WO2021195963A1 - 隔膜、电极组件、电池及电子装置 - Google Patents

隔膜、电极组件、电池及电子装置 Download PDF

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WO2021195963A1
WO2021195963A1 PCT/CN2020/082433 CN2020082433W WO2021195963A1 WO 2021195963 A1 WO2021195963 A1 WO 2021195963A1 CN 2020082433 W CN2020082433 W CN 2020082433W WO 2021195963 A1 WO2021195963 A1 WO 2021195963A1
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Prior art keywords
hollow microspheres
diaphragm
coating
battery
hybrid coating
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PCT/CN2020/082433
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English (en)
French (fr)
Inventor
樊晓贺
魏增斌
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宁德新能源科技有限公司
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Application filed by 宁德新能源科技有限公司 filed Critical 宁德新能源科技有限公司
Priority to CN202080032891.2A priority Critical patent/CN113795975A/zh
Priority to EP20864281.9A priority patent/EP3916901A4/en
Priority to PCT/CN2020/082433 priority patent/WO2021195963A1/zh
Priority to US17/202,732 priority patent/US20210305660A1/en
Publication of WO2021195963A1 publication Critical patent/WO2021195963A1/zh

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  • This application relates to the field of battery separators, and in particular to a separator, an electrode assembly including the separator, a battery including the electrode assembly, and an electronic device including the battery.
  • Lithium-ion batteries have the advantages of large specific energy, high working voltage, low self-discharge rate, small size, light weight, etc., and have a wide range of applications in the field of consumer electronics.
  • people have higher and higher requirements for battery performance (especially energy density and cycle performance).
  • the present application provides a separator, including a separator substrate.
  • the separator further includes a hybrid coating, the hybrid coating is disposed on the surface of the separator substrate, the hybrid coating includes hollow microspheres and a binder, and the hollow microspheres can be swelled in the electrolyte. damaged.
  • the diaphragm provided in the present application is provided with a hybrid coating and the hybrid coating contains hollow microspheres. Since the hollow microspheres have a certain particle size, a certain gap can exist between the diaphragm and the pole piece. On the one hand, the electrolyte can more fully infiltrate the pole piece during the liquid injection process. On the other hand, after the battery is injected, the hollow microspheres can swell to breakage in the electrolyte, and the gap in the main body area disappears under the hot pressure condition of subsequent battery formation, which can avoid the loss of battery volume energy density; and it is located in the corner area.
  • the gap still exists, which can reserve space for the cyclic expansion of the pole piece, reduce the squeezing of the corner area, avoid the discontinuous distribution of the electrolyte in the corner area, and ensure the unblocked ion channel, thereby improving the circulation capacity of the battery.
  • the hybrid coating further includes inorganic ceramic particles.
  • the diaphragm further includes a ceramic coating, the ceramic coating is coated on at least one surface of the diaphragm substrate, the hybrid coating is located on the ceramic coating and/ Or on the surface of the diaphragm substrate that is not coated with the ceramic coating.
  • the particle size D50 of the hollow microspheres is 3 ⁇ m-40 ⁇ m. If the particle size D50 of the hollow microspheres is less than 3 ⁇ m, it is difficult to form a sufficient gap between the diaphragm and the pole piece, and it is difficult to improve the discontinuous distribution of the electrolyte in the corner area; if the particle size D50 of the hollow microspheres is greater than 40 ⁇ m, it will Affect the bonding properties of the hybrid coating.
  • the thickness of the shell layer of the hollow microspheres is 0.5 ⁇ m-6 ⁇ m. If the shell thickness of the hollow microspheres is less than 0.5 ⁇ m, it is easy to be damaged, which is not conducive to improving the cycle capacity of the battery and improving the problem of lithium precipitation in the corner area; if the shell thickness of the hollow microspheres is greater than 6 ⁇ m, the hollow microspheres are difficult to electrolyze Swelling to breakage in the liquid will on the one hand lose the volume energy density of the battery, on the other hand it will affect the adhesion properties of the hybrid coating.
  • the swelling degree of the hollow microspheres in the electrolyte is 60%-200%. If the swelling degree of the hollow microspheres is less than 60%, it is difficult for the hollow microspheres to swell to break in the electrolyte. On the one hand, the thickness of the battery as a whole is increased, thereby reducing the volume energy density of the battery, and on the other hand, it will affect the performance of the mixed coating.
  • the swelling degree of the hollow microspheres is greater than 200%, the hollow microspheres are easily dissolved in the electrolyte, resulting in an increase in electrolyte concentration, thereby reducing the rate of ion transmission in the electrolyte, and dissolving in the hollow in the electrolyte at the same time
  • the composition of the microspheres will increase the probability of side reactions occurring during the charging and discharging process of the battery, resulting in a decrease in the cycle performance of the battery.
  • the shell layer of the hollow microsphere is a homopolymer or a copolymer
  • the polymerizable monomer of the shell layer of the hollow microsphere is selected from methyl acrylate, methyl methacrylate, vinyl methacrylate, At least one of ethylene glycol dimethacrylate and acrylonitrile.
  • the hollow microspheres account for 10% to 80% of the total mass of the hybrid coating, and the binder accounts for 20% to 90% of the total mass of the hybrid coating. If the mass of hollow microspheres is less than 10%, the number of hollow microspheres is too small, and it is difficult to form enough gaps in the corner area; if the mass fraction of hollow microspheres is higher than 90%, the amount of binder is too small, Affect the bonding properties of the hybrid coating.
  • the adhesive includes a first adhesive and a second adhesive, and the mass ratio of the first adhesive to the second adhesive is (85%-95%): (5%) -15%); the particle size D50 of the first binder is 0.3 ⁇ m-0.5 ⁇ m.
  • the first adhesive is a core-shell structure
  • the core and the outer shell of the core-shell structure are homopolymers or copolymers
  • the polymerizing monomers of the core are selected from acrylic monomers and aromatic monoethylenes.
  • the polymerized monomer of the outer shell is selected from at least one of an acrylic monomer, an aromatic monovinyl compound, and a nitrified vinyl compound.
  • the first binder has a non-core-shell structure
  • the non-core-shell structure is a homopolymer or a copolymer
  • the polymerized monomer of the non-core-shell structure is selected from acrylic acid, acrylate, butadiene, styrene, At least one of acrylonitrile, ethylene, chlorostyrene, fluorostyrene, and propylene.
  • the application also provides an electrode assembly including the above diaphragm.
  • the present application also provides a battery, which includes an electrolyte, and the battery further includes an electrode assembly, and the surface of the separator of the electrode assembly includes a polymer formed by the damage of the hollow microspheres.
  • the present application also provides an electronic device, including the above battery.
  • FIG. 1 is a schematic diagram of the structure when the hollow microspheres of the diaphragm provided by an embodiment of the application are not damaged.
  • FIG. 2A is a schematic diagram of the structure of the hollow microspheres of the diaphragm shown in FIG. 1 in a pie shape after being damaged.
  • FIG. 2B is a schematic diagram showing the structure of the hollow microspheres of the diaphragm shown in FIG. 1 in a ring shape after being damaged.
  • FIG. 3 is a schematic structural diagram of a diaphragm according to another embodiment of the application.
  • FIG. 4 is a schematic structural diagram of a diaphragm according to another embodiment of this application.
  • FIG. 5 is a schematic structural diagram of a diaphragm according to still another embodiment of this application.
  • FIG. 6 is a schematic structural diagram of a diaphragm according to still another embodiment of this application.
  • FIG. 7 is a schematic diagram of the structure of a diaphragm according to another embodiment of the application.
  • FIG. 8 is a schematic structural diagram of an electrode assembly provided by an embodiment of the application.
  • FIG. 9 is a schematic diagram of the structure of a battery provided by an embodiment of the application.
  • FIG. 10 is a schematic structural diagram of an electronic device provided by an embodiment of this application.
  • Example 11A is a scanning electron microscope (SEM) test image before the hollow microspheres of the diaphragm prepared in Example 1 are not damaged.
  • FIG. 11B is a scanning electron microscope test image of the hollow microspheres of the diaphragm shown in FIG. 11A after being damaged.
  • connection used in the specification and claims of the patent application of this application is not limited to physical or mechanical connections, whether direct or indirect. of. "Up”, “Down”, “Above”, “Below”, “Left”, “Right”, etc. are only used to indicate the relative position relationship. When the absolute position of the described object is changed, the relative position relationship is also correspondingly Change.
  • an embodiment of the present application provides a diaphragm 100, and the diaphragm 100 includes a diaphragm substrate 10 and a hybrid coating 30.
  • the hybrid coating 30 is provided on the surface of the separator substrate 10.
  • the hybrid coating 30 includes hollow microspheres 32 and a binder 34. The hollow microspheres 32 can be broken after being swelled in the electrolyte.
  • the diaphragm 100 further includes a ceramic coating 20, and the ceramic coating 20 is coated on at least one surface of the diaphragm substrate 10.
  • the hybrid coating 30 is located on the surface of the ceramic coating 20 and/or the diaphragm substrate 10 that is not coated with the ceramic coating 20.
