Waterproof adsorption layer and preparation method therefor, battery, and electric device

Abstract

Disclosed are an electric device, comprising a battery, wherein the battery comprises a waterproof adsorption layer. Also disclosed is a preparation method for the waterproof adsorption layer. The waterproof adsorption layer comprises an adsorption layer and a waterproof layer. The adsorption layer comprises a water-absorbing material, and the waterproof layer is arranged on a side surface of the adsorption layer.

Description

Waterproof adsorption layer, preparation method thereof, battery and electric device

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] The present application claims priority to the Chinese patent application No. 202411368056.2, filed on September 27, 2024, and entitled “Waterproof adsorption layer, preparation method thereof, battery and electric device”, the whole content of which is incorporated herein by reference. TECHNICAL FIELD

[0003] The present disclosure relates to the technical field of batteries, and in particular to a waterproof adsorption layer, a preparation method thereof, a battery and an electric device. BACKGROUND

[0004] In the production and use of batteries, when there is moisture inside the battery, the performance of the battery is prone to degradation. In the related art, a waterproof coating is often provided on the periphery of the battery cell to avoid the influence of external moisture on the battery. However, although the waterproof coating can isolate the external moisture and the battery cell, the risk of degradation of the battery performance is still relatively large, and the service life of the battery is relatively short.

[0005] DISCLOSURE

[0006] The present disclosure aims to at least solve one of the technical problems existing in the prior art. To this end, a first object of the present disclosure is to provide a waterproof adsorption layer to reduce the adverse effects of moisture on the performance of the battery, ensure the use stability of the battery, and prolong the service life of the battery.

[0007] A second object of the present disclosure is to provide a preparation method of the waterproof adsorption layer.

[0008] A third object of the present disclosure is to provide a battery.

[0009] A fourth object of the present disclosure is to provide an electric device.

[0010] According to the waterproof adsorption layer of the first aspect of the present disclosure, the waterproof adsorption layer comprises: an adsorption layer comprising a water-absorbing material; and a waterproof layer provided on one side surface of the adsorption layer.

[0011] According to the waterproof adsorption layer of the present disclosure, the waterproof layer can isolate the intrusion of external moisture into the battery cell, and the adsorption layer has strong adsorption capacity for moisture to adsorb the residual moisture inside the battery cell, thereby achieving moisture control inside the battery, reducing the adverse effects of moisture on the performance of the battery, ensuring the use stability of the battery, and prolonging the service life of the battery.

[0012] According to some embodiments of the present disclosure, the water-absorbing material comprises at least one of a zeolite, a metal organic framework material, a covalent organic framework material, a porous silica, a water-absorbing resin, and a basic water-removing agent.

[0013] According to some embodiments of the present disclosure, the desorption temperature of the water-absorbing material is greater than 150℃.

[0014] According to some embodiments of the present disclosure, the thickness of the adsorbing layer is 1-100 μm; and / or, the thickness of the waterproof layer is 1-100 μm.

[0015] According to some embodiments of the present disclosure, the adsorbing layer further comprises a binder.

[0016] According to some embodiments of the present disclosure, the water-absorbing material accounts for 20-95% of the weight percentage in the adsorbing layer.

[0017] According to some embodiments of the present disclosure, the binder comprises at least one of an inorganic binder and a resin binder.

[0018] According to some embodiments of the present disclosure, the pore size of the porous silica is no more than 50 nm.

[0019] According to some embodiments of the present disclosure, the zeolite comprises an artificially synthesized zeolite.

[0020] According to some embodiments of the present disclosure, the artificially synthesized zeolite comprises an aluminum silicate salt artificially synthesized zeolite.

[0021] According to some embodiments of the present disclosure, the waterproof layer maintains impermeability for 30 minutes under a test condition of maintaining a water pressure of 0.3 MPa.

[0022] According to some embodiments of the present disclosure, the waterproof layer comprises at least one of a non-metallic inorganic substance, a metal and its oxide, an asphalt-based waterproof coating, and a polymer-based waterproof coating.

[0023] According to some embodiments of the present disclosure, the metal and its oxide comprises at least one of aluminum, zinc, titanium, zinc oxide, titanium oxide, and triiron tetroxide; and / or, the non-metallic inorganic substance comprises ceramic and / or activated carbon; and / or, the asphalt-based waterproof coating comprises at least one of SBS modified asphalt waterproof coating, dissolved regenerated rubber asphalt waterproof coating, cationic emulsified asphalt waterproof coating, and FYT improved flexible waterproof coating for bridge deck; and / or, the polymer-based waterproof coating comprises at least one of polyurethane waterproof coating, acrylate waterproof coating, epoxy resin waterproof coating, polymer cement waterproof coating, and silicone rubber waterproof coating.

