WO2023061083A1 - 相变微胶囊、隔膜、极片、电池和用电装置 - Google Patents

相变微胶囊、隔膜、极片、电池和用电装置 Download PDF

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Publication number
WO2023061083A1
WO2023061083A1 PCT/CN2022/116271 CN2022116271W WO2023061083A1 WO 2023061083 A1 WO2023061083 A1 WO 2023061083A1 CN 2022116271 W CN2022116271 W CN 2022116271W WO 2023061083 A1 WO2023061083 A1 WO 2023061083A1
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WIPO (PCT)
Prior art keywords
phase
coating
diaphragm
battery
change
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PCT/CN2022/116271
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English (en)
French (fr)
Inventor
韩丰胜
牛少军
Original Assignee
宁德时代新能源科技股份有限公司
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Priority to EP22880029.8A priority Critical patent/EP4262006A1/en
Publication of WO2023061083A1 publication Critical patent/WO2023061083A1/zh
Priority to US18/454,812 priority patent/US20230395903A1/en

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/659—Means for temperature control structurally associated with the cells by heat storage or buffering, e.g. heat capacity or liquid-solid phase changes or transition
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/651—Means for temperature control structurally associated with the cells characterised by parameters specified by a numeric value or mathematical formula, e.g. ratios, sizes or concentrations
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6554—Rods or plates
    • H01M10/6555—Rods or plates arranged between the cells
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/658—Means for temperature control structurally associated with the cells by thermal insulation or shielding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/64—Heating or cooling; Temperature control characterised by the shape of the cells
    • H01M10/643—Cylindrical cells
    • 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 field of batteries, in particular, to a phase-change microcapsule, a separator, a pole piece, a battery and an electrical device.
  • the current collecting assembly is used to electrically connect the tabs of the battery cell and the electrode terminals, so as to transmit electric energy from the electrode assembly to the electrode terminal, and then to the outside of the battery cell through the electrode terminal; between multiple battery cells
  • the electrical connection is realized through the converging component, so as to realize the series connection, parallel connection or mixed connection of multiple battery cells.
  • the application provides a phase-change microcapsule, a separator, a pole piece, a battery and an electrical device, which can avoid the technical problem that a short circuit is easily caused inside the battery.
  • the present application example provides a phase change microcapsule, which includes: a core material and an insulating and heat-conducting wall material wrapping the core material.
  • the core material includes a first phase-change component and a second phase-change component.
  • the first phase-change component is paraffin wax with a melting point of 37-42°C
  • the second phase-change component is paraffin wax with a melting point of 65-75°C.
  • the insulating heat-conducting wall The melting point of the material is greater than 75°C.
  • the mass ratio of the first phase change component to the second phase change component is 35:45-77.
  • a phase change microcapsule with a core-shell structure is provided, which is applied to a battery, such as a lithium battery, in the form of a coating, so that the negative electrode tab of the lithium battery and the separator are bonded and connected through the coating, and the core material is used to
  • the first phase-change component and the second phase-change component with a specific melting point in the middle cooperate with each other in a specific ratio, so that when the tab is welded to the current collector assembly, the first phase-change component undergoes a phase change and quickly absorbs heat, buffering the temperature of the diaphragm.
  • the melting point of the insulating and heat-conducting wall material is greater than 75°C, which can also avoid destroying the insulating and heat-conducting wall material during the phase change of the core material, from the insulation and heat conduction Flow out from the wall material.
  • the first phase-change component and the second phase-change component cooperate with each other to absorb welding heat and melt in a gradient, thereby controlling the temperature rise rate of the diaphragm and the temperature of the diaphragm to ensure that the real-time temperature of the diaphragm is always low during welding The minimum temperature at which it can be scalded to avoid internal short circuit of the battery caused by scalding the separator.
  • the paraffin wax used in the first phase change component has a structural formula: CnH2n+2, where 18 ⁇ n ⁇ 21; the paraffin wax used in the second phase change component has a structural formula: Cn'H2n' +2 where 25 ⁇ n' ⁇ 28.
  • the paraffin wax of the above specific structural formula can better meet the melting point requirements, and also has the advantages of abundant sources.
  • the insulating and thermally conductive wall material includes a base material and ceramic particles dispersed in the base material, and the base material is a polymer.
  • the beneficial effects of the above technical solution include: the introduction of ceramic particles in the wall material, on the one hand, can make the wall material have better high temperature resistance, and at the same time, it is also beneficial for the core material to absorb the heat generated when the current collecting assembly is welded in time, and on the other hand On the one hand, it can avoid excessive shrinkage of the part where the diaphragm is in contact with the negative pole piece during welding.
  • the polymer comprises phenolic resin.
  • the mass ratio of the wall material to the core material is 1:3-4.
  • the beneficial effects of the above technical solution include: reasonably controlling the ratio range of the wall material and the core material, controlling the thickness of the wall material under the condition that the particle size of the phase-change microcapsules meets the use requirements, ensuring that the thickness of the wall material is reasonable, and ensuring that the thickness of the wall material is reasonable during use.
  • the stability of the phase change microcapsules enables it to protect the diaphragm against the instantaneous high temperature during welding.
  • the mass ratio of the substrate to the ceramic particles is 3:4-5, and the mass ratio of the substrate to the core material is 1:2-3.
  • the beneficial effects of the above technical solution include: controlling the dosage of the base material, ceramic particles and core material within the above range can ensure the stability of the phase change microcapsules, so that they can protect the diaphragm against the instantaneous high temperature during welding.
  • the ceramic particles include silica particles.
  • silica particles have excellent high temperature resistance, insulation and thermal conductivity, which can improve the high temperature resistance, insulation and thermal conductivity of wall materials, and improve the stability of phase change microcapsules when welding current collecting components and Heat absorption capacity, but also has the advantages of abundant sources and easy access.
  • the particle size of the silica particles is 60-90 nm.
  • the beneficial effects of the above-mentioned technical solution include: the above-mentioned silicon dioxide particles with a specific particle size are conducive to doping and uniformly dispersing in the substrate.
  • the particle size of the phase change microcapsules is 0.5-4 ⁇ m.
  • the phase change microcapsules have an appropriate particle size, which facilitates the formation of a coating, and effectively prevents the edge of the diaphragm on the negative electrode side from being scalded when the current collecting assembly is welded.
  • the present application provides a diaphragm, the edge of the diaphragm is provided with a coating, and the coating contains the phase change microcapsules provided in the first aspect of the present application.
  • the beneficial effects of the above-mentioned technical solution include: when the above-mentioned diaphragm is applied to a battery, the coating on the edge of the diaphragm corresponds to the tab with a thermal conductivity ⁇ 380W/m.k. Heat, to ensure that the real-time temperature of the separator is always lower than the minimum temperature that can be scalded during welding, so as to avoid the internal short circuit of the battery caused by the burnt separator, and because the coating is mainly located on the edge of the separator, it basically does not affect the performance of the separator itself.
  • the thickness of the coating is 10-35 ⁇ m, optionally 10-20 ⁇ m, and optionally 25-35 ⁇ m.
  • the beneficial effects of the above technical solution include: the thickness of the coating is reasonable, and when the above-mentioned diaphragm is applied to the battery, when the tab and the current collecting assembly are welded by laser, it can not only avoid scalding the diaphragm, but also basically not affect the size of the edge of the diaphragm.
  • the present application example provides a pole piece, the pole piece includes interconnected current collectors and tabs, the thermal conductivity of the tabs is ⁇ 380W/m.k, at least one side of the tabs is provided with a coating, and the coating Contains the phase change microcapsule provided by the first aspect of the application.
  • the thermal conductivity of the tab is ⁇ 380W/m.k
  • the coating containing phase change microcapsules is placed between the tab and the diaphragm, and the coating is used to avoid direct contact between the diaphragm and the tab.
  • the coating can be used to absorb the heat transferred by the lug, so that the real-time temperature of the diaphragm is always lower than the minimum temperature that can be scalded, so as to avoid internal short circuit caused by scalding the diaphragm.
  • the thickness of the coating is 10-35 ⁇ m, optionally 10-20 ⁇ m, and optionally 25-35 ⁇ m.
  • the thickness of the coating is reasonable, not only can avoid the burn of the diaphragm matching with the above-mentioned tab when welding the current collecting assembly, but at the same time basically do not affect the size of the edge position of the diaphragm matching with the tab.
  • the present application example provides a battery, which includes a separator and a pole piece, and the pole piece includes interconnected current collectors and tabs.
  • the coating contains the phase change microcapsules provided by the first aspect of the application.
  • a coating containing phase-change microcapsules can be provided between the tab and the diaphragm, and the coating can absorb the heat transferred by the tab when welding the current collecting assembly, ensuring that the real-time temperature of the diaphragm is always low during welding The minimum temperature at which it can be scalded to avoid internal short circuit of the battery caused by scalding the separator.
  • the thickness of the coating between the diaphragm and the tab is 20-35 ⁇ m.
  • the beneficial effects of the above technical solution include: the thickness of the coating is reasonable, not only can the edge of the diaphragm matched with the lug be avoided from being scalded when the current collecting assembly is welded, but at the same time, the size of the edge of the diaphragm is basically not affected.
  • the present application provides an example of an electrical device equipped with the battery provided in the fourth aspect of the present application.
  • FIG. 1 is a schematic structural view of a vehicle in some embodiments of the present application.
  • Fig. 2 is a schematic diagram of an exploded structure of a battery in some embodiments of the present application.
  • FIG. 3 is a schematic diagram of an exploded structure of a battery cell in some embodiments of the present application.
  • Fig. 4 is a schematic structural diagram of a wound electrode assembly provided in some embodiments after deployment
  • Fig. 5 is a schematic structural view of the flattened negative electrode region provided by some embodiments.
  • Fig. 6 is the scanning electron micrograph of the phase change microcapsule provided by embodiment 1;
  • Fig. 7 is the photograph of the diaphragm edge region that the embodiment 2-7 that expands after welding provides;
  • Fig. 8 is the photograph of the membrane edge region that the embodiment 1 that expands after welding and comparative example 1-5 provide;
  • 20-battery cell 21-end cover; 21a-electrode terminal; 22-insulator; 23-collecting assembly; 24-housing; 25-electrode assembly;
  • 251-positive electrode current collector 252-positive electrode tab; 253-negative electrode current collector; 255-negative electrode tab; 256-diaphragm;
  • multiple types refers to two or more types (including two types).
  • Power batteries are not only used in energy storage power systems such as hydraulic, thermal, wind and solar power plants, but also widely used in electric vehicles such as electric bicycles, electric motorcycles, electric vehicles, as well as military equipment and aerospace and other fields . With the continuous expansion of power battery application fields, its market demand is also constantly expanding.
