target powder that conforms to the stoichiometric ratio Ba x CeO3. Sintering can increase the density of the material, improve the properties of the material, increase the strength and hardness of the material. Sintering can densify the crystal lattice in the material and improve the mechanical properties of the target powder. Then, perform ball milling, grinding, dry pressing, and calcination treatments on the target powder in sequence to obtain an electrolyte sheet.

[0008] The preparation method of the electrolyte sheet provided in this application can inhibit the precipitation of B-site elements at high temperatures by increasing the proportion of barium elements, thereby improving the structural stability and conductivity of the electrolyte sheet.

[0009] In addition, the preparation method of the electrolyte sheet in the above technical solution provided in this application may also have the following additional technical features:

[0010] In some embodiments, optionally, the metal nitrates include: barium nitrate and cerium nitrate.

[0011] In some embodiments, optionally, dissolving the metal nitrates in deionized water to obtain a metal nitrate solution includes: adding deionized water to a container; adding the metal nitrates to the container; using a magnetic stirrer to stir and heating until the solution is completely dissolved to obtain a metal nitrate solution.

[0012] In some embodiments, optionally, adding ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution includes: weighing ethylenediaminetetraacetic acid and citric acid according to a preset molar ratio and adding ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution.

[0013] In some embodiments, optionally, the preset molar ratio is ethylenediaminetetraacetic acid:citric acid:metal ions of metal nitrate = 1:1:2.

[0014] In some embodiments, optionally, adjusting the first solution to be alkaline includes: adding ammonia water to the first solution to adjust the first solution to be alkaline so that the pH value of the first solution is equal to 8.

[0015] In some embodiments, optionally, stirring the second solution includes: continuously heating and stirring the second solution until the second solution becomes a viscous colloid; wherein, the stirring temperature is 80°C.

[0016] In some embodiments, optionally, drying the colloid to obtain a precursor powder includes: putting the colloid into a drying oven; after drying, a fluffy precursor powder is obtained.

[0017] In some embodiments, optionally, sintering the precursor powder to obtain a target powder of Ba x CeO3 includes: putting the precursor powder into a crucible; heating the crucible with a muffle furnace; sintering the precursor powder for 5 hours to obtain a target powder of Ba x CeO3.

[0018] In some embodiments, optionally, the sintering temperature is 1050°C.

[0019] In some embodiments, optionally, ball milling treatment includes: putting the target powder into absolute ethanol; ball milling for 5 hours.

[0020] In some embodiments, optionally, grinding treatment includes: collecting the mixture after ball milling treatment; putting the mixture in a mortar; grinding to obtain a dry powder.

[0021] In some embodiments, optionally, dry pressing and forming treatment includes: weighing 0.5 g of the powder after grinding treatment; under the pressure condition of 150 Mpa, dry pressing and forming.

[0022] In some embodiments, optionally, calcination treatment includes: calcining the green compact after dry pressing at 1450°C for 10 hours.

[0023] In some embodiments, optionally, after obtaining the target powder of Ba x CeO3, the preparation method further includes: weighing a preset weight of the target powder; under the pressure condition of 150 Mpa, pressing into a tablet.

[0024] In some embodiments, optionally, after pressing into a tablet, the preparation method further includes: calcining in a muffle furnace at a temperature of 1450°C for 10 hours.

[0025] In some embodiments, optionally, after calcination for 10 hours, the preparation method further includes: grinding the calcined pressed tablets into powder; collecting the powder and performing XRD characterization.

[0026] According to the second aspect of the present invention, there is provided an electrolyte sheet prepared by the preparation method of the electrolyte sheet in any one of the above embodiments.

[0027] Since the electrolyte sheet provided in this application is prepared by the preparation method of the electrolyte sheet in any one of the above embodiments, it has all the beneficial technical effects of the preparation method of the electrolyte sheet, which will not be elaborated here.

[0028] In some embodiments, optionally, the electrolyte sheet is a proton ceramic electrolyte sheet.

[0029] According to the third aspect of the present invention, there is provided a battery including: the electrolyte sheet in any one of the above embodiments.

[0030] Since the battery provided in this application includes the electrolyte sheet in any one of the above embodiments, it has all the beneficial technical effects of the electrolyte sheet, which will not be elaborated here.

[0031] The technical solution provided by the present invention at least brings the following beneficial effects:

[0032] The preparation method of the electrolyte sheet provided in this application, by increasing the proportion of barium element, inhibits the precipitation of B-site elements at high temperature, improves the structural stability and conductivity of the electrolyte sheet, and the prepared electrolyte sheet has high stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The accompanying drawings herein are incorporated into the specification and form a part of the specification, showing embodiments consistent with the present invention, and are used together with the specification to explain the principles of the present invention.

