Preparation method of room-temperature in-situ cured solid electrolyte

Abstract

The invention relates to a preparation method of a room-temperature in-situ cured solid electrolyte. The high-performance solid-state battery is constructed through in-situ polymerization, the battery is formed by sequentially stacking a positive electrode, a polymer solid-state electrolyte layer and a negative electrode, the solid-state electrolyte layer triggers electrolyte in-situ polymerization under the room temperature condition through an initiator carried by an electrolyte membrane, uniform interface combination is ensured, and the electrochemical performance is optimized. Benefited from the concentration gradient of the initiator and a polymerization degree gradient structure formed by the solid electrolyte layer, the wettability of the electrode plate is further improved, and the interface characteristic is optimized, so that the high-ionic-conductivity solid electrolyte layer is constructed, and the cycling stability is remarkably enhanced. The method is simple and convenient in process, can effectively improve the interface stability and inhibit the growth of lithium dendrites, has the advantages of high energy density, low interface impedance, long cycle life and the like, and provides technical support for industrialization of high-safety and high-performance solid-state lithium batteries.

Description

Technical Field

[0001] The invention belongs to the technical field of batteries, and in particular relates to a method for preparing a room temperature in-situ solidified solid electrolyte. Background Art

[0002] The electrification of power systems has become an important direction for the development of global transportation. As the core component of electric vehicles, lithium-ion batteries have made continuous progress in specific energy and cycle life since they were first commercialized by Sony in the 1990s. However, their further improvement is still limited by the lithium-ion deintercalation reaction mechanism. This makes it difficult for the energy density, cost and safety of batteries to achieve a qualitative leap. With the improvement of battery cell energy density and the expansion of vehicle installation scale, battery safety issues have gradually received widespread attention. Safety accidents caused by thermal runaway of batteries in new energy vehicles occur from time to time, which to a certain extent affects the large-scale application and promotion of lithium-ion batteries. Therefore, in addition to paying attention to the key indicator of battery energy density, safety issues have also become one of the major bottlenecks restricting the healthy development of the new energy vehicle industry. Solid-state lithium batteries have received widespread attention from global scientific research teams due to their potential advantages such as high safety and high energy density.

[0003] In recent years, significant progress has been made in the field of battery technology, among which solid-state lithium batteries constructed by using solid electrolytes instead of organic electrolytes have attracted much attention. This new type of battery has a potential high energy density and significantly improves the safety of lithium batteries. For this reason, countries around the world have increased their research and investment in solid-state batteries. Solid-state batteries have received widespread attention from the industry and academia due to their potential advantages and are considered to be an important development direction of future battery technology.

[0004] The electrolyte curing process of solid-state batteries requires precise control of temperature, pressure and time to ensure that the electrolyte is uniformly and stably cured in the battery structure. In addition, the in-situ curing of solid-state battery electrolytes usually requires appropriate initiators to promote the formation of solid electrolytes. However, most solid-state battery electrolytes are currently difficult to achieve in-situ curing at room temperature, which limits their large-scale manufacturing and commercial applications.

[0005] Therefore, the electrolyte solidification technology of solid-state batteries still needs to be improved. The development of room temperature in-situ solidification technology is expected to overcome the challenges of solid-state batteries in process control and interface contact. Summary of the invention

[0006] The present invention provides a method for preparing a room temperature in-situ solidified solid electrolyte, wherein an electrolyte solution is solidified into a solid electrolyte at room temperature by an initiator in an interlayer film of an interface layer, thereby improving the interface stability of a solid-state battery and increasing the lithium ion conductivity. The battery adopts a simplified manufacturing process and has the characteristics of high energy density, low impedance solid-solid interface and long cycle life. The present invention provides the following solutions.

