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

Abstract

The invention discloses a waterproof adsorption layer and a preparation method thereof, a battery and electric equipment. The waterproof adsorption layer comprises an adsorption layer and a waterproof layer. The adsorption layer comprises a water absorption material, and the waterproof layer is arranged on the surface of one side of the adsorption layer. According to the waterproof adsorption layer disclosed by the invention, the waterproof layer and the adsorption layer are combined, the waterproof layer can isolate external moisture from invading the battery cell, and the adsorption layer has strong adsorption capacity on moisture to adsorb residual moisture in the battery cell, so that moisture control in the battery is realized, and the adverse effect of the moisture on the battery performance is reduced; the use stability of the battery is ensured and the service life of the battery is prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of batteries, in particular to a waterproof adsorption layer, a preparation method thereof, a battery and an electric device. BACKGROUND

[0002] In the production and use of a battery, when water exists in the battery, the performance of the battery is prone to degradation. In the related art, a waterproof coating is often arranged on the periphery of the battery cell to avoid the influence of external water on the battery. However, although the waterproof coating can isolate the external water and the battery cell, the risk of degradation of the performance of the battery is still relatively large, and the service life of the battery is relatively short. SUMMARY

[0003] The present application aims to at least solve one of the technical problems in the prior art. To this end, a first object of the present application is to provide a waterproof adsorption layer which reduces the adverse effects of water on the performance of the battery, ensures the use stability of the battery and prolongs the service life of the battery.

[0004] A second object of the present application is to provide a preparation method of the waterproof adsorption layer.

[0005] A third object of the present application is to provide a battery.

[0006] A fourth object of the present application is to provide an electric device.

[0007] According to the waterproof adsorption layer of the first aspect of the present application, 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.

[0008] According to the waterproof adsorption layer of the present application, the waterproof layer can isolate the intrusion of external water into the battery cell, and the adsorption layer can adsorb the residual water in the battery cell due to its strong water adsorption capacity, thereby achieving water control in the battery, reducing the adverse effects of water on the performance of the battery, ensuring the use stability of the battery and prolonging the service life of the battery.

[0009] According to some embodiments of the present application, the water-absorbing material comprises at least one of zeolite, metal organic framework material, covalent organic framework material, porous silica, water-absorbing resin and alkaline water-removing agent.

[0010] According to some embodiments of the present application, the desorption temperature of the water-absorbing material is greater than 150℃.

[0011] According to some embodiments of the present application, the thickness of the adsorption layer is 1-100 μm; and / or the thickness of the waterproof layer is 1-100 μm.

[0012] According to some embodiments of the present application, the adsorption layer further comprises a binder.

[0013] According to some embodiments of the present application, the water-absorbing material accounts for 20-95% of the adsorption layer by weight.

[0014] According to some embodiments of the present application, the binder comprises at least one of an inorganic binder and a resin binder.

[0015] According to some embodiments of the present application, the porous silica has a pore size of no more than 50 nm.

[0016] According to some embodiments of the present application, the zeolite comprises an artificial synthetic zeolite.

[0017] According to some embodiments of the present application, the artificial synthetic zeolite comprises an aluminosilicate artificial synthetic zeolite.

[0018] According to some embodiments of the present application, the waterproof layer has a water permeability of 0 under a pressure of no more than 0.3 MPa for 30 minutes.

[0019] According to some embodiments of the present application, 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.

[0020] According to some embodiments of the present application, the metal and its oxide comprises 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.

[0021] According to some embodiments of the present application, the ceramic comprises at least one of silicon dioxide, calcium oxide, silicate, and aluminate.

[0022] According to some embodiments of the present application, the water-absorbing material comprises at least one of zeolite, metal organic framework material, covalent organic framework material, porous silica, water-absorbing resin, and alkaline water-removing agent.

[0023] The method for preparing the waterproof adsorption layer according to the second aspect of the present application comprises:

[0024] Preparation of the adsorption layer, the water-absorbing material is arranged on the surface of the battery cell to obtain the adsorption layer.

[0025] The waterproof layer is prepared, and raw materials of the waterproof layer are arranged on a surface of the adsorption layer away from the battery cell to obtain the waterproof layer.

