WO2022141448A1 - 电化学装置、电子装置及电化学装置的制备方法 - Google Patents

电化学装置、电子装置及电化学装置的制备方法 Download PDF

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Publication number
WO2022141448A1
WO2022141448A1 PCT/CN2020/142272 CN2020142272W WO2022141448A1 WO 2022141448 A1 WO2022141448 A1 WO 2022141448A1 CN 2020142272 W CN2020142272 W CN 2020142272W WO 2022141448 A1 WO2022141448 A1 WO 2022141448A1
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Prior art keywords
material layer
electrochemical device
positive electrode
preparation
current collector
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PCT/CN2020/142272
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English (en)
French (fr)
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刘晓欠
韩冬冬
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东莞新能源科技有限公司
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Application filed by 东莞新能源科技有限公司 filed Critical 东莞新能源科技有限公司
Priority to KR1020237019589A priority Critical patent/KR20230093520A/ko
Priority to CA3203824A priority patent/CA3203824A1/en
Priority to EP20967787.1A priority patent/EP4213231A1/en
Priority to CN202080015281.1A priority patent/CN113474913B/zh
Priority to PCT/CN2020/142272 priority patent/WO2022141448A1/zh
Publication of WO2022141448A1 publication Critical patent/WO2022141448A1/zh
Priority to US18/194,000 priority patent/US20230238585A1/en

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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present application relates to the field of electrochemistry, in particular to an electrochemical device, an electronic device and a method for preparing the electrochemical device.
  • Lithium-ion batteries have the advantages of high energy storage density, high open circuit voltage, low self-discharge rate, long cycle life, and good safety performance. They are widely used in various fields such as electrical energy storage, mobile electronic equipment, electric vehicles, and aerospace equipment. With the rapid development of mobile electronic devices and electric vehicles, the market has put forward higher and higher requirements for the energy density, safety performance, cycle performance and service life of lithium-ion secondary batteries, among which safety performance is particularly important.
  • the purpose of the present application is to provide an electrochemical device, an electronic device and a method for preparing the electrochemical device, so as to improve the safety and reliability of the electrochemical device.
  • the present application is explained by taking a lithium ion battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion battery.
  • a first aspect of the present application provides an electrochemical device including a positive electrode, the positive electrode comprising a current collector, a first material layer and a second material layer, the second material layer being disposed on at least one surface of the current collector , the first material layer is arranged between the current collector and the second material layer, wherein the first material layer includes a leveling agent, and the thickness of the first material layer is the difference between the maximum value and the minimum value The difference is not more than 3 ⁇ m.
  • the thickness uniformity of the first material layer is poor, and it is easy to cause the coating to have areas with thinner thicknesses. As a result, the structural reliability of the electrochemical device is reduced.
  • the leveling agent is a polymer with a weight average molecular weight of not higher than 50,000.
  • polymers of olefin derivatives with a weight average molecular weight of not more than 50,000 siloxane polymers, alkenoate polymers, alcohol polymers or ether polymers.
  • the leveling agent can interact with the binder to improve the leveling property of the slurry of the first material layer, thereby making the thickness of the first material layer more uniform.
  • the leveling agent may comprise an olefin derivative polymer, a carboxylate polymer, a siloxane polymer, an alkenoate polymer, an alcohol polymer or an ether At least one kind of polymer, the weight-average molecular weight of the above-mentioned leveling agent may not be higher than 50,000.
  • the leveling agent comprises at least one of sodium carboxylate polymer, oxygen-containing propylene derivative polymer or polysiloxane, preferably, the leveling agent comprises polyethylene Oxypropoxypropene.
  • the weight-average molecular weight of the above-mentioned leveling agent may also be not higher than 50,000.
  • the first material layer further includes an active material, a binder, and a conductive agent.
  • the mass percentage of the active material is 50% to 98.89%
  • the adhesive The mass percentage content of the binder is 1% to 20%
  • the mass percentage content of the conductive agent is 0.1% to 20%
  • the mass percentage content of the leveling agent is 0.01% to 10%.