  • the lithium ion battery As an example, the inventor conducted research and found that since the negative tab of the lithium ion battery is generally a thinner copper foil, Its thermal conductivity is good, but the instantaneous temperature of the laser welding current collecting assembly is very high, therefore, holes and excessive shrinkage of the edge of the diaphragm in contact with the negative electrode tab will cause burns, resulting in internal short circuit of the battery.
  • the inventors tried to install a coating on the edge of the negative electrode tab of the lithium battery and the separator to isolate the two and avoid direct contact between the two, and to apply a phase change material in the coating to absorb laser welding.
  • a phase change material in the coating to absorb laser welding.
  • the variable response speed is different, and the light emission time of laser welding is generally 0.1s, and the instantaneous temperature of the light emission can reach 1000°C, so that although the final temperature of the diaphragm is lower than the minimum temperature required for it to be scalded, during the phase transition process, due to the phase transition
  • the material cannot respond quickly to the phase change, causing the instantaneous temperature of the separator to be greater than the minimum temperature required for it to be scalded, and the separator still has the problem of being scal
  • the applicant provides a phase change microcapsule, which is arranged on the edge of the diaphragm and/or at least one side of the tab, assembled into a battery cell and applied to the battery, at a thermal conductivity ⁇ 380W/m.k
  • the first phase change component and the second phase change component with a specific ratio and different melting points in the phase change microcapsules are used to realize the first phase change.
  • the gradient melting of the change component and the second phase change component controls the temperature rise rate of the diaphragm and the real-time temperature of the diaphragm, which can effectively avoid the problem of internal short circuit of the cell caused by the burn of the diaphragm caused by laser welding the current collecting assembly.
  • the batteries disclosed in the embodiments of the present application can be used, but not limited to, in electric devices such as vehicles, ships or aircrafts.
  • the power supply system comprising the electric device such as the battery disclosed in the present application can be used, which is beneficial to avoid short circuit inside the battery and improve the stability of battery performance and battery life.
  • the embodiment of the present application provides an electric device using a battery as a power source.
  • the electric device can be, but not limited to, a mobile phone, a tablet, a notebook computer, an electric toy, an electric tool, a battery car, an electric car, a ship, a spacecraft, and the like.
  • electric toys may include fixed or mobile electric toys, such as game consoles, electric car toys, electric boat toys, electric airplane toys, etc.
  • spacecraft may include airplanes, rockets, space shuttles, spaceships, etc.
  • a vehicle 1000 as an electric device according to an embodiment of the present application is taken as an example for description.
  • FIG. 1 is a schematic structural diagram of a vehicle 1000 provided by some embodiments of the present application.
  • the vehicle 1000 can be a fuel vehicle, a gas vehicle or a new energy vehicle, and the new energy vehicle can be a pure electric vehicle, a hybrid vehicle or an extended-range vehicle.
  • the interior of the vehicle 1000 is provided with a battery 100 , and the battery 100 may be provided at the bottom, head or tail of the vehicle 1000 .
  • the battery 100 can be used for power supply of the vehicle 1000, for example, the battery 100 can be used as an operating power source of the vehicle 1000.
  • the vehicle 1000 may further include a controller 200 and a motor 300 , the controller 200 is used to control the battery 100 to supply power to the motor 300 , for example, for starting, navigating and running the vehicle 1000 .
  • the battery 100 can not only be used as an operating power source for the vehicle 1000 , but can also be used as a driving power source for the vehicle 1000 , replacing or partially replacing fuel oil or natural gas to provide driving power for the vehicle 1000 .
  • FIG. 2 is an exploded view of a battery 100 provided by some embodiments of the present application.
  • the battery 100 includes a case 10 and battery cells 20 housed in the case 10 .
  • the box body 10 is used to provide accommodating space for the battery cells 20 , and the box body 10 may adopt various structures.
  • the box body 10 may include a first part 11 and a second part 12, the first part 11 and the second part 12 cover each other, the first part 11 and the second part 12 jointly define a of accommodation space.
  • the second part 12 can be a hollow structure with one end open, the first part 11 can be a plate-like structure, and the first part 11 covers the opening side of the second part 12, so that the first part 11 and the second part 12 jointly define an accommodation space ;
  • the first part 11 and the second part 12 can also be hollow structures with one side opening, and the opening side of the first part 11 is covered by the opening side of the second part 12 .
  • the box body 10 formed by the first part 11 and the second part 12 can be in various shapes, such as a cylinder, a cuboid and the like.
  • the battery 100 there may be multiple battery cells 20 , and the multiple battery cells 20 may be connected in series, in parallel or in parallel.
  • the mixed connection means that the multiple battery cells 20 are connected in series and in parallel.
  • a plurality of battery cells 20 can be directly connected in series, in parallel or mixed together, and then the whole composed of a plurality of battery cells 20 is housed in the box 10; of course, the battery 100 can also be a plurality of battery cells 20
  • the battery modules are firstly connected in series or parallel or in combination, and then multiple battery modules are connected in series or in parallel or in combination to form a whole, which is accommodated in the case 10 .
  • the battery 100 may also include other structures, for example, the battery 100 may also include a bus component for realizing electrical connection between multiple battery cells 20 .
  • each battery cell 20 may be a secondary battery or a primary battery; it may also be a lithium-sulfur battery, a sodium-ion battery or a magnesium-ion battery, but not limited thereto.
  • the battery cell 20 may be in the form of a cylinder, a flat body, a cuboid or other shapes.
  • FIG. 3 is a schematic diagram of an exploded structure of a battery cell 20 provided in some embodiments of the present application.
  • the battery cell 20 refers to the smallest unit constituting a battery.
  • the battery cell 20 includes an end cap 21 , an insulator 22 , a current collecting assembly 23 , a casing 24 , an electrode assembly 25 , an electrolyte (not shown in the figure) and other functional components.
  • the end cap 21 refers to a component that covers the opening of the casing 24 to isolate the internal environment of the battery cell 20 from the external environment.
  • the shape of the end cap 21 can be adapted to the shape of the housing 24 to fit the housing 24 .
  • the end cap 21 can be made of a material (such as aluminum alloy) with a certain hardness and strength, so that the end cap 21 is not easy to deform when being squeezed and collided, so that the battery cell 20 can have a higher Structural strength and safety performance can also be improved.
  • the end cover 21 may also be provided with a pressure relief mechanism for releasing the internal pressure when the internal pressure or temperature of the battery cell 20 reaches a threshold value.
  • the material of the end cap 21 can also be various, for example, copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc., which is not particularly limited in this embodiment of the present application.
  • Electrodes 21 a are provided on the end cap 21 .
  • the electrode terminal 21 a may be used to be electrically connected with the electrode assembly 25 for outputting or inputting electric energy of the battery cell 20 .
  • the end cover 21 may also be provided with a pressure relief mechanism for releasing the internal pressure when the internal pressure or temperature of the battery cell 20 reaches a threshold value.
  • the material of the end cap 21 can also be various, for example, copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc., which is not particularly limited in this embodiment of the present application.
  • the insulator 22 is located inside the end cover 21 , and the insulator 22 can be used to isolate the electrical connection components in the housing 24 from the end cover 21 to reduce the risk of short circuit.
  • the insulating member 22 may be plastic, rubber or the like.
  • the current collecting assembly 23 is located on the side of the insulator 22 away from the end cap 21, and the current collecting assembly 23 is used to electrically connect the electrode terminal 21a to the electrode assembly 25, so as to transmit electric energy from the electrode assembly 25 to the electrode terminal 21a, and through the electrode terminal 21a delivered to the outside of the electrode assembly 25 .
  • the casing 24 is a component used to cooperate with the end cap 21 to form the internal environment of the battery cell 20 , wherein the formed internal environment can be used to accommodate the electrode assembly 25 , electrolyte and other components.
  • the casing 24 and the end cap 21 may be independent components, and an opening may be provided on the casing 24 , and the internal environment of the battery cell 20 is formed by making the end cap 21 cover the opening at the opening.
  • the end cover 21 and the housing 24 can also be integrated. Specifically, the end cover 21 and the housing 24 can form a common connection surface before other components are inserted into the housing. When the inside of the housing 24 needs to be encapsulated , then make the end cover 21 cover the housing 24.
  • Housing 24 can be of various shapes and various sizes, such as cuboid, cylinder, hexagonal prism, etc. Specifically, the shape of the casing 24 can be determined according to the specific shape and size of the electrode assembly 25 .
  • the housing 24 can be made of various materials, such as copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc., which is not particularly limited in this embodiment of the present application.
  • the electrode assembly 25 is a part where an electrochemical reaction occurs in the battery cell 20 .
  • One or more electrode assemblies 25 may be contained within the housing 24 .
  • the electrode assembly 25 is mainly formed by winding or stacking positive electrode sheets and negative electrode sheets, and a separator 256 is usually provided between the positive electrode sheets and the negative electrode sheets.
  • the positive electrode sheet has a positive electrode current collector 251 with a positive electrode active material on its surface
  • the negative electrode sheet has a negative electrode current collector 253 with a negative active material on its surface
  • the current collector 253 together constitutes the main body of the electrode assembly 25
  • the positive electrode tab 252 and the negative electrode tab 255 are electrically connected to the corresponding positive electrode current collector 251 and the negative electrode current collector 253 respectively and have no active material on the surface.
  • the positive pole tab 252 and the negative pole tab 255 can be located at one end of the main body together or at two ends of the main body respectively.
  • the positive electrode active material and the negative electrode active material react with the electrolyte, and the tab 23 a is connected to the electrode terminal 21 a to form a current loop.
  • the thermal conductivity of the negative tab 255 is ⁇ 380W/m.k.
  • FIG. 4 is obtained by unrolling the wound electrode assembly 25 .
  • FIG. 4 is a schematic structural view of the above-mentioned electrode assembly 25 after unrolling.
  • the separator 256 has a separator edge region 257.
  • the edge of the separator 256 is the long edge of the separator 256 close to the negative electrode tab 255 with a thermal conductivity ⁇ 380 W/m.k.
  • the edge at this time is the edge of the separator 256 close to the negative electrode tab 255 with a thermal conductivity ⁇ 380 W/m.k.
  • the negative electrode sheet has a tab region 258.
  • the diaphragm 256 faces and extends out of the negative electrode current collector 253 and is used to attach an edge to the negative electrode tab 255 as the diaphragm edge region 257.
  • a coating 259 containing phase change microcapsules is applied to the edge region 257 of the membrane.
  • the end of the diaphragm 256 protruding from the negative pole tab 255 is the first end, and the other end opposite to the first end
  • the diaphragm 256 extends from the first end to the second end, and the width here refers to the distance extending from the first end of the diaphragm 256 in the above-mentioned extending direction.