  • the ceramic coating layer 20 is located on one surface of the diaphragm substrate 10, the number of the mixed coating layer 30 is two, one mixed coating layer 30 is located on the surface of the ceramic coating layer 20, and the other mixed coating layer 30 is located on the surface of the diaphragm substrate 10.
  • the surface is provided with a ceramic coating 20.
  • the ceramic coating 20 is used to improve the heat resistance and puncture resistance of the diaphragm 100.
  • the hollow microspheres 32 after the hollow microspheres 32 are damaged due to the hollow structure, they can be spread on the surface of the diaphragm substrate 10 and/or the ceramic coating 20 in a cake shape.
  • the hollow microspheres 32 are highly damaged (that is, the hollow microspheres 32 are broken), and are laid on the surface of the diaphragm substrate 10 and/or the ceramic coating 20 in a continuous ring shape. After the hollow microspheres 32 are broken, they can be spread evenly on the surface of the diaphragm substrate 10 and/or the ceramic coating 20 in a dot-shaped ring shape.
  • the inventor of the present application found that in the prior art, the gap between the separator and the pole pieces is small due to the bonding of the separator and the pole pieces. On the one hand, it is difficult for the electrolyte to fully infiltrate the pole pieces. The sheet swells and deforms during the battery charge and discharge cycle, causing the corner area of the pole piece to be squeezed, squeezing out the electrolyte located in the corner area, resulting in the discontinuous distribution of the electrolyte located in the corner area and blocking the ion channels, resulting in During the cycle, the problem of lithium precipitation in the corner area caused by purple spots, resulting in a decrease in the dynamic performance of the battery or the low-temperature cycle performance.
  • the diaphragm 100 provided in the present application is provided with a hybrid coating 30 and the hybrid coating 30 contains hollow microspheres 32 and a binder 34.
  • the binder 34 is used to bond the hollow microspheres 32 together, and at the same time make the hybrid coating 30 adhere to the surface of the diaphragm substrate 10 and/or the ceramic coating 20. Since the hollow microspheres 32 have a certain particle size, a certain gap can be created between the diaphragm 100 and the pole piece. On the one hand, during the liquid injection process, the electrolyte can more fully infiltrate the pole piece.
  • the hollow microspheres 32 have poor electrolyte resistance and can swell to breakage in the electrolyte.
  • the gap in the main body area disappears under the heat and pressure conditions of subsequent battery formation, which can avoid the volume of the battery. Energy density loss; while the gap in the corner area still exists, it can reserve space for the cyclic expansion of the pole piece, which is beneficial to reduce the squeezing of the corner area, avoid the discontinuous distribution of electrolyte in the corner area, and ensure that the ion channel is unblocked.
  • the hollow microspheres 32 are spread on the diaphragm substrate 10 and/or in a ring shape after being broken. Or on the surface of the ceramic coating 20, it can avoid blocking the ion channels in the separator 100 to the greatest extent, thereby avoiding the degradation of the battery cycle performance.
  • another embodiment of the present application further provides a diaphragm 200.
  • the difference from the above-mentioned diaphragm 100 is that the number of the hybrid coating 30 is only one and it is located on the surface of the ceramic coating 20.
  • another embodiment of the present application further provides a diaphragm 300.
  • the difference from the above-mentioned diaphragm 100 is that the number of the mixed coating 30 is only one, and the ceramic coating 20 is not provided on the diaphragm substrate 10 s surface.
  • yet another embodiment of the present application further provides a diaphragm 400.
  • the difference from the above-mentioned diaphragm 100 is that the number of ceramic coatings 20 is two, and they are respectively located on two opposite surfaces of the diaphragm substrate 10.
  • the number of the mixed coating 30 is only one, and it is located on the surface of one of the ceramic coatings 20.
  • yet another embodiment of the present application further provides a diaphragm 500.
  • the difference from the above-mentioned diaphragm 100 is that the number of ceramic coatings 20 is two, and they are respectively located on two opposite surfaces of the diaphragm substrate 10.
  • the two hybrid coatings 30 are located on the surfaces of the two ceramic coatings 20 respectively.
  • the material of the diaphragm substrate 10 can be selected from polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), etc. At least one of the materials.
  • the separator substrate 10 may be a single-layer structure or a multi-layer composite structure of a mixture of multiple types. The thickness of the separator substrate 10 may be 3 ⁇ m-20 ⁇ m.
  • the inorganic ceramic particles in the ceramic coating 20 include at least one of aluminum oxide, boehmite, barium sulfate, titanium dioxide, and magnesium hydroxide.
  • the thickness of the ceramic coating 20 is 0.5 ⁇ m-6 ⁇ m.
  • the hybrid coating 30 also includes inorganic ceramic particles 36.
  • the inorganic ceramic particles 36 of the hybrid coating 30 include at least one of aluminum oxide, boehmite, barium sulfate, titanium dioxide, and magnesium hydroxide.
  • the thickness of the shell layer of the hollow microspheres 32 is 0.5 ⁇ m-6 ⁇ m.
  • the inventor of the present application found that if the thickness of the shell layer of the hollow microspheres 32 is less than 0.5 ⁇ m, it is easy to be damaged, and a gap cannot be formed between the separator 100 and the pole pieces, and it is difficult for the electrolyte to fully infiltrate the pole pieces, which is not conducive to improving the cycle capacity of the battery.
  • the problem of lithium precipitation in the corner area cannot be improved; if the thickness of the shell layer of the hollow microsphere 32 is greater than 6 ⁇ m, the hollow microsphere 32 is difficult to swell and break in the electrolyte, on the one hand, it will lose The energy density of the battery, on the other hand, will affect the bonding performance of the hybrid coating 30, thereby affecting the cycle performance of the battery.
  • the particle size D50 of the hollow microspheres 32 is 3 ⁇ m-40 ⁇ m.
  • the inventor of the present application found that if the particle size D50 of the hollow microspheres 32 is less than 3 ⁇ m, it is difficult to form a sufficient gap between the diaphragm 100 and the pole piece, and it is difficult to improve the problem of discontinuous electrolyte distribution in the corner area; if the hollow microspheres
  • the particle size D50 of 32 is greater than 40 ⁇ m, which will affect the bonding performance of the hybrid coating 30, thereby affecting the cycle performance of the battery.
  • the swelling degree of the hollow microspheres 32 in the electrolyte is 60%-200%.
  • the swelling degree is the ratio between the mass difference between the hollow microspheres 32 after swelling and the mass before swelling, and the mass of the hollow microspheres 32 before swelling.
  • the initial mass of the hollow microspheres 32 is weighed as W 0 , and then the hollow microspheres 32 are placed in the electrolyte and kept at a temperature of 85° C. for 24 hours, and then the mass of the swollen hollow microspheres 32 is weighed. Is Wt, the calculation formula of the swelling degree of the hollow microsphere 32 in the electrolyte is:
  • the inventor of the present application found that if the swelling degree of the hollow microspheres 32 is less than 60%, the hollow microspheres 32 are difficult to swell to breakage in the electrolyte, which will increase the thickness of the battery as a whole, thereby reducing the volumetric energy density of the battery. It will affect the bonding performance of the hybrid coating 30, thereby affecting the cycle performance of the battery; if the swelling degree of the hollow microspheres 32 is greater than 200%, the hollow microspheres 32 are easy to dissolve in the electrolyte, which causes the viscosity of the electrolyte to increase and reduces the electrolysis. The rate of ion transport in the liquid and the composition of the hollow microspheres 32 dissolved in the electrolyte will increase the probability of side reactions occurring during the charging and discharging process of the battery, resulting in a decrease in the cycle performance of the battery.
  • the hollow microspheres 32 account for 10%-80% of the total mass of the hybrid coating 30, and the binder 34 accounts for 20%-90% of the total mass of the hybrid coating 30.
  • the inventor of the present application found that if the mass of the hollow microspheres 32 is less than 10%, the number of hollow microspheres 32 is too small, and it is difficult to form sufficient gaps in the corner area; if the mass fraction of the hollow microspheres 32 is higher than 90%, If the amount of the binder 34 is too small, the bonding performance of the hybrid coating 30 will be affected.
  • the material of the shell layer of the hollow microspheres 32 is a homopolymer or a copolymer, wherein the polymerized monomer of the shell layer of the hollow microspheres 32 is selected from methyl acrylate (MA), methyl acrylate Methyl methacrylate (MMA), vinyl methacrylate (VMA), ethylene glycol dimethacrylate (EGDMA), and acrylonitrile (ACN) At least one of them.
  • the material of the shell layer of the hollow microspheres 32 depends on the type of polymerized monomer, and the material of the shell layer of the hollow microspheres 32 affects the swelling degree of the hollow microspheres 32 in the electrolyte.
  • the adhesive 34 includes a first adhesive 342 and a second adhesive 344, and the mass ratio of the first adhesive 342 to the second adhesive 344 is (85 %-95%): (5%-15%).
  • the particle size D50 of the first binder 342 is 0.3 ⁇ m-5 ⁇ m.