[0024] According to some embodiments of the present disclosure, the ceramic comprises at least one of silicon dioxide, calcium oxide, silicate, and aluminate.

[0025] According to some embodiments of the present disclosure, the water-absorbing material comprises at least one of zeolite, metal organic framework material, covalent organic framework material, porous silicon dioxide, water-absorbing resin, and alkaline water-removing agent.

[0026] According to the preparation method of the waterproof adsorption layer of the second aspect of the embodiments of the present disclosure, the method comprises: preparing an adsorption layer, comprising disposing the water-absorbing material on the surface of the battery cell to obtain the adsorption layer; and preparing a waterproof layer, comprising disposing raw materials of the waterproof layer on the surface of the side of the adsorption layer away from the battery cell to obtain the waterproof layer.

[0027] According to some embodiments of the present disclosure, the preparation of the adsorption layer comprises: mixing the water-absorbing material and the binder to obtain a mixture.

[0028] According to some embodiments of the present disclosure, the disposing manner comprises: dipping and drying, spraying, or template casting.

[0029] According to the battery of the third aspect of the embodiments of the present disclosure, the battery comprises: a battery cell; and a waterproof adsorption layer, which is the waterproof adsorption layer of the first aspect of the embodiments of the present disclosure or the waterproof adsorption layer prepared by the preparation method of the second aspect of the embodiments of the present disclosure, wherein the waterproof layer is disposed on the surface of the side of the adsorption layer away from the battery cell.

[0030] According to the power consumption device of the fourth aspect of the embodiments of the present disclosure, the power consumption device comprises at least one battery according to the third aspect of the embodiments of the present disclosure.

[0031] Additional aspects and advantages of the present disclosure will be in part apparent and in part pointed out hereinafter. DETAILED DESCRIPTION

[0032] The waterproof adsorption layer according to the first aspect of the embodiments of the present disclosure is described below.

[0033] The waterproof adsorption layer according to the first aspect of the embodiments of the present disclosure comprises an adsorption layer and a waterproof layer. The waterproof layer is used to isolate the intrusion of external water into the battery cell. The adsorption layer is used to adsorb the residual water in the battery cell, so as to control the water in the battery cell and reduce the adverse effects of water on the performance of the battery, thereby ensuring the performance of the battery.

[0034] Specifically, the adsorption layer comprises water-absorbing material, which has strong adsorption capacity for water and the like. The adsorption layer can be disposed on the side of the waterproof layer facing the inside of the battery cell, so that the water-absorbing material of the adsorption layer can adsorb the residual water in the battery cell.

[0035] The waterproof layer is arranged on one side surface of the adsorption layer, for example, on the surface of the adsorption layer away from the battery cell, which is conducive to isolating most of the external moisture from entering the battery cell, thereby preventing the external moisture from invading the battery cell and the adsorption layer, and ensuring that the adsorption layer preferentially plays a role in adsorbing the residual moisture in the battery cell.

[0036] According to the waterproof adsorption layer of the embodiments of the present disclosure, by combining the waterproof layer and the adsorption layer, the waterproof layer can isolate the invasion of external moisture into the battery, and the adsorption layer has strong adsorption capacity for moisture to adsorb the residual moisture in the battery cell, thereby achieving the control of the moisture in the battery, reducing the adverse effects of moisture on the performance of the battery, ensuring the use stability of the battery, and prolonging the service life of the battery.

[0037] According to some embodiments of the present disclosure, the water-absorbing material includes at least one of zeolite, metal organic framework material, covalent organic framework material, porous silica, water-absorbing resin, and alkaline water-removing agent. The zeolite, metal organic framework material, covalent organic framework material, porous silica, water-absorbing resin, and alkaline water-removing agent can have physical adsorption and / or chemical adsorption, which is conducive to improving the adsorption speed of the adsorption layer, increasing the adsorption capacity of the adsorption layer, reducing the residual moisture in the battery cell during the production process, and reducing the harmful gases such as hydrogen sulfide generated by sulfides, thereby avoiding the adverse effects of the residual moisture and the gases such as hydrogen sulfide on the performance of the battery cell. At the same time, the zeolite, metal organic framework material, covalent organic framework material, porous silica, water-absorbing resin, and alkaline water-removing agent all have a relatively high desorption temperature, which prevents significant desorption from occurring during the use of the battery, thereby ensuring the use stability of the battery. Specifically, the metal organic framework material includes, for example, UIO-66 metal organic framework, etc.; the covalent organic framework material includes HydCOFs (Hydrogen-bonded Covalent Organic Frameworks), etc.; and the alkaline water-removing agent includes quicklime, anhydrous calcium chloride, anhydrous copper sulfate, etc.

