WO2023137748A1 - 外壳及其修复方法、相关的二次电池、电池模块、电池包和用电装置 - Google Patents

外壳及其修复方法、相关的二次电池、电池模块、电池包和用电装置 Download PDF

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WO2023137748A1
WO2023137748A1 PCT/CN2022/073450 CN2022073450W WO2023137748A1 WO 2023137748 A1 WO2023137748 A1 WO 2023137748A1 CN 2022073450 W CN2022073450 W CN 2022073450W WO 2023137748 A1 WO2023137748 A1 WO 2023137748A1
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Prior art keywords
mushroom
insulating layer
battery
curable material
casing
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PCT/CN2022/073450
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English (en)
French (fr)
Inventor
徐冶
伍顺宏
陈仁煜
赵宾
严尊光
高佳静
Original Assignee
宁德时代新能源科技股份有限公司
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Application filed by 宁德时代新能源科技股份有限公司 filed Critical 宁德时代新能源科技股份有限公司
Priority to PCT/CN2022/073450 priority Critical patent/WO2023137748A1/zh
Priority to EP22899606.2A priority patent/EP4243107A4/en
Priority to CN202280023097.0A priority patent/CN117063326A/zh
Priority to KR1020237018701A priority patent/KR20230118561A/ko
Priority to JP2023535554A priority patent/JP7499416B2/ja
Priority to US18/327,747 priority patent/US11996524B2/en
Publication of WO2023137748A1 publication Critical patent/WO2023137748A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/209—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for prismatic or rectangular cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the technical field of lithium batteries, in particular to a casing and a repair method thereof, a secondary battery, a battery module, a battery pack and an electrical device.
  • lithium-ion batteries have been widely used in energy storage power systems such as hydraulic, thermal, wind and solar power plants, as well as electric tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, aerospace and other fields.
  • energy storage power systems such as hydraulic, thermal, wind and solar power plants
  • electric tools electric bicycles, electric motorcycles, electric vehicles, military equipment, aerospace and other fields.
  • the insulating layer such as insulating film, insulating varnish or other coating or coating
  • the entire battery module (or module) or battery pack will be scrapped due to insulation and voltage resistance problems (only Ningde Times New Energy Technology Co., Ltd. has a scrap rate of 0.2% in 2020, and the loss cost is > 100 million yuan).
  • the conventional repair method is usually to use pressure-sensitive tape to patch the defect area, but the modulus of the pressure-sensitive tape is low ( ⁇ 2MPa), and the original patch position will cause wrinkles or displacement due to creep after repeated vibrations and shocks, so the safety and service life of the battery cannot be guaranteed.
  • This application is made in view of the above-mentioned problems, and its purpose is to provide a casing for a secondary battery, which includes an insulating layer of a repaired part with a mushroom-shaped structure, which not only realizes no displacement and wrinkles during the vibration shock process, but also ensures the insulation and voltage resistance of the casing after repair; and can effectively ensure that the creepage distance can meet the original technical requirements of the battery, and will not cause the battery or battery pack to be scrapped.
  • the present application provides a casing, wherein the outer surface of the casing has an insulating layer, and the insulating layer has a repair part, wherein,
  • the repair part is a mushroom-shaped structure formed of a curable material including an upper mushroom cap and a lower mushroom handle, the mushroom handle is embedded inside the insulating layer, the mushroom cap protrudes from the insulating layer and the lower surface of the mushroom cap covers the upper surface of the insulating layer;
  • the longest dimension of the mushroom cap ⁇ the width w of the mushroom handle+the creepage distance L of the battery.
  • the longest dimension of the mushroom cover is ⁇ the width w of the mushroom handle + the creepage distance L of the battery, which can effectively ensure that the creepage distance can meet the original technical requirements of the battery, and will not cause the battery or battery pack to be scrapped.
  • the maximum thickness of the mushroom cap is ⁇ 1/2 the thickness t of the insulating layer. In this way, the insulation withstand voltage performance of the shell is guaranteed.
  • the depth of the mushroom stem embedded in the insulating layer is ⁇ 1/2 the thickness t of the insulating layer.
  • the wetting angle ⁇ of the curable material on the surface of the insulating layer satisfies 1° ⁇ 90°, and in any section of the repaired part perpendicular to the surface of the insulating layer, the width of the mushroom handle w ⁇ 10t ⁇ cot ⁇ +3, where t is the thickness of the insulating layer, in millimeters.
  • the curable material fully infiltrates the interior of the insulating layer, thereby ensuring the insulation and voltage resistance performance of the casing.
  • the curable material comprises a photocurable material or a thermoset material. In this way, the bonding force between the repaired part and the original insulating layer is ensured, thereby ensuring the insulation withstand voltage performance of the casing.
  • the viscosity of the photo-curable material or thermal-curable material is 30-500 mPa.s. In this way, the bonding force between the repaired part and the original insulating layer is ensured, thereby ensuring the insulation withstand voltage performance of the casing.
  • the photocurable material is an ultraviolet (UV) curable material
  • the UV curable material includes:
  • additives 0-20% by weight
  • the above contents are based on the total weight of the photocurable material, and the sum of the contents of each component is 100% by weight. In this way, the bonding force between the repaired part and the original insulating layer is ensured, thereby ensuring the insulation withstand voltage performance of the casing.
  • thermosetting material comprises:
  • the above content is based on the total weight of the thermosetting material, and the sum of the contents of each component is 100% by weight. In this way, the bonding force between the repaired part and the original insulating layer is ensured, thereby ensuring the insulation withstand voltage performance of the casing.
  • the diluting monomer is selected from 1,6-hexanediol diacrylate, isobornyl acrylate or isobornyl methacrylate, preferably selected from 1,6-hexanediol diacrylate and isobornyl acrylate; the photoinitiator is selected from at least kind of. In this way, the bonding force between the repaired part and the original insulating layer is ensured, thereby ensuring the insulation withstand voltage performance of the casing.
  • the second aspect of the present application also provides a method for repairing the shell, which includes the following steps:
  • a) defect location locate the defect area on the outer surface of the shell, and identify the boundary of the defect area;
  • mushroom caps using a curable material to repair the surface layer, followed by final curing to form a mushroom cap, and curing the mushroom cap and the mushroom handle together to form a mushroom-shaped structure;
  • the outer surface of the shell formed by the above step a)-step d) has an insulating layer, and the insulating layer has a repair part, wherein,
  • the repair part is a mushroom-shaped structure formed of a curable material including an upper mushroom cap and a lower mushroom handle, the mushroom handle is embedded inside the insulating layer, the mushroom cap protrudes from the insulating layer, and the lower surface of the mushroom cap covers the upper surface of the insulating layer; in any cross section of the repair part perpendicular to the surface of the insulating layer, the longest dimension of the mushroom cap is ⁇ the width w of the mushroom handle+the creepage distance L of the battery.
  • a mushroom-shaped repaired portion is formed, thereby ensuring the insulation and voltage resistance performance of the casing.
  • a third aspect of the present application provides a secondary battery, which includes the shell described in the first aspect of the present application or the shell repaired by the method described in the second aspect of the present application, wherein the inside of the shell includes an electrode assembly and an electrolyte; or, the inside of the shell includes an electrode assembly and a solid/semi-solid electrolyte.
  • a fourth aspect of the present application provides a battery module including the secondary battery of the third aspect of the present application.
  • a fifth aspect of the present application provides a battery pack, including the battery module of the fourth aspect of the present application.
  • a sixth aspect of the present application provides an electric device, including at least one selected from the secondary battery of the third aspect of the present application, the battery module of the fourth aspect of the present application, or the battery pack of the fifth aspect of the present application.
  • Fig. 1 is a schematic structural diagram of the repaired part of the casing; where I represents a defect area, 11 represents a casing, 12 represents an insulating layer, and 13 represents a repaired part.
  • FIG. 2 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 3 is an exploded view of the secondary battery according to one embodiment of the present application shown in FIG. 2 .
  • FIG. 4 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 5 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 6 is an exploded view of the battery pack according to one embodiment of the present application shown in FIG. 5 .
  • FIG. 7 is a schematic diagram of an electrical device in which a secondary battery is used as a power source according to an embodiment of the present application.
  • ranges disclosed herein are defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, ie any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are contemplated. Furthermore, if the minimum range values of 1 and 2 are listed, and if the maximum range values of 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.
  • the numerical range "a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
  • a certain parameter is an integer ⁇ 2
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed in sequence, and may also include steps (b) and (a) performed in sequence.
  • the mentioned method may also include step (c), indicating that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may also include steps (a), (c) and (b), may also include steps (c), (a) and (b), etc.
  • the “comprising” and “comprising” mentioned in this application mean open or closed.
  • the “comprising” and “comprising” may mean that other components not listed may be included or included, or only listed components may be included or included.
  • the term "or” is inclusive unless otherwise stated.
  • the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by any of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).
  • the entire battery module (or module) or battery pack will be scrapped due to insulation and voltage resistance problems (only Ningde Times New Energy Technology Co., Ltd. has a scrap rate of 0.2% in 2020, and the loss cost is > 100 million yuan).
