Sodium metal battery cell and its manufacturing method, battery, electric device

Abstract

The invention relates to the field of battery technology, and to a sodium metal battery cell, a method for manufacturing the same, a battery, and an electric device. The sodium metal battery cell comprises: an electrolyte comprising a first additive comprising an organic compound containing an unsaturated group; and a catalyst comprising at least one of an elemental transition metal and an alloy thereof. The invention can improve the performance of the sodium metal battery cell.

Description

Technology Field

[0001] This application claims priority to Chinese Patent Application No. 202310102055.2 filed on February 9, 2023, under the title “Sodium metal battery cell and method of manufacturing the same, battery, electric device”, the full details of said application are incorporated by reference into this document.

[0002] This application relates to the field of battery technology, and in particular to sodium metal battery cells and methods for manufacturing the same, batteries, and electric devices. Background Technology

[0003] As environmental pollution intensifies day by day, public interest in the new energy industry is growing. In the new energy industry, one of the key elements for its development is battery technology.

[0004] Due to the abundant reserves and low cost of sodium salt raw materials, the application of sodium metal battery cells is gradually gaining attention. However, gases such as hydrogen gas are generated during the use or storage of sodium metal battery cells, which will have a negative impact on the performance of the sodium metal battery cells. Therefore, how to provide sodium metal battery cells to improve their performance has become a technical challenge that must be urgently addressed. The problem to be solved

[0005] This application was made in consideration of the above-mentioned problems, and aims to provide a sodium metal battery cell for improving the performance of a sodium metal battery cell. means of solving the problem

[0006] To achieve the above objective, the present application provides a sodium metal battery cell and a method for manufacturing the same, a battery, and an electric device.

[0007] In a first aspect, a sodium metal battery cell is provided, comprising: an electrolyte comprising a first additive comprising an organic compound containing an unsaturated group; and a catalyst comprising at least one of an elemental transition metal and an alloy thereof.

[0008] An embodiment of the present application provides a sodium metal battery cell comprising an electrolyte and a catalyst. The electrolyte comprises a first additive comprising an organic compound containing an unsaturated group, and the catalyst comprises at least one of an elemental transition metal and an alloy thereof. Thus, when hydrogen gas is present in the sodium metal battery cell, the action of the catalyst can promote a redox reaction between the organic compound containing an unsaturated group in the first additive and the hydrogen gas, thereby consuming at least some of the hydrogen and reducing the hydrogen content of the sodium metal battery cell. Therefore, this technical solution is advantageous for improving the reliability of the sodium metal battery cell and can improve the performance of the sodium metal battery cell.

[0009] In one possible embodiment, the catalyst comprises at least one of platinum, ruthenium, palladium, rhodium, iridium, nickel, cobalt, copper, and their alloys.

[0010] In the technical solution described above, hydrogen can react with an organic compound containing an unsaturated group on the surface of the metal or alloy, and the reaction product can be easily separated from the elemental metal and its alloy, which is advantageous for promoting the consumption of hydrogen, while the elemental metal or alloy can act as a catalyst to promote the reaction between hydrogen and the organic compound containing an unsaturated group without the need to apply additional pressure to the sodium metal battery cell, making it convenient to implement the application of a catalyst in the sodium metal battery cell.

[0011] In one possible embodiment, the sodium metal battery cell further comprises a cathode plate containing the catalyst.

[0012] In the technical solution described above, the cathode plate includes a catalyst. In this way, the hydrogen gas in the sodium metal battery cell and the first additive of the electrolyte can both come into contact with the catalyst and react on the surface of the catalyst, making it convenient to install the catalyst in the sodium metal battery cell.

[0013] In one possible embodiment, the cathode electrode plate comprises a cathode current collector and a cathode film layer on the surface of the cathode current collector, and the cathode film layer comprises the catalyst.

[0014] In the technical solution described above, the cathode film layer is in contact with the electrolyte, and since the cathode film layer contains a catalyst, it is convenient to implement contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0015] In one possible embodiment, the cathode film layer comprises a cathode active material, the cathode active material comprises a cathode active material core and a coating layer coated on the cathode active material core, and the coating layer comprises the catalyst.

[0016] In the technical solution described above, the cathode film layer is in contact with the electrolyte, and the coating layer of the cathode active material in the cathode film layer contains a catalyst, which makes it convenient to achieve contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0017] In one possible embodiment, the coating layer comprises: a coating layer body coated on the cathode active material core; and the catalyst on the surface of the coating layer body.

[0018] In the technical solution described above, the catalyst is positioned on the surface of the coating layer body, which makes it convenient to achieve contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0019] In one possible embodiment, the coating layer body comprises at least one of aluminum oxide, silicon oxide, and carbon.

[0020] In the technical solution described above, materials such as aluminum oxide, silicon oxide, and carbon contained in the coating layer body can support a catalyst as a carrier to add the catalyst to the coating layer body, and additionally, the installation of the coating layer body is advantageous for further improving the performance of the cathode active material, for example, improving the surface stability of the cathode active material, promoting the transfer of sodium ions in the cathode active material, and reducing the residue of alkali compounds on the surface of the cathode active material.

[0021] In one possible embodiment, the sodium metal battery cell further comprises a separator that separates the cathode plate and the anode plate of the sodium metal battery, wherein the separator comprises a base film layer and a first coating layer on the surface of the base film layer, and the first coating comprises the catalyst.

[0022] In the technical solution described above, the separator is in contact with the electrolyte and the first coating layer of the separator contains a catalyst, which is convenient for realizing contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0023] In one possible embodiment, the first coating layer comprises a functional material, and the functional material comprises a functional material body and a catalyst on the surface of the functional material body.

[0024] In the technical solution described above, since the catalyst is located on the surface of the functional material body, it is convenient to achieve contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0025] In one possible embodiment, the functional material body comprises aluminum oxide.

[0026] In the technical solution described above, aluminum oxide can support a catalyst as a carrier, and the catalyst is added to the first coating layer.

[0027] In one possible embodiment, the sodium metal battery cell further comprises a case in which the electrolyte is received, and a second coating layer is provided on the inner wall of the case, and the second coating layer includes the catalyst.

[0028] In the technical solution described above, the inner wall of the case is in contact with the electrolyte, and a second coating layer is provided on the inner wall of the case, and the second coating layer contains a catalyst, thereby making it convenient to achieve contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0029] In one possible embodiment, the sodium metal battery cell further includes an anode electrode plate which is an anode current collector.

[0030] In the technical solution described above, the anode plate of the sodium metal battery cell is an anode current collector. As such, since there is no need to provide an anode active material on the surface of the anode current collector during the manufacturing process of the battery cell, it is advantageous to reduce the mass and volume of the sodium metal battery cell, which is advantageous to improve the energy density of the sodium metal battery cell.

[0031] In one possible embodiment, the mass ratio of the first additive to the electrolyte is 0.1% to 5%, and optionally 1% to 5%.