  • the thickness of the obtained first material layer can be made more uniform, so that the performance everywhere is consistent. Or puncture, it is not easy to be damaged locally.
  • the current collector and the adhesion between the second material layer and the first material layer are improved, thereby improving the safety and reliability of the electrochemical device.
  • the current collector includes a first material layer and a second material layer sequentially disposed on at least one surface of the current collector, which may be disposed on one surface of the current collector, or may be disposed on a surface of the current collector. on both surfaces.
  • the binder includes at least one of copolymers of propylene derivatives, polyacrylates, acrylonitrile multipolymers, and carboxymethyl cellulose salts.
  • the binder includes a polymer polymerized from at least one monomer selected from the group consisting of acrylic nitrile, acrylic acid salt, acrylamide, and acrylic acid ester.
  • the binder of the present application can be a water-based binder, wherein the metal ions in the acrylate can replace part of the hydrogen ions, thereby increasing the hydrophilicity of the binder and reducing the swelling of the binder in the electrolyte , to maintain high adhesion.
  • the metal ions in the acrylate can replace part of the hydrogen ions, thereby increasing the hydrophilicity of the binder and reducing the swelling of the binder in the electrolyte , to maintain high adhesion.
  • hydrogen ions easily obtain electrons to form hydrogen gas, when the hydrogen ions are reduced, it can also prevent the flatulence problem of lithium-ion batteries caused by too many hydrogen ions.
  • the mass percentage of acrylonitrile is 25% to 70%
  • the mass percentage of acrylate is 10% to 60%
  • the mass percentage of acrylamide is 100%.
  • the fractional content is 10% to 60%
  • the mass percentage of acrylate is 0% to 10%.
  • the weight average molecular weight of the binder is 100,000 to 2,000,000, preferably 300,000 to 800,000.
  • the weight-average molecular weight of the binder is too large, and the thickening effect of the binder is too strong, resulting in high viscosity of the slurry and poor fluidity, which is easy to cause the first material layer slurry to leak; If the weight-average molecular weight of the agent is too small, the viscosity of the slurry is too low, the film-forming property of the slurry is poor, and the slurry of the first material layer is leaked.
  • the material of the first material layer can form a film layer with a uniform thickness on the surface of the current collector, which can improve the relationship between the first material layer and the current collector and the second material layer. Adhesion between material layers.
  • the single-layer thickness of the first material layer is 0.05 ⁇ m to 20 ⁇ m, preferably 0.1 ⁇ m to 15 ⁇ m.
  • the thickness of the first material layer is too low, for example, less than 0.05 ⁇ m, the safety and reliability of the electrochemical device will be reduced, and it is difficult to ensure the overall uniformity of the first material layer during the preparation process.
  • the resistance of the positive electrode after being fully charged is 10 ⁇ or more, preferably 30 ⁇ to 100 ⁇ .
  • the Dv99 of the active material is 0.01 ⁇ m to 19.9 ⁇ m, preferably 0.01 ⁇ m to 10 ⁇ m.
  • the flatness of the first material layer can be improved. It is advisable that the Dv99 of the active material does not exceed the thickness of the first material layer, otherwise the aluminum foil will be easily stabbed during the cold pressing process.
  • the conductive agent is not particularly limited as long as it can achieve the purpose of the present application. Without being limited to any theory, the content of the conductive agent in the first material layer is too high, the conductivity of the first material layer is too high, and it is more likely to catch fire or explode during the nail penetration test; if the content of the conductive agent is too low, it will affect the lithium-ion battery. electrochemical performance.
  • the shape of the conductive agent is not particularly limited in the present application, for example, the conductive agent may comprise at least one of a sheet-like, mesh-like, linear or zero-dimensional conductive agent.
  • the conductive agent may comprise at least one of graphene, reticulated graphite fibers, carbon nanotubes, Ketjen black, graphite fibers or nanoparticle conductive carbon.
  • the monolayer thickness of the second material layer is 20 ⁇ m to 200 ⁇ m.