  • the casing of the first aspect of the present application can ensure the safety of the battery by including a repair portion with a mushroom-shaped structure of a specific size.
  • the present application proposes a casing, wherein the outer surface of the casing has an insulating layer, and the insulating layer has a repair part, wherein,
  • the repair part is a mushroom-shaped structure formed of a curable material including an upper mushroom cap and a lower mushroom handle, the mushroom handle is embedded inside the insulating layer, the mushroom cap protrudes from the insulating layer and the lower surface of the mushroom cap covers the upper surface of the insulating layer;
  • the longest dimension of the mushroom cap ⁇ the width w of the mushroom handle+the creepage distance L of the battery.
  • the present application forms a mushroom-shaped repaired part on the casing, which not only realizes no displacement and wrinkles during the vibration shock process, but also ensures the insulation and pressure resistance of the repaired casing; and in any section of the repaired part perpendicular to the surface of the insulating layer, the longest dimension of the mushroom cover is greater than or equal to the width w of the mushroom handle + the creepage distance L of the battery, which can effectively ensure that the creepage distance can meet the original technical requirements of the battery, and will not cause the battery or battery pack to be scrapped.
  • the housing is used in a secondary battery.
  • the longest dimension of the mushroom cap in any cross section of the repair part perpendicular to the surface of the insulating layer is the diameter of the circle, also called the diameter of the mushroom cap.
  • the creepage distance L of the battery is the shortest path measured along an insulating surface between two conductive parts or between a conductive part and a device shielding interface. Under different usage conditions, the insulation material appears charged due to the electrical polarization of the insulation material around the conductor.
  • the power battery creepage distance specification usually refers to the national standard "GB/T 16935.1-2008 Insulation Coordination of Equipment in Low-Voltage System Part 1: Principles, Requirements and Tests", obtained from the table. According to the effective voltage of 800V, material group I, pollution degree 3, the corresponding creepage distance requirement is ⁇ 10mm, so the creepage distance of the current power battery pack design is ⁇ 10mm. Embodiments of the present invention are also designed according to this requirement.
  • the maximum thickness of the mushroom cap is ⁇ 1/2 the thickness t of the insulating layer. In this way, the insulation withstand voltage performance of the shell is guaranteed.
  • the depth of the mushroom stem embedded in the insulating layer is ⁇ 1/2 the thickness t of the insulating layer.
  • the wetting angle ⁇ of the curable material on the surface of the insulating layer satisfies 1° ⁇ 90°, and in any section of the repaired part perpendicular to the surface of the insulating layer, the width of the mushroom handle w ⁇ 10t ⁇ cot ⁇ +3, where t is the thickness of the insulating layer, in millimeters.
  • the curable material fully infiltrates the interior of the insulating layer, thereby ensuring the insulation and voltage resistance performance of the casing.
  • the wetting angle of the curable material on the surface of the insulating layer refers to the angle between the interface between the curable material and the insulating layer and the surface tangent of the curable material at the contact point between the liquid curable material and the insulating layer.
  • the width of the mushroom handle refers to the width with the largest horizontal distance in the section of the mushroom handle.
  • the width of the mushroom stalk refers to the diameter of the circle, also referred to as the diameter of the mushroom stalk.
  • the curable material comprises a photocurable material or a thermoset material. In this way, the bonding force between the repaired part and the original insulating layer is ensured, thereby ensuring the insulation withstand voltage performance of the casing.
  • the viscosity of the photo-curable material or thermal-curable material is 30-500 mPa.s. In this way, the bonding force between the repaired part and the original insulating layer is ensured, thereby ensuring the insulation withstand voltage performance of the casing.
  • the photocurable material is an ultraviolet (UV) curable material
  • the UV curable material includes:
  • additives 0-20% by weight
  • the above contents are based on the total weight of the photocurable material, and the sum of the contents of each component is 100% by weight.
  • the bonding force between the repaired part and the original insulating layer is ensured, thereby ensuring the insulation withstand voltage performance of the casing.
  • thermosetting material comprises:
  • the above content is based on the total weight of the thermosetting material, and the sum of the contents of each component is 100% by weight. In this way, the bonding force between the repaired part and the original insulating layer is ensured, thereby ensuring the insulation withstand voltage performance of the casing.
  • the host resins in the UV curable material and the heat curable material are the same or different, and can be independently selected from acrylate resins, methacrylate resins (such as ethyl methacrylate, hydroxyethyl methacrylate) or epoxy acrylate resins, preferably acrylate resins, and epoxy acrylate resins.
  • the diluting monomer in the UV curable material is selected from 1,6-hexanediol diacrylate, isobornyl acrylate or isobornyl methacrylate, preferably from 1,6-hexanediol diacrylate and isobornyl acrylate.
  • the photoinitiator is selected from at least one of 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxycyclohexyl phenyl ketone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.
  • the catalyst is selected from the group consisting of dicumyl peroxide, cumene hydroperoxide, dicumyl hydroperoxide, dibenzoyl peroxide, dibenzoyl superoxide, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxide, or di-tert-butyl peroxide.
  • These catalysts may be used alone or in combination of several kinds. Cumene hydroperoxide is preferred.
  • the other additives in the UV curable material and the heat curable material are the same or different, and may independently include light stabilizers, heat stabilizers, plasticizers, fillers, pigment dispersants, leveling agents, defoamers, and the like.
  • the light stabilizer may be hindered amines, such as bis-1-octyloxy-2,2,6,6-tetramethylpiperidinol sebacate, CHISORB292, CHISORB770; benzophenones or benzotriazoles.
  • hindered amines such as bis-1-octyloxy-2,2,6,6-tetramethylpiperidinol sebacate, CHISORB292, CHISORB770; benzophenones or benzotriazoles.
  • the heat stabilizer is dibutyltin dilaurate or zinc fatty acid.
  • the plasticizer is at least one of dioctyl phthalate, didecyl phthalate, diisononyl phthalate, diisodecyl phthalate, dioctyl adipate, dioctyl sebacate, dioctyl azelate, triphenyl phosphate, diphenyl isooctyl phosphate, and alkylsulfonate plasticizers.
  • the filler is at least one of light calcium carbonate, fatty acid or fatty acid salt modified calcium carbonate, calcined kaolin, fumed silica, PVC powder, talcum powder, organic montmorillonite, diatomaceous earth, titanium dioxide, hollow spheres, carbon black, barium sulfate, and titanium dioxide.
  • the leveling agent includes but is not limited to polyacrylate or silicone resin or fluorocarbon surfactant, fluorine-modified acrylate or a combination thereof, such as one or more mixtures of BYK333, BYK360, Glide 432, Flow 300, Efka 3600, and 1154 of Moeneng Chemical Co., Ltd. from German BYK Chemical Co., Ltd.
  • the defoaming agent includes but is not limited to organic polymer or silicone resin or their combination, such as one or more of polydimethylsiloxane, Deqian 2700, Elementis DF7015, BYK-141, etc.
  • the pigment dispersant includes, but is not limited to, one or more combinations of synthetic polymers such as long-chain polyfatty acids and polyamine salts, polyvalent carboxylates, silicon and titanium coupling agents, and other polymers containing pigment-affinity groups, such as BYK163, BYK164, BYK358N of German BYK Chemical Company, and one or more of Disper S28 of Core Chemical Company.
  • synthetic polymers such as long-chain polyfatty acids and polyamine salts, polyvalent carboxylates, silicon and titanium coupling agents, and other polymers containing pigment-affinity groups, such as BYK163, BYK164, BYK358N of German BYK Chemical Company, and one or more of Disper S28 of Core Chemical Company.
  • the UV curable material can achieve instant drying or extremely fast curing, which is beneficial to rapid repair and has strict requirements on curing time.
  • the curing time of the heat-curing material is slower than that of the UV-curing material, but its leveling effect is good, and the infiltration effect of the material and the insulating layer is good during heat curing, and the quality of the repaired part obtained is high.
  • the present application also provides a method for repairing the shell, which includes the following steps:
  • a) defect location locate the defect area on the outer surface of the shell, and identify the boundary of the defect area;
  • the outer surface of the shell formed by the above step a)-step d) has an insulating layer, and the insulating layer has a repair part, wherein,
  • the repair part is a mushroom-shaped structure formed of a curable material including an upper mushroom cap and a lower mushroom handle, the mushroom handle is embedded inside the insulating layer, the mushroom cap protrudes from the insulating layer, and the lower surface of the mushroom cap covers the upper surface of the insulating layer; in any cross section of the repair part perpendicular to the surface of the insulating layer, the longest dimension of the mushroom cap is ⁇ the width w of the mushroom handle+the creepage distance L of the battery.
  • a mushroom-shaped repaired portion is formed, thereby ensuring the insulation and voltage resistance performance of the casing.
  • the defective area is located by a battery management system (BMS).
  • BMS battery management system
  • the temperature or voltage will be abnormal, that is, the feedback voltage will become 0V or other low voltage value, or the temperature collected by the thermistor (NTC) will increase significantly.
  • defect areas are identified by scanning electron microscopy or visual cameras (CCD).