[0026] According to some embodiments of the present application, the preparation of the adsorption layer comprises: mixing the water-absorbing material and the binder to obtain a mixture, and then arranging the mixture on a surface of the battery cell.

[0027] According to some embodiments of the present application, the arrangement comprises: dipping-drying, spraying or template casting.

[0028] The battery according to the third aspect of the embodiments of the present application comprises: a battery cell, and a waterproof adsorption layer, wherein the waterproof adsorption layer is the waterproof adsorption layer according to the first aspect of the embodiments of the present application or the waterproof adsorption layer prepared by the preparation method according to the second aspect of the embodiments of the present application, and the waterproof layer is arranged on a surface of the adsorption layer away from the battery cell.

[0029] The power consumption device according to the fourth aspect of the embodiments of the present application comprises at least one battery according to the third aspect of the embodiments of the present application.

[0030] Additional aspects and advantages of the present application will be in part apparent and in part pointed out hereinafter. DETAILED DESCRIPTION

[0031] The waterproof adsorption layer according to the first aspect of the embodiments of the present application is described below.

[0032] The waterproof adsorption layer according to the first aspect of the embodiments of the present application comprises an adsorption layer and a waterproof layer. The waterproof layer is used to prevent the invasion 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.

[0033] Specifically, the adsorption layer comprises a water-absorbing material, and the water-absorbing material has strong adsorption capacity for water and the like. The adsorption layer can be arranged on a 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.

[0034] The waterproof layer is arranged on a surface of the adsorption layer, for example, a surface of the adsorption layer away from the battery cell, so as to prevent most of the external water from entering the battery cell, thereby preventing the invasion of external water into the battery cell and the adsorption layer, and ensuring that the adsorption layer plays a role in adsorbing the residual water in the battery cell.

[0035] The waterproof adsorption layer according to the embodiment of the present application combines the waterproof layer and the adsorption layer, the waterproof layer can prevent the invasion of external water into the battery, the adsorption layer has strong adsorption capacity for water, and the residual water in the battery can be adsorbed, so that the water in the battery is controlled, the adverse effects of water on the performance of the battery are reduced, the stability of the battery is ensured, and the service life of the battery is prolonged.

[0036] According to some embodiments of the present application, 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 be beneficial to improve the adsorption speed of the adsorption layer, increase the adsorption capacity of the adsorption layer, reduce the residual water in the battery during the production process, and reduce the harmful gases such as hydrogen sulfide generated by sulfides, so as to avoid the adverse effects of the residual water and the gases such as hydrogen sulfide on the performance of the battery. 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 high desorption temperature, which can prevent the occurrence of obvious desorption phenomenon during the use of the battery, and ensure the stability of the battery. Specifically, the metal organic framework material includes UIO-66, etc.; the covalent organic framework material includes HydCOFs, etc.; and the alkaline water-removing agent includes quicklime, anhydrous calcium chloride, anhydrous copper sulfate, etc.

[0037] According to some embodiments of the present application, the desorption temperature of the water-absorbing material is greater than 150℃. The desorption temperature refers to a specific temperature that needs to be heated to release the adsorbed substances from the surface of the water-absorbing material (i.e. desorption) during the physical or chemical adsorption process. Therefore, the water-absorbing material has a high desorption temperature, that is, the water-absorbing material still has strong adsorption capacity for water and gases such as hydrogen sulfide at a high temperature, which can prevent the occurrence of obvious desorption phenomenon during the use of the battery, thereby ensuring the safety performance of the battery at high temperature.

[0038] The desorption temperature can be determined by the programmed temperature desorption (PTD) technology. However, it is not limited thereto.

[0039] According to some specific embodiments of the present application, the thickness of the adsorption layer is 1μm-100μm. The thickness of the adsorption layer is reasonably set, which can meet the adsorption requirements of the water and gases such as hydrogen sulfide in the battery, and is beneficial 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 1μm, 20μm, 50μm, 70μm or 100μm.