[0034] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or related technologies. Obviously, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without creative efforts.

[0035] Figure 1 It is one of the flow diagrams of the preparation method of the electrolyte sheet provided by the embodiment of the present invention;

[0036] Figure 2 It is another flow diagram of the preparation method of the electrolyte sheet provided by the embodiment of the present invention;

[0037] Figure 3 It is the XRD characterization diagram of the BaCeO3 electrolyte powder provided by the embodiment of the present invention;

[0038] Figure 4 XRD characterization diagram of the BaCeO3 electrolyte provided by the embodiment of the present invention after calcination at 1450°C;

[0039] Figure 5 Ba provided by the embodiment of the present invention 1.05 XRD characterization diagram of the BaCeO3 electrolyte powder;

[0040] Figure 6 Ba provided by the embodiment of the present invention 1.05 XRD characterization diagram of the BaCeO3 electrolyte after calcination at 1450°C;

[0041] Figure 7 Ba provided by the embodiment of the present invention 0.95 XRD characterization diagram of the BaCeO3 electrolyte powder;

[0042] Figure 8 Ba provided by the embodiment of the present invention 0.95 XRD characterization diagram of the BaCeO3 electrolyte after calcination at 1450°C. Detailed implementation manners

[0043] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Apparently, the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present application without creative efforts shall fall within the protection scope of the present application.

[0044] As Figure 1 shown, according to the first aspect of the present invention, a method for preparing an electrolyte sheet is provided, and the preparation method includes the following steps:

[0045] S102. Weigh metal nitrates according to the stoichiometric ratio of Ba x CeO3;

[0046] S104. Dissolve the metal nitrates in deionized water to obtain a metal nitrate solution;

[0047] S106. Add ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution to obtain a first solution;

[0048] S108. Adjust the first solution to be alkaline to obtain a second solution;

[0049] S110. Stir the second solution to obtain a colloid;

[0050] S112. Dry the colloid to obtain precursor powder.

[0051] S114. Sinter the precursor powder to obtain the target powder of Ba x CeO3 that meets the stoichiometric ratio.

[0052] S116. Perform ball milling, grinding, dry pressing and calcination on the target powder in sequence to obtain the electrolyte sheet.

[0053] Wherein, the value range of x is: x is greater than 1 and x is less than 1.09.

[0054] The preparation method of the electrolyte sheet provided by this application includes weighing metal nitrates according to the stoichiometric ratio of Ba x CeO3. The metal nitrates include metal barium ions and metal cerium ions. The value range of x is: x is greater than 1 and x is less than 1.09. Since barium is prone to evaporation at high temperatures, during the densification sintering process of the electrolyte, the temperature is usually higher than 1400°C, and the evaporation loss of barium cannot be ignored. The evaporation loss of barium has a negative impact on the sintering and conductivity of the electrolyte. By using an excessive amount of barium to compensate for the barium loss caused by evaporation. Dissolve the metal nitrates in deionized water to obtain a metal nitrate solution. Using deionized water as the solvent can avoid the influence of ions in the water on the composition of the solution. Add ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution to obtain the first solution. Adding ethylenediaminetetraacetic acid and citric acid helps to improve the performance of the battery and protect the battery from corrosion. It can also provide good conductivity and has high chemical stability. Adjust the first solution to be alkaline to obtain the second solution, which can improve ion conductivity, improve chemical properties and increase the energy density. Stir the second solution to obtain a colloid; dry the colloid to obtain precursor powder. The properties and composition of the precursor powder have an important impact on the performance of the final product. Sinter the precursor powder to obtain the target powder of Ba x CeO3 that meets the stoichiometric ratio. Sintering can increase the density of the material, improve the properties of the material, increase the strength and hardness of the material. Sintering can densify the lattice in the material and improve the mechanical properties of the target powder. Then perform ball milling, grinding, dry pressing and calcination on the target powder in sequence to obtain the electrolyte sheet.

[0055] In actual applications, x can be equal to 1.01, 1.02, 1.02, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09.

[0056] The preparation method of the electrolyte sheet provided by this application suppresses the precipitation of B-site elements at high temperatures by increasing the barium element ratio, and improves the structural stability and conductivity of the electrolyte sheet.

[0057] In some embodiments, optionally, the metal nitrate includes barium nitrate and cerium nitrate.