[0038] According to some embodiments of the present disclosure, the desorption temperature of the water-absorbing material is greater than 150°C. The desorption temperature refers to a specific temperature that needs to be heated to in order to release the adsorbed substances from the surface of the water-absorbing material (i.e., desorption) in the process of physical or chemical adsorption. Thus, the water-absorbing material has a relatively high desorption temperature, that is, the water-absorbing material still has strong adsorption capacity for moisture and gases such as hydrogen sulfide at a relatively high temperature, which can prevent significant desorption from occurring during the use of the battery cell, thereby ensuring the safety performance of the battery at high temperatures.

[0039] The desorption temperature can be determined by the programmed temperature desorption (PTD) technique, but is not limited thereto.

[0040] According to some embodiments of the present disclosure, the thickness of the adsorption layer is 1-100 pm. The thickness of the adsorption layer is reasonably set, which meets the adsorption requirements of fully absorbing moisture and hydrogen sulfide gas in the battery cell, and is conducive to the lightweight setting of the waterproof adsorption layer, thereby improving the applicability of the waterproof adsorption layer. For example, the thickness of the adsorption layer can be 1 pm, 20 pm, 50 pm, 70 pm, or 100 pm.

[0041] The thickness of the waterproof layer is 1-100 pm. The thickness of the waterproof layer is reasonably set, which improves the structural strength of the waterproof layer, facilitates the stable setting of the waterproof layer on one side surface of the adsorption layer, and at the same time, the waterproof layer can reliably isolate the intrusion of external moisture into the battery. For example, the thickness of the waterproof layer can be 1 pm, 20 pm, 50 pm, 70 pm, or 100 pm.

[0042] According to some embodiments of the present disclosure, the adsorption layer further comprises a binder. The binder is conducive to bonding the particles of the water-absorbing material together to form a stable adsorption layer, and at the same time, the binder is conducive to improving the mechanical strength of the adsorption layer, avoiding the fragmentation of the adsorption layer, thereby improving the structural strength and adsorption performance of the adsorption layer and prolonging the service life of the adsorption layer.

[0043] The weight percentage of the water-absorbing material in the adsorption layer is 20-95%. When the weight percentage of the water-absorbing material in the adsorption layer is less than 20%, the adsorption capacity of the adsorption layer is poor, and the amount of adsorbed moisture and hydrogen sulfide gas is small; when the weight percentage of the water-absorbing material in the adsorption layer is greater than 95%, the water-absorbing material is too much, which causes waste of the water-absorbing material and increases the cost of the adsorption layer. Therefore, by setting the weight percentage of the water-absorbing material in the adsorption layer to 20-95%, the weight percentage of the water-absorbing material in the adsorption layer is reasonable, which is conducive to improving the adsorption effect of the adsorption layer, while avoiding waste of the water-absorbing material and reducing the cost of the adsorption layer.

[0044] Further, the binder comprises at least one of an inorganic binder and a resin binder. Both the inorganic binder and the resin binder have good bonding effect with the battery cell. For example, in the battery using sulfide electrolyte, the inorganic binder and the resin binder have good stability with the sulfide material.

[0045] The pore size of the porous silica is not more than 50 nm. That is, the porous silica as the water-absorbing material includes microporous silica (pore size less than 2 nm) and / or mesoporous silica (pore size 2-50 nm). Therefore, the pore size of the porous silica is suitable for the needs of absorbing moisture and hydrogen sulfide gas.

[0046] According to some embodiments of the present disclosure, the zeolite comprises a synthetic zeolite. The synthetic zeolite is easy to precisely control the pore size and the number of pores, has the characteristics of low silicon aluminum ratio, small particle size, high porosity, etc., so that the synthetic zeolite can efficiently adsorb moisture and hydrogen sulfide. The silicon aluminum ratio of the synthetic zeolite is 1:1, the particle size is 2 μm, and the micropore volume is 0.2 cc / g.

