Battery cell and method for manufacturing the same, battery device, energy storage device, power consumption device

Abstract

The application relates to the technical field of energy storage, and provides a battery monomer, a manufacturing method of the battery monomer, a battery device, an energy storage device and a power utilization device. In the battery monomer, an electrolyte comprises a first subzone and a second subzone, the first subzone is close to a positive electrode, and the second subzone is close to a negative electrode; the mass content of electrolyte particles in the first subzone is greater than the mass content of electrolyte particles in the second subzone, and the mass content of polymers in the first subzone is less than the mass content of polymers in the second subzone. The application can at least effectively reduce the interface impedance of the battery monomer, the phenomenon of poor contact, and the problem of dendrite puncture is not prone to occurring.

Description

Technical Field

[0001] This application relates to the field of energy storage technology, and in particular to a battery cell and its manufacturing method, a battery device, an energy storage device, and an electrical device. Background Technology

[0002] Solid-state batteries are the next generation of mainstream lithium / sodium-ion batteries. Their main feature is the use of solid electrolytes instead of traditional electrolytes in lithium-ion batteries, resulting in higher safety performance and energy density.

[0003] Currently, batteries are mainly prepared using pre-fabricated solid electrolyte membranes or all-solid slurries. However, batteries prepared using this method face problems such as high interfacial impedance, poor contact, and dendrite puncture. Summary of the Invention

[0004] This application provides a battery cell and its manufacturing method, battery device, energy storage device, and power consumption device, which can at least effectively reduce the interface impedance and poor contact of the battery cell, and also reduce the problem of dendrite piercing.

[0005] The first aspect of this application provides a battery cell, including a casing, in which a positive electrode and a negative electrode are stacked and disposed therebetween, and an electrolyte is disposed between the positive electrode and the negative electrode; the electrolyte includes a polymer and electrolyte particles, the polymer forming a polymeric network, and the general structural formula of the polymeric monomer forming the polymer is as follows: R includes any one of C1-C3 alkyl or C1-C3 alkoxy groups, and n is any integer from 4 to 20; the electrolyte includes a first zone and a second zone, with the first zone closer to the positive electrode and the second zone closer to the negative electrode; the mass content of electrolyte particles in the first zone is greater than the mass content of electrolyte particles in the second zone, and the mass content of polymer in the first zone is less than the mass content of polymer in the second zone.

[0006] A second aspect of this application also provides a method for manufacturing a battery cell, comprising: obtaining a precursor liquid, the precursor liquid comprising a polymeric monomer, electrolyte particles, and an initiator, wherein the polymeric monomer has the following general structural formula: R includes any one of C1-C3 alkyl groups and C1-C3 alkoxy groups, and n is any integer from 4 to 20; A precursor solution is injected into the shell, which includes a negative electrode and a positive electrode stacked together, with a gap between the positive and negative electrodes. The positive electrode is placed at T1℃, while the negative electrode is placed at T2℃, so that the precursor solution solidifies to form an electrolyte, and 40≤T1-T2≤70℃. The formed electrolyte includes a first zone and a second zone, with the first zone close to the positive electrode and the second zone close to the negative electrode. The mass content of electrolyte particles in the first zone is greater than the mass content of electrolyte particles in the second zone, and the mass content of polymer in the first zone is less than the mass content of polymer in the second zone.

[0007] A third aspect of this application provides a battery device, including a battery cell as described in the first aspect, or a battery cell prepared by a manufacturing method of a battery cell as described in the second aspect. The battery device includes one or more of a battery module, a battery pack, a battery cluster, and a battery cell.

[0008] The fourth aspect of this application provides an energy storage device, including the battery device of the third aspect, the battery device being used to store electrical energy.

[0009] The fifth aspect of this application provides an electrical device, including the battery device of the third aspect, the battery device being used to provide electrical energy.

[0010] The technical solution provided in this application has at least the following advantages: In the battery cell of this application, the polymer in the electrolyte provides a flexible network and ion solvation channels, while the electrolyte particles provide channels with high ionic conductivity. Together, they enhance the ionic conductivity of the electrolyte. Furthermore, the first partition in the electrolyte effectively suppresses dendrite formation, while the second partition reduces the electrolyte's impedance. The synergistic effect of the first and second partitions effectively reduces the interfacial impedance and poor contact of the battery cell, and also minimizes the problem of dendrite penetration. In addition, the manufacturing method of this application, by first injecting a precursor solution and then allowing it to solidify, improves the contact performance between the electrolyte and the electrode, ensuring that pores are less likely to form between them. Moreover, during solidification, the positive electrode is placed at a higher temperature, and the negative electrode at a lower temperature, with a temperature difference between them within the range of 40°C to 70°C. This ensures the formation of the first and second partitions in the electrolyte, thereby effectively improving the performance of the resulting battery cell. Attached Figure Description

[0011] One or more embodiments are illustrated by way of example with corresponding pictures in the accompanying drawings. These illustrations do not constitute a limitation on the embodiments. Unless otherwise stated, the pictures in the accompanying drawings do not constitute a limitation on scale. In order to more clearly illustrate the technical solutions in the embodiments of this application or in the conventional technology, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0012] Figure 1 This is a flowchart illustrating the manufacturing process of a single battery cell in an embodiment of this application. Figure 2 This is a schematic diagram of the overall structure of the battery device in the embodiments of this application; Figure 3 This is a schematic diagram of the disassembled battery device in an embodiment of this application.

[0013] Reference numerals: 10-box; 11-first part; 12-second part; 20-cell battery; 100-battery assembly. Detailed Implementation

[0014] As mentioned in the background section, existing solid-state batteries face problems such as high interface impedance, poor contact, and dendrite puncture.

[0015] The inventors discovered that, since the existing solid-state battery manufacturing process typically involves electrolyte membrane prefabrication → stacking / winding → encapsulation → formation, solid-state battery manufacturing relies on physical contact. Poor contact between solids can easily lead to high impedance in solid-state batteries, and pores can easily form between the electrolyte and the positive and negative electrodes. The presence of pores can easily cause dendrite puncture.

[0016] Based on this, this application provides a battery cell, its manufacturing method, a battery device, an energy storage device, and an electrical device. In the battery cell of this application, the electrolyte comprises two partitions, which effectively suppresses the technical problems of dendrite penetration and high interfacial impedance. Furthermore, the manufacturing method provided in this application does not pre-fabricate an electrolyte membrane; instead, it directly forms the electrolyte from a liquid precursor solution, which can effectively reduce the interfacial impedance of the battery cell, reduce poor contact, and the resulting battery cell is less prone to dendrite penetration.