  • the thickness of the second material layer is too low, for example, less than 20 ⁇ m, the energy density of the cell is affected, and it is difficult to process; when the thickness of the second material layer is too high, for example, higher than 200 ⁇ m, it will affect the lithium ion The transfer rate, thereby affecting the electrochemical performance of lithium-ion batteries.
  • the second material layer includes a second active material.
  • the active material and the second active material in the first material layer may be the same or different.
  • the active material and the second active material in the first material layer are not particularly limited. At least one of lithium oxide, lithium iron phosphate, lithium-rich manganese-based material, lithium manganate, lithium iron manganese phosphate or lithium titanate.
  • the lithium ion battery prepared by using the above active material has higher safety and reliability.
  • the current collector is not particularly limited, such as aluminum foil, aluminum alloy foil, or composite current collector.
  • the thickness of the positive electrode current collector is not particularly limited as long as the purpose of the present application can be achieved, for example, the thickness of the positive electrode current collector is 8 ⁇ m to 15 ⁇ m.
  • a negative electrode typically includes a negative electrode current collector and a negative electrode active material layer.
  • the negative electrode current collector is not particularly limited, such as copper foil, copper alloy foil, composite current collector, and the like.
  • the negative electrode active material layer includes a negative electrode active material, and the negative electrode active material is not particularly limited.
  • the negative electrode active material is not particularly limited.
  • it can include at least one of artificial graphite, natural graphite, mesocarbon microspheres, soft carbon, hard carbon, silicon, silicon carbon, lithium titanate, and the like. A sort of.
  • the thicknesses of the negative electrode current collector and the negative electrode active material layer are not particularly limited as long as the purpose of the present application can be achieved.
  • the thickness of the anode current collector is 4 ⁇ m to 10 ⁇ m
  • the thickness of the anode active material layer is 30 ⁇ m to 120 ⁇ m.
  • the negative electrode may further comprise a conductive layer located between the negative electrode current collector and the negative electrode active material layer.
  • the conductive layer includes a conductive agent and a binder.
  • the above-mentioned conductive agent is not particularly limited as long as the purpose of the present application can be achieved.
  • the conductive agent may include at least one of conductive carbon black (Super P), carbon nanotubes (CNTs), carbon fiber or graphene, and the like.
  • the above-mentioned binder is not particularly limited as long as it can achieve the purpose of the present application.
  • the binder may include at least one of styrene-butadiene rubber (SBR), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC-Na), and the like.
  • SBR styrene-butadiene rubber
  • PVA polyvinyl alcohol
  • PTFE polytetrafluoroethylene
  • CMC-Na sodium carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • the negative electrode of the present application may have a negative electrode active material layer on one surface thereof, or may have a negative electrode active material layer on both surfaces thereof.
  • the lithium ion battery of the present application further includes a separator for separating the positive electrode and the negative electrode, preventing the internal short circuit of the lithium ion battery, allowing the free passage of electrolyte ions, and completing the role of the electrochemical charging and discharging process.
  • the separator is not particularly limited as long as the purpose of the present application can be achieved.
  • PET polyethylene terephthalate
  • cellulose films such as polyethylene terephthalate (PET) films
  • PET polyamide Imine film
  • PA polyamide film
  • spandex or aramid film woven film
  • non-woven film non-woven film (non-woven fabric)
  • microporous film composite film, diaphragm paper, laminated film, spinning film, etc. at least one of them.
  • the release film may include a substrate layer and a surface treatment layer.
  • the substrate layer can be a non-woven fabric, film or composite film with a porous structure, and the material of the substrate layer can include at least one of polyethylene, polypropylene, polyethylene terephthalate, polyimide, etc. kind.
  • polypropylene porous membranes, polyethylene porous membranes, polypropylene non-woven fabrics, polyethylene non-woven fabrics, or polypropylene-polyethylene-polypropylene porous composite membranes may be used.
  • at least one surface of the substrate layer is provided with a surface treatment layer, and the surface treatment layer can be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic substance.