[0047] According to some embodiments of the present disclosure, the synthetic zeolite comprises an aluminum silicate salt synthetic zeolite. The aluminum silicate salt synthetic zeolite has good thermal stability and can maintain its structure and performance under high temperature conditions. Therefore, using the aluminum silicate salt synthetic zeolite is beneficial to improve the thermal adaptability of the adsorption layer and the adaptability of the battery in a high temperature environment.

[0048] The preparation of the synthetic zeolite is as follows:

[0049] A. Synthesis of A-type low-silicon zeolite under vapor phase system.

[0050] 1. Preparation of solid phase reactants: an appropriate amount of aluminum hydroxide is weighed in a polytetrafluoroethylene liner according to the molar ratio n(HF):n(SiO2):n(Al2O3):n(H2O) = 0.5:1.0:0.5:5.0, then an appropriate amount of silica sol is slowly added, stirred to mix uniformly, and then an appropriate amount of hydrofluoric acid is added, and continuously stirred until a gel-like mixture is formed as a solid phase.

[0051] 2. Preparation of solution in vapor phase: an appropriate amount of ethylenediamine aqueous solution (volume ratio of ethylenediamine to water is 25:5) is added to the vapor phase reactor as a liquid phase.

[0052] 3. High temperature and high pressure reaction: the polytetrafluoroethylene liner containing the solid phase gel is transferred to the support of the vapor phase reactor, then sealed and placed in an oven at 180°C for 3 days, and the reactor is taken out and allowed to cool naturally.

[0053] 4. Product collection: the obtained solid product is washed with distilled water, centrifuged, and filtered, and this process is repeated until the filtrate is neutral. The solid product is vacuum dried at 100°C for 8 hours to obtain the target A-type low-silicon zeolite.

[0054] B. Synthesis of ultra-micro low-silicon zeolite by using alkali metal salt.

[0055] 1. Preparation: the ingredients are prepared according to the ratio Al2O3:SiO2:Na2O:H2O = 1:2:3:185. The water glass and aluminum hydroxide are respectively adjusted to a certain concentration of water glass and sodium aluminate solution by using 0.1 mol / L NaOH solution.

[0056] 2. Crystallization: After preheating to 60°C with a constant temperature water bath, add the water glass to the sodium metaaluminate solution under strong stirring to form a colloid, and add the alkali metal salt at the same time. The mixture is heated to 90°C under uniform stirring, and then crystallized for 5 hours.

[0057] 3. Product collection: suction filtration, water washing, and repeating the process until the pH value reaches 9-10. Vacuum drying at 110°C for 8 hours to obtain the target ultra-micro low-silica zeolite.

[0058] In addition, the water permeability of the waterproof layer is 0 (i.e., the waterproof layer maintains impermeability within 30 minutes under the test condition of maintaining a water pressure of 0.3 MPa) under the condition of not more than 0.3 MPa for 30 minutes. That is, the waterproof layer is impermeable under the condition of not more than 0.3 MPa for 30 minutes. Therefore, the impermeability (i.e., waterproofing ability) of the waterproof layer meets the needs of the waterproof adsorption layer, ensuring the use stability of the battery under the condition of not more than 0.3 MPa for 30 minutes, thereby facilitating the stable operation of the battery under various use conditions.

[0059] Further, the waterproof layer includes at least one of non-metallic inorganic matter, metal and its oxide, asphalt-based waterproof coating, and polymer-based waterproof coating. Non-metallic inorganic matter, metal and its oxide, asphalt-based waterproof coating, and polymer-based waterproof coating are all non-aqueous and do not contain strong polar solvents, and all have good waterproof performance, adhesion performance, and certain elasticity. Therefore, the use of non-metallic inorganic matter, metal and its oxide, asphalt-based waterproof coating, and polymer-based waterproof coating is conducive to improving the isolation effect of external moisture, while improving the use stability of the waterproof layer and prolonging the service life of the waterproof layer, thereby ensuring the long-term safe use of the battery.

[0060] According to some embodiments of the present disclosure, the metal and its oxide include at least one of aluminum, zinc, titanium, zinc oxide, titanium oxide, and magnetite. The above-mentioned metals (aluminum, zinc, and titanium) and metal oxides (zinc oxide, titanium oxide, and magnetite) all have good corrosion resistance, durability, and mechanical strength, and the use of at least one of the above-mentioned metals and their oxides is conducive to improving the mechanical strength of the waterproof layer and prolonging the service life of the waterproof layer.