  • the first adhesive 342 may be a core-shell structure, and the core-shell structure includes an inner core and an outer shell of the inner core.
  • the inner core and outer shell are homopolymers or copolymers.
  • the polymerizable monomer of the core is selected from at least one of acrylate monomers, aromatic monovinyl compounds, and acid anhydrides.
  • acrylic monomers include, but are not limited to, ethyl acrylate, butyl acrylate, and ethyl methacrylate.
  • Aromatic monovinyl compounds include, but are not limited to, styrene, chlorostyrene, fluorostyrene, and methylstyrene;
  • acid anhydrides include, but are not limited to, acrylic acid, methacrylic acid, and maleic acid.
  • the polymerizable monomer of the outer shell is selected from at least one of acrylate monomers, aromatic monovinyl compounds, and nitrified vinyl compounds.
  • Acrylic monomers include, but are not limited to, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
  • Aromatic monovinyl compounds include, but are not limited to, ethylene, chlorostyrene, fluorostyrene, and methylstyrene.
  • Nitrile vinyl compounds include, but are not limited to, acrylonitrile and methacrylonitrile.
  • the first binder 342 may also be a non-core-shell structure, and the first binder 342 is a homopolymer or a copolymer.
  • the polymerizable monomers of the first binder 342 include, but are not limited to, acrylic acid, acrylate, butadiene, styrene, acrylonitrile, ethylene, chlorostyrene, fluorostyrene, and propylene.
  • an embodiment of this application also provides an electrode assembly 2.
  • the electrode assembly 2 includes a positive pole piece 220, a negative pole piece 210, and a separator 100 (or a separator 200, 300, 400, 500, 600). 100 is located between the positive pole piece 220 and the negative pole piece 210.
  • the positive pole piece 220, the separator 100, and the negative pole piece 210 are wound to form the electrode assembly 2.
  • the electrode assembly 2 includes a corner area 234 and a main body area 232 excluding the corner area 234.
  • the gap in the main body area 232 disappears under the condition of subsequent battery formation under the heat and pressure, avoiding the loss of battery volume energy density; while the gap in the corner area 234 still exists, so as to reserve space for the cyclic expansion of the pole piece, which is beneficial to reduce the corner area
  • the squeezing of 234 avoids the discontinuous distribution of the electrolyte in the corner area 234, ensures unobstructed ion channels, and avoids the problem of lithium precipitation in the corner area 234.
  • the positive pole piece 220 includes a positive electrode material and a conductive agent.
  • the positive electrode material includes but is not limited to at least one of lithium cobaltate, lithium manganate, lithium nickel manganate, and lithium nickel cobalt manganate;
  • the conductive agent includes but is not limited to conductive At least one of carbon black, sheet graphite, carbon nanotubes, and graphene.
  • an embodiment of the present application further provides a battery 3.
  • the battery 3 includes a housing 310, an electrode assembly 2 and an electrolyte.
  • the electrode assembly 2 is contained in the housing 310, and the electrolyte is contained in the housing 310.
  • the separator 100 in the electrode assembly 2 is wetted by the electrolyte.
  • the hollow microspheres 32 on the diaphragm 100 swell and break under the action of the electrolyte, and are in the shape of a pie, a continuous ring or a dot ring (that is, a plurality of discontinuous points constitute a ring structure).
  • the polymer is supported on the surface of the separator 100.
  • an embodiment of the present application further provides an electronic device 4, and the electronic device 4 includes a battery 3.
  • the electronic device 4 may be a consumer electronic product (such as a mobile communication device, a tablet computer, a notebook computer, etc.), an electric tool, an unmanned aerial vehicle, an energy storage device, a power device, and the like.
  • the electronic device 4 is an electric vehicle.
  • Example 1 The application will be described below through specific examples and comparative examples. Among them, the following specific embodiments take the hybrid coating 30 coated on the surface of the ceramic coating 20 as an example, but it can be understood that the hybrid coating 30, the ceramic coating 20, and the diaphragm substrate 10 have various combinations. In the embodiment, it is not limited to this embodiment.
  • Example 1
  • Preparation of positive pole piece Lithium cobaltate, conductive carbon black and polyvinylidene fluoride were dissolved in N-methylpyrrolidone (NMP) solvent at a mass ratio of 97:1.4:1.6 to form a positive electrode slurry.
  • NMP N-methylpyrrolidone
  • the aluminum foil is used as the positive electrode current collector, the positive electrode slurry is coated on the positive electrode current collector, and the positive electrode pieces are obtained after drying, cold pressing, and cutting procedures.
  • Negative pole piece preparation Dissolve graphite, conductive carbon black, sodium carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR) in deionized water at a mass ratio of 96.5:1.0:1.0:1.5, and place it in a vacuum mixer Under the action of stirring until the system is uniform, the negative electrode slurry is obtained. Copper foil is used as the negative electrode current collector, the negative electrode slurry is coated on both surfaces of the negative electrode current collector, and after drying, the negative electrode piece is obtained by cold pressing and slitting.
  • CMC carboxymethyl cellulose
  • SBR styrene butadiene rubber
  • Diaphragm preparation The first binder is added to the stirrer.
  • the polymerized monomers of the first binder include styrene, isopropyl acrylate and acrylonitrile, and the mass ratio of styrene, isopropyl acrylate and acrylonitrile is 80 :10:10, then add the hollow microspheres in two times and stir (50% each time), and then add the second binder.
  • the polymerized monomers of the second binder include acrylonitrile and acrylic acid, acrylonitrile and acrylonitrile. The mass ratio of acrylic acid is 50:50. Finally, deionized water is added and stirred to obtain a mixed coating slurry.
  • the mixed coating slurry is coated on the diaphragm substrate with ceramic coating, and the drying is completed in an oven to obtain Separator with hybrid coating and ceramic coating.
  • the polymerized monomers of the hollow microspheres are methyl methacrylate (MMA), acrylonitrile (ACN) and ethylene glycol dimethacrylate (EGDMA), and the mass ratio of MMA, ACN and EGDMA is 40:40: 20.
  • the swelling degree of the hollow microspheres at 85°C is 100%, the particle size D50 of the hollow microspheres is 2 ⁇ m, the shell thickness of the hollow microspheres is 1.5 ⁇ m, and the hollow microspheres account for 40% of the total mass of the mixed coating.
  • the first binder accounts for 50% of the total mass of the mixed coating; the second binder accounts for 10% of the total mass of the mixed coating.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • the above-mentioned separator is placed between the positive pole piece and the negative pole piece, and the electrode assembly is obtained after winding.
  • the electrode assembly is placed in the outer packaging shell, dried and injected into the electrolyte, and then vacuum packaged, left standing, and formed into Shaping and other processes to obtain lithium-ion batteries.
  • Example 2 The preparation steps of Example 2 are approximately the same as that of Example 1, except that the hollow microspheres have a particle size D50 of 45 ⁇ m.
  • Example 3 The preparation steps of Example 3 are approximately the same as those of Example 1, except that the hollow microspheres have a particle size D50 of 3 ⁇ m.
  • Example 4 The preparation steps of Example 4 are approximately the same as those of Example 1, except that the hollow microspheres have a particle size D50 of 8 ⁇ m.
  • Example 5 The preparation steps of Example 5 and Example 1 are roughly the same, except that the hollow microspheres have a particle size D50 of 12 ⁇ m.
  • Example 6 The preparation steps of Example 6 are approximately the same as those of Example 1, except that the hollow microspheres have a particle size D50 of 16 ⁇ m.
  • Example 7 The preparation steps of Example 7 are approximately the same as that of Example 1, except that the hollow microspheres have a particle size D50 of 20 ⁇ m.
  • Example 8 The preparation steps of Example 8 are approximately the same as those of Example 1, except that the hollow microspheres have a particle size D50 of 30 ⁇ m.
  • Example 9 The preparation steps of Example 9 are approximately the same as those of Example 1, except that the hollow microspheres have a particle size D50 of 40 ⁇ m.
  • Example 10 and Example 4 The preparation steps of Example 10 and Example 4 are roughly the same, except that the mass ratio of the polymerized monomers MMA, ACN and EGDMA of the hollow microspheres is 5:70:25, and the swelling degree of the hollow microspheres is 40%.
  • Example 11 and Example 4 The preparation steps of Example 11 and Example 4 are roughly the same, except that the mass ratio of the polymerized monomers MMA, ACN and EGDMA of the hollow microspheres is 65:20:15, and the swelling degree of the hollow microspheres is 300%.
  • Example 12 The preparation steps of Example 12 are roughly the same as those of Example 4, except that the mass ratio of the polymerized monomers MMA, ACN and EGDMA of the hollow microspheres is 15:55:303, and the swelling degree of the hollow microspheres is 60%.
  • Example 13 The preparation steps of Example 13 are approximately the same as that of Example 4, except that the mass ratio of the polymerized monomers MMA, ACN and EGDMA of the hollow microspheres is 25:45:30, and the swelling degree of the hollow microspheres is 80%.
  • Example 14 and Example 4 are roughly the same, except that the mass ratio of the polymerized monomers MMA, ACN and EGDMA of the hollow microspheres is 55:25:20, and the swelling degree of the hollow microspheres is 200%.