  • the tab region 258 includes the diaphragm edge region 257, coating 259 and negative electrode
  • the tab 255 and the coating 259 of the tab area 258 are located directly under the tab 255 of the negative electrode, and the tab 255 of the negative electrode is bonded to the edge area 257 of the diaphragm through the coating 259 .
  • the coating 259 may have a thickness of 25-35 ⁇ m, specifically 30 ⁇ m.
  • the negative electrode tab 255 of the flattened negative electrode area is laser welded to the current collecting assembly 23. Since the laser is shot downward from the top of the current collecting assembly 23, the current collecting assembly 23 and the negative electrode tab 255 are welded together. At this time, the heat will be transferred from the current collecting assembly 23 to the negative electrode tab 255 , and then the negative electrode tab 255 will transfer the heat to the coating 259 and be absorbed by the coating 259 , thereby protecting the diaphragm edge area 257 located at the tab area 258 .
  • the present application provides a phase change microcapsule, which includes: a core material and an insulating and heat-conducting wall material wrapping the core material.
  • the core material includes a first phase-change component and a second phase-change component.
  • the first phase-change component is paraffin wax with a melting point of 37-42°C
  • the second phase-change component is paraffin wax with a melting point of 65-75°C.
  • the insulating heat-conducting wall The melting point of the material is greater than 75°C.
  • the mass ratio of the first phase change component to the second phase change component is 35:45-77.
  • the core material refers to the content encapsulated in the insulating and heat-conducting wall material.
  • the phase-change microcapsules provided by the present application have a core-shell structure.
  • the wall material When applied to a battery, the wall material is insulated under the working conditions of the battery, that is, it has a good resistivity, for example, the resistivity is 1013 ⁇ cm- 1014 ⁇ cm, so that the phase change microcapsule coating has an excellent insulating effect as a whole.
  • the wall material has a good thermal conductivity, for example, the thermal conductivity is 0.22W/mK or higher than 0.22W/mK, etc., so that the phase change microcapsules have a good heat absorption effect, and the heat generated during the welding of the current collecting components can be promptly removed Absorption, to achieve the purpose of preventing the diaphragm from being scalded.
  • the wall material is inert under the working state of the battery and does not react with the electrolyte.
  • the melting point of the wall material is greater than 75°C, so that in the process of using laser welding to connect the tabs with a thermal conductivity ⁇ 380W/m.k and the current collector assembly, the core material that has undergone a phase change and is molten will not damage the insulating and heat-conducting wall material and flow out of it.
  • the core material includes the first phase-change component and the second phase-change component, and since the first phase-change component and the second phase-change component are both paraffin wax, they are convenient to mix uniformly.
  • the first phase change component is paraffin wax with a melting point of 37-42°C
  • the second phase change component is paraffin wax with a melting point of 65-75°C. Both of them not only have good thermal phase transition performance, but also have relatively high endothermic values during the transition process.
  • the first phase-change component at a lower temperature first undergoes a phase change response quickly, Absorb enough heat to undergo phase change into a liquid state to buffer the temperature rise rate of the diaphragm and control the real-time temperature of the diaphragm, and then the second phase change component absorbs a large amount of heat to undergo a phase change to become a liquid state, further slowing down the temperature rise rate of the diaphragm and controlling the diaphragm
  • the real-time temperature that is, when the temperature is higher than the melting points of the first phase-change component and the second phase-change component, the first phase-change component and the second phase-change component change from solid to liquid.
  • first phase-change component and the second phase-change component are evenly distributed, they can be in a gradient melting state during the temperature rise as a whole, so that the real-time temperature of the diaphragm is always lower than that of the diaphragm being scalded. minimum temperature while the core material is entirely sealed in a chemically inert wall material.
  • the proportion of the first phase change component and the second phase change component affects the temperature rise rate and temperature of the diaphragm when the current collector assembly is welded.
  • the proportion of the first phase change component and the second phase change component is reasonable. Under the premise of avoiding the rapid heating rate of the diaphragm, it is ensured that the overall heat absorption capacity of the core material is good, thereby effectively reducing the temperature of the diaphragm. If the proportion of the first paraffin component is too high, the overall heat absorption capacity of the core material will be insufficient, causing the real-time temperature of the diaphragm to be higher than the minimum temperature of its burn.
  • phase change response time of the phase change component is short, so that before the phase change response of the second phase change component, the diaphragm heats up rapidly and its real-time temperature impacts to a minimum temperature higher than its scalding temperature, which may cause the diaphragm to be scalded.
  • the mass ratio of the first phase change component to the second phase change component is 35:45, 35:47, 35:50, 35:55, 35:60, 35:65, 35:70, 35 Any ratio of :75, 35:77 or between any two ratios.
  • the first phase change component can be one of the specific paraffins with a melting point of 37-42°C, or a melting point of 37-42°C
  • a mixture of at least two specific paraffin waxes in any ratio can be used similarly to obtain the composition of the second phase change component, which is not limited here.
  • the paraffin used in the first phase-change component has a structural formula: CnH2n+2, where 18 ⁇ n ⁇ 21; the paraffin used in the second phase-change component has a structural formula: Cn 'H2n'+2, where 25 ⁇ n' ⁇ 28.
  • the mass ratio of the wall material to the core material is 1:3-4.
  • the mass ratio of the wall material to the core material is any one of 1:3, 1:3.3, 1:3.5, 1:3.7, 1:3.9, 1:4 or between any two between the ratios.
  • the thickness of the wall material can be limited by using the above-mentioned ratio, and the stability of the phase-change microcapsule can be improved.
  • the thermally conductive wall material includes a base material and ceramic particles dispersed in the base material, and the base material is a polymer.
  • Ceramic particles are particles made of ceramic materials with high temperature resistance and thermal conductivity.
  • the material of ceramic particles includes but not limited to at least one of boron nitride, silicon nitride, silicon carbide, silicon dioxide, and the like.
  • the polymer is more compatible with paraffin and is insulating.
  • the polymer includes phenolic resin, that is, the polymer includes but is not limited to phenolic resin, and can also be polyacrylonitrile resin, melamine formaldehyde resin, and phenolic resin polymer. any kind.
  • the wall material not only has better insulation, but the introduction of ceramic particles can not only make the wall material have better high temperature resistance, but also facilitate the core material to absorb the heat generated when the current collecting assembly is welded in time. On the other hand, it can avoid excessive shrinkage of the part where the diaphragm is in contact with the negative pole piece during welding. And the setting of the polymer as the base material ensures good compatibility between the wall material and the paraffin, can form a stable interface with it, and improves the thermal stability of the phase change microcapsules.
  • the polymer is phenolic resin.
  • the base material of the above material has better compatibility with paraffin wax, and also facilitates the uniform dispersion of ceramic particles, ensuring the stability of the phase change microcapsules.
  • the mass ratio of the substrate to the ceramic particles is 3:4-5, and the mass ratio of the substrate to the core material is 1:2-3.
  • the mass ratio of substrate to ceramic particles is any one of 3:4, 3:4.3, 3:4.5, 3:4.6, 3:4.9, 3:5 or between any two
  • the mass ratio of base material to core material is any ratio of 1:2, 1:2.3, 1:2.5, 1:2.7, 1:2.9, 1:3 or between any two ratios .
  • phase change microcapsules can be ensured by controlling the dosage of the base material, ceramic particles and core material within the above range, so that it can protect the diaphragm against the instantaneous high temperature during welding.
  • the ceramic particles are silicon dioxide particles.
  • the use of silica particles has excellent high temperature resistance, insulation and thermal conductivity, which can improve the high temperature resistance, insulation and thermal conductivity of wall materials, improve the stability and heat absorption capacity of phase change microcapsules when welding current collecting components, and also have Abundant sources and easy access to other advantages.
  • the particle size of the silica particles is 60-90 nm.
  • the particle diameter here refers to the average particle diameter of silica particles.
  • the particle diameter of the silica particles is any value among 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 83 nm, 85 nm, 90 nm or between any two values.
  • the above-mentioned silica particles with a specific particle size are conducive to doping and uniform dispersion in the substrate.
  • the particle diameter of the phase-change microcapsules is 0.5-4 ⁇ m, where the particle diameter is the average particle diameter of the phase-change microcapsules.
  • the phase-change microcapsules of this specification facilitate the formation of a coating on the edge of the lug and the diaphragm, which effectively prevents the edge of the diaphragm mated with the lug from being scalded when the lug and the current collecting assembly are welded by laser.
  • phase change microcapsules can be obtained by in-situ polymerization method, so that the wall material covers the core material.
  • the in-situ polymerization method is: one or more mixtures of phase change materials can be dispersed in water under the action of an emulsifier to form an oil-in-water emulsion, and one or more A water-soluble monomer or low-molecular-weight prepolymer aqueous solution of resin, adjust the stirring speed, reaction temperature, pH, etc. of the system to undergo polycondensation reaction, and further remove small molecules (such as water molecules) between the prepolymer molecules to generate at the interface of the emulsion
  • the non-water-soluble polycondensate with cross-linked three-dimensional network structure forms phase-change microcapsules encapsulated with phase-change materials.
  • the preparation method of phase change microcapsules comprises the following steps:
  • the ceramic particles are dispersed in water to form an aqueous phase.
  • first phase change component and the second phase change component are mixed, they are heated to a molten state to form an oil phase.
  • the preparation method of phase change microcapsules comprises the following steps:
  • the ceramic particles are dispersed in water to form an aqueous phase.
  • the mixture After mixing the first phase-change component, the second phase-change component, the synthetic monomer of the polymer, the cross-linking agent and the initiator, the mixture is heated to a molten state to form an oil phase.
  • the in-situ polymerization method is used to form a polymer on the surface of the core material, which can ensure that the wall material is wrapped around the core material to form a core-shell structure, and it is easy to obtain the first phase change component and the second phase change component that are uniformly mixed and wrapped in the wall material components, and the preparation method is controllable, and large-scale production can be carried out.
  • phase-change microcapsule powder can be obtained by drying, which is convenient for storage and transportation.
  • the binder can be mixed to form a slurry. If it is necessary to use phase change microcapsules, after the polymer is formed on the surface of the core material by in-situ polymerization, it can be directly added to the phase change microcapsule emulsion formed after polymerization without drying. Add the binder directly, mix to form a slurry and use it.
  • binder is used to fix the phase change microcapsules on the diaphragm or tab.
  • Binders include but are not limited to water-based styrene-butadiene rubber (SBR) binders, sodium carboxymethylcellulose (CMC), for example, the binder is a separate SBR binder, or the mass ratio is 3:6- 8 CMC, SBR mixture.
  • SBR styrene-butadiene rubber
  • CMC sodium carboxymethylcellulose
  • the application provides a diaphragm, the edge of the diaphragm is provided with a coating, and the coating contains phase change microcapsules.
  • the edge of the separator at this time is the long edge of the separator close to the tab with a thermal conductivity ⁇ 380W/m.k.