[0061] The non-metallic inorganic matter includes ceramic and / or activated carbon. Among them, the microporous structure and high specific surface area of the ceramic surface can provide a large number of adsorption sites for the ceramic, thereby adsorbing gas molecules (such as water vapor and hydrogen sulfide) or other small molecular substances. The functional groups on the surface of the ceramic can chemically react with specific molecules, thereby realizing selective adsorption. The activated carbon is a porous carbon material with extremely high surface area and adsorption capacity. The developed pore structure of the activated carbon can capture various gas molecules and liquid molecules. Therefore, using one of the ceramic or activated carbon is conducive to improving the adsorption capacity of the adsorption layer and reducing the cost of the adsorption layer.

[0062] The asphalt-based waterproof coating includes at least one of SBS (Styrene-Butadiene-Styrene Block Copolymers) modified asphalt waterproof coating, dissolved type regenerated rubber asphalt waterproof coating, cationic emulsified asphalt waterproof coating and FYT (fullerene derivative) improved deck flexible waterproof coating. The above-mentioned asphalt-based waterproof coating has good adhesion, flexibility, aging resistance and water resistance. Using at least one of the above-mentioned asphalt-based waterproof coating is conducive to improving the integrity and waterproofness of the waterproof layer, prolonging the service life of the waterproof layer, and improving the environmental protection of the waterproof layer.

[0063] The polymer-based waterproof coating includes at least one of polyurethane waterproof coating, acrylate waterproof coating, epoxy resin waterproof coating, polymer cement waterproof coating and silicone rubber waterproof coating. The polymer-based waterproof coating is a waterproof material based on high molecular polymer, which can form a continuous waterproof film. The above-mentioned polymer-based waterproof coating has good water resistance, adhesion and elasticity, and using at least one of the above-mentioned polymer-based waterproof coating is conducive to maintaining the waterproof effect of the waterproof layer and increasing the setting stability and reliability of the waterproof layer on the surface of the adsorption layer.

[0064] Further, the ceramic includes at least one of silicon dioxide, calcium oxide, silicate and aluminate. The above-mentioned components are all conducive to improving the wear resistance, weather resistance and corrosion resistance of the waterproof layer, and using at least one of the above-mentioned components as ceramic applied in the waterproof layer is conducive to improving the durability and reliability of the waterproof layer.

[0065] The preparation method of the waterproof adsorption layer according to the second aspect of the present disclosure includes:

[0066] The preparation of the adsorption layer includes arranging the water-absorbing material on the surface of the battery cell to obtain the adsorption layer.

[0067] The preparation of the waterproof layer includes arranging the raw material of the waterproof layer on the side surface of the adsorption layer away from the battery cell to obtain the waterproof layer.

[0068] The preparation method of the waterproof adsorption layer according to the embodiments of the present disclosure sequentially prepares the adsorption layer and the waterproof layer on the surface of the battery cell, so that the adsorption layer can sufficiently adsorb the moisture generated in the preparation process of the battery cell, and the waterproof layer can isolate external moisture, and at the same time, the waterproof layer can ensure that the adsorption layer preferentially plays a role of adsorbing the residual moisture in the battery cell.

[0069] Further, the preparation of the adsorption layer includes mixing the water-absorbing material and the binder and disposing the mixture on the surface of the battery cell. The preparation method of the waterproof adsorption layer further includes drying the binder to remove water, adding a solvent, and configuring the binder solution. The binder solution is configured after the binder is dried, so as to avoid the water-absorbing material in the adsorption layer from adsorbing the moisture in the binder and reducing the adsorption capacity of the adsorption layer for the moisture in the battery cell.

[0070] In addition, considering the stability of the sulfide electrolyte material, the solvent used for the battery cell of the sulfide battery is limited to low-polarity solvents such as xylene, anisole, butyl butyrate, and isobutyl isobutyrate, or a thermosetting resin coating or a photocurable resin coating is directly selected. However, the present disclosure is not limited thereto.

[0071] Further, the forming of the slurry includes adding the water-absorbing material to the binder solution and stirring to mix the water-absorbing material uniformly in the binder solution, so as to improve the binding effect of the binder on the material and improve the integrity and uniformity of the adsorption layer.