[0007] A method for preparing a room temperature in-situ solidified solid electrolyte, wherein an electrolyte is injected into a battery shell containing a battery cell, and then the battery cell is packaged and in-situ solidified; the battery cell comprises a composite positive electrode sheet, a separator, and a negative electrode sheet; the separator comprises a modifier A, a modifier B, and a binder;

[0008] Wherein, the modifier A is a Lewis acid, including but not limited to stannous fluoride (SnF 2 ), Boron trifluoride (BF 3 ), aluminum chloride (AlCl 3 ), titanium tetrachloride (TiCl 4 ), antimony fluoride (SbF 3 ), indium fluoride (InF 3 ), magnesium fluoride (MgF 2 ), antimony chloride (SbCl 3 ), indium chloride (InCl 3 ), magnesium chloride (MgCl 2 ), antimony bromide (SbBr 3 ), indium bromide (InBr 3 ), magnesium bromide (MgBr 2 ), antimony iodide (SbI 3 ), indium iodide (InI 3 ), magnesium iodide (MgI 2 ) etc.;

[0009] The modifier B includes but is not limited to lithium salts such as lithium bis(trifluoromethanesulfonyl)imide (LiTFSI);

[0010] The mass ratio of modifier A to modifier B is 0.1-0.5:2.4;

[0011] The electrolyte includes a basic electrolyte and a lithium salt dissolved therein.

[0012] The innovative research of the present invention shows that the diaphragm is prepared by mixing modifier A and modifier B in the mass ratio, adding a binder and mixing again; after mixing, adding solvent dimethylformamide (DMF) to form a solution, and drying at 80°C to form a film. In this way, the solid electrolyte can be solidified at room temperature, the polymerized structure can be improved, the conduction path and rate of lithium ions can be improved, and this helps to synergistically improve the electrochemical performance of the battery.

[0013] In the present invention, modifier A improves the performance by inducing in-situ solidification of the electrolyte, while modifier B is the key to improving the ionic conductivity.

[0014] Preferably, the mass ratio of modifier A to modifier B is 0.3:2.4.

[0015] In the present invention, the binder is capable of bonding the modifier A and the modifier B to each other, including but not limited to PVDF-HFP and PVDF.

[0016] In the present invention, there is no special requirement for the amount of the binder in the diaphragm, as long as the amount of the binder can be sufficient to allow the modifier A and the modifier B to adhere to each other. Preferably, the mass ratio of the modifier A, the modifier B and the binder is 0.3:2.4:3.

[0017] The thickness of the separator can be adjusted as needed. For example, the thickness of the separator is 25 to 45 μm, and further 25 to 30 μm.

[0018] In the present invention, the diaphragm includes modifier A, modifier B and binder, which are uniformly mixed and prepared based on a coating film-making method. For example, in the present invention, modifiers A and B and a binder are mixed in advance, and then solvent dimethylformamide (DMF) is added to form a solution, which is then dried to form a diaphragm. The present invention has found that the combination of modifiers A and B with the preparation method described above helps to improve the subsequent in-situ curing behavior of the monomer, thereby synergistically improving the electrochemical performance of the solid-state battery.

[0019] In the present invention, the basic electrolyte comprises an organic solvent and a conductive lithium salt;

[0020] Preferably, the organic solvent is an ether solvent, including but not limited to 1,3-dioxolane.

[0021] The conductive lithium salt includes but is not limited to lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

[0022] In the present invention, there is no special requirement for the material type of the positive electrode sheet and the negative electrode sheet, which can be any component known in the industry that can be used for solid-state batteries, and can also be any structure in the industry.

[0023] For example, the positive electrode sheet includes a positive electrode current collector and a positive electrode material including a positive electrode active material supported on the surface of the positive electrode current collector.

[0024] Preferably, the positive electrode active material comprises a lithium-containing active material.

[0025] Preferably, the lithium-containing active material includes but is not limited to LiFePO 4 、LiNi 0.1 Co0.1 Mn 0.8 O 2 At least one of the series.

[0026] The negative electrode sheet is a lithium metal electrode sheet.

[0027] In the present invention, there is no special requirement for the in-situ curing conditions. For example, when the temperature is high, the in-situ curing time can be shortened, and when the temperature is low, the in-situ curing time can be extended. Considering the preparation effect and performance, the temperature of the in-situ curing stage is 20 to 60° C., and further 30 to 40° C. The in-situ curing time can be 12 to 36 hours, and further can be 20 to 25 hours.

[0028] The present invention also provides a solid-state battery prepared by the method for preparing the in-situ solidified solid electrolyte.

[0029] In the present invention, thanks to the combination of the special preparation process, the in-situ curing behavior can be adjusted, and a solid-state battery with a special composition and structure can be obtained. The solid-state battery prepared by this preparation method can exhibit excellent electrochemical properties.

[0030] In the present invention, the solid-state battery is an all-solid-state battery or a quasi-solid-state battery;

[0031] Preferably, the solid-state battery is a solid-state lithium-ion battery or a lithium metal battery.