  • Example 15 The preparation steps of Example 15 are approximately the same as those of Example 4, except that the hollow microspheres account for 5% of the total mass of the hybrid coating, and the first binder accounts for 85% of the total mass of the hybrid coating.
  • Example 16 and Example 4 The preparation steps of Example 16 and Example 4 are roughly the same, except that the hollow microspheres account for 85% of the total mass of the hybrid coating, and the first binder accounts for 5% of the total mass of the hybrid coating.
  • Example 17 The preparation steps of Example 17 are approximately the same as that of Example 4, except that the hollow microspheres account for 10% of the total mass of the hybrid coating, and the first binder accounts for 80% of the total mass of the hybrid coating.
  • Example 18 and Example 4 are roughly the same, except that the hollow microspheres account for 80% of the total mass of the hybrid coating, and the first binder accounts for 10% of the total mass of the hybrid coating.
  • Example 19 The preparation steps of Example 19 are approximately the same as that of Example 4, except that the thickness of the shell layer of the hollow microspheres is 0.4 ⁇ m.
  • Example 20 The preparation steps of Example 20 are approximately the same as those of Example 4, except that the thickness of the shell layer of the hollow microspheres is 7 ⁇ m.
  • Example 21 The preparation steps of Example 21 are approximately the same as those of Example 4, except that the thickness of the shell layer of the hollow microspheres is 0.5 ⁇ m.
  • Example 22 The preparation steps of Example 22 are approximately the same as those of Example 4, except that the thickness of the shell layer of the hollow microspheres is 3 ⁇ m.
  • Example 23 The preparation steps of Example 23 are approximately the same as that of Example 4, except that the thickness of the shell layer of the hollow microspheres is 5 ⁇ m.
  • Example 24 The preparation steps of Example 24 are approximately the same as those of Example 4, except that the thickness of the shell layer of the hollow microspheres is 6 ⁇ m.
  • Example 25 The preparation steps of Example 24 are approximately the same as those of Example 4, except that the thickness of the shell layer of the hollow microspheres is 6 ⁇ m.
  • Example 25 and Example 4 are roughly the same, except that there is no ceramic coating on the diaphragm substrate.
  • the hybrid coating also includes boehmite particles, the hollow microspheres account for 55% of the total mass of the hybrid coating, the boehmite particles account for 30% of the total mass of the hybrid coating, and the first binder accounts for the total mass of the hybrid coating.
  • the second binder accounts for 10% of the total mass of the mixed coating.
  • Example 26 The preparation steps of Example 26 are approximately the same as that of Example 4, except that there is no ceramic coating on the diaphragm substrate.
  • the hybrid coating also includes boehmite particles, the hollow microspheres account for 65% of the total mass of the hybrid coating, the boehmite particles account for 20% of the total mass of the hybrid coating, and the first binder accounts for the total mass of the hybrid coating.
  • the second binder accounts for 10% of the total mass of the mixed coating.
  • Example 27 The preparation steps of Example 27 are approximately the same as that of Example 4, except that there is no ceramic coating on the diaphragm substrate.
  • the hybrid coating also includes boehmite particles, the hollow microspheres account for 75% of the total mass of the hybrid coating, the boehmite particles account for 10% of the total mass of the hybrid coating, and the first binder accounts for the total mass of the hybrid coating. The second binder accounts for 10% of the total mass of the mixed coating.
  • Comparative Example 1 and Example 4 The preparation steps of Comparative Example 1 and Example 4 are roughly the same, except that the hollow microspheres account for 0% of the total mass of the mixed coating, that is, no hollow microspheres are added; the first binder accounts for 96% of the total mass of the mixed coating, The second binder accounts for 4% of the total mass of the mixed coating.
  • Comparative Example 2 and Example 4 The preparation steps of Comparative Example 2 and Example 4 are roughly the same, except that the hollow microspheres account for 0% of the total mass of the hybrid coating, that is, no hollow microspheres are added; the first binder accounts for 84% of the total mass of the hybrid coating. The second binder accounts for 16% of the total mass of the mixed coating.
  • Comparative Example 3 The preparation steps of Comparative Example 3 are approximately the same as those of Example 4, except that the preparation steps of the diaphragm are:
  • FIG. 11A After performing scanning electron microscopy tests on the diaphragm before liquid injection in Example 1, the result is shown in FIG. 11A, wherein the hollow microspheres have not been broken yet and are distributed on the surface in the form of microspheres.
  • Scanning electron microscopy was performed again on the diaphragm after infiltration in the electrolyte of Example 1, and the result is shown in FIG. 11B, where the hollow microspheres swelled to breakage, and were laid flat on the surface in a continuous ring shape. Scanning electron microscopy tests were performed on the diaphragms of other examples in the same way, and the results are recorded in Table 1.
  • the separators prepared in Examples 1-27 and Comparative Examples 1-3 were tested for the unit adhesive force of the separator and the negative electrode after dry pressing with the 180° peel strength test method. Specifically, the separator and the negative electrode piece are cut into a sample with a size of 54.2mm ⁇ 72.5mm, and the separator and the negative electrode piece are overlapped and then hot-pressed using a hot press.
  • the hot-pressing conditions are: temperature of 85°C and pressure It is 1Mpa and the time is 85s; the sample after the hot pressing is cut into a size of 15mm ⁇ 54.2mm, and the unit adhesive force is tested according to the 180° peel strength test method. The results are recorded in Table 1.
  • the batteries prepared in Examples 1-27 and Comparative Examples 1-3 were subjected to charge-discharge cycle performance tests. Specifically, the charge-discharge cycle performance is tested in an environment of 12°C.
  • the process of the charge-discharge cycle performance test includes: (1) Let the assembled battery stand for 5 minutes; (2) Charge the battery at a constant current of 2C to 4.45V, Constant voltage discharge to 0.05C; (3) stand for 5min; (4) 0.2C constant current discharge to 3.0V; (5) stand for 5min; (6) 2C constant current charge to 4.45V, constant voltage discharge to 0.05C ; (7) Let stand for 5 min; (8) 1C constant current discharge to 3.0V; (9) Let stand for 5 min; (10) Step 6 to 9 cycle 49 times; (11) 2C constant current charge to 4.45V, constant Voltage discharge to 0.05C; (12) Let stand for 5 min; (13) Discharge at 0.2C constant current to 3.0V; (14) Let stand for 5 min. Steps (11)-(14) are cycled until the capacity has decaye
  • the capacity retention rate (%) after N cycles of the battery is the ratio of the discharge capacity D N after the N cycles to the discharge capacity D 3 , that is, the battery
  • the capacity retention rate after N cycles D N /D 3 ⁇ 100%.
  • the capacity retention rate in this application specifically refers to the capacity retention rate after 800 cycles of the battery.
  • the calculation results are recorded in Table 1.
  • the particle size D50 of the hollow microspheres will affect the performance of the battery.
  • the hollow microspheres of Example 1 have a smaller particle size D50, and the gap formed between the diaphragm and the pole piece is smaller, resulting in a relatively small cycle capacity retention rate of the battery of Example 1 Lower.
  • the hollow microspheres of Example 2 have a relatively large particle size D50, which affects the bonding performance of the hybrid coating. Therefore, the battery of Example 2 has a relatively low separator bonding force and a relatively low cycle capacity retention rate.
  • the swelling degree of the hollow microspheres will also affect the performance of the battery.
  • the swelling degree of the hollow microspheres of Example 10 is relatively small, and the hollow microspheres of Example 10 are not swollen to be broken. It only collapses into a disc and is loaded on the surface of the separator, resulting in a relative decrease in the capacity retention rate of the battery.
  • the battery capacity retention rate of Example 14 is lower than that of Examples 4 and 12-13. This is because of the hollowness of Example 14.
  • the swelling degree of the microspheres is 200%, which is located at the critical point where the hollow microspheres may be dissolved in the electrolyte, resulting in that the hollow microspheres may be partially dissolved in the electrolyte, resulting in a relatively lower battery capacity retention rate; the hollow microspheres of Example 11
  • the swelling degree of the ball is relatively large, and the hollow microspheres are partially dissolved in the electrolyte, which causes the capacity retention rate of the battery to decrease relatively.
  • the proportion of hollow microspheres in the total mass of the hybrid coating also affects the performance of the battery.
  • the hollow microspheres of Example 15 have a lower mass percentage, and the gaps formed in the corner area are smaller. Therefore, the problem of discontinuous electrolyte distribution in the corner area is not sufficiently improved, resulting in battery capacity retention
  • the rate is relatively low; the hollow microspheres of Example 16 have a relatively high mass percentage, and the amount of the binder is relatively small, resulting in a relatively low bonding force.
  • the thickness of the shell layer of the hollow microspheres also affects the performance of the battery. Compared with Examples 4, 21-24, the shell thickness of the hollow microspheres of Example 19 is smaller, resulting in a relatively low battery capacity retention rate; the hollow microspheres of Example 20 have a larger shell thickness, and the hollow microspheres The ball did not swell to breakage in the electrolyte, thus resulting in a relatively low battery capacity retention rate.