  • the projected area of the groove in the horizontal direction is greater than the projected area of the defect region in the horizontal direction. In this way, it is ensured that the defect area is completely repaired, and the insulation withstand voltage performance of the casing is ensured.
  • the depth of the groove is approximately equal to the depth of the shank of the mushroom, and the width of the groove is approximately equal to the width w of the shank of the mushroom.
  • the width w of the mushroom stalk should be greater than or equal to the width of the defect area; when the width of the defect area is small, even less than 3 mm, the width w of the mushroom stalk should also satisfy w ⁇ 10t ⁇ cot ⁇ +3, where t is the thickness of the insulating layer, in millimeters, and ⁇ is the wetting angle of the curable material on the surface of the insulating layer.
  • step b) part of the insulating layer is removed by laser cleaning or mechanical grinding.
  • the laser cleaning is carried out by making the non-metallic coating absorb laser energy through a fiber pulse laser or a carbon dioxide laser, and removing a part of the coating through thermal burn and thermal expansion.
  • the mechanical grinding removes a certain thickness of the coating by means of milling or grinding.
  • the thickness of the curable material repair is from the depth of the mushroom shank to (the depth of the mushroom shank+10% of the thickness t of the insulating layer), so as to form the mushroom shank. In this way, it is ensured that the curable material fully wets the groove to form a mushroom handle, thereby ensuring the insulation and voltage resistance performance of the housing.
  • the energy required for the pre-cure of step c) and the final cure of step d) are the same or different.
  • the irradiation energy is 2000-4000mJ/cm ⁇ 2.
  • the UV irradiation energy is proportional to the thickness, and the total energy
  • t is the thickness of single layer coating, cm
  • E0 is energy required per unit thickness, mJ/cm 3 .
  • the heating temperatures of the pre-curing in step c) and the final curing in step d) are independently: pre-curing 60-80°C, preferably 70-80°C, choosing a higher temperature within the safe temperature range can reduce the duration of pre-curing, too high a temperature will cause irreversible damage to the battery; final curing 35-60°C, preferably 40-50°C
  • the curable material is as described herein above.
  • step c plasma cleaning is performed on the surface of the groove.
  • the surface tension of the insulating layer can be increased, the polarity of the surface of the insulating layer can be enhanced, and the bonding force between the repaired part and the insulating layer can be improved.
  • the method of the present application comprises the following steps:
  • a) defect location locate the defect area on the outer surface of the shell, and identify the boundary of the defect area;
  • mushroom caps Forming mushroom caps: repairing the surface with a curable material, followed by final curing to form mushroom caps, and curing the mushroom caps with the mushroom stems to form a mushroom-like structure.
  • the repairing is performed by inkjet printing process and precision dispensing process.
  • the inkjet printing process uses a curable material to precisely print with an inkjet printer to form a repair part of a certain thickness in a designated area.
  • the precision dispensing process uses precise small metering dispensing equipment to dispense curable materials on designated areas to form a certain thickness of the restoration.
  • the present application also provides a secondary battery, which includes the casing according to any one of claims 1-9 or the casing repaired by the method according to any one of claims 10-14, wherein the inside of the casing includes an electrode assembly and an electrolyte; or, the inside of the casing includes an electrode assembly and a solid/semi-solid electrolyte.
  • the insulation performance of the secondary battery is characterized by measuring its insulation resistance (in G ⁇ ) under a direct current (DC) of 500V.
  • the insulation resistance of the secondary battery is greater than or equal to 10G ⁇ .
  • the withstand voltage performance of the secondary battery is characterized by measuring its leakage current (in mA) under a direct current (DC) of 2700V.
  • the leakage current of the secondary battery is ⁇ 0.1mA.
  • a secondary battery typically includes a positive pole piece, a negative pole piece, an electrolyte, and a separator.
  • active ions are intercalated and extracted back and forth between the positive electrode and the negative electrode.
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the separator is arranged between the positive pole piece and the negative pole piece, which mainly plays a role in preventing the short circuit of the positive and negative poles, and at the same time allows ions to pass through.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode collector, and the positive electrode film layer includes the positive electrode active material according to the first aspect of the present application.
  • the positive electrode current collector has two opposing surfaces in its own thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposing surfaces of the positive electrode current collector.
  • the positive electrode current collector can be a metal foil or a composite current collector.
  • aluminum foil can be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector can be formed by forming a metal material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE) and the like).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode active material may be a positive electrode active material known in the art for batteries.
  • the positive active material may include at least one of the following materials: olivine-structured lithium-containing phosphate, lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other conventional materials that can be used as positive electrode active materials of batteries can also be used.
  • positive electrode active materials may be used alone or in combination of two or more.
  • the positive electrode film layer may further optionally include a binder.
  • the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • vinylidene fluoride-tetrafluoroethylene-propylene terpolymer vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer
  • the positive electrode film layer may also optionally include a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared in the following manner: disperse the above-mentioned components used to prepare the positive electrode sheet, such as positive electrode active material, conductive agent, binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; apply the positive electrode slurry on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N-methylpyrrolidone
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, and the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two opposing surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposing surfaces of the negative electrode current collector.
  • the negative electrode current collector can use a metal foil or a composite current collector.
  • copper foil can be used as the metal foil.
  • the composite current collector may include a base layer of polymer material and a metal layer formed on at least one surface of the base material of polymer material.
  • the composite current collector can be formed by forming metal materials (copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE) and other substrates).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode active material can be a negative electrode active material known in the art for batteries.
  • the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material, lithium titanate, and the like.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon-oxygen compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material may be selected from at least one of simple tin, tin oxide compounds and tin alloys.
  • the present application is not limited to these materials, and other conventional materials that can be used as negative electrode active materials of batteries can also be used. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode film layer may further optionally include a binder.
  • the binding agent can be selected from at least one of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer may also optionally include a conductive agent.
  • the conductive agent can be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer may optionally include other additives, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • thickeners such as sodium carboxymethylcellulose (CMC-Na)
  • CMC-Na sodium carboxymethylcellulose
  • the negative electrode sheet can be prepared in the following manner: the above-mentioned components used to prepare the negative electrode sheet, such as negative electrode active material, conductive agent, binder and any other components, are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the present application has no specific limitation on the type of electrolyte, which can be selected according to requirements.
  • electrolytes can be liquid, gel or all solid.
  • the electrolyte is an electrolytic solution.
  • the electrolyte solution includes an electrolyte salt and a solvent.
  • the electrolyte salt can be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonyl imide, lithium bistrifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium difluorooxalate borate, lithium difluorodioxalate phosphate, and lithium tetrafluorooxalate phosphate.
  • the solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethylene propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, sulfolane, dimethyl sulfone, At least one of methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte may optionally include additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain performances of the battery, such as additives that improve battery overcharge performance, additives that improve high-temperature or low-temperature performance of batteries, and the like.
  • a separator is further included in the secondary battery.
  • the present application has no particular limitation on the type of the isolation membrane, and any known porous structure isolation membrane with good chemical stability and mechanical stability can be selected.
  • the material of the isolation film can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the separator can be a single-layer film or a multi-layer composite film, and there is no particular limitation. When the separator is a multilayer composite film, the materials of each layer may be the same or different, and there is no particular limitation.
  • the positive pole piece, the negative pole piece and the separator can be made into an electrode assembly through a winding process or a lamination process.
  • a secondary battery comprises the casing of the present invention.
  • the inside of the casing includes the above-mentioned electrode assembly and electrolyte; or, the inside of the casing includes the above-mentioned electrode assembly and solid/semi-solid electrolyte.
  • the casing of the secondary battery may be a hard casing, such as a hard plastic casing, an aluminum casing, a steel casing, and the like.
  • FIG. 2 shows a square-shaped secondary battery 5 as an example.
  • the housing may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plates enclose to form an accommodating cavity.
  • the housing 51 has an opening communicating with the accommodating cavity, and the cover plate 53 can cover the opening to close the accommodating cavity.
  • the positive pole piece, the negative pole piece and the separator can be formed into an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the accommodating cavity. Electrolyte is infiltrated in the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • the secondary battery can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG. 4 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
  • the plurality of secondary batteries 5 may be fixed by fasteners.
  • the battery module 4 may also include a case having a housing space in which a plurality of secondary batteries 5 are accommodated.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3 , the upper box body 2 can cover the lower box body 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electric device, which includes at least one of the secondary battery, battery module, or battery pack provided in the present application.
  • the secondary battery, battery module, or battery pack can be used as a power source of the electric device, and can also be used as an energy storage unit of the electric device.
  • the electric devices may include mobile devices (such as mobile phones, laptop computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto.
  • a secondary battery, a battery module or a battery pack can be selected according to its use requirements.
  • FIG. 7 is an example of an electrical device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • a battery pack or a battery module may be used.
  • a device may be a cell phone, tablet, laptop, or the like.
  • the device is generally required to be light and thin, and a secondary battery can be used as a power source.