[0032] The present invention has the beneficial effects:

[0033] The innovative research of the present invention shows that including modifier A and modifier B on the diaphragm, and then using modifiers A and B to synergistically induce the electrolyte to solidify in situ, can improve the polymer structure, improve the conduction rate and path of active particles, and help to synergistically improve the electrochemical performance of the battery.

[0034] The in-situ curable solid-state lithium battery provided by the present invention prepares and assembles a highly safe and stable battery while ensuring that the traditional lithium-ion battery preparation process remains unchanged, which can greatly save the production cost of the solid-state battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more intuitively illustrate the technical solution of the embodiment of the present invention, I will briefly introduce the drawings involved in the description of the embodiment below.

[0036] Figure 1 This is a diagram of the installation sequence of room temperature in-situ cured solid-state batteries.

[0037] In the figure:

[0038] 1-positive electrode shell, 2-positive electrode plate, 3-electrolyte membrane, 4-negative electrode plate, 5-spring and gasket, 6-negative electrode shell.

[0039] Figure 2 It is a cross-sectional schematic diagram of the solid-state battery electrolyte of the present invention after solidification.

[0040] In the figure:

[0041] 1-electrode shell, 2-positive electrode plate, 3-solid electrolyte, 4-negative electrode plate.

[0042] Figure 3 The figure is a voltage curve diagram of the battery charge and discharge specific capacity of the system of the present invention.

[0043] Figure 4 The figure is the cycle number-specific capacity curve of the battery for implementing the system of the present invention. DETAILED DESCRIPTION

[0044] In order to make the purpose, technical scheme and features of the embodiments of the present invention clearer, the present invention is further described below in conjunction with specific embodiments, but is not limited thereto. Unless otherwise specified, the experimental methods described in the following embodiments all follow conventional operations; similarly, the reagents and materials mentioned, unless otherwise specified, can be purchased through commercial channels.

[0045] Example 1

[0046] Figure 1 This is a diagram of the installation sequence of various parts of the solid-state battery involved in the present invention.

[0047] like Figure 1 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment includes a positive electrode shell 1, a positive electrode plate 2, an electrolyte membrane 3, a negative electrode plate 4, a spring and a gasket 5, and a negative electrode shell 6 during the installation process.

[0048] The material of the positive electrode plate 2 is a composite material, the current collector material of the positive electrode plate 2 is aluminum foil, and the active material of the positive electrode plate 2 is prepared from lithium iron phosphate, polyvinylidene fluoride (PVDF), and conductive carbon black. The size of the positive electrode plate 2 is a circular plate with a diameter of 12 mm. The solid electrolyte membrane 3 is an inorganic composite material.

[0049] In the specific implementation, firstly, stannous fluoride (SnF 2), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) are added to the glass bottle in a mass ratio of 0.3:3:2.4. Dimethylformamide (DMF) is then added to the glass bottle as a solvent to form a solution. Stir the prepared solution for more than 8 hours and pour it into the film pouring table. Put the film pouring table into a vacuum oven, set the temperature to 80°C, and the time to 1200 minutes. Peel off the film and punch a hole with a diameter of 19 mm. The material of the negative electrode plate 4 is metallic lithium, the material of the shrapnel and gasket 5 is stainless steel, and the material of the negative electrode shell 6 is stainless steel. The positive electrode shell 1 is placed at the bottom, and the positive electrode plate 2, the electrolyte membrane 3, and the negative electrode plate 4 are placed in the positive electrode shell 1 in turn. 70 μL of electrolyte solution is dripped onto the positive electrode plate 2. The solid electrolyte solution is prepared by mixing and stirring 1,3-dioxolane (DOL) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). After the electrolyte is dripped, an electrolyte membrane 3 is placed so that the initiator in the electrolyte membrane is in full contact with the electrolyte. A negative electrode plate 4 is added to the diaphragm. When the negative electrode plate 4 is added, the negative electrode plate 4 needs to be aligned with the middle of the electrolyte membrane 3, and the negative electrode plate 4 is in full contact with the electrolyte membrane 3 to which it belongs. A gasket and a shrapnel 5 are added to the negative electrode plate 4, and the gasket 4 and the shrapnel 5 serve to stabilize the solid-state battery structure. The negative electrode shell is installed on the top of the battery, and the negative electrode shell covers all the above materials and is packaged by a tablet press.