  • the edge at this time is the edge of the diaphragm close to the tab with a thermal conductivity ⁇ 380W/m.k.
  • the coating includes a substrate and phase change microcapsules dispersed in the substrate.
  • the substrate refers to a material that can disperse the aforementioned phase change microcapsules, and can form a film and be attached to the surface of the diaphragm, such as a binder, such as an SBR binder and/or CMC, etc.
  • the SBR binder It has excellent thermal stability, and both SBR binder and CMC have strong compatibility with phase change capsules.
  • the diaphragm material includes but is not limited to polypropylene (polypropylene, PP) or polyethylene (polyethylene, PE), which can be selected according to actual needs, and is not limited here.
  • the coating completely covers the edge of the diaphragm at this time, where the full tab refers to the edge of the current collector as the tab.
  • the tab with a thermal conductivity ⁇ 380W/m.k is a tab of a single tab or a multi-tab tab
  • the coating can completely cover the edge of the diaphragm at this time, so that after the tab is bent, the coating can completely Isolate the diaphragm and the tab, or the coating is only provided on the part corresponding to the edge and the tab, or the coating can be used to completely isolate the diaphragm and the tab, where a single tab means that there is only one tab on each pole piece. Come out as a diversion. Multi-tab means that each pole piece has at least two tabs sticking out as a guide.
  • the thickness of the coating is 10-35 ⁇ m, optionally 10-20 ⁇ m, and optionally 25-35 ⁇ m.
  • the thickness of the coating formed on the diaphragm is 10-20 ⁇ m.
  • the thickness of the coating formed on the separator is 25-35 ⁇ m, for example, the thickness of the coating is any value among 25 ⁇ m, 27 ⁇ m, 28 ⁇ m, 30 ⁇ m, 35 ⁇ m or between any two values.
  • the thickness of the above-mentioned coating is reasonable to ensure that the temperature and temperature rise rate of the diaphragm can be effectively adjusted, and at the same time, the size of the edge of the diaphragm is basically not affected.
  • the coating can be prepared in the following manner: mixing the phase-change microcapsules provided by the first aspect and the binder according to, for example, a mass ratio of 1:7-9 to form a coating slurry, and then coating The slurry is coated on the edge of the diaphragm and dried, or the binder is directly added to the phase change microcapsule emulsion formed after polymerization, for example, the CMC dry powder is added first, and the SBR emulsion is added after the CMC is completely dissolved, wherein the CMC The /SBR mass ratio is 3:7 to form a coating slurry, and then apply the coating slurry to the edge of the diaphragm and dry it at 70-80°C.
  • the present application provides a pole piece, the pole piece includes interconnected current collectors and tabs, the thermal conductivity of the tabs is ⁇ 380W/m.k, and at least one side of the tabs is provided with The coating, the coating contains the phase change microcapsules provided in the first aspect of the application.
  • the coating includes a substrate and phase change microcapsules dispersed in the substrate.
  • the substrate refers to a material that can disperse the aforementioned phase change microcapsules, and can form a film and be attached to the surface of the diaphragm, such as a binder, such as an SBR binder, which has excellent thermal stability and strong compatibility with phase change capsules.
  • the coating can extend from the tab to the current collector.
  • the length of the diaphragm protruding from the tab is generally not more than 4mm, so optionally 1mm ⁇ the width of the coating on the tab ⁇ 4mm, and at the same time 0 ⁇ the width of the coating on the current collector ⁇ 4mm , that is, 4mm ⁇ total width of the coating ⁇ 8mm, where the coating width is the distance from the end of the coating close to the current collector to the end away from the current collector.
  • the thermal conductivity of the tab is ⁇ 380W/m.k, that is, the tab is a metal with high thermal conductivity, and the material of the tab can be copper, silver, silver-plated copper, etc.
  • the tab is made of copper.
  • the tabs and the current collector can be welded or integrally formed.
  • the pole piece may be a single-tab pole piece, a multi-tab pole piece or a full-tab pole piece, which is not limited here.
  • the thickness of the coating is 10-35 ⁇ m, optionally 10-20 ⁇ m, and optionally 25-35 ⁇ m.
  • the thickness of the coating formed on the tabs is 10-20 ⁇ m.
  • the thickness of the coating formed on the lug is 25-35 ⁇ m, for example, the thickness of the coating is any value among 25 ⁇ m, 27 ⁇ m, 28 ⁇ m, 30 ⁇ m, 35 ⁇ m or between any two values.
  • the thickness of the above-mentioned coating is reasonable, which can effectively adjust the temperature and temperature rise rate of the diaphragm, and at the same time basically does not affect the size of the edge position of the diaphragm matched with the tab.
  • the coating can be prepared in the following manner: mixing the phase-change microcapsules provided by the first aspect and the binder according to, for example, a mass ratio of 1:7-9 to form a coating slurry, and then coating The slurry is applied to the ear and then dried, or the binder is directly added to the phase-change microcapsule emulsion formed after polymerization, for example, the CMC dry powder is added first, and the SBR emulsion is added after the CMC is completely dissolved, wherein the CMC/ The SBR mass ratio is 3:7 to form a coating slurry, and then apply the coating slurry to the tab and dry it at 70-80°C.
  • the present application provides a battery, which includes a separator and a pole piece, the pole piece includes interconnected current collectors and tabs, and the thermal conductivity of the tabs is ⁇ 380W/m.k; the tabs There is a coating between the diaphragm and the coating formed on the lug and/or the diaphragm; the coating contains the phase change microcapsules provided by the first aspect of the application.
  • the coating absorbs the heat transferred from the tabs, reduces the heat transferred to the diaphragm and controls the temperature rise rate of the diaphragm. Ensure that the real-time temperature of the diaphragm is always lower than the minimum temperature that can be scalded during welding, so as to avoid internal short circuit caused by scalding the diaphragm.
  • the thickness of the coating between the diaphragm and the pole piece is 20-35 ⁇ m, for example, the thickness of the coating is any value in 20 ⁇ m, 25 ⁇ m, 28 ⁇ m, 30 ⁇ m, 32 ⁇ m, 35 ⁇ m or between any two values between.
  • the thickness of the above-mentioned coating is reasonable to ensure that the temperature and temperature rise rate of the diaphragm can be effectively adjusted, and at the same time, the size of the edge of the diaphragm is basically not affected.
  • the coating is only formed on one side of the tab, and is located between the tab and the diaphragm. At this time, the thickness of the coating is 20-35 ⁇ m.
  • the coating is only formed on the edge of the diaphragm, and is located between the tab and the diaphragm. At this time, the thickness of the coating is 20-35 ⁇ m.
  • the first coating is formed on the lug
  • the second coating is formed on the edge of the diaphragm
  • the first coating and the second coating are attached, wherein the thickness of the first coating is 10-20 ⁇ m, and the second coating is The thickness is 10-20 ⁇ m, and the total thickness of the first coating and the second coating is 20-35 ⁇ m.
  • the present application provides an example of an electric device equipped with a battery according to any of the above schemes.
  • the electric device may be any of the aforementioned devices or systems using batteries.
  • phase-change microcapsules, separators, pole pieces, batteries and electrical devices of the present application will be further described in detail below in conjunction with the examples.
  • phase change microcapsule it is made by following method:
  • the silica particles shown in Table 1 were dispersed in 100 g of water as an aqueous phase.
  • the melting point of the first phase-change material in Example 7 is 37°C/39°C, which refers to the mixture of paraffin wax with a melting point of 37°C and paraffin wax with a melting point of 39°C at a mass ratio of 1:1, and the melting point of the first phase-change material is 65°C.
  • °C/70°C means that it is obtained by mixing paraffin wax with a melting point of 65°C and paraffin wax with a melting point of 70°C in a mass ratio of 1:1.
  • Fig. 6 is a scanning electron micrograph of the phase-change microcapsules obtained in Example 1. According to Fig. 6, it can be seen that the particle size of the phase-change microcapsules is 0.5-4 ⁇ m.
  • Comparative Example 1 The only difference between Comparative Example 1 and Example 1 is that the core material in Example 1 is replaced by paraffin wax with a melting point of 40°C.
  • Comparative Example 2 The only difference between Comparative Example 2 and Example 1 is that the core material is only paraffin wax with a melting point of 70° C. instead of the core material in Example 1.
  • Comparative Example 3 The only difference between Comparative Example 3 and Example 1 is that the core material is only paraffin wax with a melting point of 52° C. instead of the core material in Example 1.
  • Comparative Example 4 The only difference between Comparative Example 4 and Example 1 is that the mass ratio of the first phase change component to the second phase change component is 35:80.
  • Comparative Example 5 The only difference between Comparative Example 5 and Example 1 is that the mass ratio of the first phase change component to the second phase change component is 50:45.
  • phase change microcapsule emulsion that embodiment 1-7 and comparative example 1-5 make, first add CMC dry powder shown in Table 2, after CMC dry powder dissolves, add SBR emulsion shown in Table 2, obtain slurry, slurry On the edge of the diaphragm of the same specification (the diaphragm size is: length 9310mm, width 128.5mm, material is PP, the width of the diaphragm edge is 8mm), dry, make the diaphragm edge and copper foil (as a tab, the thermal conductivity of copper foil is 400W/ (m*K)) There is a 20 ⁇ m-thick coating containing the above-mentioned phase-change microcapsules.
  • the side of the copper foil facing away from the diaphragm is fastened to the collector plate, and then the laser with the same parameters is used from the same specifications and materials.
  • the upper part of the current collecting plate is punched downward, and the current collecting plate and the copper foil are connected by laser welding (the light emitting time is 0.1s, and the instantaneous temperature of light is 1000°C). After welding, the diaphragm is unfolded, and the change of the side of the diaphragm facing away from the coating is observed.
  • comparative example 1-5 is identical with the SBR emulsion of embodiment 1, the addition amount of CMC dry powder.
  • phase change microcapsules provided by this application can be applied in the battery in the form of coating, so that the bent tabs and the separator are bonded and connected through the coating, and the above-mentioned specific melting point and specific ratio of the core material are used.
  • the first phase-change component and the second phase-change component cooperate with each other, so that when the tab laser welds the current collecting assembly, it can avoid scalding the separator and avoiding the internal short circuit of the battery.