  • UV curable material A which comprises:
  • Photoinitiator 2-hydroxy-2-methyl-1-phenyl-acetone 4% by weight
  • Photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide 2% by weight
  • UV curable material B comprising:
  • Photoinitiator 1-hydroxycyclohexyl phenyl ketone 4% by weight
  • Photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide 2% by weight
  • Pigment Dispersant Core Chemical Disper S28 1% by weight
  • a) Defect location Detect the outer surface of the casing by contact line scanning with an external voltage of 1500V, scan in the plane according to the x and y directions, find out the defect point when the leakage current is judged to be ⁇ 1mA after scanning, and locate the defect area on the outer surface of the casing at the intersection of x and y coordinates, and then use a 2D visual camera (manufacturer Keyence) to identify the boundary of the defect area, the size of which is 0.8mm ⁇ 1.2mm;
  • Forming mushroom handles Use inkjet printing to repair the groove with UV curing material A to form mushroom handles with a diameter of ⁇ 3mm and a depth of 50 ⁇ m; then use 1000mJ/cm irradiation energy for 2s for pre-curing;
  • Mushroom cap formation use UV curing material A to repair the surface layer by inkjet printing, and then irradiate with 1500mJ/ cm2 irradiation energy for 2.5s for final curing to form a mushroom cap with a thickness of 100 ⁇ m and a diameter of ⁇ 10mm, and cure the mushroom cap and the mushroom handle together to form a mushroom-shaped repaired part.
  • Example 1 The same steps as in Example 1 were repeated, except that the thickness and diameter of the mushroom cap, the depth and diameter of the mushroom shank were changed, and UV curing material A was replaced with UV curing material B.
  • Mushroom handle formation use precision dispensing to repair the groove with heat-curing material to form a mushroom handle; then heat at 70°C for 10 minutes for pre-curing;
  • Mushroom cap formation use a precision dispensing method to repair the surface layer with a thermosetting material, and then heat at 60°C for 4 hours for final curing to form a mushroom cap with a thickness of 100 ⁇ m and a diameter of ⁇ 10 mm, and cure the mushroom cap and the mushroom handle together to form a mushroom-shaped repaired part.
  • Example 11 The same procedure as in Example 11 was repeated except that the thickness and diameter of the mushroom caps were changed. The insulation resistance, leakage current, vibration shock test and bonding strength of the above repaired secondary battery were tested. The results are summarized in Table 1.
  • Example 1 The same steps as in Example 1 were repeated, except that the depth of the groove was 100 ⁇ m (>1/2 the thickness of the original coating), and the original coating was almost removed. The insulation resistance, leakage current, vibration shock test and bonding strength of the above repaired secondary battery were tested. The results are summarized in Table 1.
  • Defect repair Take a pressure-sensitive adhesive tape with a size of 10mm ⁇ 10mm and a total thickness of 110 ⁇ m (the total thickness of the pressure-sensitive adhesive is 60 ⁇ m, and the total thickness of the PET film is 50 ⁇ m) and paste it on the original coating defect area, and confirm that the defect position is centered;
  • the inner wall of the tooling is made of conductive foam material.
  • the soft conductive foam can make the tooling fully contact with the five surfaces of the battery cell (five planes except the top surface, including corner edges).
  • an insulation withstand voltage tester (supplier: Nichiki)
  • the positive probe is in contact with the bare aluminum on the top cover of the battery cell, and the negative probe is connected to the conductive foam inside the tooling.
  • the inner wall of the tooling is made of conductive foam material.
  • the soft conductive foam can make the tooling fully contact with the five surfaces of the battery cell (five planes except the top surface, including corner edges).
  • an insulation withstand voltage tester (supplier: Nichiki)
  • the positive probe is in contact with the bare aluminum on the top cover of the battery cell, and the negative probe is connected to the conductive foam inside the tooling.
  • Vibration shock test (whether displacement and wrinkling occur)
  • the vibration and shock test is carried out with battery modules or battery pack systems.
  • This example uses a 1P108S (1 parallel 108 series) battery pack system.
  • SOC is the ratio of the remaining capacity to the normal capacity, and the value is between 0 and 1 is adjusted to no less than 50% of the normal SOC range.
  • the shock test is carried out with the same type of battery pack system as the vibration test, and the test is carried out referring to Section 8.2.2 of GB38031-2020 "Safety Requirements for Traction Batteries for Electric Vehicles".