[0050] Figure 2 It is a cross-sectional schematic diagram of the solid-state battery electrolyte of the present invention after solidification.

[0051] like Figure 2 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment comprises an electrode shell 1, a positive electrode plate 2, a solid electrolyte 3, and a negative electrode plate 4 after being completely cured.

[0052] In a specific implementation, after the solid-state battery is installed, the solid electrolyte is fully in contact with the initiator in the diaphragm. During the curing process, the solid electrolyte can be cured in situ at room temperature. The curing method ensures that the electrolyte is fully cured.

[0053] Example 2

[0054] Figure 1 This is a diagram of the installation sequence of various parts of the solid-state battery involved in the present invention.

[0055] like Figure 1 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment includes a positive electrode shell 1, a positive electrode plate 2, an electrolyte membrane 3, a negative electrode plate 4, a spring and a gasket 5, and a negative electrode shell 6 during the installation process.

[0056] The material of the positive electrode plate 2 is a composite material, the current collector material of the positive electrode plate 2 is aluminum foil, and the active material of the positive electrode plate 2 is prepared from lithium iron phosphate, polyvinylidene fluoride (PVDF), and conductive carbon black. The size of the positive electrode plate 2 is a circular plate with a diameter of 12 mm. The solid electrolyte membrane 3 is an inorganic composite material.

[0057] In the specific implementation, firstly, boron trifluoride (BF 3 ), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) are added to the glass bottle in a mass ratio of 0.3:3:2.4. Dimethylformamide (DMF) is then added to the glass bottle as a solvent to form a solution. Stir the prepared solution for more than 8 hours and pour it into the film pouring table. Put the film pouring table into a vacuum oven, set the temperature to 80°C, and the time to 1200 minutes. Peel off the film and punch a hole with a diameter of 19 mm. The material of the negative electrode plate 4 is metallic lithium, the material of the shrapnel and gasket 5 is stainless steel, and the material of the negative electrode shell 6 is stainless steel. The positive electrode shell 1 is placed at the bottom, and the positive electrode plate 2, the electrolyte membrane 3, and the negative electrode plate 4 are placed in the positive electrode shell 1 in turn. 70 μL of electrolyte solution is dripped onto the positive electrode plate 2. The solid electrolyte solution is prepared by mixing and stirring 1,3-dioxolane (DOL) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). After the electrolyte is dripped, an electrolyte membrane 3 is placed so that the initiator in the electrolyte membrane is in full contact with the electrolyte. A negative electrode plate 4 is added to the diaphragm. When the negative electrode plate 4 is added, the negative electrode plate 4 needs to be aligned with the middle of the electrolyte membrane 3, and the negative electrode plate 4 is in full contact with the electrolyte membrane 3 to which it belongs. A gasket and a shrapnel 5 are added to the negative electrode plate 4, and the gasket 4 and the shrapnel 5 serve to stabilize the solid-state battery structure. The negative electrode shell is installed on the top of the battery, and the negative electrode shell covers all the above materials and is packaged by a tablet press.

[0058] Figure 2 It is a cross-sectional schematic diagram of the solid-state battery electrolyte of the present invention after solidification.

[0059] like Figure 2 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment comprises an electrode shell 1, a positive electrode plate 2, a solid electrolyte 3, and a negative electrode plate 4 after being completely cured.

[0060] In a specific implementation, after the solid-state battery is installed, the solid electrolyte is fully in contact with the initiator in the diaphragm. During the curing process, the solid electrolyte can be cured in situ at room temperature. The curing method ensures that the electrolyte is fully cured.

[0061] Example 3

[0062] Figure 1 This is a diagram of the installation sequence of various parts of the solid-state battery involved in the present invention.

[0063] like Figure 1 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment includes a positive electrode shell 1, a positive electrode plate 2, an electrolyte membrane 3, a negative electrode plate 4, a spring and a gasket 5, and a negative electrode shell 6 during the installation process.

[0064] The material of the positive electrode plate 2 is a composite material, the current collector material of the positive electrode plate 2 is aluminum foil, and the active material of the positive electrode plate 2 is prepared from lithium iron phosphate, polyvinylidene fluoride (PVDF), and conductive carbon black. The size of the positive electrode plate 2 is a circular plate with a diameter of 12 mm. The solid electrolyte membrane 3 is an inorganic composite material.