[0017] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined. Similarly, "multiple sets" refers to two or more sets (including two sets), and "multiple pieces" refers to two or more pieces (including two pieces).

[0018] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0019] In the description of the embodiments in this application, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent three cases: A exists, A and B exist simultaneously, and B exists. In addition, the character " / " in this document generally indicates that the related objects before and after it have an "or" relationship.

[0020] In the description of the embodiments of this application, the technical terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential," etc., indicating orientation or positional relationships, are based on the orientation or positional relationships shown in the accompanying drawings. They are only for the convenience of describing the embodiments of this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the embodiments of this application. For example, if the device or element in the illustration is inverted, then the element described as "below," "under," "below," or "bottom" of other elements or features will be oriented "above" or "top" of other elements or features. Therefore, the term "below" may cover both above and below orientation depending on the context in which the term is used, which will be obvious to those skilled in the art. Materials may be oriented in other ways (e.g., rotated 90 degrees, inverted, flipped), and the spatial relative descriptive terms used herein may be interpreted accordingly.

[0021] In the description of the embodiments of this application, unless otherwise expressly specified and limited, technical terms such as "installation," "connection," "joining," and "fixing" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. For those skilled in the art, the specific meaning of the above terms in the embodiments of this application can be understood according to the specific circumstances.

[0022] In the description of embodiments of this application, the terms "about," "approximately," "roughly," or "about" for reference to a specific parameter include numerical values, and those skilled in the art will understand that the deviation from the numerical value is within the acceptable tolerance of the specific parameter. For example, "about" or "about" for a numerical value may include additional numerical values ​​that are in the range of 90.0% to 110.0% of the numerical value, such as in the range of 95.0% to 105.0%, 97.5% to 102.5%, 99.0% to 101.0%, 99.5% to 100.5%, or 99.9% to 100.1%.

[0023] In the accompanying drawings corresponding to the embodiments of this application, the thickness and / or area of ​​layers, films, panels, regions, etc., are enlarged for better understanding and ease of description. Throughout the specification, the same reference numerals denote the same elements. Furthermore, when describing a component as being "generally" formed on another component, it means that the component is not formed on the entire surface (or front surface) of the other component, nor is it formed on a portion of the edge of the entire surface.

[0024] In the description of embodiments of this application, when a component "includes" another component, other components are not excluded unless otherwise stated, and may be further included. When describing a component (such as a layer, film, region, or substrate) on or on the surface of another component, the component may be "directly" located on the surface of the other component, or there may be an intermediate component between the two components. Conversely, when describing a component on the surface of another component, or a component "directly" on another component, or a component surface on which another component is formed or disposed, it indicates that there is no intermediate component between the two components. For simplicity and clarity, various components may be drawn at any scale. In the drawings, some components may be omitted for simplicity.

[0025] The terminology used in the description of the various embodiments herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used in the description of the various embodiments and the appended claims, the term "component" is also intended to include the plural form unless the context clearly indicates otherwise.

[0026] The “components” mentioned above can refer to layers, membranes, regions, parts, plates, or structures, etc.

[0027] The embodiments of this application will now be described in detail with reference to the accompanying drawings. However, those skilled in the art will understand that many technical details have been provided in the embodiments of this application to facilitate a better understanding of the application. However, the technical solutions claimed in this application can be implemented even without these technical details and various variations and modifications based on the following embodiments.

[0028] This application provides a battery cell, including a casing containing a positive electrode and a negative electrode stacked together, with an electrolyte disposed between the positive and negative electrodes. The electrolyte comprises a polymer and electrolyte particles, the polymer forming a polymeric network, and the general structural formula of the polymer monomer forming the polymer is as follows: R includes any one of C1-C3 alkyl or C1-C3 alkoxy groups, and n is any integer from 4 to 20. In this application, the electrolyte includes a first partition and a second partition, with the first partition located near the positive electrode and the second partition located near the negative electrode; the mass content of electrolyte particles in the first partition is greater than the mass content of electrolyte particles in the second partition, and the mass content of polymer in the first partition is less than the mass content of polymer in the second partition.

[0029] It should be noted that the scope of the "first zone" in this application is generally: the area extending 10μm to 30μm along the thickness direction of the battery cell, starting from the interface between the positive electrode layer and the electrolyte, towards the negative electrode; the scope of the "second zone" is generally: the area extending 10μm to 30μm along the thickness direction of the battery cell, starting from the interface between the negative electrode layer and the electrolyte, towards the positive electrode.

[0030] It should also be noted that "the mass content of electrolyte particles in the first zone is greater than the mass content of electrolyte particles in the second zone" is relative to the whole, meaning that the total mass content of electrolyte particles in the entire first zone is greater than that in the second zone. Exceptions may exist for extremely small areas. Similarly, "the mass content of polymer in the first zone is less than the mass content of polymer in the second zone" means that the mass content of polymer in the entire first zone is less than that in the second zone. Exceptions may also exist for extremely small areas. Furthermore, this application allows for some selectable ranges for the ratio between the total content of electrolyte particles and the total content of polymer in the electrolyte. In addition to electrolyte particles and polymers, the electrolyte may also include other components; since the content and ratio of these two components, as well as other components, are usually determined during the manufacturing stage, this application will describe them in detail in the subsequent manufacturing method section.

[0031] In the battery cell of this application, the polymer in the electrolyte provides a flexible network and ion solvation channels, while the electrolyte particles provide high ion conductivity channels. Together, they enhance the ion conductivity of the electrolyte. Furthermore, in the electrolyte, the first partition has a higher mass content of electrolyte particles, resulting in higher density and effectively suppressing dendrite formation. The second partition has a higher polymer mass content, leading to lower impedance. By incorporating the first and second partitions in the electrolyte, the impedance of the battery cell can be significantly reduced, dendrite formation suppressed, and the cycle performance of the battery cell improved. The "polymer forming a polymer network" in this application refers to the formation of a network-structured polymer, which facilitates the formation of an ion transport network and improves the transport efficiency of lithium or sodium ions. Additionally, in this application, since the polymer monomers in the electrolyte contain two carbon-carbon double bonds, the repeating unit of the polymer formed is: This repeating unit can be used to determine whether the polymeric monomer in the electrolyte is the same as the polymeric monomer of this application.