[0058] In this embodiment, the metal nitrate includes barium nitrate and cerium nitrate. Barium nitrate is a white crystalline powder, slightly hygroscopic, with strong oxidizing properties. Barium nitrate can be dissolved in water and concentrated sulfuric acid, and is insoluble in ethanol and concentrated nitric acid. Cerium nitrate is a white and clean solid at normal temperature and pressure, with strong hygroscopicity. In this application, barium nitrate and cerium nitrate are selected as raw materials for preparing the electrolyte sheet.

[0059] In some embodiments, optionally, the metal nitrate is dissolved in deionized water to obtain a metal nitrate solution, including: adding deionized water to a container; adding the metal nitrate to the container; using a magnetic stirrer to stir and heating until the solution is completely dissolved to obtain a metal nitrate solution.

[0060] In this embodiment, the steps of dissolving the metal nitrate in deionized water to obtain a metal nitrate solution include: adding deionized water to a container, which can be a beaker. Deionized water generally refers to pure water from which ionic impurities have been removed. Deionized water is used as a solvent to avoid the influence of ions in the water on the composition of the solution. Use a magnetic stirrer to stir. The magnetic stirrer is mainly used to stir or simultaneously heat and stir low-viscosity liquids or solid-liquid mixtures. The magnetic stirrer mainly uses the principle of repulsion between like poles and attraction between opposite poles of a magnetic field to use the magnetic field to drive the magnetic stir bar placed in the container to perform circular motion. Heat until the solution is completely dissolved. During the stirring process, heat the solution to increase the dissolution rate of the solution to obtain a metal nitrate solution.

[0061] In some embodiments, optionally, ethylenediaminetetraacetic acid and citric acid are added to the metal nitrate solution, including: weighing ethylenediaminetetraacetic acid and citric acid according to a preset molar ratio, and adding ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution.

[0062] In this embodiment, adding ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution includes: weighing ethylenediaminetetraacetic acid and citric acid according to a preset molar ratio. Ethylenediaminetetraacetic acid is an important complexing agent. It can be used to prepare electrolyte solutions and as a copper corrosion inhibitor, which helps improve the performance of the battery and protects the battery from corrosion. Ethylenediaminetetraacetic acid can protect the positive plate, increase the capacity of the battery, and inhibit the formation of lead sulfate between the positive plate grid and the positive active material. Citric acid can be used to produce high-performance lithium batteries. These lithium batteries have a high volume specific capacity and excellent cycling performance. As an electrolyte for lithium-ion batteries, citric acid can provide good conductivity and has high chemical stability. Moreover, citric acid can be used as an additive for the battery. Adding citric acid to the battery can improve the electrochemical performance of the battery, inhibit the polarization of the battery, and increase the energy density of the battery. Citric acid can also be used to prepare the positive electrode material of lithium batteries. By using citric acid as a precursor, a positive electrode material with high performance can be prepared, significantly improving the energy density and charge-discharge performance of lithium batteries.

[0063] In some embodiments, optionally, the preset molar ratio is ethylenediaminetetraacetic acid:citric acid:metal ions of metal nitrate = 1:1:2.

[0064] In this embodiment, the preset molar ratio is ethylenediaminetetraacetic acid:citric acid:metal ions of metal nitrate = 1:1:2.

[0065] In some embodiments, optionally, adjusting the first solution to be alkaline includes: adding ammonia water to the first solution to adjust the first solution to be alkaline so that the pH value of the first solution is equal to 8.

[0066] In this embodiment, adjusting the first solution to be alkaline includes: adding ammonia water to the first solution. Ammonia water can be used as an electrolyte for the battery to provide ionic conductivity and participate in the chemical reactions of the battery. Ammonia water can also be used as an additive for the battery. Adding ammonia water can improve the chemical performance of the battery and increase the energy density of the battery. In lithium-ion batteries, adding ammonia water can increase the capacity and stability of the positive electrode material, thereby increasing the energy density and charge-discharge performance of the battery. In this application, adding ammonia water to the first solution can adjust the first solution to be alkaline so that the pH value of the first solution is equal to 8.

[0067] In some embodiments, optionally, stirring the second solution includes: continuously heating and stirring the second solution until the second solution becomes a viscous colloid; wherein, the stirring temperature is 80 °C.

[0068] In this embodiment, stirring the second solution includes continuously heating and stirring the second solution. In order to increase the gelling rate of the second solution, during the stirring of the second solution, continuous heating is carried out while maintaining the stirring temperature at 80 °C. During the stirring process, the temperature should be prevented from being too high to avoid the second solution from becoming pasty. Continuously heat and stir until the second solution becomes a viscous colloid.

[0069] In some embodiments, optionally, drying the colloid to obtain a precursor powder includes: placing the colloid in a drying oven; after drying, a fluffy precursor powder is obtained.