[0065] During the specific implementation, aluminum chloride (AlCl 3 ), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) are added to the glass bottle in a mass ratio of 0.3:3:2.4. Dimethylformamide (DMF) is then added to the glass bottle as a solvent to form a solution. Stir the prepared solution for more than 8 hours and pour it into the film pouring table. Put the film pouring table into a vacuum oven, set the temperature to 80°C, and the time to 1200 minutes. Peel off the film and punch a hole with a diameter of 19 mm. The material of the negative electrode plate 4 is metallic lithium, the material of the shrapnel and gasket 5 is stainless steel, and the material of the negative electrode shell 6 is stainless steel. The positive electrode shell 1 is placed at the bottom, and the positive electrode plate 2, the electrolyte membrane 3, and the negative electrode plate 4 are placed in the positive electrode shell 1 in turn. 70 μL of electrolyte solution is dripped onto the positive electrode plate 2. The solid electrolyte solution is prepared by mixing and stirring 1,3-dioxolane (DOL) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). After the electrolyte is dripped, an electrolyte membrane 3 is placed so that the initiator in the electrolyte membrane is in full contact with the electrolyte. A negative electrode plate 4 is added to the diaphragm. When the negative electrode plate 4 is added, the negative electrode plate 4 needs to be aligned with the middle of the electrolyte membrane 3, and the negative electrode plate 4 is in full contact with the electrolyte membrane 3 to which it belongs. A gasket and a shrapnel 5 are added to the negative electrode plate 4, and the gasket 4 and the shrapnel 5 serve to stabilize the solid-state battery structure. The negative electrode shell is installed on the top of the battery, and the negative electrode shell covers all the above materials and is packaged by a tablet press.

[0066] Figure 2 It is a cross-sectional schematic diagram of the solid-state battery electrolyte of the present invention after solidification.

[0067] like Figure 2 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment comprises an electrode shell 1, a positive electrode plate 2, a solid electrolyte 3, and a negative electrode plate 4 after being completely cured.

[0068] In a specific implementation, after the solid-state battery is installed, the solid electrolyte is fully in contact with the initiator in the diaphragm. During the curing process, the solid electrolyte can be cured in situ at room temperature. The curing method ensures that the electrolyte is fully cured.

[0069] Example 4

[0070] Figure 1 This is a diagram of the installation sequence of various parts of the solid-state battery involved in the present invention.

[0071] like Figure 1 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment includes a positive electrode shell 1, a positive electrode plate 2, an electrolyte membrane 3, a negative electrode plate 4, a spring and a gasket 5, and a negative electrode shell 6 during the installation process.

[0072] The material of the positive electrode plate 2 is a composite material, the current collector material of the positive electrode plate 2 is aluminum foil, and the active material of the positive electrode plate 2 is prepared from lithium iron phosphate, polyvinylidene fluoride (PVDF), and conductive carbon black. The size of the positive electrode plate 2 is a circular plate with a diameter of 12 mm. The solid electrolyte membrane 3 is an inorganic composite material.

[0073] In the specific implementation, first antimony iodide (SbI 3 ), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) are added to the glass bottle in a mass ratio of 0.3:3:2.4. Dimethylformamide (DMF) is then added to the glass bottle as a solvent to form a solution. Stir the prepared solution for more than 8 hours and pour it into the film pouring table. Put the film pouring table into a vacuum oven, set the temperature to 80°C, and the time to 1200 minutes. Peel off the film and punch a hole with a diameter of 19 mm. The material of the negative electrode plate 4 is metallic lithium, the material of the shrapnel and gasket 5 is stainless steel, and the material of the negative electrode shell 6 is stainless steel. The positive electrode shell 1 is placed at the bottom, and the positive electrode plate 2, the electrolyte membrane 3, and the negative electrode plate 4 are placed in the positive electrode shell 1 in turn. 70 μL of electrolyte solution is dripped onto the positive electrode plate 2. The solid electrolyte solution is prepared by mixing and stirring 1,3-dioxolane (DOL) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). After the electrolyte is dripped, an electrolyte membrane 3 is placed so that the initiator in the electrolyte membrane is in full contact with the electrolyte. A negative electrode plate 4 is added to the diaphragm. When the negative electrode plate 4 is added, the negative electrode plate 4 needs to be aligned with the middle of the electrolyte membrane 3, and the negative electrode plate 4 is in full contact with the electrolyte membrane 3 to which it belongs. A gasket and a shrapnel 5 are added to the negative electrode plate 4, and the gasket 4 and the shrapnel 5 serve to stabilize the solid-state battery structure. The negative electrode shell is installed on the top of the battery, and the negative electrode shell covers all the above materials and is packaged by a tablet press.