[0032] In some embodiments of this application, the electrolyte particles in the first partition have a mass content of 50% to 80%, and the polymer content is 20% to 50%, which can better suppress dendrite formation. In other embodiments of this application, the electrolyte particles in the second partition have a mass content of 10% to 40%, and the polymer content is 60% to 90%, which can better reduce the impedance of the battery cells.

[0033] Since the thickness of the electrolyte is usually 50μm~100μm, there are other zones (i.e., transition zones) in the electrolyte in addition to the first zone and the second zone. The components of the transition zone change in a continuous gradient relative to the first zone and the second zone. Moreover, the mass content of electrolyte particles in the transition zone is usually lower than that in the first zone and higher than that in the second zone, and the mass content of polymer is usually lower than that in the second zone and higher than that in the first zone.

[0034] The battery cell in this application can be either a lithium-ion secondary battery or a sodium-ion secondary battery; there are no special requirements in this application. Generally, the type of electrolyte particle can be used to determine whether it is a lithium-ion or sodium-ion secondary battery. Specifically, in this application, the electrolyte particle includes either a lithium-based electrolyte or a sodium-based electrolyte. When the electrolyte particle includes a lithium-based electrolyte, the battery cell is a lithium-ion secondary battery; when the electrolyte particle includes a sodium-based electrolyte, the battery cell is a sodium-ion secondary battery. Furthermore, this application does not have special requirements regarding the type of lithium-based or sodium-based electrolyte, as long as it meets the purpose of this application. As an example, in some embodiments of this application, the lithium-based electrolyte includes at least one of oxide, sulfide, and halide types; wherein the oxide type includes, but is not limited to, Li7La3Zr2O. 12 (LLZO), Li 6.4 La3Zr 1.4 Ta 0.6 O 12 (LLZTO), Li 1.3 Al 0.3 Ti 1.7 (PO4)3 (LATP), Li 1.5 Al 0.5 Ge 1.5 At least one of (PO4)3 (LAGP), etc.; sulfide type including but not limited to Li 10 GeP2S 12 (LPGS), Li3PS4, Li7P3S 11 At least one of Li6PS5Cl, etc.; halide-type electrolytes include, but are not limited to, at least one of Li3YCl6, Li3InCl6, etc. In some other embodiments of this application, sodium-based electrolytes include, but are not limited to, Na3Zr2Si2PO4. 12 (NASICON), Na 1.3 Al 0.3 Ti 1.7 At least one of (PO4)3 (NATP), Na3PS4, etc.

[0035] This application does not impose any special requirements on components other than the electrolyte in a single battery cell, as long as they meet the purpose of this application. As an example, this application uses a lithium-ion secondary battery as an example to illustrate the specific structure or composition of other components, which will be described in detail below.

[0036] The positive electrode includes a positive current collector and a positive active layer disposed on at least one surface of the positive current collector. Specifically, in this application, the positive active layer can be disposed on one surface or on two surfaces along the thickness direction of the positive current collector. Furthermore, in this application, the "surface of the positive current collector" can be the entire area of ​​the positive current collector or only a portion thereof; there are no particular limitations, as long as the purpose of this application is achieved.

[0037] The positive electrode active layer comprises a positive electrode active material, which can be any material capable of reversibly inserting and de-intercalating Li. + Na + Substances containing alkali metal ions are used to ensure the normal charging and discharging of individual battery cells. For example, the positive electrode active material includes lithium salts, which can be lithium-containing phosphates. Lithium-containing phosphates refer to phosphate materials containing lithium elements and can be detected by any method known in the art. For example, detection can be performed using a combination of X-ray diffraction and energy dispersive spectroscopy (EDS) or inductively coupled plasma mass spectrometry (ICP-MS). As examples, lithium-containing phosphates include, but are not limited to, at least one of lithium iron phosphate, lithium iron phosphate doped and modified materials, lithium iron phosphate coated and modified materials, lithium manganese phosphate, or lithium manganese iron phosphate. Lithium manganese iron phosphate, as an emerging high-voltage phosphate material, combines safety and high-voltage characteristics.

[0038] For example, the positive electrode active material can also be a high-voltage system with an operating voltage greater than or equal to 4.3V, such as high-nickel ternary materials, high-voltage spinel materials, or lithium-rich manganese-based materials.

[0039] For example, high-nickel ternary materials such as LiNi 0.8 Co 0.1 Mn 0.1 O2 (NCM811), LiNi 0.6 Co 0.2 Mn 0.2 O2 (NCM622), LiNi 0.8 Co 0.15 Al 0.05 O2 (NCA) and other compounds possess operating voltages of 4.3V~4.6V and high specific capacity, making them ideal cathode choices for high-voltage lithium metal batteries. High-voltage spinel LiNi... 0.5 Mn 1.5 O4 can operate at a voltage of up to 4.7V, matching its high voltage stability.

[0040] However, this application is not limited to the materials listed above, and other materials that can be used as positive electrode active materials in battery cells may also be used. These positive electrode active materials may be used alone, or two or more may be used in combination.

[0041] In some embodiments, the positive electrode active layer further includes a positive electrode conductive agent; this application does not limit the type of positive electrode conductive agent, and any known conductive material can be used. Specifically, the positive electrode conductive agent includes, but is not limited to, at least one of the following: acetylene black, Super-P carbon black, amorphous carbon such as needle coke, carbon nanotubes, or graphene.

[0042] In some embodiments, the positive electrode active layer generally also contains a positive electrode binder. There are no particular restrictions on the type of positive electrode binder used in the manufacture of the positive electrode active layer. In the case of the coating method, any material that can be dissolved or dispersed in the liquid medium used in the electrode manufacturing process is acceptable. Positive electrode binders include, but are not limited to, any one or at least two of the following: resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, and nitrocellulose; rubber-like polymers such as styrene-butadiene rubber (SBR), nitrile rubber (NBR), fluororubber, isoprene rubber, polybutadiene rubber, and ethylene-propylene rubber; thermoplastic elastomers such as styrene-butadiene-styrene block copolymers or their hydrides, ethylene-propylene-diene terpolymers (EPDM), styrene-ethylene-butadiene-ethylene copolymers, and styrene-isoprene-styrene block copolymers or their hydrides; soft resin-like polymers such as syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymers, and propylene-α-olefin copolymers; fluorinated polymers such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene, fluorinated polyvinylidene fluoride, and polytetrafluoroethylene-ethylene copolymers; and polymer compositions with ion conductivity of alkali metal ions (especially lithium ions).