[0040] The waterproof layer has a thickness of 1 μm to 100 μm. The thickness of the waterproof layer is properly set, which improves the structural strength of the waterproof layer, so as to facilitate the stable arrangement of the waterproof layer on the one side surface of the adsorption layer. Meanwhile, the waterproof layer can reliably prevent the intrusion of external water into the battery.

[0041] According to some embodiments of the present application, 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. Meanwhile, 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.

[0042] The water-absorbing material accounts for 20% to 95% of the weight percentage in the adsorption layer. When the water-absorbing material accounts for less than 20% of the weight percentage in the adsorption layer, the adsorption capacity of the adsorption layer is poor, and the amount of water and hydrogen sulfide gas that can be adsorbed is small. When the water-absorbing material accounts for more than 95% of the weight percentage in the adsorption layer, 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% to 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.

[0043] 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 adhesion 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.

[0044] The pore diameter of the porous silica is not more than 50 nm. That is, the porous silica as the water-absorbing material includes microporous silica (pore diameter less than 2 nm) and / or mesoporous silica (pore diameter of 2 nm to 50 nm). Therefore, the pore diameter of the porous silica is suitable for the needs of absorbing water and hydrogen sulfide gas.

[0045] According to some embodiments of the present application, the zeolite comprises an artificial synthetic zeolite. The artificial synthetic zeolite is easy to accurately control the pore size and the number of pores, has the characteristics of low silicon aluminum ratio, small particle size, and high porosity, so that the artificial synthetic zeolite can efficiently adsorb water and hydrogen sulfide. The silicon aluminum ratio of the artificial synthetic zeolite is 1:1, the particle size is 2 μm, and the micropore volume is 0.2 cc / g.

[0046] According to some embodiments of the present application, the artificial zeolite includes an aluminosilicate artificial zeolite. The aluminosilicate artificial zeolite has good thermal stability and can maintain its structure and performance under high temperature conditions. Therefore, the use of the aluminosilicate artificial zeolite is beneficial to improve the thermal adaptability of the adsorption layer and the adaptability of the battery in a high temperature environment.

[0047] The artificial zeolite is prepared as follows:

[0048] A. Synthesis of A-type low-silicon zeolite under a vapor phase system:

[0049] 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 stirring is continued until a gel-like mixture is formed as a solid phase.

[0050] 2. Preparation of a solution in a 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.

[0051] 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.

[0052] 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, and the solid product is vacuum dried at 100°C for 8 hours to obtain the target A-type low-silicon zeolite.

[0053] B. Synthesis of ultra-low-silicon zeolite using alkali metal salt:

[0054] 1. Proportioning: proportioning is performed according to the ratio Al2O3:SiO2:Na2O:H2O=1:2:3:185. A 0.1 mol / L NaOH solution is used to adjust the water glass and aluminum hydroxide into water glass and sodium metaborate solutions with certain concentrations, respectively.

[0055] 2. Crystallization: the water bath is preheated to 60°C, and then the water glass is quickly added to the sodium metaborate solution under strong stirring to form a colloid, and an alkali metal salt is added, and the mixture is heated to 90°C under uniform stirring, and then left to crystallize for 5 hours.

[0056] 3. Product collection: suction filtration and water washing are performed, and this process is repeated until the pH value reaches 9-10. Vacuum drying is performed at 110°C for 8 hours to obtain the target ultra-low-silicon zeolite.

[0057] In addition, the waterproof layer has a water permeability of 0 under a condition of not more than 0.3 MPa for 30 min. That is, the waterproof layer is impermeable to water under the condition of not more than 0.3 MPa for 30 min. Thus, the impermeability of the waterproof layer (i.e., the waterproof and water-blocking capability) meets the needs of the waterproof and adsorbing layer, ensures the use stability of the battery under the condition of not more than 0.3 MPa for 30 min, and thus facilitates stable operation of the battery under various use conditions.