[0070] In this embodiment, drying the colloid to obtain a precursor powder includes: placing the colloid in a drying oven. Generally, the drying oven uses drying media such as air, nitrogen, etc. to contact the colloid, and removes the moisture or other solvents in the colloid through processes such as evaporation, desorption, and diffusion to achieve the purpose of drying the colloid. There are various types of colloid drying ovens, including batch drying ovens, continuous drying ovens, and programmable drying ovens. The batch drying oven dries the colloid by placing the colloid in the drying oven and setting the temperature and time. The continuous drying oven can achieve continuous feeding and discharging, which is suitable for large-scale production. In this application, the colloid can be dried using a batch drying oven, a continuous drying oven, or a programmable drying oven, and a fluffy precursor powder is obtained after drying. The precursor powder generally refers to the raw material powder used before manufacturing the final product, and is usually used in the preparation of materials such as ceramics and metal oxides. The precursor powder usually needs to go through a series of preparation and processing steps, such as batching, mixing, grinding, screening, etc., to obtain the required particle size, purity, composition, and morphology.

[0071] In some embodiments, optionally, sintering the precursor powder to obtain a target powder of Ba x CeO3 includes: placing the precursor powder in a crucible; heating the crucible with a muffle furnace; sintering the precursor powder for 5 hours to obtain a target powder of Ba x CeO3.

[0072] In this embodiment, sintering the precursor powder to obtain a target powder of Ba x CeO3 includes: placing the precursor powder in a crucible. The crucible, as a refractory container, is used for reactions such as melting, heating, evaporation, and sintering. The crucible has the characteristics of high temperature resistance, corrosion resistance, good heat preservation, and high purity. The crucible includes quartz crucibles, magnetic crucibles, and graphite crucibles, and a suitable crucible can be selected according to requirements. Heating the crucible with a muffle furnace. The furnace body of the muffle furnace is made of refractory materials, and the heating elements of the muffle furnace generally use electric heating wires or electric heating rods, which can facilitate local or overall heating. The sintering time of the precursor powder is 5 hours, and a target powder of Ba x CeO3 can be obtained after sintering for 5 hours.

[0073] In some embodiments, optionally, the sintering temperature is 1050 °C.

[0074] In this embodiment, a muffle furnace is used to heat the crucible so that the temperature inside the crucible is maintained at about 1050 °C. A temperature detection device can be provided on the crucible to detect the sintering temperature inside the crucible. When the sintering temperature is lower than 1050 °C, the power of the muffle furnace can be increased. When the sintering temperature is higher than 1050 °C, the power of the muffle furnace can be decreased.

[0075] In some embodiments, optionally, the ball milling treatment includes: putting the target powder into absolute ethanol; and ball milling for 5 hours.

[0076] In this embodiment, the ball milling treatment includes: putting the target powder into absolute ethanol. Absolute ethanol has a certain dissolving ability and can dissolve, passivate and cover the surface of the target powder during the ball milling process, reduce the surface energy of the particles, and promote the refinement and dispersion of the particles. Absolute ethanol can also generate forces such as hydrogen bonds and van der Waals forces to help form a closer physical bond between the abrasive and the powder, further promoting the refinement of the particles. Absolute ethanol can also adjust the solvent environment to prevent particle aggregation and coagulation. Absolute ethanol can also play a role in carrying and dispersing the powder. During the ball milling process, absolute ethanol can carry and disperse the powder, reduce the surface energy of the powder and play a role in absorbing heat. The ball milling time in absolute ethanol is 5 hours. The ball milling treatment is carried out using a ball mill, wherein the rotation speed of the ball mill is greater than 200 revolutions per minute.

[0077] In some embodiments, optionally, the grinding treatment includes: collecting the mixture after the ball milling treatment; putting the mixture in a mortar; and grinding to obtain dry powder.

[0078] In this embodiment, the grinding treatment includes: collecting the mixture after the ball milling treatment, putting the mixture in a mortar. The mortar is mainly used for grinding solid substances or mixing powdered solids. The mortar has good high-temperature resistance and corrosion resistance, and dry powder is obtained by grinding in the mortar.

[0079] In some embodiments, optionally, the dry pressing forming treatment includes: weighing 0.5 g of the powder after the grinding treatment; and dry pressing and forming under a pressure condition of 150 Mpa.

[0080] In this embodiment, the dry pressing forming process includes weighing 0.5 g of the ground powder and dry pressing it under a pressure condition of 150 Mpa. The dry pressing forming generally requires the use of a dry pressing mold as the forming tool. The dry pressing mold is a tool in which granular blanks with a moisture content lower than 6% are placed and pressure is directly applied to form the product. The pressure of 150 Mpa is generally provided by machinery or professional tools. Under the action of the pressure, the ground powder will gradually become denser, and at the same time, air will be extruded. When the pressure reaches 150 Mpa, it is maintained for a period of time to completely solidify and form the ground powder.