[0043] In the positive electrode, there are no particular restrictions on the type of positive electrode current collector; it can be any known material suitable for use as a positive electrode current collector. The positive electrode current collector can be a metal foil or a composite current collector. For example, the metal foil may include, but is not limited to, aluminum foil. The composite current collector may include a base layer and a metal layer located on at least one surface of the base layer. For example, the base layer can be a polymer material base layer, including but not limited to polypropylene (PP) base layer, polyethylene terephthalate (PET) base layer, polybutylene terephthalate (PBT) base layer, polystyrene (PS) base layer, or polyethylene (PE) base layer. The material of the metal layer may include, but is not limited to, aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, or silver alloy. Furthermore, to reduce the electronic contact resistance between the positive electrode current collector and the positive electrode active layer, a conductive additive or conductive coating may be provided on the surface of the positive electrode current collector. Conductive additives include, but are not limited to, carbon and precious metals such as gold, platinum, and silver. The conductive coating may be a mixture of inorganic oxides, conductive agents, and positive electrode binders.

[0044] The negative electrode may include a negative electrode current collector and a negative electrode active layer disposed on at least one surface of the negative electrode current collector, wherein the composition of the negative electrode active layer includes a negative electrode active material. That is, in this application, the negative electrode active layer may be disposed on one surface or on two surfaces in the thickness direction of the negative electrode current collector. Moreover, in this application, the "surface of the negative electrode current collector" may be the entire area of ​​the negative electrode current collector or a part of the negative electrode current collector; there is no particular limitation, as long as the purpose of this application can be achieved.

[0045] The negative electrode active layer generally contains a negative electrode active material, and this application does not impose any particular limitation on the negative electrode active material. Specifically, the negative electrode active material can be any negative electrode active material known in the art for use in battery cells. As an example, the negative electrode active material can be at least one of the following materials, including but not limited to: graphite, carbon materials, silicon-based materials, tin-based materials, or lithium titanate. Graphite can be artificial graphite or natural graphite. Carbon materials can be soft carbon or hard carbon. Silicon-based materials can be selected from at least one of elemental silicon, silicon-oxygen composites, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys. Tin-based materials can be selected from at least one of elemental tin, tin oxide compounds, and tin alloys. However, this application is not limited to these materials, and other materials that can be used as negative electrode active materials for battery cells can also be used. These negative electrode active materials can be used alone or in combination of two or more.

[0046] In the negative electrode, the negative electrode current collector can be a metal foil or a composite current collector. For example, the metal foil can include, but is not limited to, copper foil, and this application does not have any particular limitations.

[0047] In addition, the negative electrode can be lithium metal, lithium alloy, etc., and does not contain a negative electrode active layer.

[0048] The battery cells in this application can be various packaging forms such as button cells, pouch cells, and hard-case cells. The operating voltage range of the battery cells can be set according to the positive and negative electrode systems used, and this application does not impose any particular limitation on this. For example, for the lithium iron phosphate / graphite system, the operating voltage range can be 2.50V~3.65V; for other positive and negative electrode systems, the operating voltage range can be adjusted accordingly based on the material platform. The operating temperature range can be -20℃~60℃.

[0049] The battery cells provided in this application can be widely used in battery fields requiring high energy density and long cycle life, including high-end electric vehicle battery systems, portable electronic devices, and large-scale energy storage power stations. The battery cells provided in this application can achieve large-capacity energy storage, comprehensively improving energy density, cycle life, and safety performance. They can meet the needs of long-term energy storage, achieving 4 hours or more of long-term energy storage, for example, in energy storage scenarios of 5 hours, 6 hours, and 8 hours. Long-term energy storage refers to the ability to continuously discharge at rated power for 4 hours or even longer, or to achieve large-scale, low-cost energy storage for several days or months.

[0050] Accordingly, another embodiment of this application also provides a method for manufacturing a battery cell, which can be used to manufacture the battery cell provided in the above embodiments, and its preparation process flow diagram is as follows. Figure 1 As shown in the accompanying drawings, the manufacturing method of a battery cell according to another embodiment of this application will be described in detail below. For parts that are the same as or corresponding to the previous embodiment, please refer to the corresponding description of the foregoing embodiment, which will not be described in detail below.

[0051] The method for preparing the battery cell of this application includes the following steps: S100. Obtain the precursor liquid, which includes polymer monomers, electrolyte particles and initiator.

[0052] In this step, the precursor solution will subsequently solidify to form the electrolyte in the battery cell; the polymer monomers in the precursor solution are used to form the network structure polymer in the electrolyte, ensuring that the precursor solution can solidify. Therefore, the general structural formula of the polymer monomers is shown above.

[0053] As an example, this application provides several polymerizable monomers, such as polyethylene glycol diacrylate (PEGDA), 1,6-hexanediol diacrylate (HDDA), and polypropylene glycol diacrylate (PPGDA).

[0054] The structural formula of PEGDA is: The structural formula of HDDA is: The structural formula of PPGDA is: .

[0055] In PEGDA, the degree of polymerization of repeating units is typically between 4 and 20, where x is any integer from 4 to 20. This is because PEGDA with a degree of polymerization of 4 to 20 exhibits superior overall performance, possessing both good flexibility and mechanical strength, as well as good ion solvation capability. This ensures that the polymer formed after polymerization has good flexibility and mechanical strength, and low impedance. If there are too few repeating units in PEGDA, the mechanical strength may be insufficient; if there are too many repeating units, the viscosity may be too high, which is detrimental to subsequent liquid injection and gradient formation. In PPGDA, the degree of polymerization of repeating units is typically between 4 and 20, where y is any integer from 4 to 20. More specifically, in some embodiments of this application, the mass ratio of PEGDA, HDDA, and PPGDA is 50:30:20. PEGDA and HDDA are beneficial for improving the flexibility of the polymer, while PPGDA is beneficial for improving the mechanical strength. Setting the ratio of the three to 50:30:20 is more conducive to balancing the flexibility and mechanical strength of the polymer.

[0056] Of course, in other embodiments of this application, only one or two of the monomers may be used, or other polymeric monomers may be used instead of the polymeric monomers mentioned above. The usage ratio of the three monomers may also be changed, and adjustments may be made according to actual needs.