[0058] Further, the waterproof layer includes 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. The non-metallic inorganic substance, the metal and the oxide thereof, the asphalt-based waterproof coating, and the polymer-based waterproof coating are all non-aqueous and do not contain a strong polar solvent, and all have good waterproof performance, bonding performance, and certain elasticity. Thus, the use of the non-metallic inorganic substance, the metal and the oxide thereof, the asphalt-based waterproof coating, and the polymer-based waterproof coating facilitates the improvement of the isolation effect of external moisture, and at the same time, the use stability of the waterproof layer is improved, and the service life of the waterproof layer is prolonged, thereby ensuring that the battery can be used safely for a long time.

[0059] According to some embodiments of the present application, the metal and the oxide thereof include at least one of aluminum, zinc, titanium, zinc oxide, titanium oxide, and triiron tetroxide. The above-mentioned metal (aluminum, zinc, and titanium) and the metal oxide (zinc oxide, titanium oxide, and triiron tetroxide) all have good corrosion resistance, durability, and mechanical strength, and the use of at least one of the above-mentioned metal and the oxide thereof facilitates the improvement of the mechanical strength of the waterproof layer and the prolongation of the service life of the waterproof layer.

[0060] The non-metallic inorganic substance includes ceramic and / or activated carbon. The ceramic has a microporous structure and a high specific surface area on the surface, which can provide a large number of adsorption sites for the ceramic to adsorb 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 to achieve 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 molecules in various gases and liquids. Thus, the use of one of the ceramic and the activated carbon facilitates the improvement of the adsorption force of the adsorbing layer and the reduction of the cost of the adsorbing layer.

[0061] The asphalt-based waterproof coating includes at least one of SBS modified asphalt waterproof coating, dissolved type regenerated rubber asphalt waterproof coating, cationic emulsified asphalt waterproof coating, and FYT improved type bridge flexible waterproof coating. The above-mentioned asphalt-based waterproof coating has good bonding, flexibility, aging resistance, and water resistance. The use of at least one of the above-mentioned asphalt-based waterproof coating facilitates the improvement of the integrity and waterproofness of the waterproof layer, prolongs the service life of the waterproof layer, and at the same time, improves the environmental friendliness of the waterproof layer.

[0062] The high-molecular-based waterproof coating includes at least one of polyurethane waterproof coating, acrylate waterproof coating, epoxy waterproof coating, polymer cement waterproof coating and silicone rubber waterproof coating. The high-molecular-based waterproof coating is a waterproof material based on high-molecular polymer, and can form a continuous waterproof film. The high-molecular-based waterproof coating has good water resistance, adhesion and elasticity, and the use of at least one of the high-molecular-based waterproof coating is beneficial to maintaining the waterproof effect of the waterproof layer and increasing the stability and reliability of the waterproof layer on the surface of the adsorption layer.

[0063] Further, the ceramic includes at least one of silicon dioxide, calcium oxide, silicate and aluminate. The components are all beneficial to improving the wear resistance, weather resistance and corrosion resistance of the waterproof layer, and the use of at least one of the components as the ceramic applied in the waterproof layer is beneficial to improving the durability and reliability of the waterproof layer.

[0064] The preparation method of the waterproof adsorption layer according to the second aspect of the present application comprises:

[0065] Preparation of the adsorption layer, the water-absorbing material is arranged on the surface of the battery cell to obtain the adsorption layer;

[0066] Preparation of the waterproof layer, the raw material of the waterproof layer is arranged on the surface of the adsorption layer away from the battery cell to obtain the waterproof layer.

[0067] The preparation method of the waterproof adsorption layer according to the present application sequentially prepares the adsorption layer and the waterproof layer on the surface of the battery cell, so that the adsorption layer can fully adsorb the moisture generated during the preparation process of the battery cell, the waterproof layer can isolate external moisture, and the waterproof layer can ensure that the adsorption layer plays a role in preferentially adsorbing residual moisture in the battery cell.

[0068] Further, the preparation of the adsorption layer comprises: mixing the water-absorbing material and the binder and arranging them on the surface of the battery cell. The preparation method of the waterproof adsorption layer further comprises: drying the binder after removing water, adding a solvent, and configuring the binder solution. After drying the binder, the binder solution is configured again to avoid the water-absorbing material in the adsorption layer from adsorbing the water in the binder, thereby reducing the adsorption capacity of the adsorption layer for the moisture in the battery cell.