  • the inorganic layer includes inorganic particles and a binder
  • the inorganic particles are not particularly limited, and can be selected from aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium dioxide, tin oxide, ceria, nickel oxide, for example , at least one of zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate.
  • the binder is not particularly limited, for example, it can be selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyethylene One or a combination of rolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.
  • the polymer layer contains a polymer, and the material of the polymer includes polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly( At least one of vinylidene fluoride-hexafluoropropylene) and the like.
  • the lithium ion battery of the present application further includes an electrolyte, and the electrolyte may be one or more of a gel electrolyte, a solid electrolyte, and an electrolyte, and the electrolyte includes a lithium salt and a non-aqueous solvent.
  • the lithium salt is selected from LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2.
  • LiPF 6 can be chosen as the lithium salt because it can give high ionic conductivity and improve cycle characteristics.
  • the non-aqueous solvent may be a carbonate compound, a carboxylate compound, an ether compound, other organic solvents, or a combination thereof.
  • the above-mentioned carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound, or a combination thereof.
  • Examples of the above-mentioned chain carbonate compound are dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), carbonic acid Methyl ethyl ester (MEC) and combinations thereof.
  • Examples of cyclic carbonate compounds are ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylethylene carbonate (VEC), and combinations thereof.
  • fluorocarbonate compounds are fluoroethylene carbonate (FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate Ethyl carbonate, 1,1,2,2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-dicarbonate Fluoro-1-methylethylene, 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, and combinations thereof.
  • FEC fluoroethylene carbonate
  • 1,2-difluoroethylene carbonate 1,1-difluoroethylene carbonate
  • 1,1,2-trifluoroethylene carbonate Ethyl carbonate 1,1,2,2-tetrafluoroethylene carbonate
  • 1-fluoro-2-methylethylene carbonate 1-fluoro-1-methylethylene carbonate
  • 1,2-dicarbonate Fluoro-1-methylethylene 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethyl
  • carboxylate compounds are methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone , caprolactone, valerolactone, mevalonolactone, caprolactone, and combinations thereof.
  • ether compounds examples include dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethyl ether Oxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and combinations thereof.
  • Examples of the above-mentioned other organic solvents are dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, Formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphate esters and combinations thereof.
  • the preparation method of the binder of the present application is not particularly limited, for example, the following preparation method can be adopted:
  • Distilled water was added to the reactor, stirring was started, and after nitrogen was introduced to remove oxygen, at least one of the above-mentioned components such as acrylonitrile, acrylate, acrylamide and acrylate was added in different mass ratios, and heated to 65 °C under an inert atmosphere. °C and constant temperature, then add an initiator to initiate the reaction, and the reaction ends after about 20 hours.
  • the initiator in the present application there is no particular limitation on the initiator in the present application, as long as it can initiate the polymerization of the monomer, for example, it can be a 20% ammonium persulfate solution.
  • the added amounts of distilled water and initiator in the present application as long as the added monomers can be guaranteed to undergo a polymerization reaction. After the reaction, alkali solution is added to the reacted precipitate for neutralization, and the pH value is 6.5 to 9, and the reaction product is filtered, washed, dried, pulverized, sieved, and the like.
  • a second aspect of the present application provides a method for preparing an electrochemical device according to the first aspect, comprising: sequentially forming a first material layer and a second material layer on at least one surface of a current collector, wherein the The difference between the maximum value and the minimum value of the thickness of the first material layer is not more than 3 ⁇ m.
  • the first material layer and the second material layer are sequentially formed on at least one surface of the current collector.
  • a first material layer and a second material layer are sequentially formed on both surfaces of the current collector.
  • the method of forming the first material layer and the second material layer is not particularly limited as long as the purpose of the present application can be achieved. For example, coating method.
  • a third aspect of the present application provides an electronic device, including the electrochemical device described in the first aspect.
  • electronic devices may include, but are not limited to, notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, assisted bicycles, bicycles, Lighting equipment, toys, game consoles, clocks, power tools, flashlights, cameras, large-scale household storage batteries and lithium-ion capacitors, etc.