[0081] In some embodiments, optionally, the calcination treatment includes: calcining the green body after dry pressing at 1450 °C for 10 hours.

[0082] In this embodiment, the calcination treatment includes: calcining the green body after dry pressing at 1450 °C for 10 hours. During the calcination process, the moisture and organic matter in the green body can be removed to make the substance purer. Calcination can also change the crystal form and lattice structure of the substance, thereby changing the properties of the substance. When calcined at a high temperature of 1450 °C, the activity of the substance molecules increases, which helps the progress of chemical reactions. In addition, calcination can also improve the stability and heat resistance of the substance.

[0083] In some embodiments, optionally, after obtaining the target powder of Ba x CeO3 that meets the stoichiometric ratio, the preparation method further includes: weighing a preset weight of the target powder; and pressing it into a tablet under a pressure condition of 150 Mpa.

[0084] In this embodiment, after obtaining the target powder of Ba x CeO3 that meets the stoichiometric ratio, the preparation method further includes: weighing a preset weight of the target powder; and pressing it into a tablet under a pressure condition of 150 Mpa. The preset weight can be 0.5 g. The pressure of 150 Mpa needs to be provided by machinery or professional tools. Under the action of the pressure, the target powder will gradually become denser, and at the same time, air will be extruded. When the pressure reaches 150 Mpa, it is maintained for a period of time to press the target powder into a tablet.

[0085] In some embodiments, optionally, after pressing into a tablet, the preparation method further includes: calcining in a muffle furnace at a temperature of 1450 °C for 10 hours.

[0086] In this embodiment, after pressing into a tablet, it is calcined in a muffle furnace at a temperature of 1450 °C for 10 hours. Calcining for 10 hours can remove the moisture and organic matter in the pressed tablet. When calcined at a high temperature of 1450 °C, the activity of the substance molecules increases, which helps the progress of chemical reactions. Calcination can also improve the stability and heat resistance of the substance.

[0087] In some embodiments, optionally, after calcination for 10 hours, the preparation method further includes: grinding the calcined compact into powder; collecting the powder and performing XRD characterization.

[0088] In this embodiment, after calcination for 10 hours, the calcined compact is ground into powder. The compact is placed in a mortar and ground to obtain dry powder. The powder is collected and subjected to XRD characterization. XRD characterization, i.e., X-ray diffraction, can be used to characterize the crystal structure of materials. By analyzing the diffraction pattern, information such as the lattice constant, unit cell parameter, and crystal symmetry of the material can be determined, thereby determining the crystal structure type and lattice distortion of the crystal.

[0089] In a specific embodiment, as Figure 2 shown, the preparation method of the electrolyte sheet provided by the present invention includes the following steps:

[0090] S202: Weigh barium nitrate and cerium nitrate according to the stoichiometric ratio Ba x CeO3;

[0091] S204: Add deionized water to a container; add metal nitrates to the container; use a magnetic stirrer to stir and heat until the solution is completely dissolved to obtain a metal nitrate solution;

[0092] S206: According to the molar ratio ethylenediaminetetraacetic acid: citric acid: metal ions of metal nitrates = 1:1:2, weigh ethylenediaminetetraacetic acid and citric acid, and add ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution to obtain a first solution;

[0093] S208: Add ammonia water to the first solution to adjust the first solution to be alkaline so that the pH value of the first solution is equal to 8;

[0094] S210: Continuously heat and stir the second solution until the second solution becomes a viscous colloid; wherein, the stirring temperature is 80°C;

[0095] S212: Place the colloid in an oven; after drying, obtain a fluffy precursor powder;

[0096] S214: Place the precursor powder in a crucible; heat the crucible with a muffle furnace; sinter the precursor powder for 5 hours to obtain a target powder conforming to the stoichiometric ratio Ba x CeO3; wherein, the sintering temperature is 1050°C;

[0097] S216: Place the target powder in absolute ethanol; ball mill for 5 hours;

[0098] S218: Collect the mixture after ball milling treatment; place the mixture in a mortar; grind to obtain dry powder;

[0099] S220. Weigh 0.5 g of the ground powder; under a pressure condition of 150 Mpa, perform dry pressing to form a green body.

[0100] S222. Calcinate the dry-pressed green body at 1450 °C for 10 hours to obtain an electrolyte sheet.

[0101] Wherein, the value range of x is: x is greater than 1 and x is less than 1.09.