[0069] Among them, considering the stability of the sulfide electrolyte material, for the battery cell of the sulfide battery, the selected solvent is limited to low-polarity solvents such as xylene, anisole, butyl butyrate and isobutyl isobutyrate, or directly selected to be a thermosetting resin coating or a light-cured resin coating. But not limited to this.

[0070] Further, the forming of the slurry comprises: adding the water-absorbing material to the binder solution and stirring to mix uniformly. In this way, the water-absorbing material is uniformly mixed in the binder solution, the bonding effect of the binder on the material is improved, and the overall and uniformity of the adsorption layer is improved.

[0071] According to some specific embodiments of the present application, the setting mode includes dip-dry, spraying or template casting. The dip-dry has better uniformity, can be repeated multiple times to control the thickness of the adsorption layer and / or the waterproof layer, and has lower cost. The spraying has faster efficiency and better uniformity, increases the quality of the adsorption layer and / or the waterproof layer, and can make the adhesion of the raw material of the waterproof layer on the adsorption layer better. The template casting has higher compactness and precision of the coated adsorption layer and / or waterproof layer, and forms a shape at one time, which is beneficial to improving the coating efficiency.

[0072] The battery according to the third aspect of the embodiments of the present application includes: an electric core, a waterproof adsorption layer, the waterproof adsorption layer is the waterproof adsorption layer according to the first aspect of the embodiments of the present application or prepared by the preparation method according to the second aspect of the embodiments of the present application, and the waterproof layer is arranged on the surface of the adsorption layer away from the electric core.

[0073] The battery according to the embodiments of the present application is beneficial to improving the use stability of the battery and prolonging the service life of the battery.

[0074] The battery can be a solid-state battery. The solid-state battery has lower internal resistance, can support 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, and therefore the use of the waterproof adsorption layer is beneficial to adsorbing the small amount of moisture and the like in the solid-state electrolyte of the solid-state battery, and adsorbing harmful gases (such as hydrogen sulfide) in the solid-state electrolyte, thereby improving the use stability and reliability of the solid-state battery.

[0075] The power consuming device according to the fourth aspect of the embodiments of the present application includes at least one battery according to the third aspect of the embodiments of the present application.

[0076] The power consuming device according to the embodiments of the present application is beneficial to improving the energy supply stability and reliability of the power consuming device by using the above battery, thereby improving the operation stability of the power consuming device, and further improving the market competitiveness of the power consuming device.

[0077] The embodiments of the present application are described in detail below. It should be noted that the embodiments described below are exemplary and are used to explain the present application, and cannot be understood as a limitation of the present application. 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, and the reaction conditions not listed are also easily obtained by those skilled in the art.

[0078] Example 1

[0079] The components and weight percentage of the slurry of the adsorption layer in this embodiment are as follows:

[0080] Artificially synthesized zeolite (aluminum silicate): 63%; styrene-butadiene rubber (SBR, relative molecular mass: 600000): 7%; xylene (molecular formula C8H 10 ): 30%.

[0081] The components of the slurry of the waterproof layer in this embodiment are as follows: solvent-free single-component polyurethane waterproof coating.

[0082] The manufacturing process of the waterproof adsorption layer is as follows: 1. High-temperature activation of artificially synthesized zeolite, 400℃ activation for 4h in a dry inert atmosphere (argon, nitrogen, etc.) or an environment with strict dew point control (-50℃ or below), and cooling for standby. 2. Preparation of the binder solution. 3. Add the activated zeolite to the prepared binder solution and mix uniformly with a ball mill. 4. Apply the adsorption layer to the side of the cell of the sulfide battery. 5. Apply a waterproof layer on the outside of the adsorption layer. The manufacturing and application of the adsorption layer and the waterproof layer described above are all carried out in a dew point environment below -30℃, and the assembly of the battery is carried out after 24 hours of storage in this environment after the application is completed. The thickness of the adsorption layer is 50μm, and the thickness of the waterproof layer is 50μm.