  • Example 4 Compared with Example 4, since the ceramic coating is omitted in Examples 25-27, and a certain content of inorganic ceramic particles is added to the mixed coating, the proportion of the binder in the total mass of the mixed coating is relatively reduced. , Which affects the bonding performance of the hybrid coating. Therefore, compared with Example 4, the batteries of Examples 25-27 have lower membrane adhesion and a relatively lower cycle capacity retention rate.

Abstract

一种隔膜（100、200、300、400、500、600），隔膜（100、200、300、400、500、600）包括隔膜基材（10）。所述隔膜（100、200、300、400、500、600）还包括混合涂层（30），所述混合涂层（30）设置于所述隔膜基材（10）的表面，所述混合涂层（30）包括中空微球（32）以及粘结剂（34），所述中空微球（32）能够在电解液中溶胀后破损。一种包括隔膜（100、200、300、400、500、600）的电极组件（2）、包括电极组件（2）的电池（3）及包括电池（3）的电子装置（4）。

Description

隔膜、电极组件、电池及电子装置 技术领域
本申请涉及电池隔膜领域，尤其涉及一种隔膜、包括隔膜的电极组件、包括电极组件的电池及包括电池的电子装置。
背景技术
锂离子电池具有比能量大、工作电压高、自放电率低、体积小、重量轻等优势，在消费电子领域具有广泛的应用。然而随着电动汽车和可移动电子设备的高速发展，人们对电池的性能(尤其是能量密度以及循环性能)的要求越来越高。
现有技术中，通常需要设置具有高粘结性能的隔膜，将正负极极片分别与隔膜紧密粘结在一起，保证隔膜与极片的界面粘结力，减少电芯膨胀变形，并保证电池的循环能力。然而，通过设置具有高粘结性能的隔膜，不利于锂离子电池动力学性能或低温循环性能的提升。
发明内容
为解决现有技术以上不足，有必要提供一种能够有效提升电池动力学或低温循环性能的隔膜。
另，还有必要提供一种包括该隔膜的电极组件。
另，还有必要提供一种包括该电极组件的电池。
另，还有必要提供一种包括该电池的电子装置。
本申请提供一种隔膜，包括隔膜基材。所述隔膜还包括混合涂层，所述混合涂层设置于所述隔膜基材的表面，所述混合涂层包括中空微球以及粘结剂，所述中空微球能够在电解液中溶胀后破损。
本申请提供的隔膜设有混合涂层且混合涂层中含有中空微球。 由于中空微球具有一定的粒径，能够使得隔膜和极片之间存在一定的间隙，一方面，在注液过程中，电解液能够更充分地浸润极片。另一方面，在电池注液后，中空微球可在电解液中溶胀至破损，位于主体区域的间隙在后续电池化成的热压条件下消失，可避免电池体积能量密度损失；而位于拐角区域的间隙仍存在，可为极片循环膨胀预留空间，减小拐角区域受到的挤压，避免拐角区域电解液不连续分布，保证离子通道畅通，从而提高电池的循环能力。
在本申请一些实施例中，所述混合涂层还包括无机陶瓷颗粒。
在本申请一些实施例中，所述隔膜还包括陶瓷涂层，所述陶瓷涂层涂覆在所述隔膜基材的至少一个表面上，所述混合涂层位于所述陶瓷涂层上和/或未涂覆所述陶瓷涂层的隔膜基材的表面上。
在本申请一些实施例中，中空微球的粒径D50为3μm-40μm。若中空微球的粒径D50小于3μm，则难以在隔膜与极片之间形成足够的间隙，较难改善拐角区域电解液不连续分布的问题；若中空微球的粒径D50大于40μm，会影响混合涂层的粘结性能。
在本申请一些实施例中，中空微球的壳层厚度为0.5μm-6μm。若中空微球的壳层厚度小于0.5μm，易于破损，不利于提高电池的循环能力并改善拐角区域紫斑析锂的问题；若中空微球的壳层厚度大于6μm，则中空微球难以在电解液中溶胀至破损，一方面会损失电池的体积能量密度，另一方面会影响混合涂层的粘结性能。
在本申请一些实施例中，中空微球在电解液中溶胀度为60％-200％。若中空微球的溶胀度小于60％，则中空微球在电解液中难以溶胀至破损，一方面增加了电池整体的厚度，从而降低电池的体积能量密度，另一方面会影响混合涂层的粘结性能；若中空微球的溶胀度大于200％，则中空微球易溶解于电解液中，导致电解液浓度增加，从而降低电解液中离子传输的速率，同时溶解于电解液中的中空微球的成分会增加电池充放电过程中副反应发生的概率，导致电池循环性能的下降。
在本申请一些实施例中，中空微球的壳层为均聚物或共聚物，中空微球的壳层的聚合单体选自丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙烯酯、乙二醇二甲基丙烯酸酯以及丙烯腈中的至少一种。
在本申请一些实施例中，中空微球占混合涂层总质量的10％-80％，粘结剂占混合涂层总质量的20％-90％。若中空微球的质量低于10％，则中空微球数量太少，较难在拐角区域形成足够的间隙；若中空微球的质量分数高于90％，则粘结剂的量过少，影响混合涂层的粘结性能。
在本申请一些实施例中，粘结剂包括第一粘结剂以及第二粘结剂，第一粘结剂与第二粘结剂的质量比为(85％-95％)：(5％-15％)；第一粘结剂的粒径D50为0.3μm-0.5μm。
在本申请一些实施例中，第一粘结剂为核壳结构，核壳结构的内核和外壳为均聚物或共聚物，内核的聚合单体选自丙烯酸酯类单体、芳香族单乙烯基化合物以及马来酸等羧酸的酸酐中的至少一种；外壳的聚合单体选自丙烯酸酯类单体、芳香族单乙烯基化合物以及腈化乙烯基化合物中的至少一种。
在本申请一些实施例中，第一粘结剂为非核壳结构，非核壳结构为均聚物或共聚物，非核壳结构的聚合单体选自丙烯酸、丙烯酸酯、丁二烯、苯乙烯、丙烯腈、乙烯、氯苯乙烯、氟苯乙烯以及丙烯中的至少一种。
本申请还提供一种电极组件，包括如上隔膜。
本申请还提供一种电池，包括电解液，电池还包括电极组件，电极组件的隔膜表面包括由中空微球破损形成的聚合物。
本申请还提供一种电子装置，包括如上电池。
附图说明
图1为本申请一实施方式提供的隔膜的中空微球未破损时的结构示意图。
图2A为图1所示的隔膜的中空微球破损后呈饼状的结构示意图。
图2B为图1所示的隔膜的中空微球破损后呈环形的结构示意图。
图3为本申请另一实施方式的隔膜的结构示意图。
图4为本申请又一实施方式的隔膜的结构示意图。
图5为本申请再一实施方式的隔膜的结构示意图。
图6为本申请再一实施方式的隔膜的结构示意图。
图7为本申请其它实施方式的隔膜的结构示意图。
图8为本申请一实施方式提供的电极组件的结构示意图。
图9为本申请一实施方式提供的电池的结构示意图。
图10为本申请一实施方式提供的电子装置的结构示意图。
图11A为实施例1制备的隔膜的中空微球未破损之前的扫描电镜(SEM)测试图。
图11B为图11A所示的隔膜的中空微球破损后的扫描电镜测试图。
主要元件符号说明
电极组件                      2
电池                          3
电子装置                      4
隔膜基材                      10
陶瓷涂层                      20
混合涂层                      30
中空微球                      32
粘结剂                        34
无机陶瓷颗粒                  36
隔膜                          100、200、300、400、500、600
第一粘结剂                    342
第二粘结剂                    344
负极极片                      210
正极极片                      220
主体区域                      232
拐角区域                      234
壳体                          310
如下具体实施方式将结合上述附图进一步说明本申请。
具体实施方式