[0032] In the technical solution described above, the mass ratio of the first additive to the electrolyte is 0.1% to 5%. In this way, the hydrogen content of the sodium metal battery cell can be lowered, and the risk of side reactions caused by the excessive content of the first additive and adverse effects on the energy density of the sodium metal battery cell can be reduced, which is advantageous for improving the performance of the sodium metal battery cell. When the mass ratio of the first additive to the electrolyte is 1% to 5%, it is advantageous for further improving the performance of the sodium metal battery cell.

[0033] In one possible embodiment, the first additive comprises at least one of phenylacetylene, styrene, phenol, 1,3,5-triphenylethine, naphthalene, benzene, N-ethylcarbazole, toluene, monobenzyltoluene, dibenzyltoluene, and cinnamaldehyde, and optionally, the first additive comprises at least one of phenol, phenylacetylene, and naphthalene.

[0034] In the technical solution described above, the type of the first additive can be flexibly selected according to actual conditions. When the first additive includes at least one of phenol, phenylacetylene, and naphthalene, the first additive has a better effect on hydrogen consumption, which is advantageous for further reducing the hydrogen content of the sodium metal battery cell.

[0035] In one possible embodiment, the content of the catalyst in the sodium metal battery cell is 0.01 μg / mAh to 1000 μg / mAh, and optionally, 1 μg / mAh to 500 μg / mAh.

[0036] In the technical solution described above, the content of the catalyst in the sodium metal battery cell is 0.01 μg / mAh to 1000 μg / mAh. In this way, the reaction between hydrogen and the first additive can be promoted, and the decrease in energy density of the battery cell due to excessive catalyst content can be reduced, thereby balancing the reliability and energy density of the sodium metal battery cell. Since the content of the catalyst in the sodium metal battery cell is 1 μg / mAh to 500 μg / mAh, it is advantageous to further balance the reliability and energy density of the sodium metal battery cell.

[0037] In a second aspect, a method for manufacturing a sodium metal battery cell is provided, comprising the steps of: providing an electrode assembly and a case so that the electrode assembly is accommodated in a case—wherein a catalyst is installed on the inner wall of the electrode assembly and / or the case, and the catalyst comprises at least one of an elemental transition metal and an alloy thereof; and injecting an electrolyte comprising a first additive comprising an organic compound containing an unsaturated group into the case.

[0038] In the embodiment of the present application, since the hydrogen of the sodium metal battery cell manufactured through the above technical method can react with the first additive through the action of a catalyst, the hydrogen content of the sodium metal battery cell can be reduced, which is advantageous for improving the performance of the sodium metal battery cell.

[0039] In one possible embodiment, the first additive comprises at least one of platinum, ruthenium, palladium, rhodium, iridium, nickel, cobalt, copper, and their alloys.

[0040] In one possible embodiment, the mass ratio of the first additive to the electrolyte is 0.1% to 5%, and optionally 1% to 5%.

[0041] In one possible embodiment, the first additive comprises at least one of phenylacetylene, styrene, phenol, 1,3,5-triphenylethine, naphthalene, benzene, N-ethylcarbazole, toluene, monobenzyltoluene, dibenzyltoluene, and cinnamaldehyde, and optionally, the first additive comprises at least one of phenol, phenylacetylene, and naphthalene.

[0042] In one possible embodiment, the content of the catalyst is 0.01 μg / mAh to 1000 μg / mAh, and optionally, 1 μg / mAh to 500 μg / mAh.

[0043] In a third aspect, a battery is provided comprising a sodium metal battery cell according to any one of the first aspect and its possible embodiments, or a sodium metal battery cell manufactured by a method according to any one of the second aspect and its possible embodiments.

[0044] In the fourth aspect, an electric device including a battery according to the third aspect is provided. Effects of the invention

[0045] An embodiment of the present application provides a metal battery cell comprising an electrolyte and a catalyst. The electrolyte comprises a first additive comprising an organic compound containing an unsaturated group, and the catalyst comprises at least one of an elemental transition metal and an alloy thereof. Thus, when hydrogen gas is present in the sodium metal battery cell, the action of the catalyst can promote a redox reaction between the organic compound containing an unsaturated group in the first additive and the hydrogen gas, thereby consuming at least some of the hydrogen and reducing the hydrogen content of the sodium metal battery cell. Therefore, the present technical solution is advantageous for improving the reliability of the sodium metal battery cell and can improve the performance of the sodium metal battery cell. Brief explanation of the drawing

[0046] FIG. 1 is a schematic diagram of a sodium metal battery cell according to one embodiment of the present application. FIG. 2 is a schematic diagram of a method for manufacturing a sodium metal battery cell according to one embodiment of the present application. FIG. 3 is a schematic diagram of a battery according to one embodiment of the present application. FIG. 4 is a schematic diagram of an electric device according to one embodiment of the present application. Specific details for implementing the invention

[0047] In the following, embodiments of a sodium metal battery cell, a method for manufacturing the same, a battery, and an electric device according to the present application will be described in detail with appropriate reference to the attached drawings. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of known matters and repetitive descriptions of configurations that are actually identical may be omitted. This is intended to prevent unnecessary duplication in the following description and to facilitate understanding by those skilled in the art. Furthermore, the drawings and the following description are provided to enable those skilled in the art to fully understand the present application and are not intended to limit the gist of the claims.

[0048] The “range” disclosed in this application is defined in the form of a lower limit and an upper limit, and a given range is defined by the selection of the lower limit and the upper limit, and the selected lower limit and upper limit define the limits of a specific range. A range defined in this way may or may not include the limit values ​​themselves and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60 to 120 and 80 to 110 are enumerated for a specified parameter, it is understood that ranges of 60 to 110 and 80 to 120 are also considered. Furthermore, if the enumerated ranges have minimum values ​​of 1 and 2 and maximum values ​​of 3, 4, and 5, ranges of 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5 may all be considered. Unless otherwise specified, the numeric range “a–b” in this application represents an abbreviated expression for any combination of real numbers between a and b, where a and b are both real numbers. For example, the numeric range “0–5” means that all real numbers between “0–5” are listed in this document, and “0–5” is merely an abbreviated expression for such combinations of numbers. Additionally, if a parameter is described as an integer greater than or equal to 2, it is equivalent to disclosing that the parameter is an integer, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. Unless otherwise specified, all embodiments and optional embodiments of this application may be combined with one another to form a new technical solution. Unless otherwise specified, all technical features and optional technical features of this application may be combined with one another to form a new technical solution.

[0049] Unless otherwise specified, all steps according to the present application may be performed sequentially or randomly, but preferably sequentially. For example, the method comprising steps (a) and (b) may comprise steps (a) and (b) performed sequentially, or steps (b) and (a) performed sequentially. For example, the method described above further comprising step (c) may be added to the method in any order, and for example, the method may comprise steps (a), (b), and (c), steps (a), (c), and (b), and also steps (c), (a), and (b).