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Abstract

本申请涉及一种相变微胶囊、隔膜、极片、电池和用电装置，属于电池领域。相变微胶囊包括：芯材以及包裹芯材的绝缘导热壁材。芯材包括第一相变组分以及第二相变组分，第一相变组分为熔点37-42℃的石蜡，第二相变组分为熔点65-75℃的石蜡，绝缘导热壁材的熔点大于75℃。第一相变组分与第二相变组分的质量比为35:45-77。将相变微胶囊以涂层的方式应用于电池中，使弯折后的极耳与隔膜经涂层贴合连接，利用芯材中特定熔点以及特定配比的上述特定的第一相变组分以及第二相变组分互相配合，使得极耳激光焊接集流组件时能够避免烫伤隔膜，避免电池内部短路。

Description

相变微胶囊、隔膜、极片、电池和用电装置
交叉引用
本申请要求享有于2021年10月12日提交的名称为“相变微胶囊、隔膜、极片、电池和用电装置”的第202111189223.3号中国专利申请的优先权，该申请的全部内容通过引入并入本文中。
技术领域
本申请涉及电池领域，具体而言，涉及一种相变微胶囊、隔膜、极片、电池和用电装置。
背景技术
在电池生产过程中，集流组件用于将电芯的极耳和电极端子电连接，以将电能从电极组件输送至电极端子，经电极端子输送至电芯的外部；多个电芯之间通过汇流部件实现电连接，以实现多个电芯的串联、并联或者混联。
但实际发现采用激光焊接集流组件后，电池内部容易造成短路。
发明内容
本申请提供了一种相变微胶囊、隔膜、极片、电池和用电装置，其能够避免电池内部容易造成短路的技术问题。
本申请的实施例是这样实现的：
在第一方面，本申请示例提供了一种相变微胶囊，其包括：芯材以及包裹芯材的绝缘导热壁材。
芯材包括第一相变组分以及第二相变组分，第一相变组分为熔点37-42℃的石蜡，第二相变组分为熔点65-75℃的石蜡，绝缘导热壁材的熔点大于75℃。
第一相变组分与第二相变组分的质量比为35:45-77。
本申请的技术方案的有益效果包括：
本申请中，提供具有核壳结构的相变微胶囊，将其以涂层的方式应用于电池，例如锂电池中，使锂电池的负极极耳与隔膜经涂层贴合连接，利用芯材中特定熔点第一相变组分以及第二相变组分以特定配比互相配合，使得极耳与集流组件焊接时，第一相变组分发生相变并快速吸收热量，缓冲隔膜温升速率，避免在第二相变组分发生相变前隔膜瞬时温度高于其被烫伤的最低温度，并且在保持隔膜瞬时温度低于其被烫伤的最低温度的前提下使第二相变组分相变以持续吸收大量热量，避免隔膜在激光焊接后期因温度过高被烫伤，同时绝缘导热壁材的熔点大于75℃，也可避免芯材相变时破坏绝缘导热壁材，从绝缘导热壁材中流出。
也即是，第一相变组分以及第二相变组分互相配合，能够吸收焊接热量并能够呈梯度熔融，从而控制隔膜的温升速率以及隔膜的温度，保证焊接时隔膜实时温度始终低于其能够被烫伤的最小温度，以避免因烫伤隔膜导致的电池内部短路。
在一些示例性的实施例中，第一相变组分采用的石蜡的结构式为：CnH2n+2，其中18≤n≤21；第二相变组分采用的石蜡的结构式为：Cn’H2n’+2，其中25≤n’≤28。
上述技术方案的有益效果包括：上述特定结构式的石蜡能较好地满足熔点要求，还具有来源丰富等优势。
在一些示例性的实施例中，绝缘导热壁材包括基材以及分散于基材中的陶瓷颗粒，基材为聚合物。
上述技术方案的有益效果包括：壁材中的陶瓷颗粒的引入，一方面可使壁材具有更佳 的耐高温性，同时也利于芯材及时将集流组件焊接时产生的热量吸收，另一方面可避免焊接时隔膜与负极极片接触的部分过度收缩。
可选地，聚合物包括酚醛树脂。
在一些示例性的实施例中，相变微胶囊中，壁材与芯材的质量比为1:3-4。
上述技术方案的有益效果包括：合理控制壁材以及芯材的配比范围，在相变微胶囊的粒径满足使用需求的条件下可控制壁材的厚度，保证壁材厚度合理，保证使用时相变微胶囊的稳定性，使其能够针对焊接时的瞬时高温，起到保护隔膜的功能。
在一些示例性的实施例中，相变微胶囊中，基材与陶瓷颗粒的质量比为3:4-5，且基材与芯材质量比为1:2-3。
上述技术方案的有益效果包括：将基材、陶瓷颗粒、芯材的用量控制在上述范围可以保证相变微胶囊的稳定性，使其能够针对焊接时的瞬时高温，起到保护隔膜的功能。
在一些示例性的实施例中，陶瓷颗粒包括二氧化硅颗粒。
上述技术方案的有益效果包括：二氧化硅颗粒具有优异的耐高温、绝缘以及导热性能，可提高壁材的耐高温、绝缘以及导热性能，提高焊接集流组件时相变微胶囊的稳定性以及吸热能力，同时还具有来源丰富且容易获得等优势。
在一些示例性的实施例中，二氧化硅颗粒的粒径为60-90nm。
上述技术方案的有益效果包括：上述特定粒径的二氧化硅颗粒有利于掺杂并均匀分散于基材中。
在一些示例性的实施例中，相变微胶囊的粒径为0.5-4μm。
上述技术方案的有益效果包括：相变微胶囊具有合适的粒径，便于形成涂层，有效避免焊接集流组件时位于负极侧的隔膜边缘被烫伤。
在第二方面，本申请示例提供了一种隔膜，隔膜的边缘设有涂层，涂层含有本申请第一方面提供的相变微胶囊。
上述技术方案的有益效果包括：将上述隔膜应用于电池时，使隔膜边缘的涂层与导热系数≥380W/m.k的极耳对应，此时在焊接集流组件时涂层可吸收极耳传递的热量，保证焊接时隔膜实时温度始终低于其能够被烫伤的最小温度，以避免因烫伤隔膜导致的电池内部短路，并且由于涂层主要位于隔膜的边缘，因此基本不影响隔膜本身的性能。
在一些示例性的实施例中，涂层的厚度为10-35μm，可选为10-20μm,可选为25-35μm。
上述技术方案的有益效果包括：涂层厚度合理，将上述隔膜应用于电池中时，在采用激光焊接极耳与集流组件时，不仅可以避免烫伤隔膜，同时基本不影响隔膜边缘位置的尺寸。
在第三方面，本申请示例提供了一种极片，极片包括互相连接的集流体以及极耳，极耳的导热系数≥380W/m.k，极耳的至少一侧面设有涂层，涂层含有本申请第一方面提供的相变微胶囊。
上述技术方案的有益效果包括：
由于极耳的导热系数≥380W/m.k，因此将其应用于电池中使含有相变微胶囊的涂层设置于极耳与隔膜之间，利用涂层避免隔膜和极耳直接接触。在焊接集流组件时，可以利用涂层吸收极耳传递的热量，使隔膜实时温度始终低于其能够被烫伤的最小温度，以避免因烫伤隔膜导致的内部短路。
在一些示例性的实施例中，涂层的厚度为10-35μm，可选为10-20μm,可选为25-35μm。
上述技术方案的有益效果包括：涂层厚度合理，在焊接集流组件时不仅可以避免与上述极耳配合的隔膜烫伤，同时基本不影响与极耳配合的隔膜边缘位置的尺寸。
在第四方面，本申请示例提供了一种电池，其包括隔膜以及极片，极片包括互相连接的集流体以及极耳。
极耳与隔膜之间具有涂层，涂层形成于极耳和/或形成于隔膜。
涂层含有本申请第一方面提供的相变微胶囊。
上述技术方案的有益效果包括：可在极耳与隔膜之间具有含有相变微胶囊的涂层，可在焊接集流组件时涂层吸收极耳传递的热量，保证焊接时隔膜实时温度始终低于其能够被烫伤的最小温度，以避免因烫伤隔膜导致的电池内部短路。
在一些示例性的实施例中，隔膜和极耳之间的涂层的厚度为20-35μm。
上述技术方案的有益效果包括：涂层厚度合理，在焊接集流组件时不仅可以避免与极耳配合的隔膜边缘被烫伤，同时基本不影响隔膜边缘位置的尺寸。
在第五方面，本申请示例提供了一种用电装置，其装配有本申请第四方面提供的电池。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本申请的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本申请一些实施例的车辆的结构示意图；
图2位本申请一些实施例的电池的分解结构示意图；
图3为本申请一些实施例的电池单体的分解结构示意图；
图4为一些实施例提供的卷绕的电极组件展开后的结构示意图；
图5为一些实施例提供的揉平后的负极区的结构示意图；
图6为实施例1提供的相变微胶囊的扫描电镜图；
图7为焊接后展开的实施例2-7提供的隔膜边缘区的照片；
图8为焊接后展开的实施例1以及对比例1-5提供的隔膜边缘区的照片；
在附图中，附图并未按照实际的比例绘制。
具体实施方式中的附图标号如下：
1000-车辆；
100-电池；200-控制器；300-马达；
10-箱体；11-第一部分；12-第二部分；
20-电池单体；21-端盖；21a-电极端子；22-绝缘件；23-集流组件；24-壳体；25-电极组件；
251-正极集流体；252-正极极耳；253-负极集流体；255-负极极耳；256-隔膜；257-隔膜边缘区；258-极耳区；259-涂层。
具体实施方式
下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同；本文中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请；本申请中术语“包括”和“具有”以及它们的任何变形，意图在于覆盖不排他的包含。
在本申请实施例的描述中，技术术语“第一”“第二”等仅用于区别不同对象，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量、特定顺序或主次关系。
在本申请实施例的描述中，术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。另外，本文中字符“/”，一般表示前后关联对象是一种“或”的关系。
在本申请实施例的描述中，术语“多种”指的是两种以上(包括两种)。
目前，从市场形势的发展来看，动力电池的应用越加广泛。动力电池不仅被应用于水力、火力、风力和太阳能电站等储能电源系统，而且还被广泛应用于电动自行车、电动摩托车、电动汽车等电动交通工具，以及军事装备和航空航天等多个领域。随着动力电池应用领域的不断扩大，其市场的需求量也在不断地扩增。