为了能够更清楚地理解本申请的上述目的、特征和优点，下面结合附图和具体实施方式对本申请进行详细描述。需要说明的是，在不冲突的情况下，本申请的实施方式及实施方式中的特征可以相互组合。在下面的描述中阐述了很多具体细节以便于充分理解本申请，所描述的实施方式仅仅是本申请一部分实施方式，而不是全部的实施方式。基于本申请中的实施方式，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，都属于本申请保护的范围。
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。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本申请。本文所使用的术语“和/或”包括一个或多个相关的所列项目的所有的和任意的组合。
在本申请的各实施例中，为了便于描述而非限制本申请，本申请专利申请说明书以及权利要求书中使用的术语“连接”并非限定于物理的或者机械的连接，不管是直接的还是间接的。“上”、“下”、“上方”、“下方”、“左”、“右”等仅用于表示相对位置关系，当被描述对象的绝对位置改变后，则该相对位置关系也相应地改变。
请参阅图1，本申请一实施方式提供一种隔膜100，隔膜100包括隔膜基材10以及混合涂层30。混合涂层30设置于隔膜基材10的表面。混合涂层30包括中空微球32以及粘结剂34，中空微球32能够在电解液中溶胀后破损。
如图1所示，在一实施方式中，隔膜100还包括陶瓷涂层20，陶瓷涂层20涂覆于隔膜基材10的至少一个表面上。混合涂层30位于陶瓷涂层20和/或未涂覆所述陶瓷涂层20的隔膜基材10的表面。例如，陶瓷涂层20位于隔膜基材10的一个表面，混合涂层30的数量为两个，一个混合涂层30位于陶瓷涂层20的表面，另一混合涂层30位于隔膜基材10未设有陶瓷涂层20的表面。其中，陶瓷涂层20用于提高隔膜100的耐热性和抗穿刺能力。
请参阅图2A，内部中空的结构使得中空微球32破损后，可呈饼状平铺于隔膜基材10和/或陶瓷涂层20的表面。请参阅图2B，中空微球32破损程度较高(即，中空微球32发生破碎)，呈连续环形平铺于隔膜基材10和/或陶瓷涂层20的表面。所述中空微球32破碎后还可以呈点状环形平铺于隔膜基材10和/或陶瓷涂层20的表面。
本申请发明人发现，现有技术中由于隔膜与极片粘结在一起，导致隔膜与极片之间的间隙较小，一方面电解液较难充分浸润极片，另一方面，由于负极极片在电池充放电循环过程中膨胀变形，使得极片拐角区域受到挤压，将位于拐角区域的电解液挤出，导致位于拐角区域的电解液不连续分布，离子通道受阻断，从而导致在循环过程中拐角区域产生紫斑析锂问题，导致电池的动力学性能或低温循环性能下降。
本申请提供的隔膜100设有混合涂层30且混合涂层30中含有中空微球32以及粘结剂34。粘结剂34用于将中空微球32粘结在一起，同时使混合涂层30粘附于隔膜基材10和/或陶瓷涂层20的表面。由于中空微球32具有一定的粒径，能够使得隔膜100和极片 之间产生一定的间隙，一方面，在注液过程中，电解液能够更充分地浸润极片。
另一方面，电池注液后，由于中空微球32的耐电解液性能差，可在电解液中溶胀至破损，位于主体区域的间隙在后续电池化成的热压条件下消失，可避免电池体积能量密度损失；而位于拐角区域的间隙仍存在，可为极片循环膨胀预留空间，有利于减小拐角区域受到的挤压，避免拐角区域电解液不连续分布，保证离子通道畅通。进一步地，相较于中空微球32破损后呈饼状平铺于隔膜基材10和/或陶瓷涂层20的表面，当中空微球32破损后呈环形平铺于隔膜基材10和/或陶瓷涂层20的表面时，可最大程度地避免堵塞隔膜100中的离子通道，从而避免造成电池循环性能的下降。
请参阅图3，本申请另一实施方式还提供一种隔膜200，与上述隔膜100不同之处在于，混合涂层30的数量仅为一个，且位于陶瓷涂层20的表面。
请参阅图4，本申请又一实施方式还提供一种隔膜300，与上述隔膜100不同之处在于，混合涂层30的数量仅为一个，且位于隔膜基材10未设有陶瓷涂层20的表面。
请参阅图5，本申请再一实施方式还提供一种隔膜400，与上述隔膜100不同之处在于，陶瓷涂层20的数量为两个，且分别位于隔膜基材10相对的两表面。混合涂层30的数量仅为一个，且位于其中一陶瓷涂层20的表面。
请参阅图6，本申请再一实施方式还提供一种隔膜500，与上述隔膜100不同之处在于，陶瓷涂层20的数量为两个，且分别位于隔膜基材10相对的两表面。两个混合涂层30分别位于两个陶瓷涂层20的表面。
在本实施方式中，隔膜基材10的材质可以选自聚乙烯(polyethylene，简称PE)、聚丙烯(Polypropylene，简称PP)以及聚对苯二甲酸乙二醇酯(Polyethylene terephthalate，简称PET) 等材料中的至少一种。隔膜基材10可以是单层结构或者多种混合的多层复合结构。隔膜基材10的厚度可以为3μm-20μm。
在本实施方式中，陶瓷涂层20中的无机陶瓷颗粒包括三氧化二铝、勃姆石、硫酸钡、二氧化钛以及氢氧化镁中的至少一种。陶瓷涂层20的厚度为0.5μm-6μm。
请参阅图7，本申请其它实施方式还提供一种隔膜600，与上述隔膜100不同之处在于，隔膜600不含有陶瓷涂层。此时，混合涂层30还包括无机陶瓷颗粒36。混合涂层30的无机陶瓷颗粒36包括三氧化二铝、勃姆石、硫酸钡、二氧化钛以及氢氧化镁中的至少一种。通过在混合涂层30中添加无机陶瓷颗粒36，可同样提高隔膜600的耐热性和抗穿刺能力。
在本申请一些实施方式中，由于中空微球32为内部中空的球体结构，即中空微球32具有壳层，在本实施方式中，中空微球32的壳层厚度为0.5μm-6μm。本申请发明人发现，若中空微球32的壳层厚度小于0.5μm，易于破损，无法在隔膜100和极片之间形成间隙，电解液较难充分浸润极片，不利于提高电池的循环能力，进一步地由于未在拐角区域形成间隙，无法改善拐角区域紫斑析锂的问题；若中空微球32的壳层厚度大于6μm，则中空微球32难以在电解液中溶胀破损，一方面会损失电池的能量密度，另一方面会影响混合涂层30的粘结性能，从而影响电池的循环性能。
中空微球32的粒径D50为3μm-40μm。本申请发明人发现，若中空微球32的粒径D50小于3μm，则难以在隔膜100与极片之间形成足够的间隙，较难改善拐角区域电解液不连续分布的问题；若中空微球32的粒径D50大于40μm，会影响混合涂层30的粘结性能，从而影响电池的循环性能。
中空微球32在电解液中的溶胀度为60％-200％。其中，溶胀度为中空微球32溶胀后与溶胀前的质量之差与中空微球32溶胀前的质量之间的比值。具体地，称取中空微球32的初始质量为W 0，然 后将中空微球32置于电解液中，并在85℃的温度下保温24h后，称取溶胀后的中空微球32的质量为Wt，则中空微球32在电解液中的溶胀度的计算公式为：
Figure PCTCN2020082433-appb-000001
本申请发明人发现，若中空微球32的溶胀度小于60％，则中空微球32在电解液中难以溶胀至破损，会增加电池整体的厚度，从而降低电池的体积能量密度，另一方面会影响混合涂层30的粘结性能，从而影响电池的循环性能；若中空微球32的溶胀度大于200％，则中空微球32易溶解于电解液中，导致电解液粘度增加，降低电解液中离子传输的速率，同时溶解于电解液中的中空微球32的成分会增加电池充放电过程中副反应发生的概率，导致电池循环性能的下降。
中空微球32占混合涂层30总质量的10％-80％，粘结剂34占混合涂层30总质量的20％-90％。本申请发明人发现，若中空微球32的质量低于10％，则中空微球32数量太少，较难在拐角区域形成足够的间隙；若中空微球32的质量分数高于90％，则粘结剂34的量过少，影响混合涂层30的粘结性能。
在本实施方式中，中空微球32的壳层的材质为均聚物或共聚物，其中，中空微球32的壳层的聚合单体选自丙烯酸甲酯(methyl acrylate，简称MA)、甲基丙烯酸甲酯(methyl methacrylate，简称MMA)、甲基丙烯酸乙烯酯(vinyl methacrylate，简称VMA)、乙二醇二甲基丙烯酸酯(ethylene glycol dimethacrylate，简称EGDMA)以及丙烯腈(acrylonitrile，简称ACN)中的至少一种。其中，中空微球32的壳层的材质取决于聚合单体的种类，而中空微球32的壳层的材质会影响中空微球32在电解液中的溶胀度。
如图1所示，在本实施方式中，粘结剂34包括第一粘结剂342以及第二粘结剂344，第一粘结剂342与第二粘结剂344的质量比 为(85％-95％)：(5％-15％)。其中，第一粘结剂342的粒径D50为0.3μm-5μm。