[0102] According to the second aspect of the present invention, there is provided an electrolyte sheet prepared by the preparation method of the electrolyte sheet in any one of the above embodiments.

[0103] Since the electrolyte sheet provided in this application is prepared by the preparation method of the electrolyte sheet in any one of the above embodiments, it has all the beneficial technical effects of the preparation method of the electrolyte sheet, which will not be elaborated here.

[0104] In some embodiments, optionally, the electrolyte sheet is a proton ceramic electrolyte sheet.

[0105] In this embodiment, the electrolyte sheet is a proton ceramic electrolyte sheet. The proton ceramic electrolyte sheet is mainly used in fields such as fuel cells and hydrogen production by electrolyzing water. It has beneficial electrical conductivity and stability, can remain stable at high temperatures and in harsh environments, and also has high mechanical strength and corrosion resistance, and can be used for a long time in complex environments.

[0106] According to the third aspect of the present invention, there is provided a battery, comprising: the electrolyte sheet in any one of the above embodiments.

[0107] The battery provided in this application comprises the electrolyte sheet in any one of the above embodiments, so it has all the beneficial technical effects of the electrolyte sheet, which will not be elaborated here.

[0108] In a specific embodiment, taking x equal to 1 as an example, then Ba x CeO3 is BaCeO3, and the specific synthesis steps are as follows:

[0109] Weigh barium nitrate and cerium nitrate in corresponding stoichiometric ratios according to the chemical formula BaCeO3. Add them to a beaker containing an appropriate amount of deionized water, stir using a magnetic stirrer, and heat until the solution is completely dissolved. According to the molar ratio ethylenediaminetetraacetic acid: citric acid: metal ions = 1:1:2, weigh ethylenediaminetetraacetic acid and citric acid and add them to the above nitrate solution. Then continue to add ammonia water to adjust the pH to make the solution weakly alkaline (pH = 8). The stirring temperature is 80 °C, and continue to heat and stir until the solution becomes a viscous colloid; put it into a drying oven to dry to obtain a fluffy precursor powder. Put the fluffy powder into a crucible, put it into a muffle furnace and sinter at 1050 °C for 5 hours to obtain the target powder, denoted as BaCeO3. The XRD pattern of the phase structure is as Figure 3as shown

[0110] Weigh an appropriate amount of BaCeO3 electrolyte powder, press it into tablets at 150 Mpa, calcine it in a muffle furnace at 1450 °C for 10 hours, grind the calcined tablets into powder, collect the powder for XRD characterization, as Figure 4 shown. Ball-mill the initial sintered BaCeO3 powder in absolute ethanol for 5 hours, collect the ball-milled mixture and grind it in a mortar to obtain dry powder. Weigh 0.5 g of the ground BaCeO3 powder, dry-press it into a green body at 150 Mpa, and calcine the dry-pressed green body at 1450 °C for 10 hours to obtain an electrolyte sheet.

[0111] In a specific embodiment, taking x equal to 1.05 as an example, then Ba x CeO3 is Ba 1.05 CeO3, and the specific synthesis steps are as follows:

[0112] Weigh barium nitrate and cerium nitrate in the corresponding stoichiometric ratio according to the chemical formula Ba 1.05 CeO3. Add them to a beaker containing an appropriate amount of deionized water, stir using a magnetic stirrer, and heat until the solution is completely dissolved. According to the molar ratio ethylenediaminetetraacetic acid:citric acid:metal ions = 1:1:2, weigh ethylenediaminetetraacetic acid and citric acid and add them to the above nitrate solution. Then continue to add ammonia water to adjust the pH to weakly alkaline (pH = 8). The stirring temperature is 80 °C, and continue to heat and stir until the solution becomes a viscous colloid; put it in a drying oven to dry to obtain a fluffy precursor powder. Put the fluffy powder into a crucible, put it in a muffle furnace and sinter it at 1050 °C for 5 hours to obtain the target powder, denoted as Ba 1.05 CeO3, and the XRD pattern of the phase structure is as Figure 5 shown.

[0113] Weigh an appropriate amount of Ba 1.05 CeO3 electrolyte powder, press it into tablets at 150 Mpa, calcine it in a muffle furnace at 1450 °C for 10 hours, grind the calcined tablets into powder, collect the powder for XRD characterization, as Figure 6 shown. Ball-mill the initial sintered Ba 1.05 CeO3 powder in absolute ethanol for 5 hours, collect the ball-milled mixture and grind it in a mortar to obtain dry powder. Weigh 0.5 g of the ground Ba 1.05 CeO3 powder, dry-press it into a green body at 150 Mpa, and calcine the dry-pressed green body at 1450 °C for 10 hours to obtain an electrolyte sheet.