[0050] As the application of lithium-ion battery technology gradually expands in various fields such as electronic devices, electric vehicles, and energy storage, issues such as lithium resource shortages and rising prices have also begun to emerge. Since sodium and lithium have similar physicochemical properties, and sodium is an abundant and inexpensive raw material, the utilization of sodium-ion batteries is gradually gaining attention. However, the diffusion and application of sodium-ion batteries are limited due to their low energy density and cycle performance. Compared to sodium-ion batteries, the sodium metal anode of a sodium metal battery has a higher theoretical specific capacity and a lower operating potential, which is why the energy density of the sodium metal battery is higher.

[0051] However, during the use or storage of sodium metal batteries, a large amount of hydrogen gas is generated in the sodium metal batteries, which is detrimental to improving the reliability of sodium metal batteries and detrimental to improving the performance of sodium metal batteries.

[0052] In light of this, the present application provides a sodium metal battery cell comprising an electrolyte and a catalyst. The electrolyte comprises a first additive comprising an organic compound containing an unsaturated group, and the catalyst comprises at least one of an elemental transition metal and an alloy thereof. Through the catalytic action of the catalyst, the organic compound containing an unsaturated group undergoes an oxidation-reduction reaction with the hydrogen of the sodium metal battery cell to consume at least some of the hydrogen, thereby reducing the hydrogen content within the sodium metal battery cell and improving the reliability of the sodium metal battery cell, which can improve the performance of the sodium metal battery cell.

[0053] [Sodium Metal Battery Cell]

[0054] An embodiment of the present application provides a metal battery cell comprising an electrolyte and a catalyst.

[0055] The electrolyte includes a first additive comprising an organic compound containing an unsaturated group.

[0056] Unsaturated groups can include carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen triple bonds, carbon-nitrogen triple bonds, and benzene rings. Organic compounds containing unsaturated groups are prone to addition reactions, such as redox reactions with hydrogen. Taking the case where the unsaturated group is a carbon-carbon double bond as an example, during the addition reaction between the carbon-carbon double bond and hydrogen, the carbon-carbon double bond opens, hydrogen is consumed, and eventually forms a carbon-carbon single bond (this addition reaction is also called a hydrogenation reaction).

[0057] The catalyst includes at least one of an elemental transition metal and its alloy.

[0058] The catalyst comprises an elemental transition metal, wherein the elemental transition metal may include an elemental metal formed from a group d element of the periodic table. Examples include palladium and platinum.

[0059] Catalysts include alloys of elemental transition metals, such as palladium-molybdenum alloys and platinum-palladium alloys.

[0060] By adding a catalyst to a sodium metal battery cell, the reaction between unsaturated groups and hydrogen can be promoted. Specifically, hydrogen is dissociated and adsorbed on the catalyst surface, and organic compounds containing unsaturated groups are adsorbed on the catalyst surface; in this way, the dissociated hydrogen reacts with the unsaturated groups on the catalyst surface, thereby consuming the hydrogen in the sodium metal battery cell. Compared to a direct reaction between hydrogen and unsaturated groups, adding a catalyst lowers the energy barrier for the reaction between hydrogen and unsaturated groups and allows the reaction between hydrogen and unsaturated groups to proceed more easily.

[0061] When the hydrogenation reaction of organic compounds containing hydrogen and unsaturated groups is completed, hydrogenation products are formed on the catalyst surface. For example, carbon-carbon triple bonds are converted into carbon-carbon double bonds or carbon-carbon single bonds, carbonyl groups are converted into hydroxyl groups, and benzene is converted into cyclohexane.

[0062] In the present application, the shape of the sodium metal battery cell is not particularly limited and may be cylindrical, rectangular, or any other shape. FIG. 1 is a schematic diagram of a sodium metal battery cell according to one embodiment of the present application. For example, as shown in FIG. 1, the sodium metal battery cell (3) is rectangular and includes a case (31), a cover (32), and an electrode assembly (33) installed within the case (31). The case (31) and the cover (32) may be used to seal the electrode assembly (33) and the electrolyte.

[0063] The case (31) and cover (32) may be hard cases such as hard plastic cases, aluminum cases, steel cases, etc. The case (31) and cover (32) may be soft packages such as pouch-type soft packages. The material of the soft package may be plastic, and examples of plastics include polypropylene, polybutylene terephthalate, and polybutylene succinate.

[0064] The electrode assembly (33) includes a cathode electrode plate, an anode electrode plate, and a separator, and the electrode assembly (33) is formed by the cathode electrode plate, an anode electrode plate, and a separator through a winding process or a lamination process.

[0065] The electrolyte may further include an electrolyte salt and an organic solvent. Here, the electrolyte salt may be sodium hexafluorophosphate (NaPF6), and the organic solvent may be a carbonate or an ether-based solvent. The carbonate solvent includes cyclic ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), and chain-type dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), etc., and the ether-based solvent includes ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 1,3-dioxolane, etc.

[0066] An embodiment of the present application provides a sodium metal battery cell comprising an electrolyte and a catalyst. The electrolyte comprises a first additive comprising an organic compound containing an unsaturated group, and the catalyst comprises at least one of an elemental transition metal and an alloy thereof. Thus, when hydrogen gas is present in the sodium metal battery cell, the action of the catalyst can promote a redox reaction between the organic compound containing an unsaturated group in the first additive and the hydrogen gas, thereby consuming at least some of the hydrogen and reducing the hydrogen content of the sodium metal battery cell. Therefore, the present technical solution is advantageous for improving the reliability of the sodium metal battery cell and can improve the performance of the sodium metal battery cell.

[0067] In some embodiments, the catalyst comprises at least one of platinum, ruthenium, palladium, rhodium, iridium, nickel, cobalt, copper, and their alloys.

[0068] The catalyst may be an elemental metal or an alloy containing said elemental metal. For example, the catalyst may be a nickel-cobalt alloy, a palladium-molybdenum alloy, a platinum-palladium alloy, a platinum-iridium alloy, a platinum-rhodium alloy, a platinum-nickel alloy, a platinum-cobalt alloy, and an iridium-nickel alloy.

[0069] The above elemental metal and its alloy have strong dissociation and adsorption capabilities for hydrogen, so hydrogen is easily adsorbed and dissociated on the surface of the elemental metal and its alloy. The above elemental metal and its alloy possess appropriate adsorption capabilities for organic compounds containing unsaturated groups. Thus, organic compounds containing unsaturated groups can react with hydrogen on the surface of the elemental metal and its alloy, and the reaction products can be removed from the surface of the elemental metal and its alloy, making it convenient for hydrogen and organic compounds containing unsaturated groups to continue reacting on the surface of the elemental metal and its alloy. Therefore, selecting the above elemental metal and its alloy as a catalyst is advantageous for promoting the reaction between hydrogen and organic compounds containing unsaturated groups, thereby facilitating hydrogen consumption.