[0074] Figure 2It is a cross-sectional schematic diagram of the solid-state battery electrolyte of the present invention after solidification.

[0075] like Figure 2 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment comprises an electrode shell 1, a positive electrode plate 2, a solid electrolyte 3, and a negative electrode plate 4 after being completely cured.

[0076] In a specific implementation, after the solid-state battery is installed, the solid electrolyte is fully in contact with the initiator in the diaphragm. During the curing process, the solid electrolyte can be cured in situ at room temperature. The curing method ensures that the electrolyte is fully cured.

[0077] Example 4

[0078] Figure 1 This is a diagram of the installation sequence of various parts of the solid-state battery involved in the present invention.

[0079] like Figure 1 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment includes a positive electrode shell 1, a positive electrode plate 2, an electrolyte membrane 3, a negative electrode plate 4, a spring and a gasket 5, and a negative electrode shell 6 during the installation process.

[0080] The material of the positive electrode plate 2 is a composite material, the current collector material of the positive electrode plate 2 is aluminum foil, and the active material of the positive electrode plate 2 is prepared from lithium iron phosphate, polyvinylidene fluoride (PVDF), and conductive carbon black. The size of the positive electrode plate 2 is a circular plate with a diameter of 12 mm. The solid electrolyte membrane 3 is an inorganic composite material.

[0081] In the specific implementation, firstly titanium tetrachloride (TiCl 4), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) are added to the glass bottle in a mass ratio of 0.3:3:2.4. Dimethylformamide (DMF) is then added to the glass bottle as a solvent to form a solution. Stir the prepared solution for more than 8 hours and pour it into the film pouring table. Put the film pouring table into a vacuum oven, set the temperature to 80°C, and the time to 1200 minutes. Peel off the film and punch a hole with a diameter of 19 mm. The material of the negative electrode plate 4 is metallic lithium, the material of the shrapnel and gasket 5 is stainless steel, and the material of the negative electrode shell 6 is stainless steel. The positive electrode shell 1 is placed at the bottom, and the positive electrode plate 2, the electrolyte membrane 3, and the negative electrode plate 4 are placed in the positive electrode shell 1 in turn. 70 μL of electrolyte solution is dripped onto the positive electrode plate 2. The solid electrolyte solution is prepared by mixing and stirring 1,3-dioxolane (DOL) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). After the electrolyte is dripped, an electrolyte membrane 3 is placed to allow the initiator in the electrolyte membrane to fully contact the electrolyte. A negative electrode plate 4 is added to the diaphragm. When the negative electrode plate 4 is added, the negative electrode plate 4 needs to be aligned with the middle of the electrolyte membrane 3, and the negative electrode plate 4 is in full contact with the electrolyte membrane 3. A gasket and a spring 5 are added to the negative electrode plate 4. The gasket 4 and the spring 5 serve to stabilize the solid-state battery structure. The negative electrode shell is installed on the top of the battery, and the negative electrode shell is covered with all the above materials and packaged by a tablet press.

[0082] Figure 2 It is a cross-sectional schematic diagram of the solid-state battery electrolyte of the present invention after solidification.

[0083] like Figure 2 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment comprises an electrode shell 1, a positive electrode plate 2, a solid electrolyte 3, and a negative electrode plate 4 after being completely cured.

[0084] In a specific implementation, after the solid-state battery is installed, the solid electrolyte is fully in contact with the initiator in the diaphragm. During the curing process, the solid electrolyte can be cured in situ at room temperature. The curing method ensures that the electrolyte is fully cured.

[0085] Example 5

[0086] Figure 1 This is a diagram of the installation sequence of various parts of the solid-state battery involved in the present invention.

[0087] like Figure 1 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment includes a positive electrode shell 1, a positive electrode plate 2, an electrolyte membrane 3, a negative electrode plate 4, a spring and a gasket 5, and a negative electrode shell 6 during the installation process.