  • the half-sine wave as specified in Table 4 is applied to the test object, 6 times each in the ⁇ z direction, a total of 12 times. After the impact test is over, after 2 hours of observation, disassemble the battery pack system, and visually observe whether the external insulation layer of the battery cell (including the insulation layer after repair) is intact, whether there are wrinkles, displacements, etc. If there are, it is judged that the test is not qualified.
  • Adhesive strength test (only test the strength in the shear direction)
  • High-temperature and high-humidity storage Take the shell samples of each example and comparative example and store them in a constant temperature and humidity chamber at 85°C and 85% relative humidity for a certain period of time. When the storage time reaches 1000 hours, take them out, and after standing at room temperature for 2 hours, test the 1000-hour shear strength by referring to step 1. When the 1000-hour shear strength is ⁇ 2.0 MPa, and the failure mode is not falling off or tearing of the repaired part, it is judged to be qualified, that is, the sample meets the 1000-hour adhesive shear strength test, otherwise it is unqualified.
  • Comparative Example 2 In contrast, after removing all the thickness of the insulating layer in Comparative Example 1, its insulation resistance and bonding strength are not as good as those of the embodiment of the present invention. In Comparative Example 2, the pressure-sensitive adhesive tape was used to repair the defect of the insulating layer. Although its insulation withstand voltage performance meets the requirements of the prior art, it is prone to wrinkles and displacements during vibration and shock, and cannot meet the requirements of bond strength.
  • the present application is not limited to the above-mentioned embodiments.
  • the above-mentioned embodiments are merely examples, and within the scope of the technical solution of the present application, embodiments that have substantially the same configuration as the technical idea and exert the same function and effect are included in the technical scope of the present application.
  • other forms constructed by adding various modifications conceivable to those skilled in the art to the embodiments and combining some components in the embodiments are also included in the scope of the present application without departing from the scope of the present application.

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Abstract

本申请提供一种二次电池用的外壳，其中，所述外壳的外表面具有绝缘层，所述绝缘层上具有修复部，其中，所述修复部为由可固化材料形成的包含上部的蘑菇盖和下部的蘑菇柄的蘑菇状结构，所述蘑菇柄嵌入于所述绝缘层内部，所述蘑菇盖突出于所述绝缘层并且所述蘑菇盖的下表面覆盖于所述绝缘层上表面；其中，在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇盖的最长尺寸≥所述蘑菇柄的宽度w+电池的爬电距离L。

Description

外壳及其修复方法、相关的二次电池、电池模块、电池包和用电装置 技术领域
本申请涉及锂电池技术领域，尤其涉及一种外壳及其修复方法、二次电池、电池模块、电池包和用电装置。
背景技术
近年来，随着锂离子电池的应用范围越来越广泛，锂离子电池广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。当前以铝壳电芯为主的电池模组或电池包成组完毕且连接片焊接后，若此时出现电芯外表面的绝缘层(如绝缘膜、绝缘漆或其他涂层或覆层)破损或划伤，则会造成整个电池模组(或模块)或电池包因绝缘耐压问题报废(仅宁德时代新能源技术有限公司在2020年报废率达0.2％，损失成本＞1亿元)。
电池或电池包生产完毕后其整体结构不可拆卸，若此时发生绝缘层破损，无法将绝缘层全部去除后再返修。常规的修复方法通常为使用压敏胶带在缺陷区域打补丁，但是压敏胶带模量低(＜2MPa)，在多次振动冲击后原有补丁位置会因蠕变问题造成褶皱或位移，从而无法保证电池的安全性和使用寿命。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种二次电池用的外壳，其包含具有蘑菇状结构的修复部的绝缘层，既实现了振动冲击过程不发生位移和褶皱，并且保证了修复后外壳的绝缘耐压性能；而且能有效保证爬电距离能满足电池原本的技术要求，不会造成电池或电池包报废。
为了达到上述目的，本申请提供了一种外壳，其中，所述外壳的外表面具有绝缘层，所述绝缘层上具有修复部，其中，
所述修复部为由可固化材料形成的包含上部的蘑菇盖和下部的蘑菇柄的蘑菇状结构，所述蘑菇柄嵌入于所述绝缘层内部，所述蘑菇盖突出于所述绝缘层并且所述蘑菇盖的下表面覆盖于所述绝缘层上表面；其中，
在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇盖的最长尺寸≥所述蘑菇柄的宽度w+电池的爬电距离L。
本申请通过在外壳上形成蘑菇状结构的修复部，既实现了振动冲击过程不发生位移和褶皱，并且保证了修复后外壳的绝缘耐压性能；而且在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇盖的最长尺寸≥所述蘑菇柄的宽度w+电池的爬电距离L，能有效保证爬电距离能满足电池原本的技术要求，不会造成电池或电池包报废。
在一些实施方式中，在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇盖的最大厚度≥1/2所述绝缘层厚度t。由此保证外壳的绝缘耐压性能。
在一些实施方式中，所述蘑菇柄嵌入于所述绝缘层内部的深度≤1/2所述绝缘层厚度t。由此，最大限度保证原绝缘层的完整性，从而保证外壳的绝缘耐压性能。
在一些实施方式中，所述可固化材料在绝缘层表面的润湿角θ满足1°<θ<90°，并且在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇柄的宽度w≥10t×cotθ+3，其中t为所述绝缘层厚度，单位毫米。由此，所述可固化材料充分浸润绝缘层内部，从而保证外壳的绝缘耐压性能。
在一些实施方式中，所述可固化材料包含光固化材料或热固性材料。由此，保证修复部与原绝缘层的结合力，从而保证外壳的绝缘耐压性能。
在一些实施方式中，所述光固化材料或热固化材料的粘度为30-500mPa.s。由此，保证修复部与原绝缘层的结合力，从而保证外壳的绝缘耐压性能。
在一些实施方式中，所述光固化材料为紫外光(UV)固化材料，所述紫外光固化材料包括：
主体树脂 30-60重量％，
稀释单体 30-50重量％，
光引发剂 3-15重量％，以及
其他助剂 0-20重量％；
上述含量基于光固化材料的总重量计，并且各组分含量之和为100重量％。由此，保证修复部与原绝缘层的结合力，从而保证外壳的绝缘耐压性能。
在一些实施方式中，所述热固化材料包括：
主体树脂 45-70重量比％；
催化剂   0.1-5重量％；
助剂     29.9-50重量％；
上述含量基于热固化材料的总重量计，并且各组分含量之和为100重量％。由此，保证修复部与原绝缘层的结合力，从而保证外壳的绝缘耐压性能。
在任意实施方式中，所述稀释单体选自1,6-己二醇双丙烯酸酯、丙烯酸异冰片酯或甲基丙烯酸异冰片酯，优选选自1,6-己二醇双丙烯酸酯、丙烯酸异冰片酯；所述光引发剂选自2-羟基-2-甲基-1-苯基-丙酮、1-羟基环己基苯基甲酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基-二苯基氧膦中的至少一种。由此，保证修复部与原绝缘层的结合力，从而保证外壳的绝缘耐压性能。
本申请的第二方面还提供一种外壳的修复方法，其包含以下步骤：
a)缺陷定位：定位所述外壳外表面的缺陷区域，并识别缺陷区域的边界；
b)去除绝缘层：去除缺陷区域的部分绝缘层，以形成覆盖整个缺陷区域的凹槽；
c)形成蘑菇柄：使用可固化材料修补凹槽，以形成蘑菇柄；然后进行预固化；
d)形成蘑菇盖：使用可固化材料修补面层，然后进行最终固化， 以形成蘑菇盖，并使所述蘑菇盖与所述蘑菇柄固化在一起，从而形成蘑菇状结构；
其中，由上述步骤a)-步骤d)形成的外壳的外表面具有绝缘层，所述绝缘层上具有修复部，其中，