[0070] In a sodium metal battery cell, the elemental metal and alloy act as catalysts to promote the reaction between hydrogen and an organic compound containing an unsaturated group without the need to apply additional pressure to the sodium metal battery cell, making it convenient to implement catalyst application in the sodium metal battery cell.

[0071] In the above embodiment, the elemental metal and its alloy are selected as catalysts, which is advantageous for promoting hydrogen consumption and also makes it convenient to apply the catalyst to sodium metal battery cells.

[0072] In some embodiments, the sodium metal battery cell further includes a cathode plate containing a catalyst.

[0073] In a sodium metal battery cell, the cathode plate contains a catalyst, and the electrolyte contains a first additive containing an organic compound containing an unsaturated group. Since the cathode plate is in contact with the electrolyte, the organic compound containing an unsaturated group and hydrogen can react on the surface of the cathode plate, thereby consuming the hydrogen of the sodium metal battery cell.

[0074] A catalyst is included in the cathode plate, that is, the catalyst can be added during the manufacturing process of the cathode plate so that the catalyst becomes part of the cathode plate, and thus it is convenient to install the catalyst in the sodium metal battery.

[0075] In the above embodiment, the cathode plate includes a catalyst. In this way, the hydrogen gas in the sodium metal battery cell and the first additive of the electrolyte can both come into contact with the catalyst and react on the surface of the catalyst, making it convenient to install the catalyst in the sodium metal battery cell.

[0076] In some embodiments, the cathode electrode comprises a cathode current collector and a cathode film layer on the surface of the cathode current collector, and the cathode film layer comprises a catalyst.

[0077] The cathode current collector has two surfaces opposite in the direction of its own thickness, and the cathode film layer is installed on one or both of the two opposite surfaces of the cathode current collector.

[0078] Optionally, the cathode current collector may use a metal foil sheet or a composite current collector. For example, aluminum foil may be used as the metal foil sheet. The composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, silver alloy, etc.) on a polymer material substrate (e.g., a substrate such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).

[0079] The cathode film layer may further include a cathode active material, a conductor, and a binder. For example, the cathode active material is a sodium-containing transition metal oxide, the conductor is carbon black, and the binder is polyvinylidene fluoride.

[0080] In this embodiment, a cathode active material, a conductor, a binder, and a catalyst are mixed to form a slurry, and then coated on the surface of a cathode current collector to form a cathode film layer.

[0081] In the above embodiment, the cathode film layer is in contact with the electrolyte and the cathode film layer contains a catalyst, which makes it convenient to implement contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0082] In some embodiments, the cathode film layer comprises a cathode active material, the cathode active material comprises a cathode active material core and a coating layer coated on the cathode active material core, and the coating layer comprises a catalyst.

[0083] The core of the cathode active material may include at least one of a layered transition metal oxide, a polyvalent anionic compound, and a Prussian blue compound.

[0084] In the above embodiment, the cathode film layer is in contact with the electrolyte, and the cathode active material coating layer in the cathode film layer contains a catalyst, which is convenient for implementing contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0085] In some embodiments, the coating layer comprises: a coating layer body coated on a cathode active material core; and a catalyst on the surface of the coating layer body.

[0086] In the above embodiment, since the catalyst is located on the surface of the coating layer body, it is convenient to implement contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0087] In some embodiments, the coating layer body comprises at least one of aluminum oxide, silicon oxide, and carbon.

[0088] In the above embodiment, materials such as aluminum oxide, silicon oxide, and carbon included in the coating layer body can support a catalyst as a carrier to add the catalyst to the coating layer body, and additionally, the installation of the coating layer body is advantageous for further improving the performance of the cathode active material, for example, improving the surface stability of the cathode active material, promoting the transfer of sodium ions in the cathode active material, and reducing the residue of alkali compounds on the surface of the cathode active material.

[0089] In some embodiments, the sodium metal battery cell further comprises a separator that separates the cathode electrode plate and the anode electrode plate of the sodium metal battery, the separator comprises a base film layer and a first coating layer on the surface of the base film layer, and the first coating comprises the catalyst.

[0090] In this embodiment, the separator may be a composite film. The base film layer has two surfaces opposite in its own thickness direction, and the first coating layer is installed on either one or both of the two opposite surfaces of the base film layer.

[0091] The base layer material of the separator may include at least one of glass fiber, nonwoven fabric, polyethylene, polypropylene, and polyvinylidene fluoride.

[0092] In the above embodiment, the separator is in contact with the electrolyte and the first coating layer of the separator contains a catalyst, which makes it convenient to achieve contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0093] In some embodiments, the first coating layer comprises a functional material, and the functional material comprises a functional material body and a catalyst on the surface of the functional material body.

[0094] In the above embodiment, since the catalyst is located on the surface of the functional material body, it is convenient to implement contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0095] In some embodiments, the functional material body includes aluminum oxide.

[0096] In the above embodiment, aluminum oxide can support a catalyst as a carrier, so the catalyst is added to the first coating layer, and furthermore, aluminum oxide is advantageous for improving the high-temperature durability of the separator.

[0097] In some embodiments, the sodium metal battery cell further comprises a case in which an electrolyte is received, and a second coating layer is provided on the inner wall of the case, and the second coating layer includes a catalyst.

[0098] For example, as shown in FIG. 1, a second coating layer is provided on the inner wall of the case (31), and the catalyst of the second coating layer can come into contact with the electrolyte inside the case (31).

[0099] Optionally, the second coating layer further includes a material such as aluminum oxide. The catalyst can be attached to the aluminum oxide; in other words, the aluminum oxide can be commercially used as a support for the catalyst so that the catalyst is installed in the second coating layer.

[0100] In the above embodiment, the inner wall of the case is in contact with the electrolyte, and a second coating layer is provided on the inner wall of the case, and the second coating layer contains a catalyst, so that it is convenient to realize contact between the catalyst, the first additive of the electrolyte, and the hydrogen gas of the sodium metal battery.

[0101] In some embodiments, the sodium metal battery cell further includes an anode plate which is an anode current collector.

[0102] The fact that the anode plate is an anode current collector may mean that an active material layer is not installed on the anode current collector. In some embodiments, for normal use of the anode plate, a conductive film layer may be deposited on the anode current collector.

[0103] The anode plate is an anode current collector, or in other words, the anode current collector acts as the anode plate, and this type of sodium metal battery cell can also be called an "anode-free battery." During the charging process, sodium ions detached from the cathode plate are deposited on the anode current collector to form a sodium metal anode.

[0104] In the above embodiment, the anode electrode plate of the sodium metal battery cell is an anode current collector. As such, since there is no need to provide an anode active material on the surface of the anode current collector during the manufacturing process of the battery cell, it is advantageous to reduce the mass and volume of the sodium metal battery cell, which is advantageous to improve the energy density of the sodium metal battery cell.