进一步地，第一粘结剂342可以为核壳结构，核壳结构包括内核以及内核的外壳。内核以及外壳为均聚物或共聚物。
内核的聚合单体选自丙烯酸酯类单体、芳香族单乙烯基化合物以及酸酐中的至少一种。其中，丙烯酸酯类单体包括但不限于丙烯酸乙酯、丙烯酸丁酯以及甲基丙烯酸乙酯。芳香族单乙烯基化合物包括但不限于苯乙烯、氯苯乙烯、氟苯乙烯以及甲基苯乙烯；酸酐包括但不限于丙烯酸、甲基丙烯酸以及马来酸。
外壳的聚合单体选自丙烯酸酯类单体、芳香族单乙烯基化合物以及腈化乙烯基化合物中的至少一种。丙烯酸酯类单体包括但不限于丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯以及甲基丙烯酸丁酯。芳香族单乙烯基化合物包括但不限于乙烯、氯苯乙烯、氟苯乙烯以及甲基苯乙烯。腈化乙烯基化合物包括但不限于丙烯腈以及甲基丙烯腈。
在另一实施方式中，第一粘结剂342也可以为非核壳结构，第一粘结剂342为均聚物或共聚物。第一粘结剂342的聚合单体包括但不限于丙烯酸、丙烯酸酯、丁二烯、苯乙烯、丙烯腈、乙烯、氯苯乙烯、氟苯乙烯以及丙烯。
请参阅图8，为本申请一实施方式还提供一种电极组件2，电极组件2包括正极极片220、负极极片210以及隔膜100(或隔膜200、300、400、500、600)，隔膜100位于正极极片220以及负极极片210之间。正极极片220、隔膜100和负极极片210经卷绕形成电极组件2。
其中，电极组件2包括拐角区域234和除拐角区域234之外的主体区域232。位于主体区域232的间隙在后续电池化成的热压条件下消失，避免电池体积能量密度损失；而位于拐角区域234的间隙仍存在，从而为极片循环膨胀预留空间，有利于减小拐角区域234 受到的挤压，避免拐角区域234的电解液不连续分布，保证离子通道畅通，避免拐角区域234产生紫斑析锂的问题。
其中，正极极片220包括正极材料以及导电剂，正极材料包括但不限于钴酸锂、锰酸锂、镍锰酸锂以及镍钴锰酸锂中的至少一种；导电剂包括但不限于导电炭黑、片层石墨、碳纳米管以及石墨烯中的至少一种。
请参阅图9，本申请一实施方式还提供一种电池3，电池3包括壳体310、电极组件2以及电解液，电极组件2收容于壳体310中，电解液容置于壳体310中，电极组件2中的隔膜100被电解液浸润。请一并参照图2A和图2B，隔膜100上的中空微球32在电解液的作用下溶胀破损，呈饼状、连续环形或点状环形(即多个不连续的点构成环形结构)的聚合物负载于隔膜100的表面。
请参阅图10，本申请一实施方式还提供一种电子装置4，电子装置4包括电池3。其中，电子装置4可以是消费性电子产品(如移动通信装置、平板电脑、笔记本电脑等)、电动工具、无人机、储能装置、动力装置等。参照图10，在一实施方式中，电子装置4为电动汽车。
以下通过具体实施例和对比例来对本申请进行说明。其中，以下具体实施例以混合涂层30涂覆于陶瓷涂层20的表面为例，但是可以理解，混合涂层30与陶瓷涂层20以及隔膜基材10具有多种组合形式，在其他的实施例中，并不限于此种实施方式。实施例1
正极极片制备：将钴酸锂、导电炭黑以及聚偏二氟乙烯按质量比为97：1.4：1.6的比例溶于N-甲基吡咯烷酮(NMP)溶剂中，形成正极浆料。采用铝箔作为正极集流体，将正极浆料涂覆于正极集流体上，经过干燥、冷压、裁切程序后得到正极极片。
负极极片制备：将石墨、导电炭黑、羧甲基纤维素钠(CMC)以及丁苯橡胶(SBR)按质量比为96.5：1.0：1.0：1.5的比例溶于去离子水中，在真空搅拌机作用下搅拌至体系呈均一状，获得负极 浆料。采用铜箔作为负极集流体，将负极浆料涂覆于负极集流体的两个表面上，烘干后经过冷压、分切得到负极极片。
隔膜制备：将第一粘结剂加入搅拌器中，第一粘结剂的聚合单体包括苯乙烯、丙烯酸异丙酯以及丙烯腈，苯乙烯、丙烯酸异丙酯以及丙烯腈的质量比为80：10：10，然后分两次加入中空微球并搅拌(每次加入50％)，然后再加入第二粘结剂，第二粘结剂的聚合单体包括丙烯腈以及丙烯酸，丙烯腈和丙烯酸的质量比为50：50，最后加入去离子水进行搅拌，得到混合涂层浆料，将混合涂层浆料涂覆于具有陶瓷涂层的隔膜基材上，在烘箱中完成干燥，得到具有混合涂层和陶瓷涂层的隔膜。其中，中空微球的聚合单体为甲基丙烯酸甲酯(MMA)、丙烯腈(ACN)以及乙二醇二甲基丙烯酸酯(EGDMA)，MMA、ACN和EGDMA的质量比为40：40：20，中空微球在85℃下的溶胀度为100％，中空微球粒径D50为2μm，中空微球的壳层厚度为1.5μm，中空微球占混合涂层总质量的40％，第一粘结剂占混合涂层总质量的50％；第二粘结剂占混合涂层总质量的10％。
电解液的制备：在干燥氩气气氛中，首先将有机溶剂碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)和碳酸二乙酯(DEC)以质量比EC:EMC:DEC＝30:50:20混合，然后向有机溶剂中加入六氟磷酸锂(LiPF 6)溶解并混合均匀，得到锂盐的浓度为1.15M的电解液。
电池制备：将上述隔膜置于正极极片以及负极极片之间，卷绕后得到电极组件，将电极组件置于外包装壳中，干燥后注入电解液，经过真空封装、静置、化成、整形等工序，获得锂离子电池。
实施例2
实施例2与实施例1的制备步骤大致相同，区别在于中空微球粒径D50为45μm。
实施例3
实施例3与实施例1的制备步骤大致相同，区别在于中空微球 粒径D50为3μm。
实施例4
实施例4与实施例1的制备步骤大致相同，区别在于中空微球粒径D50为8μm。
实施例5实施例5与实施例1的制备步骤大致相同，区别在于中空微球粒径D50为12μm。
实施例6
实施例6与实施例1的制备步骤大致相同，区别在于中空微球粒径D50为16μm。
实施例7
实施例7与实施例1的制备步骤大致相同，区别在于中空微球粒径D50为20μm。
实施例8
实施例8与实施例1的制备步骤大致相同，区别在于中空微球粒径D50为30μm。
实施例9
实施例9与实施例1的制备步骤大致相同，区别在于中空微球粒径D50为40μm。
实施例10
实施例10与实施例4的制备步骤大致相同，区别在于中空微球的聚合单体MMA、ACN和EGDMA的质量比为5：70：25，中空微球的溶胀度为40％。
实施例11
实施例11与实施例4的制备步骤大致相同，区别在于中空微球的聚合单体MMA、ACN和EGDMA的质量比为65：20：15，中空微球的溶胀度为300％。
实施例12
实施例12与实施例4的制备步骤大致相同，区别在于中空微球 的聚合单体MMA、ACN和EGDMA的质量比为15：55：303，中空微球的溶胀度为60％。
实施例13
实施例13与实施例4的制备步骤大致相同，区别在于中空微球的聚合单体MMA、ACN和EGDMA的质量比为25：45：30，中空微球的溶胀度为80％。
实施例14
实施例14与实施例4的制备步骤大致相同，区别在于中空微球的聚合单体MMA、ACN和EGDMA的质量比为55：25：20，中空微球的溶胀度为200％。
实施例15
实施例15与实施例4的制备步骤大致相同，区别在于中空微球占混合涂层总质量的5％，第一粘结剂占混合涂层总质量的85％。
实施例16
实施例16与实施例4的制备步骤大致相同，区别在于中空微球占混合涂层总质量的85％，第一粘结剂占混合涂层总质量的5％。
实施例17
实施例17与实施例4的制备步骤大致相同，区别在于中空微球占混合涂层总质量的10％，第一粘结剂占混合涂层总质量的80％。
实施例18
实施例18与实施例4的制备步骤大致相同，区别在于中空微球占混合涂层总质量的80％，第一粘结剂占混合涂层总质量的10％。
实施例19
实施例19与实施例4的制备步骤大致相同，区别在于中空微球的壳层厚度为0.4μm。
实施例20
实施例20与实施例4的制备步骤大致相同，区别在于中空微球的壳层厚度为7μm。
实施例21
实施例21与实施例4的制备步骤大致相同，区别在于中空微球的壳层厚度为0.5μm。
实施例22
实施例22与实施例4的制备步骤大致相同，区别在于中空微球的壳层厚度为3μm。
实施例23
实施例23与实施例4的制备步骤大致相同，区别在于中空微球的壳层厚度为5μm。
实施例24
实施例24与实施例4的制备步骤大致相同，区别在于中空微球的壳层厚度为6μm。实施例25
实施例25与实施例4的制备步骤大致相同，区别在于隔膜基材上不具有陶瓷涂层。而且，混合涂层还包括勃姆石颗粒，中空微球占混合涂层总质量的55％，勃姆石颗粒占混合涂层总质量的30％，第一粘结剂占混合涂层总质量的5％；第二粘结剂占混合涂层总质量的10％。
实施例26