[0083] The manufacturing process of the battery is as follows: set the negative electrode sheet, the separator, and the positive electrode sheet in sequence, and set the electrolyte or solid-state electrolyte between the negative electrode sheet and the positive electrode sheet to form a cell; then set the waterproof adsorption layer on the surface of the cell, and stack multiple cells in sequence to form a battery. The electrolyte or solid-state electrolyte contains sulfide, the negative electrode sheet contains silicon, and the positive electrode sheet contains ternary material.

[0084] Example 2

[0085] Example 2 is basically the same as Example 1, except that the waterproof layer material is silicon dioxide.

[0086] Example 3

[0087] Example 3 is basically the same as Example 1, except that the waterproof layer material is SBS modified asphalt waterproofing.

[0088] Example 4

[0089] Example 4 is basically the same as Example 1, except that the waterproof layer material is titanium oxide.

[0090] Example 5

[0091] Example 5 is basically the same as Example 1, except that the waterproof layer material is SBS modified asphalt waterproofing for bridge deck, and the surface is coated with an aluminum film.

[0092] Example 6

[0093] Example 6 is substantially the same as Example 1, except that the water-absorbing material in the adsorption layer is a metal-organic framework material (specifically, UIO-66).

[0094] Example 7

[0095] 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).

[0096] Example 8

[0097] 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).

[0098] Comparative Example 1

[0099] Comparative Example 1 is substantially the same as Example 1, except that the sulfide solid-state battery cell is manufactured in an environment with a strictly controlled dew point (below -50°C), and the battery cell is assembled directly without the adsorption layer and the waterproof layer coating on the side of the battery cell.

[0100] Comparative Example 2

[0101] Comparative Example 2 is substantially the same as Example 1, except that the adsorption layer is not coated, and the other procedures are consistent.

[0102] Comparative Example 3

[0103] Comparative Example 3 is substantially the same as Example 1, except that the waterproof layer is not coated, and the other procedures are consistent.

[0104] Comparative Example 4

[0105] Comparative Example 4 is substantially the same as Example 1, except that the adsorption layer and the waterproof layer are not coated, and the other procedures are consistent.

[0106] Performance Test

[0107] Battery capacity performance test: the batteries of Examples 1-5 and Comparative Examples 1-4 above are subjected to battery charge and discharge tests under the same working pressure and working temperature, and the test procedure is as follows: stand for 12 hours, charge at 0.05C to the upper voltage limit, and then discharge at 0.05C to the lower voltage limit, and record the specific capacity of the discharge. The discharge specific capacity of Comparative Example 1 is taken as the standard (100%) (strictly controlled dew point (-50°C) environment defaults no moisture), and the discharge specific capacity of each example is evaluated, and recorded in Table 1.

[0108] Table 1 Discharge specific capacity of each example-Example 5 and Comparative Examples 2-5 relative to Comparative Example 1

[0109] Example Discharge specific capacity (Example / Comparative Example, %) Example 1 98％ Example 2 97％ Example 3 97％ Example 4 97.5％ Example 5 98％ Example 6 96.5％ Example 7 96％ Example 8 96％ Comparative Example 2 90％ Comparative Example 3 95％ Comparative Example 4 80％

[0110] The cells of Examples 1 to 8 were prepared at -30℃ dew point, with some residual moisture, and, before being packaged into batteries, the cells of Examples 1 to 8 were left exposed to the -30℃ dew point environment for 24 hours. In Example 1, the waterproof layer blocked the subsequent invasion of external moisture, and the adsorption layer fully played the role of adsorbing the residual moisture and hydrogen sulfide gas in the cell, so that the capacity of the battery was close to that of the battery of Comparative Example 1. In Comparative Example 2, the internal residual moisture in the cell was not reduced because the adsorption layer was not applied, which affected the capacity of the battery. In Comparative Example 3, the adsorption layer simultaneously adsorbed the moisture from the outside and the inside of the cell because the waterproof layer was not applied, and the removal capacity of the residual moisture in the cell decreased, so the capacity of the battery was slightly lower than that of Example 1. In Comparative Example 4, the moisture continuously invaded the cell because there was no adsorption layer and waterproof layer, which caused the battery performance to deteriorate, and the capacity of the battery was the lowest.