所述修复部为由可固化材料形成的包含上部的蘑菇盖和下部的蘑菇柄的蘑菇状结构，所述蘑菇柄嵌入于所述绝缘层内部，所述蘑菇盖突出于所述绝缘层并且所述蘑菇盖的下表面覆盖于所述绝缘层上表面；在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇盖的最长尺寸≥所述蘑菇柄的宽度w+电池的爬电距离L。由此，通过两次修补，形成蘑菇状的修复部，从而保证外壳的绝缘耐压性能。
本申请的第三方面提供一种二次电池，其包括本申请的第一方面所述的外壳或者由本申请的第二方面所述的方法修复的外壳，其中，所述外壳内部包括电极组件和电解液；或者，所述外壳内部包括电极组件和固态/半固态电解质。
本申请的第四方面提供一种电池模块，包括本申请的第三方面的二次电池。
本申请的第五方面提供一种电池包，包括本申请的第四方面的电池模块。
本申请的第六方面提供一种用电装置，包括选自本申请的第三方面的二次电池、本申请的第四方面的电池模块或本申请的第五方面的电池包中的至少一种。
本申请通过在外壳上形成特定尺寸的蘑菇状结构的修复部，既实现了振动冲击过程不发生位移和褶皱，并且保证了修复后外壳的绝缘耐压性能；而且有效保证爬电距离能满足电池原本的技术要求，不会造成电池或电池包报废。
附图说明
图1为外壳的修复部的结构示意图；其中I表示缺陷区域，11表示外壳，12表示绝缘层，13表示修复部。
图2是本申请一实施方式的二次电池的示意图。
图3是图2所示的本申请一实施方式的二次电池的分解图。
图4是本申请一实施方式的电池模块的示意图。
图5是本申请一实施方式的电池包的示意图。
图6是图5所示的本申请一实施方式的电池包的分解图。
图7是本申请一实施方式的二次电池用作电源的用电装置的示意图。
附图标记说明：
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组件；53顶盖组件
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的外壳及其修复方法、二次电池、电池模块、电池包和电学装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、 12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
当前以铝壳电芯为主的电池模组或电池包成组完毕且连接片焊接后，若此时出现电芯外表面的绝缘层(如绝缘膜、绝缘漆或其他涂层或覆层)破损或划伤，则会造成整个电池模组(或模块)或电池包因绝缘耐压问题报废(仅宁德时代新能源技术有限公司在2020年报废率达0.2％，损失成本＞1亿元)。
电池或电池包生产完毕后其整体结构不可拆卸，若此时发生绝缘层破损，无法将绝缘层全部去除后再返修。常规的修复方法通常为使用压敏胶带在缺陷区域打补丁，但是压敏胶带模量低(＜2MPa)，在多次振动冲击后原有补丁位置会因蠕变问题造成褶皱或位移，从而无法保证电池的安全性和使用寿命。发明人在经过大量研究后发 现，本申请第一方面的外壳能够通过包含特定尺寸的蘑菇状结构的修复部确保电池的安全性。
一种外壳
本申请的一个实施方式中，本申请提出了一种外壳，其中，所述外壳的外表面具有绝缘层，所述绝缘层上具有修复部，其中，
所述修复部为由可固化材料形成的包含上部的蘑菇盖和下部的蘑菇柄的蘑菇状结构，所述蘑菇柄嵌入于所述绝缘层内部，所述蘑菇盖突出于所述绝缘层并且所述蘑菇盖的下表面覆盖于所述绝缘层上表面；其中，
在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇盖的最长尺寸≥所述蘑菇柄的宽度w+电池的爬电距离L。
虽然机理尚不明确，但本申请人意外地发现：本申请通过在外壳上形成蘑菇状结构的修复部，既实现了振动冲击过程不发生位移和褶皱，并且保证了修复后外壳的绝缘耐压性能；而且在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇盖的最长尺寸≥所述蘑菇柄的宽度w+电池的爬电距离L，能有效保证爬电距离能满足电池原本的技术要求，不会造成电池或电池包报废。
在一些实施方式中，所述外壳用于二次电池中。
在一些实施方式中，当所述蘑菇盖的俯视图为规则的圆形时，在则所述修复部的任意垂直于所述绝缘层表面的截面中所述蘑菇盖的最长尺寸为所述圆形的直径，也称为蘑菇盖的直径。
在一些实施方式中，所述电池的爬电距离L是沿绝缘表面测得的两个导电零部件之间或导电零部件与设备防护界面之间的最短路径。在不同的使用情况下，由于导体周围的绝缘材料被电极化，导致绝缘材料呈现带电现象。动力电池爬电距离规范通常参考国标《GB/T 16935.1-2008低压系统内设备的绝缘配合第1部分：原理、要求和试验》，查表所得。按照有效电压800V，材料组别Ⅰ，污染等级3，对应的爬电距离要求≥10mm，因此当前动力电池包设计的爬电距离≥10mm。本发明的实施例也是按照此要求进行设计。
在一些实施方式中，在所述修复部的任意垂直于所述绝缘层表 面的截面中，所述蘑菇盖的最大厚度≥1/2所述绝缘层厚度t。由此保证外壳的绝缘耐压性能。
在一些实施方式中，所述蘑菇柄嵌入于所述绝缘层内部的深度≤1/2所述绝缘层厚度t。由此，最大限度保证原绝缘层的完整性，从而保证外壳的绝缘耐压性能。
在一些实施方式中，所述可固化材料在绝缘层表面的润湿角θ满足1°<θ<90°，并且在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇柄的宽度w≥10t×cotθ+3，其中t为所述绝缘层厚度，单位毫米。由此，所述可固化材料充分浸润绝缘层内部，从而保证外壳的绝缘耐压性能。
所述可固化材料在绝缘层表面的润湿角是指液态的可固化材料与绝缘层的接触点处可固化材料与绝缘层界面和可固化材料的表面切线的夹角。
在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇柄的宽度是指在蘑菇柄的截面中水平距离最大的宽度。在一些实施方式中，当所述蘑菇柄的水平截面为规则的圆形时，则所述蘑菇柄的宽度是指所述圆形的直径，也称为蘑菇柄的直径。
在一些实施方式中，所述可固化材料包含光固化材料或热固性材料。由此，保证修复部与原绝缘层的结合力，从而保证外壳的绝缘耐压性能。
在一些实施方式中，所述光固化材料或热固化材料的粘度为30-500mPa.s。由此，保证修复部与原绝缘层的结合力，从而保证外壳的绝缘耐压性能。
在一些实施方式中，所述光固化材料为紫外光(UV)固化材料，所述紫外光固化材料包括：
主体树脂 30-60重量％，
稀释单体 30-50重量％，
光引发剂 3-15重量％，以及
其他助剂 0-20重量％；
上述含量基于光固化材料的总重量计，并且各组分含量之和为100重量％。由此，保证修复部与原绝缘层的结合力，从而保证外壳 的绝缘耐压性能。
在一些实施方式中，所述热固化材料包括：
主体树脂 45-70重量比％；
催化剂   0.1-5重量％；
其他助剂 29.9-50重量％；
上述含量基于热固化材料的总重量计，并且各组分含量之和为100重量％。由此，保证修复部与原绝缘层的结合力，从而保证外壳的绝缘耐压性能。
在一些实施方式中，在UV固化材料和热固化材料中所述主体树脂相同或不同，可各自独立地选自丙烯酸酯类树脂、甲基丙烯酸酯类树脂(例如甲基丙烯酸乙酯、甲基丙烯酸羟乙酯)或环氧丙烯酸酯类树脂，优选丙烯酸酯类树脂，以及环氧丙烯酸酯类树脂。
在一些实施方式中，在UV固化材料材料中所述稀释单体选自1,6-己二醇双丙烯酸酯、丙烯酸异冰片酯或甲基丙烯酸异冰片酯，优选选自1,6-己二醇双丙烯酸酯、丙烯酸异冰片酯。
在一些实施方式中，所述光引发剂选自2-羟基-2-甲基-1-苯基-丙酮、1-羟基环己基苯基甲酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基-二苯基氧膦中的至少一种。由此，保证修复部与原绝缘层的结合力，从而保证外壳的绝缘耐压性能。
在一些实施方式中，所述催化剂选自过氧化二异丙苯、过氧化氢异丙苯、过氧化氢二异丙苯、过氧化二苯甲酰、超氧化二苯甲酰、叔丁基过氧化氢、过氧化叔丁基苯甲酸酯、过氧化叔丁基异丙基碳酸酯、过氧化叔丁基或过氧化二叔丁基。这些催化剂可单独使用或者数种合并使用。优选过氧化氢异丙苯。
在一些实施方式中，在UV固化材料和热固化材料中所述其他助剂相同或不同，可各自独立地包括光稳定剂、热稳定剂、增塑剂、填料、颜料分散剂、流平剂、消泡剂等。
所述光稳定剂可为受阻胺类，例如癸二酸双1-辛氧基-2,2,6,6-四甲基哌啶醇酯、CHISORB292、CHISORB770；二苯甲酮类或苯并三唑类。
所述热稳定剂为二月桂酸二丁基锡或脂肪酸锌。
所述增塑剂为邻苯二甲酸二辛酯、邻苯二甲酸二癸酯、邻苯二甲酸二异壬酯、邻苯二甲酸二异癸酯、己二酸二辛酯、癸二酸二辛酯、壬二酸二辛酯、磷酸三苯酯、磷酸二苯异辛酯、烷基磺酸酯类增塑剂中的至少一种。
所述填料为轻质碳酸钙、脂肪酸或脂肪酸盐改性的碳酸钙、煅烧高岭土、气相二氧化硅、PVC粉、滑石粉、有机蒙脱土、硅藻土、二氧化钛、空心球、炭黑、硫酸钡、钛白粉中的至少一种。
所述的流平剂包括但不限于聚丙烯酸酯或有机硅树脂或氟碳表面活性剂、氟改性的丙烯酸酯或其组合，如德国毕克化学公司的BYK333、BYK360、Glide 432、Flow 300、Efka 3600、摩能化工有限公司的1154等一种或一种以上的混合物。
所述消泡剂包括但不限于有机聚合物或有机硅树脂或它们的组合，如聚二甲基硅氧烷、德谦2700、海名斯DF7015、BYK-141等一种或一种以上。
所述颜料分散剂包括但不限于长链聚脂肪酸和多氨基盐等合成高分子类、多价羧酸盐、硅类和钛系偶联剂等含有颜料亲和基团的聚合物等一种或一种以上组合，如德国毕克化学公司的BYK163、BYK164、BYK358N，核心化学公司的Disuper S28中的一种或一种以上。
所述UV固化材料可做到瞬干或极快速固化，利于快速返修且对固化时间有苛刻要求的情况。所述热固化材料固化时间较UV固化材料慢，但其流平效果好，且热固化时材料与绝缘层的浸润效果好，得到的修复部质量高。
在一些实施方式中，本申请还提供一种外壳的修复方法，其包含以下步骤：
a)缺陷定位：定位所述外壳外表面的缺陷区域，并识别缺陷区域的边界；
b)去除绝缘层：去除缺陷区域的部分绝缘层，以形成覆盖整个缺陷区域的凹槽；
c)形成蘑菇柄：使用可固化材料修补凹槽，以形成蘑菇柄；然后进行预固化；
d)形成蘑菇盖：使用可固化材料修补面层，然后进行最终固化，以形成蘑菇盖，并使所述蘑菇盖与所述蘑菇柄固化在一起，从而形成蘑菇状结构；
其中，由上述步骤a)-步骤d)形成的外壳的外表面具有绝缘层，所述绝缘层上具有修复部，其中，
所述修复部为由可固化材料形成的包含上部的蘑菇盖和下部的蘑菇柄的蘑菇状结构，所述蘑菇柄嵌入于所述绝缘层内部，所述蘑菇盖突出于所述绝缘层并且所述蘑菇盖的下表面覆盖于所述绝缘层上表面；在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇盖的最长尺寸≥所述蘑菇柄的宽度w+电池的爬电距离L。由此，通过两次修补，形成蘑菇状的修复部，从而保证外壳的绝缘耐压性能。
在一些实施方式中，在所述步骤a)中，缺陷区域通过电池管理系统(BMS)进行定位。在BMS中，缺陷区域一旦出现，温度或电压会异常，即反馈的电压变为0V或其它低电压值，或热敏电阻器(NTC)采集的温度明显升高。
缺陷区域的边界通过扫描电子显微镜或者视觉相机(CCD)进行识别。
在一些实施方式中，在所述步骤b)中，所述凹槽在水平方向上的投影面积＞所述缺陷区域在水平方向上的投影面积。由此，保证缺陷区域被完全修复，确保外壳的绝缘耐压性能。
在一些实施方式中，在步骤b)中凹槽深度约等于蘑菇柄深度，凹槽的宽度约等于蘑菇柄的宽度w。同时需要说明的是，通常情况下蘑菇柄的宽度w应当大于等于缺陷区域的宽度；当缺陷区域的宽度较小，甚至不足3毫米时，蘑菇柄的宽度w也应当满足w≥10t×cotθ+3，其中t为所述绝缘层厚度，单位毫米，θ为可固化材料在绝缘层表面的润湿角。