  • an electrochemical device can be manufactured by the following process: overlapping the positive electrode and the negative electrode through a separator, and putting them into a case after winding, folding, etc. as required, injecting the electrolyte into the case and sealing, the separator used therein The above-mentioned separator provided in this application.
  • an overcurrent preventing element, a guide plate, etc. may be placed in the case to prevent pressure rise and overcharge and discharge inside the electrochemical device.
  • the application provides an electrochemical device, including a positive electrode, the positive electrode includes a current collector, a first material layer and a second material layer, the second material layer is disposed on at least one surface of the current collector, the first material layer A material layer is disposed between the current collector and the second material layer, wherein the first material layer includes a leveling agent, and the difference between the maximum value and the minimum thickness of the first material layer is not greater than 3 ⁇ m .
  • the obtained positive electrode has high thickness uniformity and strong bonding force between the current collector and the second material layer and the first material layer. When it is applied to an electrochemical device or an electronic device, it can effectively avoid the impact caused by external force or puncture. safety accidents occur, thereby improving the safety and reliability of electrochemical devices or electronic devices.
  • FIG. 1 is a schematic structural diagram of a positive pole piece according to an embodiment of the application.
  • FIG. 2 is a schematic structural diagram of a positive electrode sheet according to another embodiment of the application.
  • FIG. 3 is a top view of a positive pole piece according to an embodiment of the application.
  • Fig. 4 is the top view of the positive pole piece of another embodiment of the application.
  • FIG. 5 is a top view of a positive electrode sheet according to still another embodiment of the present application.
  • the present application is explained by taking a lithium ion battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion battery.
  • FIG. 1 is a schematic structural diagram of a positive electrode sheet according to an embodiment of the present application.
  • the first material layer 20 and the second material layer 30 are sequentially arranged on the surface of the positive electrode current collector 10 , and are only coated on one of the positive electrode current collectors 10 . on the surface.
  • the area of the coating region of the first material layer 20 and the second material layer 30 is less than or equal to the area of the positive electrode current collector 10 .
  • FIG. 2 is a schematic structural diagram of a positive electrode sheet according to another embodiment of the present application.
  • the first material layer 20 and the second material layer 30 are sequentially arranged on the surface of the positive electrode current collector 10, and are coated on two surfaces of the positive electrode current collector 10. on the surface.
  • 3 to 5 are top views of the positive electrode sheet according to some embodiments of the present application.
  • the coating area 50 of the first material layer 20 and the second material layer 30 on the positive electrode current collector is less than or equal to the surface area of the positive electrode current collector.
  • the uncoated area 40 may surround the coated area 50 , and the widths of the upper, lower, left and right uncoated areas 40 may be the same or different. It may also be the case as shown in FIG. 4 , where the uncoated regions 40 are located on both sides along the length direction of the current collector, and the widths of the left and right uncoated regions 40 may be the same or different.
  • the uncoated regions 40 are located on both sides in a direction perpendicular to the length of the current collector, and the lengths of the uncoated regions 40 on the upper and lower sides may be the same or different.
  • the first material layer thickness difference test The first material layer thickness difference test:
  • the weight-average molecular weight of the leveling agent and binder was measured by gel permeation chromatography (GPC).
  • the weight-average molecular weight refers to a molecular weight that is statistically averaged by mass.
  • the first material layer at one end of the sample is adhered to the steel plate through double-sided tape, and the adhesion length is not less than 40mm; then the steel plate is fixed in the corresponding position of the high-speed railway tensile machine, and the test
  • the other end of the sample is not adhered to the steel plate, and the pole piece sample is put into the chuck through the connector or directly clamped, and the angle between the pulled-up sample part and the steel plate is 90° in space.
  • the clip pulls the pole piece at a speed of 5 mm/min to separate the first material layer from the current collector, and the average tensile force in the final measured plateau area is recorded as the bonding force between the first material layer and the current collector.