[0111] In the description of the present specification, the description referring to the terms "one embodiment", "some embodiments", "exemplary embodiment", "example", "specific example", or "some examples" and the like 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 application. In the present specification, the exemplary description of the above terms does not necessarily mean the same embodiment or example.

[0112] Although the embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, and alterations can be made to these embodiments without departing from the principles and the spirit of the present application.

Claims

1. A waterproof absorbent layer, characterized in that, include: Adsorption layer, the adsorption layer comprising a water-absorbing material; A waterproof layer is disposed on one side surface of the adsorption layer.

2. The waterproof absorbent layer according to claim 1, wherein the absorbent material comprises: At least one of zeolite, metal-organic framework materials, covalent organic framework materials, porous silica, water-absorbing resin and alkaline dehydrating agent.

3. The waterproof absorbent layer according to claim 1 or 2, characterized in that, The desorption temperature of the absorbent material is greater than 150℃.

4. The waterproof adsorption layer according to claim 1, characterized in that, 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 waterproof adsorption layer according to any one of claims 1-4, characterized in that, The adsorption layer also includes an adhesive.

6. The waterproof adsorption layer according to claim 5, characterized in that, The water-absorbing material accounts for 20% to 95% of the weight percentage of the adsorption layer.

7. The waterproof adsorption layer according to claim 5, characterized in that, The adhesive includes at least one of inorganic adhesives and resin adhesives.

8. The waterproof adsorption layer according to claim 2, characterized in that, The pore size of the porous silica does not exceed 50 nm.

9. The waterproof adsorption layer according to claim 2, characterized in that, The zeolite includes synthetic zeolite.

10. The waterproof adsorption layer according to claim 9, characterized in that, The synthetic zeolites include aluminum silicate synthetic zeolites.

11. The waterproof absorbent layer according to claim 1 or 4, characterized in that, Under conditions not exceeding 0.3 MPa·30 min, the water permeability of the waterproof layer is 0.

12. The waterproof absorbent layer according to any one of claims 1-11, characterized in that, The waterproof layer includes at least one of the following: non-metallic inorganic materials, metals and their oxides, asphalt-based waterproof coatings, and polymer-based waterproof coatings.

13. The waterproof adsorption layer according to claim 12, characterized in that, The metal and its oxides include at least one of aluminum, zinc, titanium, zinc oxide, titanium oxide, and iron(III) oxide; And / or, the non-metallic inorganic material includes ceramics and / or activated carbon; And / or, the bitumen-based waterproof coating includes at least one of SBS modified bitumen waterproof coating, soluble recycled rubber bitumen waterproof coating, cationic emulsified bitumen waterproof coating and FYT improved bridge deck flexible waterproof coating; And / or, the polymer-based waterproof coating includes at least one of polyurethane waterproof coating, acrylic waterproof coating, epoxy resin waterproof coating, polymer cement waterproof coating and silicone rubber waterproof coating.

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

15. A method for preparing a waterproof adsorbent layer according to any one of claims 1-14, characterized in that, include: An adsorption layer is prepared by placing the water-absorbing material on the surface of the battery cell to obtain the adsorption layer; To prepare a waterproof layer, the raw material for the waterproof layer is placed on the surface of the adsorption layer away from the battery cell, thereby obtaining the waterproof layer.

16. The method for preparing the waterproof adsorbent layer according to claim 15, characterized in that, The preparation of the adsorption layer includes: mixing the water-absorbing material and the binder to obtain a mixture, and then setting the mixture on the surface of the battery cell.

17. The method for preparing the waterproof adsorbent layer according to claim 15 or 16, characterized in that, The methods of setting include: immersion-drying, spraying, or template casting.

18. A battery, characterized in that, include: Battery cell, A waterproof adsorption layer, wherein the waterproof adsorption layer is the waterproof adsorption layer according to any one of claims 1-14, or the waterproof adsorption layer prepared by the preparation method according to any one of claims 15-17. The waterproof layer is located on the surface of the adsorption layer away from the battery cell.

19. An electrical appliance, characterized in that, Includes at least one battery as described in claim 18.