[0105] In some embodiments, the mass ratio of the first additive to the electrolyte is 0.1% to 5%, and optionally 1% to 5%. For example, the mass ratio of the first additive to the electrolyte is 0.1%, 1%, and 5%.

[0106] When the mass ratio of the first additive to the electrolyte is less than 0.1%, the content of the first additive is low and the number of unsaturated groups in the electrolyte is low, so the consumption of hydrogen in the sodium metal battery cell is low.

[0107] If the mass ratio of the first additive to the electrolyte exceeds 5%, the content of the first additive is high, which is disadvantageous for improving the energy density of the sodium metal battery cell, and also the risk of adverse effects caused by the first additive increases.

[0108] In the above example, the mass ratio of the first additive to the electrolyte is 0.1% to 5%. In this way, the hydrogen content of the sodium metal battery cell can be lowered, and the risk of side reactions caused by an excessive amount of the first additive and adverse effects on the energy density of the sodium metal battery cell can be reduced, which is advantageous for improving the performance of the sodium metal battery cell.

[0109] When the mass ratio of the first additive and the electrolyte is 1% to 5%, it is advantageous to further balance the consumption of hydrogen and the energy density of the sodium metal battery cell, which is advantageous for further improving the performance of the sodium metal battery cell.

[0110] In some embodiments, the first additive comprises at least one of phenylacetylene (C8H6), styrene (C8H8), phenol (C6H6O), 1,3,5-triphenylethyn (C12H6), naphthalene (NAP), benzene (BZ), N-ethylcarbazole (NEC), toluene (TOL), monobenzyltoluene (MBT), dibenzyltoluene (DBT), and cinnamaldehyde (C9H8O), and optionally, the first additive comprises at least one of phenol, phenylacetylene, and naphthalene.

[0111] In the above embodiment, the type of the first additive can be flexibly selected according to actual conditions. When the first additive includes at least one of phenol, phenylacetylene, and naphthalene, the first additive has a better effect on hydrogen consumption, which is advantageous for further reducing the hydrogen content of the sodium metal battery cell.

[0112] In some embodiments, the content of the catalyst in the sodium metal battery cell is 0.01 μg / mAh to 1000 μg / mAh, and optionally, 1 μg / mAh to 500 μg / mAh.

[0113] When the catalyst content in a sodium metal battery cell is less than 0.01 μg / mAh, the catalyst content is low and the catalytic effect on the reaction between an organic compound containing an unsaturated group and hydrogen is weak, so the hydrogen consumption of the sodium metal battery cell is low.

[0114] When the catalyst content in a sodium metal battery cell exceeds 1000 μg / mAh, the high catalyst content is disadvantageous for improving the energy density of the sodium metal battery cell.

[0115] In the above example, the catalyst content in the sodium metal battery cell is 0.01 μg / mAh to 1000 μg / mAh. In this way, the reaction between hydrogen and the first additive can be promoted, and the decrease in energy density of the battery cell due to excessive catalyst content can be reduced, thereby balancing the reliability and energy density of the sodium metal battery cell.

[0116] Since the catalyst content in the sodium metal battery cell is 1 μg / mAh to 500 μg / mAh, it is advantageous to further balance the reliability and energy density of the sodium metal battery cell.

[0117] In some embodiments, the reaction temperature between the first additive of the sodium metal battery cell and hydrogen is 20°C to 60°C, for example, 20°C or 60°C.

[0118] Optionally, the reaction temperature between the first additive and the hydrogen of the sodium metal battery cell is the operating temperature of the sodium metal battery cell. For example, when the sodium metal battery cell is used in a vehicle, the temperature of the sodium metal battery cell during vehicle driving and charging is, for example, 20°C to 30°C.

[0119] Optionally, the temperature of the sodium metal battery cell may be set according to actual conditions. For example, the temperature is 30°C or 50°C.

[0120] In the above embodiment, when the temperature is 20°C to 60°C, not only is it favorable for the reaction between the first additive and hydrogen, but excessively high temperatures can also reduce adverse effects on the sodium metal battery cell.

[0121] In the foregoing, a technical method for a sodium metal battery cell according to the present application has been described with reference to FIG. 1. Below, a method for manufacturing a sodium metal battery cell will be described with reference to FIG. 2. Herein, regarding the part corresponding to the sodium metal battery cell, the above description is sufficient, and a detailed description will be omitted.

[0122] [Method for manufacturing a sodium metal battery cell]

[0123] FIG. 2 is a schematic diagram of a method for manufacturing a sodium metal battery cell according to one embodiment of the present application. As shown in FIG. 2, the method (200) includes step (210) and step (220).

[0124] Step (210): An electrode assembly and a case are provided so that the electrode assembly is accommodated in the case. Here, a catalyst is provided on the inner wall of the electrode assembly and / or the case, and the catalyst comprises at least one of an elemental transition metal and an alloy thereof.

[0125] The catalyst provided in the electrode assembly may be included in the cathode plate or in the separator.

[0126] Providing a catalyst on the inner wall of the electrode assembly and / or case may include cases where the catalyst is provided only on the electrode assembly, cases where the catalyst is provided only on the inner wall of the case, and cases where the catalyst is provided on both the electrode assembly and the inner wall of the case.

[0127] Step (220): Inject the electrolyte into the case. The electrolyte contains a first additive comprising an organic compound containing an unsaturated group.

[0128] In the embodiment of the present application, since the hydrogen of the sodium metal battery cell manufactured through the above technical method can react with the first additive through the action of a catalyst, the hydrogen content of the sodium metal battery cell can be reduced, which is advantageous for improving the performance of the sodium metal battery cell.

[0129] In some embodiments, the first additive comprises at least one of platinum, ruthenium, palladium, rhodium, iridium, nickel, cobalt, copper, and their alloys.

[0130] In some embodiments, the mass ratio of the first additive to the electrolyte is 0.1% to 5%, and optionally 1% to 5%.

[0131] In some embodiments, the first additive comprises at least one of phenylacetylene, styrene, phenol, 1,3,5-triphenylethyn, naphthalene, benzene, N-ethylcarbazole, toluene, monobenzyltoluene, dibenzyltoluene, and cinnamaldehyde, and optionally, the first additive comprises at least one of phenol, phenylacetylene, and naphthalene.

[0132] In some embodiments, the content of the catalyst is 0.01 μg / mAh to 1000 μg / mAh, and optionally, 1 μg / mAh to 500 μg / mAh.

[0133] In some embodiments, the reaction temperature between hydrogen of the sodium metal battery cell and the first additive is 20°C to 60°C.

[0134] [battery]

[0135] An embodiment of the present application provides a battery comprising a sodium metal battery cell according to any one of the embodiments or a sodium metal battery cell manufactured by any one of the methods according to the embodiments.

[0136] FIG. 3 is a schematic diagram of a battery according to one embodiment of the present application. As shown in FIG. 3, the present application provides a battery (5) comprising a sodium metal battery cell (3) according to any one of the embodiments. The sodium metal battery cell (3) may be directly assembled into the battery (5), or it may be first assembled into a battery module and then assembled into the battery (5) by a plurality of battery modules.