本发明人注意到，采用激光焊接集流组件后，电池内部容易造成短路，以锂离子电池为例，发明人进行研究发现，由于锂离子电池的负极极耳一般为厚度较薄的铜箔，其导热性能好，而激光焊接集流组件时由于瞬时温度很高，因此，导致隔膜与负极极耳接触的隔膜边缘出现孔洞、过度收缩等烫伤的情形，从而造成电池内部短路。
基于上述发现，发明人尝试在锂电池的负极极耳与隔膜贴合的边缘设置涂层，以隔绝二者，避免二者直接接触，并在涂层中应用相变材料以吸收激光焊接时传递至极耳的热量，以降低隔膜的温度，理论上而言，利用相变材料的相变吸热以降低隔膜的温度能够解决上述技术问题，但实际操作过程中发现，不同的相变材料的相变响应速度不同，而激光焊接出光时间一般为0.1s，出光瞬时温度可达1000℃，致使虽然隔膜的最终温度低于其被烫伤所需的最低温度，但是在相变过程中，由于相变材料无法快速相变响应，导致隔膜瞬时温度大于其被烫伤所需的最低温度，隔膜依然存在被烫伤的问题。
基于此，申请人提供了一种相变微胶囊，将其设置于隔膜的边缘和/或极耳的至少一侧面，装配成电池单体并应用于电池中，在导热系数≥380W/m.k的极耳和集流组件经激光焊接以连接在一起的过程中，利用相变微胶囊中特定配比且熔点不同的第一相变组分以及第二相变组分的配合，实现第一相变组分以及第二相变组分的梯度熔融，从而控制隔膜的温升速率以及隔膜的实时温度，可有效避免因激光焊接集流组件时导致隔膜被烫伤，导致电芯内部短路的问题。
本申请实施例公开的电池可以但不限用于车辆、船舶或飞行器等用电装置中。可以使用具备本申请公开的电池等组成该用电装置的电源系统，这样，有利于避免电池内部短路，提升电池性能的稳定性和电池寿命。
本申请实施例提供一种使用电池作为电源的用电装置，用电装置可以为但不限于手机、平板、笔记本电脑、电动玩具、电动工具、电瓶车、电动汽车、轮船、航天器等等。其中，电动玩具可以包括固定式或移动式的电动玩具，例如，游戏机、电动汽车玩具、电动轮船玩具和电动飞机玩具等等，航天器可以包括飞机、火箭、航天飞机和宇宙飞船等等。
以下实施例为了方便说明，以本申请一实施例的一种用电装置为车辆1000为例进行说明。
请参照图1，图1为本申请一些实施例提供的车辆1000的结构示意图。车辆1000可以为燃油汽车、燃气汽车或新能源汽车，新能源汽车可以是纯电动汽车、混合动力汽车或增程式汽车等。车辆1000的内部设置有电池100，电池100可以设置在车辆1000的底部或头部或尾部。电 池100可以用于车辆1000的供电，例如，电池100可以作为车辆1000的操作电源。车辆1000还可以包括控制器200和马达300，控制器200用来控制电池100为马达300供电，例如，用于车辆1000的启动、导航和行驶时的工作用电需求。
在本申请一些实施例中，电池100不仅可以作为车辆1000的操作电源，还可以作为车辆1000的驱动电源，代替或部分地代替燃油或天然气为车辆1000提供驱动动力。
请参照图2，图2为本申请一些实施例提供的电池100的爆炸图。电池100包括箱体10和电池单体20，电池单体20容纳于箱体10内。其中，箱体10用于为电池单体20提供容纳空间，箱体10可以采用多种结构。在一些实施例中，箱体10可以包括第一部分11和第二部分12，第一部分11与第二部分12相互盖合，第一部分11和第二部分12共同限定出用于容纳电池单体20的容纳空间。第二部分12可以为一端开口的空心结构，第一部分11可以为板状结构，第一部分11盖合于第二部分12的开口侧，以使第一部分11与第二部分12共同限定出容纳空间；第一部分11和第二部分12也可以是均为一侧开口的空心结构，第一部分11的开口侧盖合于第二部分12的开口侧。当然，第一部分11和第二部分12形成的箱体10可以是多种形状，比如，圆柱体、长方体等。
在电池100中，电池单体20可以是多个，多个电池单体20之间可串联或并联或混联，混联是指多个电池单体20中既有串联又有并联。多个电池单体20之间可直接串联或并联或混联在一起，再将多个电池单体20构成的整体容纳于箱体10内；当然，电池100也可以是多个电池单体20先串联或并联或混联组成电池模块形式，多个电池模块再串联或并联或混联形成一个整体，并容纳于箱体10内。电池100还可以包括其他结构，例如，该电池100还可以包括汇流部件，用于实现多个电池单体20之间的电连接。
其中，每个电池单体20可以为二次电池或一次电池；还可以是锂硫电池、钠离子电池或镁离子电池，但不局限于此。电池单体20可呈圆柱体、扁平体、长方体或其它形状等。
请参照图3，图3为本申请一些实施例提供的电池单体20的分解结构示意图。电池单体20是指组成电池的最小单元。如图3，电池单体20包括有端盖21、绝缘件22、集流组件23、壳体24、电极组件25、电解液(图未示)以及其他的功能性部件。
端盖21是指盖合于壳体24的开口处以将电池单体20的内部环境隔绝于外部环境的部件。不限地，端盖21的形状可以与壳体24的形状相适应以配合壳体24。可选地，端盖21可以由具有一定硬度和强度的材质(如铝合金)制成，这样，端盖21在受挤压碰撞时就不易发生形变，使电池单体20能够具备更高的结构强度，安全性能也可以有所提高。在一些实施例中，端盖21上还可以设置有用于在电池单体20的内部压力或温度达到阈值时泄放内部压力的泄压机构。端盖21的材质也可以是多种的，比如，铜、铁、铝、不锈钢、铝合金、塑胶等，本申请实施例对此不作特殊限制。
端盖21上设置有如电极端子21a等的功能性部件。电极端子21a可以用于与电极组件25电连接，以用于输出或输入电池单体20的电能。在一些实施例中，端盖21上还可以设置有用于在电池单体20的内部压力或温度达到阈值时泄放内部压力的泄压机构。端盖21的材质也可以是多种的，比如，铜、铁、铝、不锈钢、铝合金、塑胶等，本申请实施例对此不作特殊限制。
绝缘件22位于端盖21的内侧，绝缘件22可以用于隔离壳体24内的电连接部件与端盖21，以降低短路的风险。示例性的，绝缘件22可以是塑料、橡胶等。
集流组件23位于绝缘件22远离端盖21的一侧，集流组件23用于将电极端子21a与电极组件25电连接，以将电能从电极组件25输送至电极端子21a，经电极端子21a输送至电极组件25的外部。
壳体24是用于配合端盖21以形成电池单体20的内部环境的组件，其中，形成的内部环境可以用于容纳电极组件25、电解液以及其他部件。壳体24和端盖21可以是独立的部件，可以于壳体24上设置开口，通过在开口处使端盖21盖合开口以形成电池单体20的内部环境。不限地，也可以使端盖21和壳体24一体化，具体地，端盖21和壳体24可以在其他部件入壳前先形成一个共同的连接面，当需要封装壳体24的内部时，再使端盖21盖合壳体24。壳体24可以是多种 形状和多种尺寸的，例如长方体形、圆柱体形、六棱柱形等。具体地，壳体24的形状可以根据电极组件25的具体形状和尺寸大小来确定。壳体24的材质可以是多种，比如，铜、铁、铝、不锈钢、铝合金、塑胶等，本申请实施例对此不作特殊限制。
电极组件25是电池单体20中发生电化学反应的部件。壳体24内可以包含一个或更多个电极组件25。
参阅图4以及图5，电极组件25主要由正极片和负极片卷绕或层叠放置形成，并且通常在正极片与负极片之间设有隔膜256。正极片具有表面设有正极活性物质的正极集流体251，负极片具有表面设有负极活性物质的负极集流体253，涂覆有正极活性物质的正极集流体251和涂覆有负极活性物质的负极集流体253共同构成电极组件25的主体部，正极极耳252和负极极耳255分别与对应的正极集流体251和负极集流体253电连接且表面不具有活性物质。
正极极耳252和负极极耳255可以共同位于主体部的一端或是分别位于主体部的两端。在电池100的充放电过程中，正极活性物质和负极活性物质与电解液发生反应，极耳23a连接电极端子21a以形成电流回路。
以电池单体20为锂离子电池为例，可选地，负极极耳255的导热系数≥380W/m.k。
将卷绕的电极组件25展开获得图4，图4为上述电极组件25展开后的结构示意图。隔膜256具有隔膜边缘区257，实际使用过程中，当隔膜256应用于卷绕电池时，此时隔膜256的边缘为隔膜256靠近导热系数≥380W/m.k的负极极耳255的长边边缘。当隔膜256应用于叠片电池时，此时边缘为隔膜256靠近导热系数≥380W/m.k负极极耳255的边缘。
根据图4，负极片具有极耳区258，极耳区258在未揉弯前，隔膜256面向并伸出负极集流体253并用于与负极极耳255贴合的一边缘作为隔膜边缘区257，在隔膜边缘区257涂敷含有相变微胶囊的涂层259。
由于隔膜256伸出极耳的长度不超过4mm，因此，4mm≤隔膜边缘区257的宽度≤8mm，以隔膜256伸出负极极耳255的一端为第一端，与第一端相对的另一端作为第二端，隔膜256自第一端向第二端延伸所得，此处的宽度是指自隔膜256第一端开始在上述延伸方向上延伸的距离。
将隔膜边缘区257与负极极耳255同时揉弯，获得如图5所示的揉平后的负极区的结构示意图，根据图5，极耳区258包括隔膜边缘区257、涂层259以及负极极耳255，极耳区258的涂层259位于负极极耳255的正下方，且负极极耳255经涂层259与隔膜边缘区257贴合。
其中涂层259的厚度可为25-35μm，具体例如为30μm。
此时，将揉平后的负极区的负极极耳255与集流组件23激光焊接，由于激光从集流组件23正上方向下打出，使集流组件23与负极极耳255焊接到一起，此时热量将由集流组件23传递至负极极耳255，然后负极极耳255将热量传递到涂层259被涂层259吸收，从而保护位于极耳区258的隔膜边缘区257。
根据本申请的一些实施例，本申请提供了一种相变微胶囊，其包括：芯材以及包裹芯材的绝缘导热壁材。芯材包括第一相变组分以及第二相变组分，第一相变组分为熔点37-42℃的石蜡，第二相变组分为熔点65-75℃的石蜡，绝缘导热壁材的熔点大于75℃。第一相变组分与第二相变组分的质量比为35:45-77。