  • the ratio of the standard deviation to the average value of the adhesion data in the above-mentioned plateau area does not exceed 10%.
  • Dv99 represents the particle size at which the volume-based particle size distribution of the inorganic particles reaches 99% by volume from the small particle size side.
  • Charge state record the appearance of the lithium-ion battery before the test.
  • the battery is subjected to a piercing test in an environment of 25 ⁇ 3°C.
  • the diameter of the steel nail is 4mm
  • the piercing speed is 30mm/s
  • the piercing position is located on the side of the lithium-ion battery.
  • Distilled water was added to the reaction kettle and stirring was started. After nitrogen was introduced for deoxygenation for 2 hours, the following monomers were added to the reaction kettle in a mass ratio of 45:45:10: acrylonitrile, sodium acrylate and acrylamide, and heated to an Heating to 65°C under an inert atmosphere and maintaining a constant temperature, then adding 20% ammonium persulfate solution as an initiator to start the reaction, taking out the precipitate after 22 hours of reaction, adding lye to neutralize the pH to 6.5. Among them, the mass ratio between distilled water, monomer and initiator is 89.5:10:0.5. After the reaction, the reaction product is filtered, washed, dried, pulverized, sieved and the like to obtain a binder.
  • the positive electrode active material lithium iron phosphate, the binder obtained in step (1), the conductive agent nanoparticle conductive carbon, the conductive agent carbon nanotube and the leveling agent polyethoxypropoxypropene are mass ratio 95.5:3 : 0.7: 0.5: 0.3, and then add N-methylpyrrolidone (NMP) as a solvent to prepare a slurry with a solid content of 30%, and stir evenly.
  • NMP N-methylpyrrolidone
  • the slurry was uniformly coated on the anode current collector aluminum foil with a thickness of 10 ⁇ m, and dried at 90 °C to obtain a first material layer with a thickness of 5 ⁇ m; wherein, the Dv99 of lithium iron phosphate was 4 ⁇ m;
  • the weight-average molecular weight of the base propylene olefin is 20,000;
  • the positive active material lithium cobalt oxide (LCO), the binder polyvinylidene fluoride (PVDF), the conductive agent conductive carbon black, and the conductive agent carbon nanotubes are mixed in a mass ratio of 97.7:1.3:0.5:0.5, and then N- Methylpyrrolidone (NMP) was used as a solvent to prepare a slurry with a solid content of 75%, and the mixture was stirred uniformly. uniformly coating the slurry on the first material layer, and drying at 90°C to obtain a second material layer with a thickness of 85 ⁇ m;
  • NMP N- Methylpyrrolidone
  • the above steps are repeated on the other surface of the positive electrode sheet to obtain a positive electrode sheet coated on both sides.
  • the positive electrode sheet is cut into sheets with a size of 74 mm ⁇ 867 mm, and the tabs are welded for use.
  • the negative electrode active material graphite, styrene-butadiene polymer and sodium carboxymethyl cellulose are mixed in a weight ratio of 97.5:1.3:1.2, and deionized water is added as a solvent to prepare a slurry with a solid content of 70%. and stir well.
  • the slurry was uniformly coated on the negative electrode current collector copper foil with a thickness of 10 ⁇ m, dried at 110° C., and then cold-pressed to obtain a negative electrode pole piece with a negative electrode active material layer thickness of 150 ⁇ m coated on one side with a negative electrode active material layer.
  • the above steps are repeated on the other surface of the negative pole piece to obtain a negative pole piece coated on both sides.
  • the negative pole pieces are cut into sheets with a size of 76mm ⁇ 851mm, and the tabs are welded for use.
  • Alumina and polyvinylidene fluoride were mixed in a mass ratio of 90:10 and dissolved in deionized water to form a ceramic slurry with a solids content of 50%. Then, the ceramic slurry was uniformly coated on one side of the porous substrate (polyethylene, thickness 7 ⁇ m, average pore size 0.073 ⁇ m, porosity 26%) by gravure coating, and dried to obtain a ceramic coating
  • the bilayer structure with the porous substrate, the thickness of the ceramic coating is 50 ⁇ m.