[0057] The initiator in this application is used to initiate the polymerization reaction of the monomers. Therefore, this application does not have any particular limitation on the specific type of initiator, as long as it can initiate the polymerization of the monomers and does not significantly impair the performance of the battery cells. As an example, the initiator may include, but is not limited to, at least one of azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), etc.

[0058] In some embodiments of this application, based on the total mass of the precursor liquid, the mass content of the polymeric monomer is 40% to 60%, the mass content of the electrolyte particles is 30% to 50%, and the mass content of the initiator is 1% to 2%. For example, the mass content of the polymeric monomer can be 40%, 45%, 48%, 50%, 52%, 56%, 60%, etc., or within any two of the above values; the mass content of the electrolyte particles can be 30%, 32%, 38%, 42%, 45%, 48%, 50%, etc., or within any two of the above values; and the mass content of the initiator can be 1%, 1.2%, 1.4%, 1.8%, 2%, etc., or within any two of the above values.

[0059] In addition, in some embodiments of this application, in order to better improve the cycle performance of the prepared battery cells, the mass ratio of polymeric monomers to electrolyte particles is 1:0.5 to 1:1.25. If the specific gravity of the electrolyte particles is too high, the electrolyte particles are prone to agglomeration, resulting in an increase in the impedance of the battery cells. If the proportion of electrolyte particles is too low, the difference in the mass content of electrolyte particles in the first and second zones of the subsequently formed battery cells will not be significant, thus the dendrite puncture suppression effect of the battery cells will not be significant. Since the polymeric monomers are copolymerized, the mass of the polymer in the subsequently formed electrolyte can be regarded as the total mass of the polymeric monomers. Since the other components in the precursor liquid (electrolyte particles, initiator, plasticizer) have almost no mass loss during the curing process, the mass content of the polymer in the electrolyte can be approximately equal to the mass content of the polymeric monomers in the precursor liquid. The mass ratio of the polymer to the electrolyte particles can also be approximately equal to the mass ratio of the total mass of the polymeric monomers to the mass ratio of the solid electrolyte particles.

[0060] In addition, in this application, besides the polymerizing monomers, electrolyte particles, and initiator, other additives can be added to the precursor liquid as needed. After the precursor liquid solidifies to form the electrolyte, the additives remain in the electrolyte. For example, in some embodiments of this application, the precursor liquid also includes a plasticizer, and the mass content of the plasticizer is 0.5% to 2% based on the total mass of the precursor liquid, such as 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, etc., or within any two of the above values. A specific content of plasticizer can reduce the viscosity of the precursor liquid and subsequently increase the ion transference number of the electrolyte. Specifically, the plasticizer includes at least one of succinate (SN) or ethylene carbonate (EC). Of course, in other embodiments of this application, other types of additives can also be added as needed, and this application does not impose any particular restrictions on this.

[0061] S200. Inject precursor liquid into the housing, which includes a negative electrode and a positive electrode stacked together, with a gap between the positive electrode and the negative electrode.

[0062] In this step, since the precursor solution is a liquid, it can fill the gap between the positive and negative electrodes very well, and there is no technical problem of poor contact between solids. This further ensures that gaps are not easily generated between the electrolyte and the electrodes in the prepared battery cell.

[0063] S300. Place the positive electrode at T1℃ and the negative electrode at T2℃ to allow the precursor solution to solidify and form an electrolyte, with 40≤T1-T2≤70.

[0064] As a liquid, the precursor solution can make excellent and complete contact with both the positive and negative electrodes. Even after the precursor solution solidifies to form the electrolyte, it maintains good contact performance with both electrodes, effectively reducing the interfacial impedance of the battery cells. Furthermore, the temperature environments of the positive and negative electrodes differ in this step, resulting in different particle movement and reaction rates. Due to the higher temperature of the positive electrode, the particle movement rate in the precursor solution near the positive electrode is faster, allowing for the aggregation of a large number of smaller electrolyte particles. Thus, when the precursor solution near the positive electrode solidifies, the mass content of electrolyte particles is higher. Moreover, because the polymerizable monomers in the precursor solution near the positive electrode can also rapidly complete the polymerization reaction and solidify, the polymer content of the electrolyte near the positive electrode is lower. The aggregation of a large number of small electrolyte particles forms a relatively dense structure, which effectively suppresses dendrite penetration. Meanwhile, compared to the positive electrode, the negative electrode has a lower temperature, resulting in a lower content of electrolyte particles in the precursor liquid near the negative electrode. This leads to a slower polymerization reaction and slower solidification, allowing for the aggregation of a large number of monomers. After the precursor liquid near the negative electrode solidifies, the mass content of electrolyte particles is lower, while the mass content of polymers is higher, effectively reducing the impedance of the battery cell. The solidified precursor liquid near the positive electrode forms the first partition within the battery cell, while the solidified precursor liquid near the negative electrode forms the second partition. Furthermore, in this step, a temperature difference between the positive and negative electrodes within the range of 40°C to 70°C ensures the formation of distinct first and second partitions. Additionally, in some embodiments of this application, to accelerate the solidification of the precursor liquid, photoactivation can be applied to the entire precursor liquid before setting the temperature difference between the positive and negative electrodes for solidification. Of course, a photoinitiator is also added to the precursor liquid before photoactivation.

[0065] In addition, this step can also generate a LiF or NaF buffer layer in situ at the positive electrode, further improving the cycle performance of the battery cell.

[0066] In this step, since both the positive and negative electrodes are located within the casing, which contains the precursor solution and is stacked, it is often impossible to directly place the positive or negative electrodes in different temperature environments simultaneously. However, the casing can be used to place the positive and negative electrodes in different temperature environments, as detailed below: The positive electrode has a positive electrode tab at its edge, and the negative electrode has a negative electrode tab at its edge. The positive and negative electrode tabs are not stacked. Therefore, the temperature of the entire positive and negative electrode can be controlled by adjusting the temperature of the positive and negative electrode tabs. Specifically, in this embodiment, the battery cell is typically rectangular, and the outer casing is also rectangular. Therefore, a temperature-controlled clamp is used to hold the side of the casing near the positive and negative electrode tabs, so that the temperatures of the corresponding areas of the casing are T1℃ and T2℃, respectively. After a period of time, the positive electrode is considered to be in an environment of T1℃, and the negative electrode in an environment of T2℃. Furthermore, since the precursor liquid conducts heat, the temperature of the positive electrode will inevitably be conducted to the negative electrode. Therefore, to minimize this effect, the curing time of the precursor liquid is usually controlled within the range of 20-90 minutes. The values ​​of T1 and T2 can be adjusted according to the needs of the actual polymer monomers used; this application does not impose any particular restrictions on this. As an example, in the embodiments of this application, 60≤T1≤80, 10≤T2≤20.