其中，芯材是指封装于作为绝缘导热壁材内的内容物。
本申请提供的相变微胶囊为核壳结构，在应用于电池中时，壁材在电池的工作条件下是绝缘的，也即是其具有良好的电阻率，例如电阻率为1013Ω·cm-1014Ω·cm，从而使相变微胶囊涂层整体上具有优良的绝缘效果。壁材具有良好的导热系数，例如导热系数为0.22W/mK或高于0.22W/mK等，从而可以使相变微胶囊具有良好的吸热效果，能及时将集流组件焊接时产生的热量吸收，达到防止隔膜烫伤的目的，同时壁材在电池工作状态下是惰性的，不与电解液等发生反应。同时壁材的熔点大于75℃，从而在采用激光焊接连接导热系数≥380W/m.k的极耳以及集流组件的 过程中，已发生相变呈熔融状的芯材不会破坏绝缘导热壁材并从其中流出。
芯材包括第一相变组分以及第二相变组分，由于第一相变组分以及第二相变组分均为石蜡，因此便于混合均匀。第一相变组分为熔点37-42℃的石蜡，第二相变组分为熔点65-75℃的石蜡，二者不仅均具有良好的热相转变性能，且转变过程中吸热值较高，并且第一相变组分的最高熔点显著低于第二相变组分的最低熔点，使得激光焊接集流组件时，较低温度的第一相变组分先快速发生相变响应，吸取足够的热量进行相变成为液态，以缓冲隔膜的温升速率以及控制隔膜实时温度，然后第二相变组分吸收大量热量进行相变以成为液态，进一步减缓隔膜的温升速率以及控制隔膜的实时温度，也即是当温度高于第一相变组分和第二相变组分的熔点时，第一相变组分和第二相变组分从固态转变为液态。由于第一相变组分和第二相变组分均匀分布，因此可以使二者整体上在温度升高的过程中，会呈梯度熔融态，以控制隔膜的实时温度始终小于隔膜被烫伤的最小温度，同时芯材整体上会密封于化学惰性的壁材中。
第一相变组分和第二相变组分的配比影响集流组件焊接时隔膜的温升速率和温度，上述第一相变组分和第二相变组分的配比合理，在避免隔膜升温速率偏快的前提下，保证芯材整体吸热能力佳，从而有效降低隔膜温度。若第一石蜡组分占比偏高，会造成芯材整体吸热能力不足，导致隔膜实时温度高于其烫伤的最低温度，若第一石蜡组分占比偏低，则留给第二相变组分相变响应时间短，以使第二相变组分相变响应前，导致隔膜快速升温且其实时温度冲击至高于其烫伤的最低温度，可造成隔膜烫伤。
可选地，第一相变组分与第二相变组分的质量比为35:45、35:47、35:50、35:55、35:60、35:65、35:70、35:75、35:77中的任一比值或介于任意两个比值之间。
其中，需要说明的是，熔点37-42℃的石蜡有多种，第一相变组分可以为其中一种熔点在37-42℃内的具体石蜡，也可以为熔点分别在37-42℃中的至少两种具体石蜡的以任意比混合的混合物，同理，可得第二相变组分的组成，在此不做限定。
根据本申请的一些实施例，可选地，第一相变组分采用的石蜡的结构式为：CnH2n+2，其中18≤n≤21；第二相变组分采用的石蜡的结构式为：Cn’H2n’+2，其中25≤n’≤28。
根据本申请的一些实施例，可选地，相变微胶囊中，壁材与芯材的质量比为1:3-4。例如相变微胶囊中，壁材与芯材的质量比为1:3、1:3.3、1:3.5、1:3.7、1:3.9、1:4中的任一比值或介于任意两个比值之间。
在相变微胶囊的粒径一定的条件下，利用上述配比可限定壁材的厚度，提高相变微胶囊的稳定性。
根据本申请的一些实施例，可选地，缘导热壁材包括基材以及分散于基材中的陶瓷颗粒，基材为聚合物。
陶瓷颗粒是由具有耐高温性和导热性的陶瓷材料制成的颗粒物，陶瓷颗粒的材料包括但不局限于氮化硼、氮化硅、碳化硅、二氧化硅等中的至少一种。
聚合物与石蜡相容性较佳且绝缘。
根据本申请的一些实施例，可选地，聚合物包括酚醛树脂，也即是聚合物包括但不局限于酚醛树脂，还可以为聚丙烯腈树脂、三聚氰胺甲醛树脂、以及酚醛树脂聚合物中的任一种。
上述设置下，壁材不仅具有较佳的绝缘性，同时陶瓷颗粒的引入，一方面可使壁材具有更佳的耐高温性，同时也利于芯材及时将集流组件焊接时产生的热量吸收，另一方面可避免焊接时隔膜与负极极片接触的部分过度收缩。并且聚合物作为基材的设置，保证壁材与石蜡与相容性佳，能够与其形成稳定的界面，提高相变微胶囊的热稳定性。
可选地，聚合物为酚醛树脂。
上述材质的基材与石蜡具有更好的相容性，同时也便于陶瓷颗粒均为均匀的分散，保证相变微胶囊的稳定性。
根据本申请的一些实施例，可选地，相变微胶囊中，基材与陶瓷颗粒的质量比为3:4-5，且基材与芯材质量比为1:2-3。例如相变微胶囊中，基材与陶瓷颗粒的质量比为3:4、3:4.3、3:4.5、3:4.6、3:4.9、3:5中的任一比值或介于任意两个比值之间，且基材与芯材质量比为1:2、1:2.3、1:2.5、1:2.7、1:2.9、1:3中的任一比值或介于任意两个比值之间。
通过将基材、陶瓷颗粒、芯材的用量控制在上述范围可以保证相变微胶囊的稳定性，使其能够针对焊接时的瞬时高温，起到保护隔膜的功能。
根据本申请的一些实施例，可选地，陶瓷颗粒为二氧化硅颗粒。利用二氧化硅颗粒具有优异的耐高温、绝缘以及导热性能，可提高壁材的耐高温、绝缘以及导热性能，提高焊接集流组件时相变微胶囊的稳定性以及吸热能力，同时还具有来源丰富且容易获得等优势。
可选地，二氧化硅颗粒的粒径为60-90nm。此处的粒径是指二氧化硅颗粒的平均粒径。例如二氧化硅颗粒的粒径为60nm、65nm、70nm、75nm、80nm、83nm、85nm、90nm中的任一值或介于任意两个值之间。上述特定粒径的二氧化硅颗粒有利于掺杂并均匀分散于基材中。
根据本申请的一些实施例，可选地，相变微胶囊的粒径为0.5-4μm，此处的粒径为相变微胶囊的平均粒径。此规格的相变微胶囊便于形成位于极耳与隔膜边缘的涂层，有效避免极耳与集流组件采用激光焊接时烫伤与极耳配合的隔膜边缘。
上述相变微胶囊可采用原位聚合法，使壁材包覆芯材所得。
原位聚合法为：将一种或多种混合物的相变材料可在乳化剂的作用下分散于水中形成水包油的乳液，向该乳液中一步滴加或分步滴加一种或多种水溶性的单体或树脂的低分子量预聚物水溶液，调节体系的搅拌速度、反应温度、pH等发生缩聚反应，预聚体分子间进一步脱去小分子(如水分子)于乳液界面处生成交联立体网状结构的非水溶性缩聚物，即形成封装有相变材料的相变微胶囊。
在一些示例性的实施例中，相变微胶囊的制备方法包括以下步骤：
将陶瓷颗粒分散在水中，形成水相。
将第一相变组分、第二相变组分混合后，加热至熔融状态，形成油相。
将水相和油相混合后，搅拌，形成Pickering乳液，在Pickering乳液中加入树脂的低分子量预聚物水溶液，常温搅拌聚合至少4h。
在另一些示例性的实施例中，相变微胶囊的制备方法包括以下步骤：
将陶瓷颗粒分散在水中，形成水相。
将第一相变组分、第二相变组分、聚合物的合成单体、交联剂以及引发剂混合后，加热至熔融状态，形成油相。
将水相和油相混合后，搅拌，形成Pickering乳液，在60-80℃搅拌聚合。
采用原位聚合法在芯材的表面形成聚合物，可保证壁材包裹于芯材外形成核壳结构，易于获得混合均匀且包裹于壁材内的第一相变组分以及第二相变组分，同时制备方法可控，可进行规模化生产。
需要说明的是，采用原位聚合法在芯材的表面形成聚合物后，若暂时不使用相变微胶囊，可干燥获得相变微胶囊粉体，便于存储以及运输，使用时按照实际需求与粘结剂混合形成浆料即可，若需要使用相变微胶囊，可在采用原位聚合法在芯材的表面形成聚合物后，无需干燥，直接在聚合后形成的相变微胶囊乳液中直接添加粘结剂，混合形成浆料即可使用。
其中，粘结剂用于将相变微胶囊固定于隔膜或极耳上。粘结剂包括但不局限于水性丁苯橡胶(SBR)粘结剂、羧甲基纤维素钠(CMC)，例如粘结剂为单独的SBR粘结剂，或者为质量比为3:6-8的CMC、SBR混合物。
根据本申请的一些实施例，本申请提供一种隔膜，隔膜的边缘设有涂层，涂层含有相 变微胶囊。
实际使用过程中，例如当隔膜应用于卷绕电池时，此时隔膜的边缘为隔膜靠近导热系数≥380W/m.k的极耳的长边边缘。当隔膜应用于叠片电池时，此时边缘为隔膜靠近导热系数≥380W/m.k的极耳的边缘。
涂层包括基底以及分散于基底中的相变微胶囊。其中，基底是指可以分散前述相变微胶囊，以及可以成膜并且附着于隔膜表面的材料，例如为粘结剂，粘结剂例如为SBR粘结剂和/或CMC等，SBR粘结剂有优越的热稳定性，SBR粘结剂、CMC均与相变胶囊相容性强。其中，隔膜材质包括但不局限为聚丙烯(polypropylene，PP)或聚乙烯(polyethylene，PE)等等，具体可根据实际需求选择，在此不做限定。
实际使用过程中，当导热系数≥380W/m.k的极耳为全极耳时，此时涂层完全覆盖隔膜的边缘，其中全极耳是指将集流体的边缘作为极耳。当导热系数≥380W/m.k的极耳为单极耳极片或多极耳极片的极耳时，此时涂层可完全覆盖隔膜的边缘，以在极耳弯折后，利用涂层完全隔绝隔膜与极耳，或者涂层仅设置于该边缘与极耳对应的部分，也可以利用涂层完全隔绝隔膜与极耳，其中单极耳是指每张极片上面仅有一个极耳伸出来作为导流用。多极耳是指每张极片上面有至少两个极耳伸出来作为导流用。
根据本申请的一些实施例，可选地，涂层的厚度为10-35μm，可选为10-20μm，可选为25-35μm。
在装配电池时，当隔膜及极耳均形成有涂层时，此时形成于隔膜的涂层的厚度为10-20μm，当仅隔膜形成有涂层而极耳未形成有涂层时，此时形成于隔膜的涂层的厚度为25-35μm，例如涂层的厚度为25μm、27μm、28μm、30μm、35μm中的任一值或介于任意两个值之间。上述涂层厚度合理，保证有效调节隔膜的温度以及温升速率，同时基本不影响隔膜边缘位置的尺寸。