  • PVDF Polyvinylidene fluoride
  • polyacrylate was mixed in a mass ratio of 96:4 and dissolved in deionized water to form a polymer slurry with a solids content of 50%. Then, the polymer slurry is uniformly coated on both surfaces of the above-mentioned double-layer structure of the ceramic coating layer and the porous substrate by the gravure coating method, and is subjected to drying treatment to obtain a separator, wherein the single layer formed by the polymer slurry is The coating thickness is 2 ⁇ m.
  • the above-prepared positive electrode, separator, and negative electrode are stacked in sequence, so that the separator is in the middle of the positive and negative electrodes for isolation, and the electrode assembly is obtained by winding.
  • the electrode assembly is put into an aluminum-plastic film packaging bag, and the moisture is removed at 80 ° C, the prepared electrolyte is injected, and the lithium ion battery is obtained through vacuum packaging, standing, forming, and shaping.
  • sodium polycarboxylate is selected as the leveling agent, and the mass ratio of lithium iron phosphate to sodium polycarboxylate is 94.8:1, the rest are the same as those in Example 1.
  • polysiloxane is selected as the leveling agent, and the mass ratio of lithium iron phosphate to polysiloxane is 95.6:0.2, the rest are the same as those in Example 1.
  • the leveling agent is selected from polypropylene alcohol, and the mass ratio of lithium iron phosphate to polypropylene alcohol is 96.8:2, the rest are the same as in Example 1.
  • the weight average molecular weight of the leveling agent polyethoxypropoxypropene is 5000, the rest is the same as that of Example 1.
  • the weight-average molecular weight of the leveling agent polyethoxypropoxypropene is 30,000, the rest is the same as that of Example 1.
  • the weight average molecular weight of the leveling agent polyethoxypropoxypropene is 50000, the rest is the same as that of Example 1.
  • the positive electrode active material is selected from lithium iron manganese phosphate, the rest is the same as that of Example 20.
  • lithium manganate is selected as the positive electrode active material, the rest is the same as that of Example 20.
  • the preparation of the positive electrode plate is as follows: lithium iron manganese phosphate, the binder obtained in step (1), carbon nanotubes and polyethoxypropoxypropene are mass ratio 96.6:3 : 0.2: 0.2, and then add N-methylpyrrolidone (NMP) as a solvent to prepare a slurry with a solid content of 30%, and stir evenly.
  • NMP N-methylpyrrolidone
  • the slurry was uniformly coated on the anode current collector aluminum foil with a thickness of 10 ⁇ m, and dried at 90°C to obtain a first material layer with a thickness of 0.06 ⁇ m; wherein, the Dv99 of lithium iron phosphate was 0.02 ⁇ m; the rest were the same as those in Example 1. same.
  • the procedure is the same as that of Example 23, except that in the preparation of the positive electrode plate in step (2), the Dv99 of lithium iron phosphate is 0.06 ⁇ m and the thickness of the first material layer is 0.15 ⁇ m.
  • the positive electrode active material is selected from lithium iron manganese phosphate, the binder obtained in step (1), lithium iron manganese phosphate, nanoparticle conductive carbon, carbon nanotubes, polyethylene oxide
  • the mass ratio of propoxypropene was 96:3:0.3:0.5:0.2
  • the thickness of the first material layer was 2 ⁇ m
  • the Dv99 of lithium iron manganese phosphate was 0.5 ⁇ m, and the rest were the same as in Example 1.
  • the thickness of the first material layer is 3 ⁇ m, and the Dv99 of lithium iron manganese phosphate is 1 ⁇ m, the rest is the same as that of Example 25.
  • the thickness of the first material layer is 5 ⁇ m, and the Dv99 of lithium iron manganese phosphate is 3 ⁇ m, the rest is the same as that of Example 21.
  • the thickness of the first material layer is 9 ⁇ m, and the Dv99 of lithium iron manganese phosphate is 7 ⁇ m, the rest is the same as that of Example 21.