[0137] [Electrical device]

[0138] An embodiment of the present application provides an electric device comprising a battery according to the above embodiment.

[0139] FIG. 4 is a schematic diagram of an electric device according to one embodiment of the present application. As shown in FIG. 4, the present application provides an electric device (6) comprising a battery (5) according to the embodiment.

[0140] The following describes embodiments of the present application. The embodiments described below are illustrative and are used merely to interpret the present application, and should not be understood as limiting the application. In the embodiments, where specific techniques or conditions are not indicated, they shall be in accordance with the techniques or conditions described in the literature of the art or product specifications. If the reagents or equipment used do not bear a manufacturer's mark, they are general products available on the market.

[0141] [Example]

[0142] Example 1

[0143] In the sodium metal battery cell of Example 1, the first additive was phenylacetylene and the catalyst was metallic platinum, and the catalyst was installed on the coating layer of the cathode active material. The mass ratio (A) of the first additive to the electrolyte was 1%, and the catalyst content (B) in the sodium metal battery cell was 10 μg / mAh. In the sodium metal battery cell, the electrolyte salt of the electrolyte was NaPF6 and the solvent was ethylene glycol dimethyl ether.

[0144] Examples 2~7

[0145] The difference between Examples 2 to 7 and Example 1 was that the mass ratio (A) of the first additive and the electrolyte was different. In Examples 2 to 7, A was 0.5%, 0.1%, 3%, 5%, 0.05%, and 10%, respectively.

[0146] Examples 8~17

[0147] The difference between Examples 8 to 17 and Example 1 was that the catalyst content (B) in the sodium battery cell was different. In Examples 8 to 17, B was 1 μg / mAh, 0.01 μg / mAh, 50 μg / mAh, 100 μg / mAh, 300 μg / mAh, 500 μg / mAh, 800 μg / mAh, 1000 μg / mAh, 0.001 μg / mAh, and 2000 μg / mAh, respectively.

[0148] Examples 18-21

[0149] The difference between Examples 18–21 and Example 1 was that the type of the first additive was different. In Examples 18–21, the first additive was phenol, naphthalene, toluene, and cinnamaldehyde, respectively.

[0150] Examples 22-26

[0151] The difference between Examples 22–26 and Example 1 was that the type of the first additive was different. In Examples 22–26, the catalysts were metallic palladium, metallic ruthenium, platinum-cobalt alloy, platinum-palladium alloy, and iridium-nickel alloy, respectively.

[0152] Examples 27-29

[0153] The difference between Examples 27–29 and Example 1 was that the specific location of the first additive was different.

[0154] In Example 27, the catalyst is provided in the cathode film layer. Specifically, the catalyst was supported on Hanwha Aluminum through impregnation and sintering, and the aluminum oxide powder supported with the catalyst was mixed with PVDF as a binder, a cathode active material, and a conductor to prepare a slurry, which was then coated onto a cathode current collector and, after drying, formed a cathode film layer.

[0155] In Example 28, the catalyst was installed on the second coating layer of the inner wall of the case. Specifically, the catalyst was supported on Hanwha Aluminum through impregnation and sintering, and after preparing a slurry of aluminum oxide powder supported with the catalyst, the slurry was coated on the inner wall of the case, and after drying, a second coating layer was formed.

[0156] In Example 29, the catalyst was provided in the first coating layer on the surface of the base layer of the separator. Specifically, the catalyst was supported on Hanwha Aluminum through impregnation and sintering, and the aluminum oxide powder supported with the catalyst was mixed with a binder to form a slurry, which was then coated onto the base layer and dried to form the first coating layer. The material of the base layer was polyethylene.

[0157] Example 30

[0158] The difference between Example 30 and Example 1 was that sodium metal was pre-deposited on the anode of Example 30, that is, Examples 1 to 29 were "anode-free" sodium metal batteries.

[0159] Comparative Example 1

[0160] Compared to Example 1, in Comparative Example 1, the first additive was not included in the electrolyte of the sodium metal battery cell, and the catalyst was not provided in the sodium metal battery cell.

[0161] [Manufacturing of Sodium Metal Battery Cells]

[0162] (1) Manufacturing of cathode plates

[0163] Preparation of cathode electrode plates of Examples 1 to 26: First, metal oxides CuO, Fe2O3, Mn2O3 and sodium carbonate, which are sodium salts, were uniformly mixed in proportions, placed in a dagger of a box-type furnace, and sintered according to a specific sintering system. After sintering was completed, the mixture was cooled to room temperature and crushed to obtain a cathode active material core.

[0164] 20 nm of Al2O3, diammonium phosphate, and a catalyst (see Table 1 for the catalyst of each example) were weighed in a certain ratio and uniformly mixed using a ball mill. Then, this mixture and the cathode active material core were uniformly mixed in a certain ratio using a mixer. The mixed material was placed in a muffle furnace and sintered by flowing dry air at 350°C for 8 hours. After heating was completed, it was naturally cooled to room temperature to obtain a cathode active material with a catalyst.

[0165] A cathode active material with a catalyst, a conductor Super P, a binder polyvinylidene fluoride (PVDF), and N-methylpyrrolidone (NMP) were mixed in a weight ratio of 80:15:5 to obtain a cathode slurry, the cathode slurry was coated onto an aluminum foil serving as a cathode current collector, the aluminum foil was dried at room temperature, transferred to a 120°C oven and dried for 1 hour, and then a cathode electrode plate was obtained through cold rolling and cutting.

[0166] Preparation of the cathode electrode plate of Example 27: A cathode slurry was obtained by uniformly mixing a catalyst (metal platinum), a cathode active material (i.e., the cathode active material core obtained in Examples 1 to 26), a conductor (Super P), and a binder (PVDF). The cathode slurry was evenly coated onto an aluminum foil serving as a cathode current collector. After drying the aluminum foil at room temperature, it was transferred to an oven at 120°C and dried for 1 hour. Subsequently, a cathode electrode plate was obtained through cold rolling and cutting.

[0167] Preparation of cathode plates of Examples 28-30: A cathode slurry was obtained by uniformly mixing a cathode active material (i.e., the cathode active material core obtained in Examples 1-26), a conductor Super P, and a binder PVDF. The cathode slurry was evenly coated onto an aluminum foil serving as a cathode current collector. After drying the aluminum foil at room temperature, it was transferred to an oven at 120°C and dried for 1 hour. Subsequently, a cathode plate was obtained through cold rolling and cutting.

[0168] (2) Manufacturing of anode plates

[0169] Preparation of anode plates of Examples 1 to 29: Carbon nanotubes and sodium alginate were added to deionized water and stirred to form a uniform slurry; the slurry was coated onto an anode current collector made of aluminum foil, dried, and cut to obtain an "anode-free" anode plate, wherein the undercoating layer had an areal density of 20 g / m² 2 It was.