[0067] This application also provides a battery device, which includes the aforementioned battery cell, or a battery cell prepared by the aforementioned method. The battery device of this application can take the form of one or more of the following: battery module, battery pack, and energy storage battery.

[0068] Specifically, such as Figures 2-3 As shown, the battery device 100 includes a housing 10 and battery cells 20, with the battery cells 20 housed within the housing 10. The housing 10 provides space for the battery cells 20, and the housing 10 can have various structures.

[0069] In some embodiments, the housing 10 may include a first portion 11 and a second portion 12, which overlap each other, and together define a receiving space for accommodating the battery cell 20. The second portion 12 may be a hollow structure with one open end, and the first portion 11 may be a plate-like structure, with the first portion 11 covering the open side of the second portion 12 so that the first portion 11 and the second portion 12 together define the receiving space. Figure 3 As shown. The first part 11 and the second part 12 can both be hollow structures with an opening on one side, with the opening side of the first part 11 covering the opening side of the second part 12. Of course, the box 10 formed by the first part 11 and the second part 12 can be of various shapes, such as a cylinder, a cuboid, etc.

[0070] In the battery device 100, the battery cell 20 can be a single cell or multiple cells. Multiple battery cells 20 can be connected in series, parallel, or a combination thereof. A combination thereof means that multiple battery cells 20 are connected in both series and parallel configurations. Multiple battery cells 20 can be directly connected in series, parallel, or a combination thereof to form a whole, which is then housed within the housing 10. Alternatively, the battery device 100 can also consist of multiple battery cells 20 first connected in series, parallel, or a combination thereof to form battery modules, which are then connected in series, parallel, or a combination thereof to form a whole, which is also housed within the housing 10.

[0071] The battery device 100 may also include other structures, for example, the battery device 100 may also include a busbar for realizing electrical connection between multiple battery cells 20.

[0072] This application also provides an energy storage device, including the aforementioned battery device, wherein the battery device is used to store electrical energy. The energy storage device of this application is not limited to, but is also including, residential energy storage cabinets, commercial energy storage cabinets, energy storage containers, energy storage racks, energy storage power stations, energy storage battery packs, or portable energy storage systems. The energy storage device may also include an energy management system (EMS), a battery management system (BMS), and a power conversion system (PCS).

[0073] This application also provides an electrical device, including the aforementioned battery device, wherein the battery device is used to provide electrical energy. The electrical devices of this application include, but are not limited to, mobile phones, tablets, laptops, electric toys, power tools, electric vehicles, electric cars, ships, spacecraft, etc. Among them, electric toys can include stationary or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc., and spacecraft can include airplanes, rockets, space shuttles, and spacecraft, etc.

[0074] The embodiments and comparative examples provided below illustrate the implementation of this application in more detail. Various tests and evaluations were conducted according to the methods described below. Furthermore, unless otherwise specified, "parts" and "%" are quality standards.

[0075] Example 1 <Components of the precursor solution> 45wt% NASICON, 50wt% PEGDA [structural formula CH2=CHCOO-(CH2CH2O)] 10 [-COCH=CH2], 1.5wt% AIBN, 3.5wt% SN.

[0076] <Preparation of battery cells> The positive and negative electrodes are stacked inside the casing, with a gap between them; the positive electrode is made of NaNi. 1 / 3 Fe 1 / 3Mn 1 / 3 O2 is used as the positive electrode active material, and hard carbon is used as the negative electrode.

[0077] A precursor solution was injected into the shell. The positive electrode was placed at 80°C and the negative electrode at 15°C for 45 minutes to solidify the precursor solution into an electrolyte. In the electrolyte, the first zone contained 70% electrolyte particles and 30% polymer. The second zone contained 20% electrolyte particles and 80% polymer.

[0078] Example 2 <Components of the precursor solution> 40wt% LLZO, 55wt% HDDA [structural formula CH2=CHCOO-(CH2)] 6- [OCOCH=CH2], 1.8 wt% BPO, 3.2 wt% EC.

[0079] <Preparation of battery cells> The positive and negative electrodes are stacked inside the casing, with a gap between them; the positive electrode uses NCM811 as the positive electrode active material, and the negative electrode is lithium metal.

[0080] A precursor solution was injected into the shell. The positive electrode was placed at 70°C and the negative electrode at 12°C for 60 minutes to solidify the precursor solution into an electrolyte. In the electrolyte, the mass content of electrolyte particles in the first zone was 65%, and the polymer content was 35%. The mass content of electrolyte particles in the second zone was 15%, and the polymer content was 85%.

[0081] Example 3 <Components of the precursor solution> 35wt% LGPS, 30wt% PEGDA, 30wt% PPGDA [structural formula CH2=CHCOO-(CH2CH(CH3)O)8-COCH=CH2], 1.2wt% AIBN, and 3.8wt% SN.

[0082] <Preparation of battery cells> The positive and negative electrodes are stacked inside the casing, with a gap between them; the positive electrode uses NCM811 as the positive electrode active material, and the negative electrode is lithium metal.

[0083] A precursor solution was injected into the shell. The positive electrode was placed at 75°C and the negative electrode at 18°C ​​for 50 minutes to solidify the precursor solution into an electrolyte. In the electrolyte, the first zone contained 70% electrolyte particles and 30% polymer. The second zone contained 17% electrolyte particles and 83% polymer.

[0084] Example 4 <Components of the precursor solution> 50wt% NASICON, 45wt% HDDA, 1.5wt% BPO, 3.5wt% EC.

[0085] <Preparation of battery cells> The positive and negative electrodes are stacked inside the casing, with a gap between them; the positive electrode is made of NaNi. 1 / 3 Fe 1 / 3Mn 1 / 3 O2 is used as the positive electrode active material, and hard carbon is used as the negative electrode.

[0086] A precursor solution was injected into the shell. The positive electrode was placed at 65°C and the negative electrode at 20°C for 40 minutes to solidify the precursor solution into an electrolyte. In the electrolyte, the first zone contained 75% electrolyte particles and 25% polymer. The second zone contained 25% electrolyte particles and 75% polymer.