可选地，涂层可由以下方式制得：将第一方面提供的相变微胶囊和粘结剂按照例如质量比为1:7-9的比例混合，形成涂敷浆料，然后将涂敷浆料涂敷于隔膜的边缘后干燥所得，或者，将直接在聚合后形成的相变微胶囊乳液中直接添加粘结剂，例如先加CMC干粉，待CMC完全溶解后加入SBR乳液，其中CMC/SBR质量比为3:7，形成涂敷浆料，然后将涂敷浆料涂敷于隔膜的边缘后在70-80℃下烘干所得。
根据本申请的一些实施例，可选地，本申请提供一种极片，极片包括互相连接的集流体以及极耳，极耳的导热系数≥380W/m.k，极耳的至少一侧面设有涂层，涂层含有本申请第一方面提供的相变微胶囊。
其中涂层包括基底以及分散于基底中的相变微胶囊。其中，基底是指可以分散前述相变微胶囊，以及可以成膜并且附着于隔膜表面的材料，例如为粘结剂，粘结剂例如为SBR粘结剂，该粘结剂有优越的热稳定性，且与相变胶囊相容性强。
将极片装配至电池后，为了进一步避免极片和隔膜接触，涂层可自极耳向集流体延伸。
由于将极片装配至电池后，一般隔膜伸出极耳的长度不超过4mm，因此，可选地1mm≤涂层在极耳的宽度≤4mm，同时0≤涂层在集流体的宽度≤4mm，也即是4mm≤涂层的总宽度≤8mm，此处的涂层宽度是涂层靠近集流体的一端向远离集流体的一端的距离。
其中，极耳的导热系数≥380W/m.k，也即是极耳为高导热性金属，极耳的材质可为铜、银、镀银铜等。
可选地，极耳的材质为铜。
极耳与集流体可以焊接连接，也可以一体成型。
其中，极片可以为单极耳极片、多极耳极片或全极耳极片，在此不做限定。
根据本申请的一些实施例，可选地，涂层的厚度为10-35μm，可选为10-20μm,可选为 25-35μm。
在装配电池时，当隔膜以及极耳均形成有涂层时，此时形成于极耳的涂层的厚度为10-20μm，当仅极耳形成有涂层而隔膜未形成有涂层时，此时形成于极耳的涂层的厚度为25-35μm，例如涂层的厚度为25μm、27μm、28μm、30μm、35μm中的任一值或介于任意两个值之间。上述涂层厚度合理，有效调节隔膜的温度以及温升速率，同时基本不影响与极耳配合的隔膜边缘位置的尺寸。
可选地，涂层可由以下方式制得：将第一方面提供的相变微胶囊和粘结剂按照例如质量比为1:7-9的比例混合，形成涂敷浆料，然后将涂敷浆料涂敷于极耳后干燥所得，或者，将直接在聚合后形成的相变微胶囊乳液中直接添加粘结剂，例如先加CMC干粉，待CMC完全溶解后加入SBR乳液，其中CMC/SBR质量比为3:7，形成涂敷浆料，然后将涂敷浆料涂敷于极耳后在70-80℃下烘干所得。
根据本申请的一些实施例，可选地，本申请提供一种电池，其包括隔膜以及极片，极片包括互相连接的集流体以及极耳，极耳的导热系数≥380W/m.k；极耳与隔膜之间具有涂层，涂层形成于极耳和/或形成于隔膜；涂层含有本申请第一方面提供的相变微胶囊。
利用涂层将隔膜的边缘和极耳隔开，避免二者直接接触，进而在焊接集流组件时，涂层吸收极耳传递的热量，降低传递至隔膜的热量以及控制隔膜的温升速率，保证焊接时隔膜实时温度始终低于其能够被烫伤的最小温度，以避免因烫伤隔膜导致的内部短路。
可选地，隔膜和极片之间的涂层的厚度为20-35μm，例如涂层的厚度为20μm、25μm、28μm、30μm、32μm、35μm中的任一值或介于任意两个值之间。上述涂层厚度合理，保证有效调节隔膜的温度以及温升速率，同时基本不影响隔膜边缘位置的尺寸。
在一些实施例中，涂层仅形成于极耳的单侧，并且位于极耳与隔膜之间。此时，涂层的厚度为20-35μm。
在一些实施例中，涂层仅形成于隔膜的边缘，并且位于极耳与隔膜之间。此时，涂层的厚度为20-35μm。
在一些实施例中，极耳形成第一涂层，隔膜的边缘形成第二涂层，第一涂层和第二涂层贴合，其中第一涂层厚度为10-20μm，第二涂层厚度为10-20μm，且第一涂层和第二涂层的总厚度为20-35μm。
根据本申请的一些实施例，可选地，本申请示例提供了一种用电装置，其装配有以上任一方案的电池。
用电装置可以是前述任一应用电池的设备或系统。
以下结合实施例对本申请的相变微胶囊、隔膜、极片、电池和用电装置作进一步的详细描述。
实施例1-6
一种相变微胶囊，其由以下方法制得：
将如表1所示的二氧化硅颗粒分散于100g水中，作为水相。
将如表1所示的第一相变组分、第二相变组分混合后升温至75℃，形成熔融状的油相。
将油相和水相混合后，高速搅拌10min，搅拌速度不低于5000rar/min，得到Pickering乳液。
在Pickering乳液中加入乳化剂、酚醛树脂，然后在25℃聚合5h，得到相变微胶囊乳液。表1中乳化剂的添加量为对应的Pickering乳液的质量百分比。
表1成分及其配比参数
Figure PCTCN2022116271-appb-000001
其中，实施例7第一相变材料的熔点37℃/39℃是指熔点为37℃的石蜡和熔点为39℃的石蜡按质量比为1:1混合所得，第一相变材料的熔点65℃/70℃是指其由熔点为65℃的石蜡和熔点为70℃的石蜡按质量比为1:1混合所得。
将实施例1的相变微胶囊乳液干燥，获得图6。图6为实施例1获得的相变微胶囊的扫描电镜图，根据图6，可以看出相变微胶囊的粒径为0.5-4μm。
对比例1-5
对比例1与实施例1的区别仅在于：采用熔点为40℃的石蜡替换实施例1中的芯材。
对比例2与实施例1的区别仅在于：芯材仅为熔点为70℃的石蜡替换实施例1中的芯材。
对比例3与实施例1的区别仅在于：芯材仅为熔点为52℃的石蜡替换实施例1中的芯材。
对比例4与实施例1的区别仅在于：第一相变组分与第二相变组分的质量比为35:80。
对比例5与实施例1的区别仅在于：第一相变组分与第二相变组分的质量比为50:45。
试验例1
将实施例1-7以及对比例1-5制得的相变微胶囊乳液，先添加表2所示CMC干粉，待CMC干粉溶解后添加表2所示SBR乳液，获得浆料，将浆料在相同规格的隔膜边缘(隔膜尺寸为：长9310mm，宽128.5mm，材质为PP，隔膜边缘的宽度为8mm)，干燥，使隔膜边缘和铜箔(作为极耳，铜箔导热系数为400W/(m*K))之间有20μm厚的含有上述相变微胶囊的涂层，揉平后，铜箔背离隔膜的一面与集流盘紧固，然后采用相同参数的激光从规格及材质相同的集流盘的正上方向下打出，采用激光焊(出光时间0.1s，出光瞬时温度1000℃)接集流盘与铜箔，焊接后将隔膜展开，观察隔膜背离涂层的一面的变化。
其中，对比例1-5与实施例1的SBR乳液、CMC干粉的添加量相同。
表2CMC干粉以及SBR乳液添加量
Figure PCTCN2022116271-appb-000002
试验结果如图7以及图8所示，其中，因试验过程中极耳需要揉平处理，再展开，因此不可避免的，隔膜表面具有折痕。
根据图7以及图8，可以明显看出，实施例1-7隔膜的边缘平整，无烫伤，根据图8，其中框线中为隔膜边缘烫伤的部分，其中对比例1-5隔膜边缘区相比于实施例1均存在不同程度的因烫伤导致的收缩以及缺口等。
说明本申请提供的相变微胶囊能够以涂层的方式应用于电池中，使弯折后的极耳与隔膜经涂层贴合连接，利用芯材中特定熔点以及特定配比的上述特定的第一相变组分以及第二相变组分互相配合，使得极耳激光焊接集流组件时能够避免烫伤隔膜，避免电池内部短路。
以上仅为本申请的具体实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (14)

  1. 一种相变微胶囊，其中，包括：芯材以及包裹所述芯材的绝缘导热壁材；
    所述芯材包括第一相变组分以及第二相变组分，所述第一相变组分为熔点37-42℃的石蜡，所述第二相变组分为熔点65-75℃的石蜡，所述绝缘导热壁材的熔点大于75℃；
    所述第一相变组分与所述第二相变组分的质量比为35:45-77。
  2. 根据权利要求1所述的相变微胶囊，其中，所述第一相变组分采用的石蜡的结构式为：CnH2n+2，其中18≤n≤21；
    所述第二相变组分采用的石蜡的结构式为：Cn’H2n’+2，其中25≤n’≤28。
  3. 根据权利要求1或2所述的相变微胶囊，其中，所述相变微胶囊中，所述壁材与所述芯材的质量比为1:3-4。
  4. 根据权利要求1-3任一项所述的相变微胶囊，其中，所述绝缘导热壁材包括基材以及分散于所述基材中的陶瓷颗粒，所述基材为聚合物；
    可选地，所述聚合物包括酚醛树脂。
  5. 根据权利要求4所述的相变微胶囊，其中，所述相变微胶囊中，所述基材与所述陶瓷颗粒的质量比为3:4-5，且所述基材与所述芯材的质量比为1:2-3。
  6. 根据权利要求4所述的相变微胶囊，其中，所述陶瓷颗粒包括二氧化硅颗粒；
    可选地，所述二氧化硅颗粒的粒径为60-90nm。
  7. 根据权利要求1-3任意一项所述的相变微胶囊，其中，所述相变微胶囊的粒径为0.5-4μm。
  8. 一种隔膜，其中，所述隔膜的边缘设有涂层，所述涂层含有如权利要求1-7任意一项所述的相变微胶囊。
  9. 根据权利要求8所述的隔膜，其中，所述涂层的厚度为10-35μm，可选为10-20μm，可选为25-35μm。
  10. 一种极片，其中，所述极片包括互相连接的集流体以及极耳，所述极耳的导热系数≥380W/m.k，所述极耳的至少一侧面设有涂层，所述涂层含有如权利要求1-7任意一项所述的相变微胶囊。
  11. 根据权利要求10所述的极片，其中，所述涂层的厚度为10-35μm，可选为10-20μm，可选为25-35μm。
  12. 一种电池，其中，包括隔膜以及极片，所述极片包括互相连接的集流体以及极耳；
    所述极耳与所述隔膜之间具有涂层，所述涂层形成于所述极耳和/或形成于所述隔膜；
    所述涂层含有如权利要求1-7任意一项所述的相变微胶囊。
  13. 根据权利要求12所述的电池，其中，所述隔膜和所述极耳之间的所述涂层的厚度为20-35μm。
  14. 一种用电装置，其中，装配有如权利要求12-13任意一项所述的电池。
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