[0114] In a specific embodiment, taking x equal to 0.95 as an example, then Ba x CeO3 is Ba 0.95 CeO3, and the specific synthesis steps are as follows:

[0115] According to the chemical formula Ba 0.95 CeO3, weigh corresponding stoichiometric ratios of barium nitrate and cerium nitrate. Add them into a beaker containing an appropriate amount of deionized water, stir using a magnetic stirrer, and heat until the solution is completely dissolved. According to the molar ratio ethylenediaminetetraacetic acid:citric acid:metal ions = 1:1:2, weigh ethylenediaminetetraacetic acid and citric acid and add them into the above nitrate solution. Then continue to add ammonia water to adjust the pH to weakly alkaline (pH = 8). The stirring temperature is 80 °C, and continuously heat and stir until the solution becomes a viscous colloid; put it into a drying oven to dry to obtain a fluffy precursor powder. Put the fluffy powder into a crucible, and sinter it in a muffle furnace at 1050 °C for 5 hours to obtain the target powder, denoted as Ba 0.95 CeO3, and the XRD pattern of the phase structure is as Figure 7 shown.

[0116] Weigh an appropriate amount of Ba 0.95 CeO3 electrolyte powder, press it into tablets at 150 Mpa, and calcine it in a muffle furnace at 1450 °C for 10 hours. Grind the calcined tablets into powder, collect the powder for XRD characterization, as Figure 8 shown.

[0117] Ball-mill the initial sintered Ba 0.95 CeO3 powder in absolute ethanol for 5 hours, collect the ball-milled mixture and grind it in a mortar to obtain a dry powder. Weigh 0.5 g of the ground Ba 0.95 CeO3 powder, dry-press it into shape at 150 Mpa, and calcine the dry-pressed green body at 1450 °C for 10 hours to obtain an electrolyte sheet.

[0118] The XRD characterization results are as follows:

[0119] Figure 3 、 Figure 5 and Figure 7 The XRD patterns in show that the prepared BaCeO3, Ba 1.05 CeO3, Ba 0.95 CeO3 are all pure perovskite phases. After high-temperature sintering at 1450 °C, a distinct CeO2 impurity phase appears in the structure with a barium stoichiometric ratio of 1, as Figure 4 shown. As the barium stoichiometric ratio decreases to 0.95, the content of the CeO2 impurity phase further increases, as Figure 6As shown, when we increased the barium stoichiometry to 1.05 during the synthesis of the powder, no obvious CeO2 impurity phase was produced after calcination at 1450 °C. From the XRD characterization results, it can be seen that during the high-temperature sintering process for the preparation of the BaCeO3 electrolyte material in the battery, along with the volatilization of barium at the A site of the perovskite, the precipitation of cerium at the B site occurred, forming an obvious CeO2 impurity phase. Increasing the barium stoichiometry during the synthesis can inhibit the precipitation of elements at the B site during the high-temperature sintering of the electrolyte membrane, thereby improving the structural stability of the perovskite and increasing the stability of the electrolyte membrane (electrolyte sheet).

[0120] Although this specification contains many specific implementation details, these should not be construed as limiting the scope of any invention or the scope of what is claimed, but rather are mainly used to describe the features of specific embodiments of a particular invention. Certain features described in multiple embodiments in this specification can also be implemented in combination in a single embodiment. On the other hand, the various features described in a single embodiment can also be implemented separately in multiple embodiments or in any suitable sub-combination. In addition, although features may operate in certain combinations as described above and are even initially claimed as such, one or more features from the claimed combination can in some cases be removed from the combination, and the claimed combination can be directed to a sub-combination or a variation of the sub-combination.

[0121] Similarly, although the operations are depicted in the drawings in a particular order, this should not be construed as requiring that the operations be performed in the particular order shown or sequentially, or that all of the illustrated operations be performed, to achieve the desired result. In some cases, multitasking and parallel processing may be advantageous. In addition, the separation of the various system modules and components in the above embodiments should not be construed 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.

[0122] Thus, specific embodiments of the subject matter have been described. Other embodiments are within the scope of the appended claims. In some cases, the acts recited in the claims can be performed in a different order and still achieve the desired result. In addition, the processes depicted in the drawings are not necessarily in the particular order or sequential order shown to achieve the desired result. In some implementations, multitasking and parallel processing may be advantageous.

[0123] It should be noted that in this text, relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or elements inherent to such process, method, article or device. Without further limitation, an element defined by the statement "comprising an..." does not exclude the presence of additional identical elements in the process, method, article or device comprising said element.