[0087] Example 5 <Components of the precursor solution> 42wt% LLZO, 52wt% PEGDA, 1wt% AIBN, 0.5wt% photoinitiator (Irgacure 2959), and 4.5wt% SN.

[0088] <Preparation of battery cells> The positive and negative electrodes are stacked inside the casing, with a gap between them; the positive electrode uses NCM811 as the positive electrode active material, and the negative electrode is lithium metal.

[0089] A precursor solution was injected into the shell and irradiated with 365nm light for 5 minutes. Then, the positive electrode was placed at 75℃ and the negative electrode at 10℃ for 30 minutes to solidify the precursor solution into an electrolyte. In the electrolyte, the first zone contained 67% electrolyte particles and 33% polymer. The second zone contained 17% electrolyte particles and 83% polymer.

[0090] Example 6 Compared to Example 3, the main difference lies in the composition of the precursor solution, as detailed below: <Components of the precursor solution> 32wt% LGPS, 32wt% PEGDA, 32wt% PPGDA, 1.8wt% AIBN, 2.2wt% SN.

[0091] In addition, in this embodiment, the electrolyte in the first zone has a mass content of 60% electrolyte particles and a polymer content of 40%. The electrolyte in the second zone has a mass content of 13% electrolyte particles and a polymer content of 87%.

[0092] Example 7 Compared to Example 4, the main difference lies in the composition of the precursor solution, as detailed below: <Components of the precursor solution> 52.5 wt% NASICON, 42 wt% HDDA, 1.5 wt% BPO, 4 wt% EC.

[0093] In addition, in this embodiment, the electrolyte in the first zone has a mass content of 72% to 82% electrolyte particles and a polymer content of 18% to 28%. The electrolyte in the second zone has a mass content of 25% to 35% electrolyte particles and a polymer content of 65% to 75%.

[0094] Example 8 Compared to Example 1, the main difference lies in the composition of the precursor solution, as detailed below: <Components of the precursor solution> 16wt% NASICON, 80wt% PEGDA, 1.5wt% AIBN, 3.5wt% SN.

[0095] Comparative Example 1 Compared to Example 1, the main difference lies in the preparation method of the battery cells, as detailed below: <Preparation of battery cells> The positive and negative electrodes are stacked inside the casing, with a gap between them; the positive electrode is made of NaNi. 1 / 3 Fe 1 / 3Mn 1 / 3 O2 is used as the positive electrode active material, and hard carbon is used as the negative electrode.

[0096] A precursor solution was injected into the shell, and the entire electrolyte was placed at 45°C for 45 minutes to solidify the precursor solution into the electrolyte. The composition of each region in the electrolyte is relatively uniform, and there are no first or second zones.

[0097] Comparative Example 2 Example 1 differs primarily in the preparation method of the battery cells, as detailed below: <Preparation of battery cells> The positive and negative electrodes are stacked inside the casing, with a gap between them; the positive electrode is made of NaNi. 1 / 3 Fe 1 / 3Mn 1 / 3 O2 is used as the positive electrode active material, and hard carbon is used as the negative electrode.

[0098] A precursor solution was injected into the shell. The positive electrode was placed at 60°C and the negative electrode at 40°C for 45 minutes to solidify the precursor solution into an electrolyte. The component content of the first and second zones of the electrolyte was identical.

[0099] Test methods Interface impedance test Interfacial impedance was measured using electrochemical impedance spectroscopy (EIS). A prismatic cell was disassembled and reassembled into a coin cell. The symmetrical cell was connected to an electrochemical workstation at room temperature (25℃±2℃). The test frequency range was 1MHz to 0.1Hz, and the AC excitation signal amplitude was 10mV. Nyquist plots were acquired, and an equivalent circuit model was used to fit the EIS data to extract the interfacial impedance values.

[0100] Cyclic capacity test Charge-discharge cycles were performed at a constant current density at room temperature (25℃±2℃) or the target test temperature. The charge-discharge voltage range was set according to the positive and negative electrode material system (e.g., Li / solid electrolyte / NCM811, voltage range is 2.8V~4.3V). Capacity retention (%) = (discharge capacity in cycle n / discharge capacity in cycle 1) × 100%.

[0101] Conductivity test The precursor solution is injected into an inert substrate (such as a polytetrafluoroethylene mold or aluminum-plastic film bag) and cured under the same temperature gradient conditions (positive electrode side temperature, negative electrode side temperature, curing time) as the prismatic battery to obtain a self-supporting electrolyte sheet with a thickness similar to the electrolyte layer in the prismatic battery (50μm~100μm). The electrolyte sheet is then clamped between two blocking electrodes (stainless steel sheets, diameter known, area S, unit: cm²). 2Assemble a symmetrical blocked cell consisting of a blocked electrode / electrolyte / blocked electrode. Measure the thickness L (cm) of the electrolyte sheet using a micrometer or film thickness gauge, taking the average value at at least three different locations. Connect the assembled symmetrical cell to an electrochemical workstation at room temperature (25℃±2℃). The test frequency range is 1 MHz to 0.1 Hz, with an AC excitation signal amplitude of 10 mV. For temperature-dependent ionic conductivity testing, place the sample in a temperature-controlled chamber and equilibrate for 1 hour at different temperatures (e.g., 25℃, 35℃, 45℃, 55℃, 65℃, etc.) before performing EIS testing. Acquire a Nyquist plot; the intersection of the semicircle in the high-frequency region and the real axis represents the bulk resistance R. b (Including the bulk resistance of the electrolyte and a small amount of interfacial contact resistance; since there is no electrochemical reaction at the blocked electrode interface, the main contribution is in the bulk resistance). An equivalent circuit R is used. s (R b CPE) fitting, extracting R b Calculation of ionic conductivity: σ=L / (R b ×S) σ: Ionic conductivity (S / cm); L: Electrolyte thickness (cm); R b Volume resistance (Ω); S: Electrode area (cm²).

[0102] Each sample should be tested in parallel at least three times, and the arithmetic mean should be taken. The room temperature ionic conductivity results should be retained to two significant figures.

[0103] Dendrite suppression rate test A comprehensive evaluation was conducted using a combination of post-cycle disassembly of the prismatic battery and scanning electron microscopy (SEM) observation. The battery cells, after 100 cycles at 0.5C, were disassembled, the negative electrode was removed, and the electrode sheets were treated with dimethyl carbonate (DMC) to remove residual electrolyte from the surface, followed by room temperature drying in a vacuum oven. SEM was used to observe the surface of the negative electrode, focusing on the edges and central region, with at least five different locations (each with an area ≥100 μm × 100 μm) photographed. Simultaneously, cross-sections of the negative electrode were prepared to observe dendrite penetration depth.