[0072] According to some embodiments of the present disclosure, the setting method includes dipping and drying, spraying, or template casting. The dipping and drying method has good uniformity and can be repeated multiple times to control the thickness of the adsorption layer and / or the waterproof layer, and has low cost. The spraying method has high efficiency and good uniformity, which increases the quality of the adsorption layer and / or the waterproof layer and improves the adhesion of the raw material of the waterproof layer on the adsorption layer. The template casting method has high compactness and precision of the coated adsorption layer and / or the waterproof layer, and the coating is formed at one time, which is beneficial to improving the coating efficiency.

[0073] The battery according to the third aspect of the embodiments of the present disclosure includes a battery cell and a waterproof adsorption layer. The waterproof adsorption layer is the waterproof adsorption layer according to the first aspect of the embodiments of the present disclosure or the waterproof adsorption layer prepared by the preparation method according to the second aspect of the embodiments of the present disclosure. The waterproof layer is disposed on the surface of the adsorption layer away from the battery cell.

[0074] The battery according to the embodiments of the present disclosure is beneficial to improving the use stability of the battery and prolonging the service life of the battery.

[0075] The battery can be a solid-state battery. The solid-state battery has a lower internal resistance, can support a faster charging speed, reduce charging time, and improve charging efficiency. The solid-state battery uses a solid-state electrolyte instead of a liquid-state electrolyte, and has higher chemical and thermal stability. Therefore, a small amount of moisture and the like is often retained in the solid-state electrolyte. Therefore, the use of the waterproof adsorption layer described above is beneficial to adsorb the small amount of moisture and the like in the solid-state electrolyte of the solid-state battery, and to adsorb harmful gases (such as hydrogen sulfide) in the solid-state electrolyte, thereby improving the use stability and reliability of the solid-state battery.

[0076] According to the fourth aspect of the present disclosure, the power consuming device comprises at least one battery according to the third aspect of the present disclosure.

[0077] According to the power consuming device of the present disclosure, the use of the battery described above is beneficial to improve the energy supply stability and reliability of the power consuming device, thereby improving the operation stability of the power consuming device, and further improving the market competitiveness of the power consuming device.

[0078] The embodiments of the present disclosure are described in detail below. It should be noted that the embodiments described below are exemplary and are used to explain the present disclosure, and cannot be understood as a limitation of the present disclosure. In addition, if not specifically stated, all reagents used in the following embodiments are commercially available or can be synthesized according to the methods described herein or known methods. The reaction conditions not listed are also easily obtained by those skilled in the art.

[0079] Embodiment 1

[0080] The components and weight percentages of the slurry of the adsorption layer in this embodiment are as follows:

[0081] Artificially synthesized zeolite (aluminum silicate salt): 63%; butadiene styrene rubber (SBR, relative molecular mass: 600000): 7%; dimethylbenzene (molecular formula C8H 10 ): 30%.

[0082] The components of the slurry of the waterproof layer in this embodiment are as follows: solvent-free single-component polyurethane waterproof coating.

[0083] The manufacturing process of the waterproof adsorption layer is as follows: 1. High-temperature activation of synthetic zeolite: Activate at 400℃ for 4 hours in a dry, inert atmosphere (argon, nitrogen, etc.) or under strict dew point control (below -50℃), then cool and set aside. 2. Prepare the binder solution. 3. Add the activated zeolite to the prepared binder solution and mix thoroughly using a ball mill. 4. Apply the adsorption layer to the side of the sulfide battery cell, wherein: the desorption temperature of the water-absorbing material is greater than 150℃, for example, 200℃; the weight percentage of the water-absorbing material in the adsorption layer is 20%–95%, for example, 55%. 5. Apply a waterproof layer to the outside of the adsorption layer, wherein the water permeability of the waterproof layer is 0 under conditions of 0.2MPa for 30 minutes. The manufacturing and application of the adsorption layer and the waterproof layer are all carried out in a dew point environment below -30℃. After application, the battery is placed in this environment for another 24 hours before assembly. The thickness of the adsorption layer is 1μm to 100μm (e.g., 50μm in this embodiment), and the thickness of the waterproof layer is 1μm to 100μm (e.g., 50μm in this embodiment).

[0084] The battery manufacturing process is as follows: The negative electrode, separator, and positive electrode are arranged sequentially, with an electrolyte or solid electrolyte placed between the negative and positive electrodes to form a battery cell; then, the aforementioned waterproof adsorption layer is applied to the surface of the battery cell, and multiple battery cells are stacked sequentially to form a battery. The electrolyte or solid electrolyte includes sulfides, the negative electrode includes silicon, and the positive electrode includes ternary materials.