实施例26与实施例4的制备步骤大致相同，区别在于隔膜基材上不具有陶瓷涂层。而且，混合涂层还包括勃姆石颗粒，中空微球占混合涂层总质量的65％，勃姆石颗粒占混合涂层总质量的20％，第一粘结剂占混合涂层总质量的5％；第二粘结剂占混合涂层总质量的10％。
实施例27
实施例27与实施例4的制备步骤大致相同，区别在于隔膜基材上不具有陶瓷涂层。而且，混合涂层还包括勃姆石颗粒，中空微球占混合涂层总质量的75％，勃姆石颗粒占混合涂层总质量的10％，第一粘结剂占混合涂层总质量的5％；第二粘结剂占混合涂层总质 量的10％。
对比例1
对比例1与实施例4的制备步骤大致相同，区别在于中空微球占混合涂层总质量的0％，即未添加中空微球；第一粘结剂占混合涂层总质量的96％，第二粘结剂占混合涂层总质量的4％。
对比例2
对比例2与实施例4的制备步骤大致相同，区别在于中空微球占混合涂层总质量的0％，即未添加中空微球；第一粘结剂占混合涂层总质量的84％，第二粘结剂占混合涂层总质量的16％。
对比例3
对比例3与实施例4的制备步骤大致相同，区别在于隔膜的制备步骤为：
将勃姆石颗粒、丙烯酸和羧甲基纤维素钠按质量比为94.5：5：0.5的比例加入搅拌器中，加入去离子水进行搅拌，得到混合涂层浆料，将混合涂层浆料涂覆于隔膜上，在烘箱中完成干燥，最后形成隔膜。。
经对实施例1注液之前的隔膜进行扫描电镜测试，结果如图11A所示，其中，中空微球尚未破碎，且呈微球状分布于表面。对实施例1电解液浸润之后的隔膜再次进行扫描电镜测试，结果如图11B所示，其中，中空微球发生溶胀至破损，呈连续环形平铺于表面。用相同的方法对其它实施例的隔膜进行扫描电镜测试，结果记录于表1中。
将实施例1-27以及对比例1-3制备的隔膜采用180°剥离强度测试方法测试隔膜与负极极片干压后的单位粘结力。具体地，将隔膜以及负极极片裁切成尺寸为54.2mm×72.5mm的样品，将隔膜与负极极片重叠放置后采用热压机进行热压，热压条件为：温度为85℃，压力为1Mpa，时间为85s；将热压后的样品裁切成尺寸为15mm×54.2mm，按照180°剥离强度测试方法测试单位粘结力，结果 记录于表1中。
对实施例1-27以及对比例1-3制备的电池进行充放电循环性能测试。具体地，充放电循环性能是在12℃的环境下进行测试，充放电循环性能测试的流程包括：(1)将组装完成的电池静置5min；(2)以2C恒流充电至4.45V，恒压放电至0.05C；(3)静置5min；(4)0.2C恒流放电至3.0V；(5)静置5min；(6)2C恒流充电至4.45V，恒压放电至0.05C；(7)静置5min；(8)1C恒流放电至3.0V；(9)静置5min；(10)第6至9步循环49次；(11)2C恒流充电至4.45V，恒压放电至0.05C；(12)静置5min；(13)0.2C恒流放电至3.0V；(14)静置5min。将步骤(11)-(14)循环至容量衰减至首次放电容量的60％或者循环至800次。
然后，以第三次循环结束时电池的放电容量D 3为基准，电池循环N次后的容量保持率(％)为循环N次后的放电容量D N与放电容量D 3的比值，即电池循环N次后的容量保持率＝D N/D 3×100％，本申请容量保持率特指电池循环800次后的容量保持率，计算结果记录于表1中。
表1
Figure PCTCN2020082433-appb-000002
从表1的测试结果可知，相较于对比例1-3，由于实施例1-27在隔膜的混合涂层中引入中空微球，因此实施例1-27的电池具有较高的循环容量保持率。
其中，在隔膜的混合涂层中引入中空微球的条件下，中空微球的粒径D50会影响电池的性能。其中，相较于实施例3-9，实施例1的中空微球的粒径D50较小，在隔膜与极片之间形成的间隙较小， 导致实施例1的电池的循环容量保持率相对较低。实施例2的中空微球的粒径D50较大，影响了混合涂层的粘结性能，因此实施例2的电池的隔膜粘结力较低，循环容量保持率也相对较低。
而且，中空微球的溶胀度也会影响电池的性能。其中，相较于实施例4、12-13的中空微球破裂后呈连续或者不连续的圆环状，实施例10的中空微球的溶胀度较小，中空微球未溶胀至破碎，而是仅坍塌为圆饼状负载于隔膜表面，导致电池的容量保持率相对下降，其中，实施例14的电池容量保持率相对实施例4、12-13较低，这是因为实施例14的中空微球的溶胀度为200％，位于可能使中空微球溶解于电解液的临界点，导致中空微球可能部分溶解于电解液中，使得电池的容量保持率相对下降；实施例11的中空微球的溶胀度较大，中空微球部分溶解于电解液中，导致电池的容量保持率也相对下降。
中空微球在混合涂层总质量中的占比也会影响电池的性能。相较于实施例4、17-18，实施例15的中空微球的质量占比较低，在拐角区域形成的间隙较小，因此未充分改善拐角区域电解液不连续分布问题，导致电池容量保持率相对较低；实施例16的中空微球的质量占比较高，则粘结剂的量相对较少，使得粘结力相对较低。
中空微球的壳层厚度也会影响电池的性能。相较于实施例4、21-24，实施例19的中空微球的壳层厚度较小，导致电池容量保持率相对较低；实施例20的中空微球的壳层厚度较大，中空微球未在电解液中溶胀至破损，因此导致电池容量保持率相对较低。
相较于实施例4，由于实施例25-27省略了陶瓷涂层，同时在混合涂层中增加一定含量的无机陶瓷颗粒，导致粘结剂在混合涂层总质量中的占比相对减小，影响了混合涂层的粘结性能。因此相较于实施例4，实施例25-27的电池的隔膜粘结力较低，循环容量保持率也相对较低。
以上实施方式仅用以说明本申请的技术方案而非限制，尽管参 照以上较佳实施方式对本申请进行了详细说明，本领域的普通技术人员应当理解，可以对本申请的技术方案进行修改或等同替换都不应脱离本申请技术方案的精神和范围。

Claims (14)

  1. 一种隔膜，包括隔膜基材，其特征在于，所述隔膜还包括：
    混合涂层，所述混合涂层设置于所述隔膜基材的表面，所述混合涂层包括中空微球以及粘结剂，所述中空微球能够在电解液中溶胀后破损。
  2. 根据权利要求1所述的隔膜，其特征在于，所述混合涂层还包括无机陶瓷颗粒。
  3. 根据权利要求1所述的隔膜，其特征在于，所述隔膜还包括陶瓷涂层，所述陶瓷涂层涂覆在所述隔膜基材的至少一个表面上，所述混合涂层位于所述陶瓷涂层上和/或未涂覆所述陶瓷涂层的隔膜基材的表面上。
  4. 根据权利要求1所述的隔膜，其特征在于，所述中空微球的粒径D50为3μm-40μm。
  5. 根据权利要求1所述的隔膜，其特征在于，所述中空微球的壳层厚度为0.5μm-6μm。
  6. 根据权利要求1所述的隔膜，其特征在于，所述中空微球在所述电解液中溶胀度为60％-200％。
  7. 根据权利要求1所述的隔膜，其特征在于，所述中空微球的壳层为均聚物或共聚物，所述中空微球的壳层的聚合单体选自丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙烯酯、乙二醇二甲基丙烯酸酯以及丙烯腈中的至少一种。
  8. 根据权利要求1所述的隔膜，其特征在于，所述中空微球占所述混合涂层总质量的10％-80％，所述粘结剂占所述混合涂层总质量的20％-90％。
  9. 根据权利要求1所述的隔膜，其特征在于，所述粘结剂包括第一粘结剂以及第二粘结剂，所述第一粘结剂与所述第二粘结剂的质量比为(85％-95％)：(5％-15％)；所述第一粘结剂的粒径D50为0.3μm-0.5μm。
  10. 根据权利要求9所述的隔膜，其特征在于，所述第一粘结剂为核壳结构，所述核壳结构的内核和外壳为均聚物或共聚物，所述内核的聚合单体选自丙烯酸酯类单体、芳香族单乙烯基化合物以及马来酸等羧酸的酸酐中的至少一种；所述外壳的聚合单体选自丙烯酸酯类单体、芳香族单乙烯基化合物以及腈化乙烯基化合物中的至少一种。
  11. 根据权利要求9所述的隔膜，其特征在于，所述第一粘结剂为非核壳结构，所述非核壳结构为均聚物或共聚物，所述非核壳结构的聚合单体选自丙烯酸、丙烯酸酯、丁二烯、苯乙烯、丙烯腈、乙烯、氯苯乙烯、氟苯乙烯以及丙烯中的至少一种。
  12. 一种电极组件，其特征在于，包括如权利要求1-11项中任一项所述的隔膜。
  13. 一种电池，包括电解液，其特征在于，所述电池还包括如权利要求12所述的电极组件，所述电极组件的隔膜表面包括由所述中空微球破损形成的聚合物。
  14. 一种电子装置，包括如权利要求13所述的电池。
PCT/CN2020/082433 2020-03-31 2020-03-31 隔膜、电极组件、电池及电子装置 WO2021195963A1 (zh)

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