[0170] Preparation of the anode plate of Example 30: The anode plates obtained in Examples 1 to 29 were assembled into a battery cell together with a cathode plate and a separator, and the assembled battery cell was charged to 3.8V with a constant current of 0.5C to pre-deposit metallic sodium on the anode plate. After the battery was fully charged, the fully charged anode plate was disassembled from the glove box and used as the anode plate of this example.

[0171] (3) Manufacturing of separators

[0172] Preparation of separators for Examples 1 to 28 and 30: A porous polyethylene (PE) polymer film with a thickness of 9 μm was used for the separator.

[0173] Preparation of the separator of Example 29: Platinum chloride and aluminum oxide were uniformly mixed in a certain ratio and then sintered in a 350°C pipe for 3 hours using 5% H2 / N2, cooled to room temperature to obtain aluminum oxide supported with a catalyst, and then a slurry was prepared using aluminum oxide supported with a catalyst and polyvinylidene fluoride as a binder, coated onto a base film layer (material is polyethylene), and after drying, a first coating layer was formed.

[0174] An electrode assembly was obtained by stacking a cathode plate, a separator, and an anode plate in sequence so that a separator is interposed between the cathode plate and the anode plate to serve as an isolation agent, and then winding the layers. The electrode assembly was placed in a case, a prepared electrolyte was injected, and the case was sealed to obtain a sodium metal battery cell.

[0175] [Determination of Catalyst Type and Content]

[0176] The catalyst type and content were measured by inductively coupled plasma optical emission spectroscopy (ICP-AES).

[0177] [Determination of Type and Content of First Additive]

[0178] The scent and content of the first additive were determined by gas chromatography and gas chromatography-mass spectrometry.

[0179] [Test of room temperature cycle performance]

[0180] One charge-discharge cycle was performed by charging at a constant current of 0.5C at 25°C and atmospheric pressure (0.1MPa) until the voltage reached 3.8V, and then discharging at a constant current of 1C until the voltage reached 2.0V. After repeating the charge-discharge cycle 500 times with an initial discharge capacity of 100%, the test was stopped and the cycle capacity retention rate was recorded, and the room temperature capacity retention rate was used as an indicator to evaluate the battery's room temperature cycle performance.

[0181] [Test for high-temperature cycle performance]

[0182] One charge-discharge cycle was to charge at a constant current of 0.5C at 60°C and atmospheric pressure (0.1MPa) until the voltage reached 3.8V, and then discharge at a constant current of 1C until the voltage reached 2.0V. After repeating the charge-discharge cycle 500 times with an initial discharge capacity of 100%, the test was stopped and the cycle capacity retention rate was recorded, and the high-temperature capacity retention rate was used as an indicator to evaluate the battery's high-temperature cycle performance.

[0183] [Test for Room Temperature Thickness Expansion Rate]

[0184] The battery was charged to 3.8V with a constant current of 0.5C at room temperature (25°C), and after the battery was fully charged, the initial capacity of the battery was tested using the drainage method. The battery was stored at room temperature for 24 days, and the capacity of the battery after storage was tested using the drainage method. The battery volume expansion rate was calculated based on the battery volume tested before storage. After storage at room temperature for 24 days, the battery volume expansion rate (%) = (battery volume measured after storage / battery volume measured before storage) - 1.

[0185] [Test for High-Temperature Thickness Expansion Rate]

[0186] The battery was charged to 3.8V at 60°C with a constant current of 0.5C, and after the battery was fully charged, the initial volume of the battery was tested using the drainage method. The battery was stored in an oven at 60°C for 24 days, after which it was removed. It was left at room temperature for 60 minutes. The battery volume was tested using the drainage method within 60 minutes of being cooled to room temperature. The battery volume expansion rate was calculated based on the battery volume tested before storage. The battery volume expansion rate (%) after storage at 60°C for 24 days was = (Battery volume measured after storage / Battery volume measured before storage) - 1.

[0187] Experimental parameters and results of examples and comparative examples First additive catalyst Room temperature cycle performance High-temperature cycle performance Room temperature expansion rate High temperature expansion rate type A / % type B / μg / mAh Example 1 Phenylacetylene 1 platinum metal 10 82.0% 80.2% 0.05% 0.37% Example 2 Phenylacetylene 0.5 platinum metal 10 82.9% 79.3% 0.05% 1.08% Example 3 Phenylacetylene 0.1 platinum metal 10 81.3% 78.1% 0.08% 3.11% Example 4 Phenylacetylene 3 platinum metal 10 81.0% 79.9% 0.03% 0.38% Example 5 Phenylacetylene 5 platinum metal 10 79.3% 75.9% 0.02% 0.21% Example 6 Phenylacetylene 0.05 platinum metal 10 81.0% 76.0% 0.11% 3.44% Example 7 Phenylacetylene 10 platinum metal 10 67.1% 55.0% 0.03% 0.33% Example 8 Phenylacetylene 1 platinum metal 1 81.9% 77.6% 0.06% 1.17% Example 9 Phenylacetylene 1 platinum metal 0.01 80.1% 75.4% 0.13% 2.89% Example 10 Phenylacetylene 1 platinum metal 50 81.0% 80.5% 0.05% 0.43% Example 11 Phenylacetylene 1 platinum metal 100 82.1% 79.3% 0.03% 0.25% Example 12 Phenylacetylene 1 platinum metal 300 81.8% 79.9% 0.04% 0.19% Example 13 Phenylacetylene 1 platinum metal 500 81.9% 80.8% 0.02% 0.21% Example 14 Phenylacetylene 1 platinum metal 800 80.9% 79.2% 0.05% 0.25% Example 15 Phenylacetylene 1 platinum metal 1000 81.0% 79.9% 0.03% 0.20% Example 16 Phenylacetylene 1 platinum metal 0.001 81.1% 76.0% 0.15% 3.52% Example 17 Phenylacetylene 1 platinum metal 2000 80.3% 77.9% 0.03% 0.25% Example 18 phenol 1 platinum metal 10 80.9% 78.1% 0.08% 1.41% Example 19 naphthalene 1 platinum metal 10 81.8% 79.7% 0.11% 0.92% Example 20 toluene 1 platinum metal 10 82.2% 78.1% 0.13% 1.52% Example 21 Cinnamaldehyde 1 platinum metal 10 82.3% 78.9% 0.03% 0.57% Example 22 Phenylacetylene 1 metallic palladium 10 81.1% 78.2% 0.08% 1.47% Example 23 Phenylacetylene 1 metallic ruthenium 10 81.9% 76.0% 0.09% 1.66% Example 24 Phenylacetylene 1 platinum cobalt alloy 10 82.3% 79.1% 0.03% 0.54% Example 25 Phenylacetylene 1 platinum palladium alloy 10 81.5% 80.4% 0.06% 0.41% Example 26 Phenylacetylene 1 Iridium nickel alloy 10 81.0% 78.8% 0.07% 0.91% Example 27 Phenylacetylene 1 platinum metal 10 81.3% 79.5% 0.05% 0.75% Example 28 Phenylacetylene 1 platinum metal 10 81.9% 78.0% 0.03% 0.55% Example 29 Phenylacetylene 1 platinum metal 10 80.9% 79.1% 0.08% 0.48% Example 30 Phenylacetylene 1 platinum metal 10 82.8% 81.2% 0.15% 1.37% Comparative Example 1 / / / / 81.2% 75.8% 0.13% 3.31%

[0188] The high-temperature expansion rate and room-temperature expansion rate of the sodium metal battery cell were related to the hydrogen content of the sodium metal battery cell. The lower the hydrogen content in the sodium metal battery cell, the smaller the expansion rate of the sodium metal battery cell.