[0088] The material of the positive electrode plate 2 is a composite material, the current collector material of the positive electrode plate 2 is aluminum foil, and the active material of the positive electrode plate 2 is prepared from lithium iron phosphate, polyvinylidene fluoride (PVDF), and conductive carbon black. The size of the positive electrode plate 2 is a circular plate with a diameter of 12 mm. The solid electrolyte membrane 3 is an inorganic composite material.

[0089] In the specific implementation, first antimony fluoride (SbF 3 ), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) are added to the glass bottle in a mass ratio of 0.3:3:2.4. Dimethylformamide (DMF) is then added to the glass bottle as a solvent to form a solution. Stir the prepared solution for more than 8 hours and pour it into the film pouring table. Put the film pouring table into a vacuum oven, set the temperature to 80°C, and the time to 1200 minutes. Peel off the film and punch a hole with a diameter of 19 mm. The material of the negative electrode plate 4 is metallic lithium, the material of the shrapnel and gasket 5 is stainless steel, and the material of the negative electrode shell 6 is stainless steel. The positive electrode shell 1 is placed at the bottom, and the positive electrode plate 2, the electrolyte membrane 3, and the negative electrode plate 4 are placed in the positive electrode shell 1 in turn. 70 μL of electrolyte solution is dripped onto the positive electrode plate 2. The solid electrolyte solution is prepared by mixing and stirring 1,3-dioxolane (DOL) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). After the electrolyte is dripped, an electrolyte membrane 3 is placed to allow the initiator in the electrolyte membrane to fully contact the electrolyte. A negative electrode plate 4 is added to the diaphragm. When the negative electrode plate 4 is added, the negative electrode plate 4 needs to be aligned with the middle of the electrolyte membrane 3, and the negative electrode plate 4 is in full contact with the electrolyte membrane 3. A gasket and a spring 5 are added to the negative electrode plate 4. The gasket 4 and the spring 5 serve to stabilize the solid-state battery structure. The negative electrode shell is installed on the top of the battery, and the negative electrode shell is covered with all the above materials and packaged by a tablet press.

[0090] Figure 2 It is a cross-sectional schematic diagram of the solid-state battery electrolyte of the present invention after solidification.

[0091] like Figure 2 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment comprises an electrode shell 1, a positive electrode plate 2, a solid electrolyte 3, and a negative electrode plate 4 after being completely cured.

[0092] In a specific implementation, after the solid-state battery is installed, the solid electrolyte is fully in contact with the initiator in the diaphragm. During the curing process, the solid electrolyte can be cured in situ at room temperature. The curing method ensures that the electrolyte is fully cured.

[0093] Example 6

[0094] Figure 1 This is a diagram of the installation sequence of various parts of the solid-state battery involved in the present invention.

[0095] like Figure 1 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment includes a positive electrode shell 1, a positive electrode plate 2, an electrolyte membrane 3, a negative electrode plate 4, a spring and a gasket 5, and a negative electrode shell 6 during the installation process.

[0096] The material of the positive electrode plate 2 is a composite material, the current collector material of the positive electrode plate 2 is aluminum foil, and the active material of the positive electrode plate 2 is prepared from lithium iron phosphate, polyvinylidene fluoride (PVDF), and conductive carbon black. The size of the positive electrode plate 2 is a circular plate with a diameter of 12 mm. The solid electrolyte membrane 3 is an inorganic composite material.

[0097] In the specific implementation, firstly, indium fluoride (InF 3 ), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) are added to the glass bottle in a mass ratio of 0.3:3:2.4. Dimethylformamide (DMF) is then added to the glass bottle as a solvent to form a solution. Stir the prepared solution for more than 8 hours and pour it into the film pouring table. Put the film pouring table into a vacuum oven, set the temperature to 80°C, and the time to 1200 minutes. Peel off the film and punch a hole with a diameter of 19 mm. The material of the negative electrode plate 4 is metallic lithium, the material of the shrapnel and gasket 5 is stainless steel, and the material of the negative electrode shell 6 is stainless steel. The positive electrode shell 1 is placed at the bottom, and the positive electrode plate 2, the electrolyte membrane 3, and the negative electrode plate 4 are placed in the positive electrode shell 1 in turn. 70 μL of electrolyte solution is dripped onto the positive electrode plate 2. The solid electrolyte solution is prepared by mixing and stirring 1,3-dioxolane (DOL) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). After the electrolyte is dripped, an electrolyte membrane 3 is placed to allow the initiator in the electrolyte membrane to fully contact the electrolyte. A negative electrode plate 4 is added to the diaphragm. When the negative electrode plate 4 is added, the negative electrode plate 4 needs to be aligned with the middle of the electrolyte membrane 3, and the negative electrode plate 4 is in full contact with the electrolyte membrane 3. A gasket and a spring 5 are added to the negative electrode plate 4. The gasket 4 and the spring 5 serve to stabilize the solid-state battery structure. The negative electrode shell is installed on the top of the battery, and the negative electrode shell is covered with all the above materials and packaged by a tablet press.