[0104] The dendrite coverage area in SEM images was statistically analyzed using image analysis software (such as ImageJ). The dendrite suppression rate was calculated using the following formula: Dendrite suppression rate (%) = (1-S sample / S ref )×100%.

[0105] S sampleThe average dendrite coverage area of ​​the battery in the embodiment of this application in the SEM image of the negative electrode surface after cycling.

[0106] S ref The average dendrite coverage area in the SEM image of the negative electrode surface of the control sample under the same cycling conditions.

[0107] The control sample was the negative electrode of a commercial liquid lithium iron phosphate battery.

[0108] The test results are shown in Table 1.

[0109] Table 1

[0110] As can be seen from the above, in the embodiments of this application, the electrolyte partitioning of the battery cell can effectively suppress dendrite formation and reduce electrolyte impedance. The synergistic effect of the two partitions can at least effectively reduce the interfacial impedance and poor contact of the battery cell, and also reduce the likelihood of dendrite puncture. In addition, the preparation method of this application can effectively ensure the formation of the first and second partitions in the electrolyte.

[0111] Those skilled in the art will understand that the above embodiments are specific examples of implementing this application, and in practical applications, various changes in form and detail can be made without departing from the spirit and scope of this application. Any person skilled in the art can make various alterations and modifications without departing from the spirit and scope of this application; therefore, the scope of protection of this application should be determined by the scope defined in the claims.

Claims

1. A battery cell, characterized in that, include: A housing, comprising a positive electrode and a negative electrode stacked together, with a gap between the positive electrode and the negative electrode, and an electrolyte disposed between the positive electrode and the negative electrode; The electrolyte comprises a polymer and electrolyte particles, wherein the polymer forms a polymeric network, and the general structural formula of the polymer monomers forming the polymer is as follows: R includes any one of C1-C3 alkyl groups and C1-C3 alkoxy groups, and n is any integer from 4 to 20; The electrolyte includes a first partition and a second partition, the first partition being closer to the positive electrode and the second partition being closer to the negative electrode; the mass content of the electrolyte particles in the first partition is greater than the mass content of the electrolyte particles in the second partition, and the mass content of the polymer in the first partition is less than the mass content of the polymer in the second partition; a transition region is provided between the first partition and the second partition. The method for preparing the electrolyte includes: injecting a precursor liquid into the shell, placing the positive electrode at T1℃ and the negative electrode at T2℃, so that the precursor liquid solidifies to form the electrolyte; the precursor liquid includes the polymer monomer, electrolyte particles and initiator.

2. The battery cell according to claim 1, characterized in that, In the first partition, the mass content of the electrolyte particles is 50%~80%, the mass content of the polymer is 20%~50%, and / or; In the second partition, the mass content of the electrolyte particles is 10% to 40%, and the mass content of the polymer is 60% to 90%.

3. The battery cell according to claim 1, characterized in that, The electrolyte particles include either lithium-based electrolytes or sodium-based electrolytes.

4. The battery cell according to claim 3, characterized in that, The lithium-based electrolyte includes Li7La3Zr2O 12 Li 6.4 La3Zr 1.4 Ta 0.6 O 12 Li 1.3 Al 0.3 Ti 1.7 (PO4)3, Li 1.5 Al 0.5 Ge 1.5 (PO4)3, Li 10 GeP2S 12 Li3PS4, Li7P3S 11 At least one of Li6PS5Cl, Li3YCl6, or Li3InCl6; and / or, The sodium-based electrolyte includes Na3Zr2Si2PO4 12 Na 1.3 Al 0.3 Ti 1.7 At least one of (PO4)3 and Na3PS4.

5. A method for manufacturing a single battery cell, characterized in that, include: A precursor solution is obtained, the precursor solution comprising a polymeric monomer, electrolyte particles, and an initiator, wherein the polymeric monomer has the following general structural formula: R includes any one of C1-C3 alkyl groups and C1-C3 alkoxy groups, and n is any integer from 4 to 20; The precursor liquid is injected into the housing, which includes a negative electrode and a positive electrode stacked together, with a gap between the positive electrode and the negative electrode; The positive electrode is placed at T1℃ and the negative electrode is placed at T2℃ to allow the precursor solution to solidify and form an electrolyte, with 40≤T1-T2≤70. The formed electrolyte includes a first partition and a second partition, with a transition region between the first partition and the second partition; the first partition is close to the positive electrode, and the second partition is close to the negative electrode; the mass content of the electrolyte particles in the first partition is greater than the mass content of the electrolyte particles in the second partition, and the mass content of the polymer in the first partition is less than the mass content of the polymer in the second partition.

6. The method for manufacturing a single battery cell according to claim 5, characterized in that, 60≤T1≤80, 10≤T2≤20.

7. The method for manufacturing a battery cell according to claim 5 or 6, characterized in that, The curing time of the precursor liquid is 20 min to 90 min.

8. The method for manufacturing a single battery cell according to claim 5, characterized in that, Based on the total mass of the precursor solution, the mass content of the polymeric monomer is 40%~60%, the mass content of the electrolyte particles is 30%~50%, and the mass content of the initiator is 1%~2%.

9. The method for manufacturing a battery cell according to claim 5 or 8, characterized in that, The mass ratio of the polymer monomer to the electrolyte particles is 1:0.5 to 1:1.

25.

10. The method for manufacturing a single battery cell according to claim 9, characterized in that, The precursor liquid also includes a plasticizer, and the mass content of the plasticizer is 0.5% to 2% based on the total mass of the precursor liquid; the plasticizer includes at least one of succinic anionyl nitrile or ethylene carbonate.

11. The method for manufacturing a single battery cell according to claim 5, characterized in that, The polymeric monomer includes at least one of the following: , , , where x is any integer from 4 to 20, and y is any integer from 4 to 20.

12. A battery device, characterized in that, The battery device includes one or more of the following: battery cell as described in any one of claims 1 to 4, or battery cell prepared by the manufacturing method of the battery cell as described in any one of claims 5 to 11.

13. An energy storage device, characterized in that, Includes the battery device as described in claim 12, wherein the battery device is used to store electrical energy.

14. An electrical appliance, characterized in that, Includes the battery device as described in claim 12, the battery device being used to provide electrical energy.

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