[0085] Example 2

[0086] Example 2 is basically the same as Example 1, except that the waterproof layer material is silicon dioxide.

[0087] Example 3

[0088] Example 3 is basically the same as Example 1, except that the waterproof layer material is SBS modified bitumen waterproofing.

[0089] Example 4

[0090] Example 4 is the same as Example 1, except that the waterproof layer material is titanium oxide.

[0091] Example 5

[0092] Example 5 is basically the same as Example 1, except that the waterproof layer material is SBS modified asphalt bridge deck waterproof coating, and an aluminum film is then coated on the surface.

[0093] Example 6

[0094] Example 6 is basically the same as Example 1, except that the water-absorbing material in the adsorption layer is a metal-organic framework material (specifically UIO-66).

[0095] Example 7

[0096] Example 7 is substantially the same as Example 1, except that the water-absorbing material in the adsorption layer is a covalent organic framework material (specifically, HydCOFs).

[0097] Example 8

[0098] Example 8 is substantially the same as Example 1, except that the water-absorbing material in the adsorption layer is a basic water-removing agent (specifically, quicklime).

[0099] Example 9

[0100] Example 8 is substantially the same as Example 1, except that the desorption temperature of the water-absorbing material is 100°C.

[0101] Example 10

[0102] Example 10 is substantially the same as Example 1, except that the thickness of the adsorption layer is 150 μm and the thickness of the waterproof layer is 150 μm.

[0103] Example 11

[0104] Example 11 is substantially the same as Example 1, except that the weight percentage of the water-absorbing material in the adsorption layer is 10%.

[0105] Example 12

[0106] Example 12 is substantially the same as Example 1, except that the weight percentage of the water-absorbing material in the adsorption layer is 98%.

[0107] Example 13

[0108] Example 13 is substantially the same as Example 1, except that the water permeability of the waterproof layer is tested under the condition of 0.5 MPa, 30 min.

[0109] Comparative Example 1

[0110] Comparative Example 1 is substantially the same as Example 1, except that the sulfide solid-state battery is manufactured in an environment with a strictly controlled dew point (below -50°C), and the battery is assembled directly without the adsorption layer and the waterproof layer coating on the side of the battery.

[0111] Comparative Example 2

[0112] Comparative Example 2 is substantially the same as Example 1, except that the adsorption layer is not coated, and the other procedures are consistent.

[0113] Comparative Example 3

[0114] Comparative Example 3 is substantially the same as Example 1, except that no water-proof layer is coated, and the other procedures are consistent.

[0115] Comparative Example 4

[0116] Comparative Example 4 is substantially the same as Example 1, except that no adsorption layer and no water-proof layer are coated, and the other procedures are consistent.

[0117] Performance Test

[0118] Battery capacity performance test: the batteries of Example 1-Example 8 and Comparative Example 1-Comparative Example 4 are tested for battery charge and discharge under the same working pressure and working temperature, and the test procedure is as follows: 12 hours of standing, 0.05C rate charging to the upper voltage limit, and then 0.05C rate discharging to the lower voltage limit, and the specific capacity of the discharge is recorded. The discharge specific capacity of Comparative Example 1 is taken as the standard (100%) (assuming that there is no moisture in the environment with a dew point of -50°C or lower), and the discharge specific capacity of each example is evaluated, and recorded in Table 1.

[0119] Table 1 Discharge specific capacity of Example 1-Example 13 and Comparative Example 2-Comparative Example 5 relative to Comparative Example 1

[0120] The battery cells of Example 1-Example 8 are prepared at a dew point of -30°C, and there is some residual moisture, and the battery cells of Example 1-Example 8 are left to stand in an environment with a dew point of -30°C for 24 hours before being packaged into batteries. In Example 1, the water-proof layer prevents the subsequent invasion of external moisture, and the adsorption layer fully plays a role in adsorbing residual moisture and hydrogen sulfide gas in the battery cell, so that the capacity performance of the battery is close to that of the battery of Comparative Example 1. In Comparative Example 2, the residual moisture in the battery cell is not reduced due to the absence of the adsorption layer, which affects the battery capacity performance of the battery. In Comparative Example 3, the adsorption layer simultaneously adsorbs the moisture in the external environment and the battery cell, and the removal capacity of the residual moisture in the battery cell is reduced, so the battery capacity performance is slightly lower than that of Example 1. In Comparative Example 4, there is no adsorption layer and no water-proof layer, and the moisture continuously invades the battery cell, causing the battery performance of the battery to deteriorate, and exhibiting the lowest capacity performance.