[0189] As illustrated in Examples 1 to 7, the volume expansion rate of the sodium metal battery cell could be effectively controlled by reasonably setting the mass ratio of the first additive and the electrolyte. As illustrated in Examples 8 to 17, the volume expansion rate of the sodium metal battery cell could be effectively controlled by reasonably setting the content of the catalyst. As illustrated in Examples 18 to 21, the addition of various types of the first additive could also reduce the volume expansion rate of the sodium metal battery cell. As illustrated in Examples 22 to 26, various types of catalysts could also reduce the volume expansion rate of the sodium metal battery cell. As illustrated in Examples 27 to 29, the volume expansion rate of the sodium metal battery cell could be reduced by installing the catalyst at various locations. As illustrated in Example 30, the catalyst and the first additive could be applied to a sodium metal battery cell in which the anode is metallic sodium.

[0190] It must be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any embodiments having substantially the same configuration as the technical concept and achieving the same effect within the scope of the technical solution of the present application will also be included within the technical scope of the present application. Furthermore, various modifications to the embodiments that a person skilled in the art could conceive without departing from the gist of the present application, and other forms configured by combining some of the components of the embodiments, will also be included within the scope of the present application.

Claims

Claim 1 A sodium metal battery cell comprising: an electrolyte comprising a first additive comprising an organic compound containing an unsaturated group; a catalyst comprising at least one of an elemental transition metal and an alloy thereof; and a cathode plate, wherein the organic compound containing an unsaturated group is capable of undergoing an addition reaction with hydrogen, and the cathode plate comprises a cathode current collector and a cathode film layer on the surface of the cathode current collector, and the cathode film layer comprises a cathode active material, wherein the cathode active material comprises at least one of a layered transition metal oxide, a polyvalent anionic compound, and a Prussian blue compound. Claim 2 A sodium metal battery cell according to claim 1, wherein the catalyst comprises at least one of platinum, ruthenium, palladium, rhodium, iridium, nickel, cobalt, copper, and their alloys. Claim 3 In claim 1, the cathode electrode comprises the catalyst, forming a sodium metal battery cell. Claim 4 A sodium metal battery cell according to claim 3, wherein the cathode film layer comprises the catalyst. Claim 5 A sodium metal battery cell according to claim 4, wherein the cathode active material comprises a cathode active material core and a coating layer coated on the cathode active material core, and the coating layer comprises the catalyst. Claim 6 A sodium metal battery cell according to claim 5, wherein the coating layer comprises: a coating layer body coated on the cathode active material core; and the catalyst on the surface of the coating layer body. Claim 7 In claim 6, the coating layer body comprises at least one of aluminum oxide, silicon oxide, and carbon, forming a sodium metal battery cell. Claim 8 A sodium metal battery cell according to any one of claims 1 to 7, wherein the sodium metal battery cell further comprises a separator for separating the cathode electrode plate and the anode electrode plate of the sodium metal battery, the separator comprises a base film layer and a first coating layer on the surface of the base film layer, and the first coating comprises the catalyst. Claim 9 A sodium metal battery cell according to claim 8, wherein the first coating layer comprises a functional material, and the functional material comprises a functional material body and a catalyst on the surface of the functional material body. Claim 10 In claim 9, the functional material body is a sodium metal battery cell comprising aluminum oxide. Claim 11 A sodium metal battery cell according to any one of claims 1 to 7, wherein the sodium metal battery cell further comprises a case in which the electrolyte is received, a second coating layer is provided on the inner wall of the case, and the second coating layer comprises the catalyst. Claim 12 A sodium metal battery cell according to any one of claims 1 to 7, wherein the sodium metal battery cell further comprises an anode electrode plate which is an anode current collector. Claim 13 A sodium metal battery cell according to any one of claims 1 to 7, wherein the mass ratio of the first additive to the electrolyte is 0.1% to 5%. Claim 14 A sodium metal battery cell according to any one of claims 1 to 7, wherein the mass ratio of the first additive to the electrolyte is 1% to 5%. Claim 15 A sodium metal battery cell according to any one of claims 1 to 7, wherein the first additive comprises at least one of phenylacetylene, styrene, phenol, 1,3,5-triphenylethine, naphthalene, benzene, N-ethylcarbazole, toluene, monobenzyltoluene, dibenzyltoluene, and cinnamaldehyde. Claim 16 A sodium metal battery cell according to any one of claims 1 to 7, wherein the first additive comprises at least one of phenol, phenylacetylene, and naphthalene. Claim 17 A sodium metal battery cell according to any one of claims 1 to 7, wherein the content of the catalyst in the sodium metal battery cell is 0.01 μg / mAh to 1000 μg / mAh. Claim 18 A sodium metal battery cell according to any one of claims 1 to 7, wherein the content of the catalyst in the sodium metal battery cell is 1 μg / mAh to 500 μg / mAh. Claim 19 A method for manufacturing a sodium metal battery cell comprising: providing an electrode assembly and a case so that the electrode assembly is accommodated in a case—wherein a catalyst is coated on the inner wall of the electrode assembly and / or the case, and the catalyst comprises at least one of an elemental transition metal and an alloy thereof; and injecting an electrolyte into the case comprising a first additive comprising an organic compound containing an unsaturated group; wherein the organic compound containing an unsaturated group is capable of undergoing an addition reaction with hydrogen, and the electrode assembly comprises a cathode plate, the cathode plate comprises a cathode current collector and a cathode film layer on the surface of the cathode current collector, the cathode film layer comprises a cathode active material, and the cathode active material comprises at least one of a layered transition metal oxide, a polyvalent anionic compound, and a Prussian blue compound. Claim 20 A method for manufacturing a sodium metal battery cell according to claim 19, wherein the catalyst comprises at least one of platinum, ruthenium, palladium, rhodium, iridium, nickel, cobalt, copper, and alloys thereof. Claim 21 A battery comprising a sodium metal battery cell according to any one of claims 1 to 7 or a sodium metal battery cell manufactured by a method for manufacturing a sodium metal battery cell according to any one of claims 19 and 20. Claim 22 An electric device comprising a battery according to claim 21.

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