在一些实施方式中，在步骤b)中，使用激光清洗或者机械磨削的方式去除部分绝缘层。所述激光清洗是通过光纤脉冲激光器或二氧化碳激光器使非金属涂层吸收激光能量，通过热灼伤和热膨胀将涂层去除一部分进行。所述机械磨削通过铣或磨的方式机械加工去 除一定厚度涂层。
在一些实施方式中，在步骤c)中，所述可固化材料修补厚度为所述蘑菇柄深度至(蘑菇柄深度+所述绝缘层厚度t的10％)，以形成所述蘑菇柄。由此，确保可固化材料充分浸润凹槽以形成蘑菇柄，从而确保外壳的绝缘耐压性能。
在一些实施方式中，步骤c)的预固化和步骤d)的最终固化所需的能量相同或不同。在所述可固化材料为光固化材料的情况下，照射能量为2000-4000mJ/cm^2。其中UV照射能量与厚度成正比，总能量
E＝E0*t，
t为单层涂层厚度，cm；
E0为单位厚度所需能量，mJ/cm 3。
在所述可固化材料为热固化材料的情况下，步骤c)的预固化和步骤d)的最终固化的加热温度各自独立地为：预固化60-80℃，优选70-80℃，选择安全温度范围内较高的温度可缩减预固化时长，过高温度会造成电芯不可逆的损伤；终固化35-60℃，优选40-50℃
在一些实施方式中，所述可固化材料为如本文中以上所述。
在一些实施方式中，在步骤c)之前，对所述凹槽表面进行等离子清洗。由此，可以提升绝缘层表面张力，使绝缘层表面极性增强，能提升修复部与绝缘层的结合力。
因此，在一些实施方式中，本申请的方法包含以下步骤：
a)缺陷定位：定位所述外壳外表面的缺陷区域，并识别缺陷区域的边界；
b)去除绝缘层：去除缺陷区域的部分绝缘层，以形成覆盖整个缺陷区域的凹槽；
c0)对所述凹槽表面进行等离子清洗；
c)形成蘑菇柄：使用可固化材料修补凹槽，以形成蘑菇柄；然后进行预固化；
d)形成蘑菇盖：使用可固化材料修补面层，然后进行最终固化，以形成蘑菇盖，并使所述蘑菇盖与所述蘑菇柄固化在一起，从而形成蘑菇状结构。
在一些实施方式中，在步骤c)和步骤d)中，所述修补通过喷墨打印工艺和精密点胶工艺进行。所述喷墨打印工艺为使用可固化材料通过喷墨打印机精确打印在指定区域形成一定厚度的修复部。精密点胶工艺为使用精确的小计量点胶设备将可固化材料点涂在指定区域形成一定厚度的修复部。
在一些实施方式中，本申请还提供一种二次电池，其包括权利要求1-9中任一项所述的外壳或者由权利要求10-14中任一项所述的方法修复的外壳，其中，所述外壳内部包括电极组件和电解液；或者，所述外壳内部包括电极组件和固态/半固态电解质。
所述二次电池的绝缘性能通过在500V的直流电(DC)下测定其绝缘阻抗(以GΩ计)来表征。所述二次电池的绝缘阻抗≥10GΩ。
所述二次电池的耐压性能通过在2700V的直流电(DC)下测定其漏电电流(以mA计)来表征。所述二次电池的漏电电流≤0.1mA。
通常情况下，二次电池包括正极极片、负极极片、电解质和隔离膜。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使离子通过。
[正极极片]
正极极片包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，所述正极膜层包括本申请第一方面的正极活性材料。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极膜层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在一些实施方式中，所述正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，正极活性材料可采用本领域公知的用于电池的正极活性材料。作为示例，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO 2)、锂镍氧化物(如LiNiO 2)、锂锰氧化物(如LiMnO 2、LiMn 2O 4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi 1/3Co 1/3Mn 1/3O 2(也可以简称为NCM 333)、LiNi 0.5Co 0.2Mn 0.3O 2(也可以简称为NCM 523)、LiNi 0.5Co 0.25Mn 0.25O 2(也可以简称为NCM 211)、LiNi 0.6Co 0.2Mn 0.2O 2(也可以简称为NCM 622)、LiNi 0.8Co 0.1Mn 0.1O 2(也可以简称为NCM 811)、锂镍钴铝氧化物(如LiNi 0.85Co 0.15Al 0.05O 2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO 4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO 4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
在一些实施方式中，正极膜层还可选地包括粘结剂。作为示例，所述粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在一些实施方式中，正极膜层还可选地包括导电剂。作为示例，所述导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，所述负极膜层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施方式中，所述负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。所述硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。所述锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施方式中，负极膜层还可选地包括粘结剂。所述粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施方式中，负极膜层还可选地包括导电剂。导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，负极膜层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施方式中，可以通过以下方式制备负极极片：将上述 用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
[电解质]
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中，所述电解质采用电解液。所述电解液包括电解质盐和溶剂。
在一些实施方式中，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
在一些实施方式中，溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施方式中，所述电解液还可选地包括添加剂。例如添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
[隔离膜]
在一些实施方式中，二次电池中还包括隔离膜。本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。
在一些实施方式中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层 薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
在一些实施方式中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
[外壳]
在一些实施方式中，二次电池包含本发明的外壳。所述外壳内部包括上述电极组件和电解液；或者，所述外壳内部包括上述电极组件和固态/半固态电解质。
在一些实施方式中，二次电池的外壳可为硬壳，例如硬塑料壳、铝壳、钢壳等。
本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图2是作为一个示例的方形结构的二次电池5。
在一些实施方式中，参照图3，外壳可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图4是作为一个示例的电池模块4。参照图4，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。
在一些实施方式中，上述电池模块还可以组装成电池包，电池 包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图5和图6是作为一个示例的电池包1。参照图5和图6，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。
作为所述用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。
图7是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用二次电池作为电源。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
所使用的材料
UV固化材料A，其包含：
主体树脂：丙烯酸酯预聚物   55重量％
稀释单体：丙烯酸异冰片酯   22重量％
稀释单体：1,6-己二醇双丙烯酸酯  15重量％
光引发剂：2-羟基-2-甲基-1苯基-丙酮  4重量％
光引发剂：2,4,6-三甲基苯甲酰基-二苯基氧膦  2重量％
流平剂：德国毕克Byk360  2重量％
UV固化材料B，其包含：
主体树脂：环氧丙烯酸酯预聚物    35重量％
稀释单体：丙烯酸异冰片酯        30重量％
稀释单体：1,6-己二醇双丙烯酸酯  20重量％
光引发剂：1-羟基环己基苯基甲酮  4重量％
光引发剂：2,4,6-三甲基苯甲酰基-二苯基氧膦  2重量％
流平剂：德国毕克Byk360  2重量％
颜料分散剂：核心化学Disuper S28  1重量％
填料：钛白粉  5重量％
填料：硫酸钡  1重量％
双组分热固化材料(质量比A：B＝4：1)，其包含：
A组分：
Figure PCTCN2022073450-appb-000001
B组分：
聚甲基丙烯酸甲酯(PMMA)  5.0g
三乙基苯胺              0.5g
醋酸丁酯                7.5g
实施例
实施例1
提供一块具有待修复的外壳的二次电池，其中其爬电距离最小 值为10mm(按照800V电压平台，材料组别1)，外壳的绝缘层厚度为110μm；对其外壳通过以下步骤修复：
a)缺陷定位：通过外置1500V的电压的接触式线扫描方式检测外壳外表面，平面内按照x、y方向分别扫描，扫描后判断泄露电流≥1mA时找出缺陷点，x和y坐标交叉点即为缺陷中心点来定位所述外壳外表面的缺陷区域，然后使用2D视觉相机(厂家基恩士)识别缺陷区域的边界，所述缺陷区域尺寸为0.8mm×1.2mm；
b)去除绝缘层：利用1000W脉冲光纤激光器清洗去除所述缺陷区域的部分绝缘层，以形成直径为φ3mm和深度为50μm的凹槽；
c)形成蘑菇柄：利用喷墨打印方式使用UV固化材料A修补凹槽，以形成直径为φ3mm和深度为50μm蘑菇柄；然后利用1000mJ/cm的照射能量照射2s时间进行预固化；