[0121] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "exemplary embodiment", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present disclosure. In the present specification, the exemplary description of the above terms does not necessarily refer to the same embodiment or example.

[0122] While the embodiments of the present disclosure have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, and refinements can be made thereto without departing from the principles and concepts disclosed.

Claims

1. A waterproof adsorption layer, characterized in that, The waterproof adsorption layer comprises: an adsorption layer comprising a water-absorbing material; and a waterproof layer arranged on one side surface of the adsorption layer.

2. The water-resistant adsorption layer of claim 1, the water-absorbing material comprising: at least one of a zeolite, a metal organic framework material, a covalent organic framework material, porous silica, a water-absorbing resin, and a basic water-removing agent.

3. The water-repellent adsorbing layer according to claim 1 or 2, characterized by The desorption temperature of the water-absorbing material is greater than 150°C.

4. The water-resistant adsorption layer according to any one of claims 1-3, wherein, The thickness of the adsorption layer is 1 μm to 100 μm; and / or the thickness of the waterproof layer is 1 μm to 100 μm.

5. The water-resistant adsorption layer according to any one of claims 1-4, wherein, The adsorption layer further comprises a binder.

6. The water-resistant absorbent layer of any one of claims 1-5, wherein, The weight percentage of the water-absorbing material in the adsorption layer is 20% to 95%.

7. The waterproof adsorption layer according to claim 5, wherein, The binder comprises at least one of an inorganic binder and a resin binder.

8. The waterproof adsorption layer according to claim 2, wherein, The pore size of the porous silica is no more than 50 nm.

9. The waterproof adsorption layer according to claim 2, wherein, The zeolite comprises an artificially synthesized zeolite.

10. The waterproof adsorption layer according to claim 9, characterized in that, The artificially synthesized zeolite comprises an artificially synthesized zeolite of an alumino-silicate type.

11. The waterproof adsorption layer according to any one of claims 1-10, wherein, The waterproof layer maintains impermeability for 30 minutes under a test condition of maintaining a water pressure of 0.3 MPa.

12. The water-resistant absorbent layer of any one of claims 1-11, wherein, The waterproof layer comprises at least one of a non-metallic inorganic substance, a metal and an oxide thereof, an asphalt-based waterproof coating, and a polymer-based waterproof coating.

13. The water-resistant absorbent layer of claim 12, wherein, The metal and the oxide thereof comprise at least one of aluminum, zinc, titanium, zinc oxide, titanium oxide, and magnetite; and / or The non-metallic inorganic substance comprises ceramic and / or activated carbon; and / or The asphalt-based waterproof coating comprises at least one of SBS modified asphalt waterproof coating, dissolved regenerated rubber asphalt waterproof coating, cationic emulsified asphalt waterproof coating, and FYT improved flexible waterproof coating for bridge deck; and / or The polymer-based waterproof coating comprises at least one of polyurethane waterproof coating, acrylate waterproof coating, epoxy resin waterproof coating, polymer cement waterproof coating, and silicone rubber waterproof coating.

14. The waterproof adsorption layer according to claim 13, wherein, The ceramic comprises at least one of silicon dioxide, calcium oxide, silicate, and aluminate.

15. A method of preparing a waterproof adsorbing layer according to any one of claims 1-14, characterized by, The waterproof adsorption layer is prepared by: preparing an adsorption layer by using the water-absorbing material; and preparing a waterproof layer by arranging raw materials of the waterproof layer on one side surface of the adsorption layer.

16. The method of claim 15, wherein the water-repellent adsorbing layer is prepared by a method comprising: The preparation of the adsorption layer comprises mixing the water-absorbing material and a binder to obtain a mixture.

17. The method of claim 15 or 16, wherein the water-repellent adsorbing layer is prepared by a method comprising: The arrangement of the raw materials of the waterproof layer on one side surface of the adsorption layer comprises dipping and drying, spraying, or template casting.

18. A battery, characterized by The waterproof adsorption layer is prepared by: an electric core; and a waterproof adsorption layer according to any one of claims 1-14, or prepared according to any one of claims 15-17, wherein the waterproof layer is arranged on a surface of the adsorption layer away from the electric core. The battery comprises at least one electric battery according to claim 18.

19. An electrical device, comprising: ​

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