[0098] Figure 2 It is a cross-sectional schematic diagram of the solid-state battery electrolyte of the present invention after solidification.

[0099] like Figure 2 As shown, a room temperature cured high specific energy solid state battery provided in this embodiment comprises an electrode shell 1, a positive electrode plate 2, a solid electrolyte 3, and a negative electrode plate 4 after being completely cured.

[0100] In a specific implementation, after the solid-state battery is installed, the solid electrolyte is fully in contact with the initiator in the diaphragm. During the curing process, the solid electrolyte can be cured in situ at room temperature. The curing method ensures that the electrolyte is fully cured.

[0101] The technical connotation and characteristics of the present invention have been deeply analyzed. For experts in this field, they are fully capable of carrying out innovative optimization work at the technical detail level based on the basic concept of the present invention. These innovative optimizations may involve upgrading or fine-tuning the technical details. Therefore, it should be clearly pointed out that the scope of protection of the present invention is not limited to specific embodiments, but includes all equivalent substitutions and reasonable improvements made to the technical solution without departing from the core idea of ​​the present invention.

Claims

1. A method for preparing a room temperature in-situ solid electrolyte, characterized in that: An electrolyte is injected into the battery cell, which is then packaged and then in-situ polymerization is initiated. The battery cell includes a positive electrode sheet, an electrolyte membrane and a negative electrode sheet. An initiator is added to the electrolyte membrane. After the electrolyte is injected, the initiator induces the electrolyte to solidify in situ during the packaging process. The raw materials include an initiator, an organic solvent, an electrolyte membrane and a lithium salt.

2. The method for preparing a room temperature in-situ solidified solid electrolyte according to claim 1, characterized in that: The modifier A is a Lewis acid, including but not limited to at least one of stannous fluoride (SnF2), boron trifluoride (BF3), aluminum trichloride (AlCl3), titanium tetrachloride (TiCl4), antimony fluoride (SbF3), indium fluoride (InF3), magnesium fluoride (MgF2), antimony chloride (SbCl3), indium chloride (InCl3), magnesium chloride (MgCl2), antimony bromide (SbBr3), indium bromide (InBr3), magnesium bromide (MgBr2), antimony iodide (SbI3), indium iodide (InI3), and magnesium iodide (MgI2).

3. The method for preparing a room temperature in-situ solidified solid electrolyte according to claim 1, characterized in that: The modifier B includes, but is not limited to, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and other lithium salts.

4. The electrolyte membrane according to claim 1, characterized in that The electrolyte membrane is composed of a binder including but not limited to vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), a lithium salt including but not limited to lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), a Lewis acid and dimethylformamide (DMF) mixed in a mass ratio of 3:2.4:0.3:50, and a uniform solution is formed after being fully mixed. After coating, the solution is formed into a membrane after being baked in an oven for a certain period of time.

5. A method for preparing a room temperature in-situ solidified solid electrolyte according to any one of claims 1 to 4, characterized in that: By initiating curing through an in-situ initiator in the electrolyte membrane, a stable solid-solid interface is formed, the interface compatibility is improved, it is compatible with existing lithium-ion battery manufacturing equipment, and the manufacturing process steps are reduced, thereby reducing the production cost of solid-state batteries.

6. The method for preparing a room temperature in-situ solidified solid electrolyte according to claim 5, characterized in that: The process includes: injecting electrolyte into the battery cell, encapsulating it, allowing the electrolyte to fully contact the initiator in the electrolyte membrane, and curing it at room temperature to form an in-situ cured solid electrolyte.

7. The preparation method according to claim 3, characterized in that: The packaging is carried out under an argon atmosphere; Preferably, the electrolyte membrane drying temperature is 80°C; Preferably, the electrolyte membrane drying time is 12h; Preferably, the room temperature curing time is 24 to 48 hours.

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