[0124] The above are only specific embodiments of the present application, enabling those skilled in the art to understand or implement the present application. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown herein, but rather will conform to the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A method for preparing an electrolyte sheet, characterized in that, The preparation method includes: According to the stoichiometric ratio Ba x CeO3, weigh out metal nitrates; Dissolve the metal nitrate in deionized water to obtain a metal nitrate solution; Add ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution to obtain a first solution; Adjust the first solution to be alkaline to obtain a second solution; Stir the second solution to obtain a colloid; Dry the colloid to obtain a precursor powder; Sinter the precursor powder to obtain a target powder of Ba x CeO3 that meets the stoichiometric ratio; Perform ball milling, grinding, dry pressing, and calcination on the target powder in sequence to obtain an electrolyte sheet; Among them, the value range of x is: x is greater than 1 and x is less than 1.

09.

2. The method for preparing an electrolyte sheet according to claim 1, wherein, The metal nitrate includes: barium nitrate and cerium nitrate.

3. The method for preparing the electrolyte sheet according to claim 1, wherein The step of dissolving the metal nitrate in deionized water to obtain a metal nitrate solution includes: Add deionized water to a container; Add the metal nitrate to the container; Stir using a magnetic stirrer and heat until the solution is completely dissolved to obtain the metal nitrate solution.

4. The method for preparing an electrolyte sheet according to claim 1, characterized in that, The step of adding ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution includes: Weigh ethylenediaminetetraacetic acid and citric acid according to a preset molar ratio, and add the ethylenediaminetetraacetic acid and citric acid to the metal nitrate solution.

5. The preparation method of the electrolyte sheet according to claim 4, wherein, The preset molar ratio is ethylenediaminetetraacetic acid:citric acid:metal ions of the metal nitrate = 1:1:

2.

6. The method for preparing an electrolyte sheet according to claim 1, characterized in that, The step of adjusting the first solution to be alkaline includes: Add ammonia water to the first solution to adjust the first solution to be alkaline so that the pH value of the first solution is equal to 8.

7. The method for preparing the electrolyte sheet according to claim 1, characterized in that, The step of stirring the second solution includes: Continuously heat and stir the second solution until the second solution becomes a viscous colloid; Among them, the stirring temperature is 80 °C.

8. The method for preparing an electrolyte sheet according to claim 1, wherein The step of drying the colloid to obtain a precursor powder includes: Put the colloid into a drying oven; After drying, a fluffy precursor powder is obtained.

9. The method for preparing an electrolyte sheet according to claim 1, wherein Sintering the precursor powder to obtain a target powder of Ba x CeO3 that meets the stoichiometric ratio, including: Put the precursor powder into a crucible; Heat the crucible with a muffle furnace; Sinter the precursor powder for 5 hours to obtain the target powder of stoichiometric Ba x CeO3.

10. The method for preparing an electrolyte sheet according to claim 9, characterized in that, The sintering temperature is 1050 °C.

11. The method for preparing an electrolyte sheet according to any one of claims 1 to 10, characterized in that, The ball milling treatment includes: Put the target powder into absolute ethanol; Ball mill for 5 hours.

12. The method for preparing an electrolyte sheet according to claim 11, wherein The grinding treatment includes: Collect the mixture after ball milling; Place the mixture in a mortar; Grind to obtain a dry powder.

13. The method for preparing the electrolyte sheet according to claim 12, wherein The dry pressing treatment includes: Weigh 0.5 g of the powder after grinding; Under the pressure condition of 150 Mpa, perform dry pressing to form.

14. The method for preparing the electrolyte sheet according to claim 13, characterized in that, The calcination treatment includes: Calcine the green compact after dry pressing at 1450 °C for 10 hours.

15. The method for preparing an electrolyte sheet according to any one of claims 1 to 10, characterized in that, After obtaining the target powder of stoichiometric Ba x CeO3, the preparation method further includes: Weigh a preset weight of the target powder; Under the pressure condition of 150 Mpa, press into a sheet.

16. The method for preparing an electrolyte sheet according to claim 15, wherein, After pressing into a sheet, the preparation method further includes: Calcine in a muffle furnace at a temperature of 1450 °C for 10 hours.

17. The method for preparing an electrolyte sheet according to claim 16, wherein, After calcining for 10 hours, the preparation method further includes: Grind the calcined pressed sheet into powder; Collect the powder and perform XRD characterization.

18. An electrolyte sheet, characterized in that, Prepared by the preparation method of the electrolyte sheet according to any one of claims 1 to 17.

19. The electrolyte sheet according to claim 18, wherein The electrolyte sheet is a proton ceramic electrolyte sheet.

20. A battery, characterized in that, It includes: The electrolyte sheet according to claim 18 or 19.

Images