d)形成蘑菇盖：利用喷墨打印方式使用UV固化材料A修补面层，然后利用1500mJ/cm 2的照射能量照射2.5s时间进行最终固化，以形成100μm厚度和φ10mm直径的蘑菇盖，并使所述蘑菇盖与所述蘑菇柄固化在一起，从而形成蘑菇状结构的修复部。
测试上述修复后的二次电池的绝缘阻抗、漏电电流、振动冲击测试以及粘结强度。相关参数和结果汇总于表1中。
实施例2-10
重复与实施例1相同的步骤，不同之处在于改变蘑菇盖的厚度和直径、蘑菇柄的深度和直径、用UV固化材料B替换UV固化材料A。
测试上述修复后的二次电池的绝缘阻抗、漏电电流、振动冲击测试以及粘结强度。相关参数和结果汇总于表1中。
实施例11
重复与实施例1相同的步骤，不同之处在于：
c)形成蘑菇柄：利用精密点胶方式使用热固化材料修补凹槽，以形成蘑菇柄；然后在70℃温度下加热10min时间进行预固化；
d)形成蘑菇盖：利用精密点胶方式使用热固化材料修补面层，然后在60℃温度下加热4h时间进行最终固化，以形成100μm厚度和φ10mm直径的蘑菇盖，并使所述蘑菇盖与所述蘑菇柄固化在一 起，从而形成蘑菇状结构的修复部。
测试上述修复后的二次电池的绝缘阻抗、漏电电流、振动冲击测试以及粘结强度。结果汇总于表1中。
实施例12-14
重复与实施例11相同的步骤，不同之处在于改变蘑菇盖的厚度和直径。测试上述修复后的二次电池的绝缘阻抗、漏电电流、振动冲击测试以及粘结强度。结果汇总于表1中。
对比例1
重复与实施例1相同的步骤，不同之处在于：凹槽的深度100μm(＞1/2原涂层厚度)，近乎去除原有涂层。测试上述修复后的二次电池的绝缘阻抗、漏电电流、振动冲击测试以及粘结强度。结果汇总于表1中。
对比例2
a)缺陷定位：与实施例1步骤a相同
b)缺陷修补：取大小为10mm×10mm，总厚度110μm的压敏胶带(其中压敏胶总厚度60μm，PET膜总厚度50μm)粘贴于原有涂层缺陷区域上方，确认缺陷位置居中；
c)胶带压紧：使用重量为5kg，与胶带接触面大小为50mm×50mm的辅助压紧模块压在胶带正上方，保压1min；
测试上述修复后的二次电池的绝缘阻抗、漏电电流、振动冲击测试以及粘接性能，相关参数和结果汇总于表1中。
相关的测试方法
二次电池的耐压漏电流测试
将电池放置在测试工装内，工装内壁为导电泡棉材质，柔软的导电泡棉能使工装与电芯五个面(除顶面外的五个平面，包含拐角棱边)充分接触，使用绝缘耐压测试仪(供应商：日置)，正极探针接触在电芯顶盖的裸铝位置，负极探针与工装内的导电泡棉相连。
将绝缘耐压测试仪测试电压调整至2700VDC(DC为直流电)，升压时间1s，保压时间60s，启动测试后观察记录仪器显示的漏电流值，若漏电流值≤0.1mA即为合格，若超出此电流值或仪器在升压到2700VDC前即报警，则判断为不合格。
二次电池的绝缘阻抗测试
将电池放置在测试工装内，工装内壁为导电泡棉材质，柔软的导电泡棉能使工装与电芯五个面(除顶面外的五个平面，包含拐角棱边)充分接触，使用绝缘耐压测试仪(供应商：日置)，正极探针接触在电芯顶盖的裸铝位置，负极探针与工装内的导电泡棉相连。
将绝缘耐压测试仪测试电压调整至1000VDC(DC为直流电)，测试时间5s，启动测试后观察记录仪器显示的电阻值，若电阻值≥10GΩ即为合格，若低于10GΩ，则判断为不合格。
振动冲击测试(是否发生位移和褶皱)
a)振动冲击测试采用电池模组或电池包系统进行测试，本实施例采用的是1P108S(1并108串)电池包系统，测试前系统SOC(SOC为剩余容量占正常容量的比值，取值0～1之间)调整至不低于正常SOC范围的50％
振动测试参照GB38031-2020《电动汽车用动力蓄电池安全要求》8.2.1小节中的测试方法，参照表2进行x、y、z三个方向振动测试(x为车辆行驶方向，y为垂直于行驶方向的水平方向，z为垂直于行驶方向的竖直方向)。振动测试结束，观察2h后，拆解电池包系统，肉眼观察电芯外部绝缘层(包括返修后的绝缘层)是否完好，有无褶皱、位移等现象，若有，则判断为测试不合格。
b)冲击测试采用与振动测试相同型号电池包系统进行，参照GB38031-2020《电动汽车用动力蓄电池安全要求》8.2.2小节进行测试，对试验对象施加如表4规定的半正弦波，±z方向各6次，共计12次。冲击测试结束，观察2h后，拆解电池包系统，肉眼观察电芯外部绝缘层(包括返修后的绝缘层)是否完好，有无褶皱、位移等现象，若有，则判断为测试不合格。
粘接强度测试(仅测试剪切方向的强度)
参照GB/T 7124-2008《胶粘剂 拉伸剪切强度的测定》
1)剪切强度测试：将试样在10000N拉伸试验机上装夹好后(测试夹钳处各垫一个与试片厚度相当的垫片，使试样受力平行于胶接平面，注意控制上下夹钳不要发生明显扭转)，拉伸试验机测试速度设定为5mm/min，将“拉力”、“位移”、“最大拉力”三个选项全部清 零，启动拉伸试验机，观察并等待试样拉脱后，记录此时的“最大拉力”数值和“位移”数值，并记录拉脱位置的情况(是界面破坏AF还是胶本体的内聚破坏CF)。
2)高温高湿存储：取各实施例和对比例的外壳样品放入85℃85％相对湿度的恒温恒湿箱中存储一定时间，当存储时间达到1000h后取出，常温静置2h后参照步骤1的方式测试1000h剪切强度，当1000h剪切强度≥2.0MPa，且失效模式不是修复部脱落或撕裂时，判断合格，即该试样满足1000h粘接剪切强度测试，反之不合格。
表1各实施例和对比例的相关参数和测试结果
Figure PCTCN2022073450-appb-000002
根据上述结果可知，符合本发明的相关参数的实施例1、5、10、14在绝缘、耐压、振动冲击和粘结强度方面均取得了良好的效果。
而相对于此，对比例1除去全部绝缘层厚度后，其绝缘阻抗和粘结强度均不及本发明的实施例。对比例2使用压敏胶带修复绝缘 层缺陷，虽然其绝缘耐压性能满足现有技术的需求，但是其在振动冲击过程中容易出现褶皱和位移，并且不能满足粘结强度的要求。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (18)

  1. 一种外壳，其中，所述外壳的外表面具有绝缘层，所述绝缘层上具有修复部，其中，
    所述修复部为由可固化材料形成的包含上部的蘑菇盖和下部的蘑菇柄的蘑菇状结构，所述蘑菇柄嵌入于所述绝缘层内部，所述蘑菇盖突出于所述绝缘层并且所述蘑菇盖的下表面覆盖于所述绝缘层上表面；其中，
    在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇盖的最长尺寸≥所述蘑菇柄的宽度w+电池的爬电距离L。
  2. 根据权利要求1所述的外壳，其中，在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇盖的最大厚度≥1/2所述绝缘层厚度t。
  3. 根据权利要求1或2所述的外壳，其中，所述蘑菇柄嵌入于所述绝缘层内部的深度≤1/2所述绝缘层厚度t。
  4. 根据权利要求1-3中任一项所述的外壳，其中，所述可固化材料在绝缘层表面的润湿角θ满足1°<θ<90°，并且在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇柄的宽度w≥10t×cotθ+3，其中t为所述绝缘层厚度，单位毫米。
  5. 根据权利要求1-4中任一项所述的外壳，其中，所述可固化材料包含光固化材料或热固性材料。
  6. 根据权利要求5所述的外壳，其中，所述光固化材料或热固化材料的粘度为30-500mPa.s。
  7. 根据权利要求5或6所述的外壳，其中，所述光固化材料为紫外光固化材料，所述紫外光固化材料包括：
    主体树脂 30-60重量％，
    稀释单体 30-50重量％，
    光引发剂 3-15重量％，以及
    其他助剂 0-20重量％；
    上述含量基于光固化材料的总重量计，并且各组分含量之和为 100重量％。
  8. 根据权利要求5或6所述的外壳，其中，所述热固化材料包括：
    主体树脂 45-70重量比％；
    催化剂   0.1-5重量％；
    助剂     29.9-50重量％；
    上述含量基于热固化材料的总重量计，并且各组分含量之和为100重量％。
  9. 根据权利要求7所述的外壳，其中，
    所述稀释单体选自1,6-己二醇双丙烯酸酯、丙烯酸异冰片酯或甲基丙烯酸异冰片酯，优选选自1,6-己二醇双丙烯酸酯、丙烯酸异冰片酯；所述光引发剂选自2-羟基-2-甲基-1-苯基-丙酮、1-羟基环己基苯基甲酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基-二苯基氧膦中的至少一种。
  10. 一种外壳的修复方法，其包含以下步骤：
    a)缺陷定位：定位所述外壳外表面的缺陷区域，并识别缺陷区域的边界；
    b)去除绝缘层：去除缺陷区域的部分绝缘层，以形成覆盖整个缺陷区域的凹槽；
    c)形成蘑菇柄：使用可固化材料修补凹槽，以形成蘑菇柄；然后进行预固化；
    d)形成蘑菇盖：使用可固化材料修补面层，然后进行最终固化，以形成蘑菇盖，并使所述蘑菇盖与所述蘑菇柄固化在一起，从而形成蘑菇状结构；
    其中，由上述步骤a)-步骤d)形成的外壳的外表面具有绝缘层，所述绝缘层上具有修复部，其中，
    所述修复部为由可固化材料形成的包含上部的蘑菇盖和下部的蘑菇柄的蘑菇状结构，所述蘑菇柄嵌入于所述绝缘层内部，所述蘑菇盖突出于所述绝缘层并且所述蘑菇盖的下表面覆盖于所述绝缘层上表面；在所述修复部的任意垂直于所述绝缘层表面的截面中，所述蘑菇盖的最长尺寸≥所述蘑菇柄的宽度w+电池的爬电距离L。
  11. 根据权利要求10所述的方法，其中，在所述步骤b)中，所述凹槽在水平方向上的投影面积＞所述缺陷区域在水平方向上的投影面积。
  12. 根据权利要求10或11所述的方法，其中，在步骤c)中，所述可固化材料修补厚度为所述蘑菇柄深度至(蘑菇柄深度+所述绝缘层厚度t的10％)，以形成所述蘑菇柄。
  13. 根据权利要求10-12中任一项所述的方法，其中，步骤c)的预固化和步骤d)的最终固化所需的能量相同或不同。
  14. 根据权利要求10-13中任一项所述的方法，其中，在步骤c)之前，对所述凹槽表面进行等离子清洗。
  15. 一种二次电池，其包括权利要求1-9中任一项所述的外壳或者由权利要求10-14中任一项所述的方法修复的外壳，其中，所述外壳内部包括电极组件和电解液；或者，所述外壳内部包括电极组件和固态/半固态电解质。
  16. 一种电池模块，其包括权利要求15所述的二次电池。
  17. 一种电池包，其包括权利要求16所述的电池模块。
  18. 一种用电装置，包括权利要求15所述的二次电池、权利要求16所述的电池模块或权利要求17所述的电池包中的至少一种。
PCT/CN2022/073450 2022-01-24 2022-01-24 外壳及其修复方法、相关的二次电池、电池模块、电池包和用电装置 WO2023137748A1 (zh)

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EP22899606.2A EP4243107A4 (en) 2022-01-24 2022-01-24 HOUSING AND REPAIR METHOD THEREFOR, ASSOCIATED SECONDARY BATTERY, BATTERY MODULE, BATTERY PACK AND ELECTRICAL DEVICE
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