  • the thickness of the first material layer is 13 ⁇ m, and the Dv99 of lithium iron manganese phosphate is 11 ⁇ m, the rest is the same as that of Example 21.
  • the thickness of the first material layer is 17 ⁇ m, and the Dv99 of lithium iron manganese phosphate is 15 ⁇ m, the rest is the same as that of Example 21.
  • the thickness of the first material layer is 19.5 ⁇ m, and the Dv99 of lithium iron manganese phosphate is 18 ⁇ m, the rest is the same as that of Example 21.
  • the thickness of the first material layer is 20 ⁇ m, and the Dv99 of lithium iron manganese phosphate is 19.9 ⁇ m, the rest is the same as that of Example 21.
  • the conductive agent is selected from mesh graphite fibers, the rest are the same as those in Example 21.
  • the conductive agent is selected from graphite fiber, the rest is the same as that of Example 21.
  • the conductive agent is selected from reticulated graphite fibers, lithium iron manganese phosphate, the binder obtained in step (1), reticulated graphite fibers, polyethoxypropoxyprop
  • the mass ratio of olefins was the same as in Example 21 except that the mass ratio was 98.7:1:0.1:0.2.
  • the quality of lithium iron manganese phosphate, the binder obtained in step (1), carbon nanotubes, and polyethoxypropoxypropene was the same as in Example 21 except that the ratio was 98.3:1:0.5:0.2.
  • the mass ratio of lithium iron manganese phosphate, nanoparticle conductive carbon, and carbon nanotubes is 96.2:0.1:0.5, the rest is the same as that in Example 21.
  • the mass ratio of lithium iron manganese phosphate, nanoparticle conductive carbon, and carbon nanotubes is 95.2:1.1:0.5, the rest is the same as that in Example 21.
  • the mass ratio of lithium iron manganese phosphate, nanoparticle conductive carbon, and carbon nanotubes is 96:0.5:0.3, the rest is the same as that in Example 21.
  • the mass ratio of lithium iron manganese phosphate, nanoparticle conductive carbon, and carbon nanotubes is 95.4:0.5:0.9, the rest is the same as that in Example 21.
  • the mass ratio of lithium iron manganese phosphate, nanoparticle conductive carbon, and carbon nanotubes is 95.2:0.5:1.1, the rest is the same as that in Example 21.
  • the mass ratio of lithium iron manganese phosphate and nanoparticle conductive carbon is 95.3:1.5, the rest is the same as that of Example 21.
  • the mass ratio of lithium iron manganese phosphate and nanoparticle conductive carbon is 94.8:2, the rest is the same as that of Example 51.
  • the mass ratio of lithium iron manganese phosphate, nanoparticle conductive carbon, and binder is 86.8:5:8, the rest is the same as that of Example 51.
  • the mass ratio of lithium iron manganese phosphate, nanoparticle conductive carbon, carbon nanotube, and binder is 59.8:15:5:20, the rest is the same as that in Example 21.
  • the adhesive is selected from polyacrylic acid amine, the rest is the same as that in Example 21.
  • the mass ratio of lithium iron manganese phosphate to the binder obtained in step (1) is 96.6:2, the rest are the same as those in Example 21.
  • the mass ratio of lithium iron manganese phosphate to the binder obtained in step (1) is 94.6:4, the rest are the same as those in Example 21.
  • the mass ratio of lithium iron manganese phosphate to the binder obtained in step (1) is 93.6:5, the rest are the same as those in Example 21.
  • the mass ratio of lithium iron manganese phosphate to the binder obtained in step (1) is 90.6:8, the rest are the same as those in Example 21.
  • the mass ratio of lithium iron manganese phosphate to the binder obtained in step (1) is 88.6:10, the rest are the same as those in Example 21.
  • the mass ratio of lithium iron manganese phosphate to the binder obtained in step (1) is 86.6:12, the rest are the same as those in Example 21.
  • the mass ratio of lithium iron manganese phosphate to the binder obtained in step (1) is 83.6:15, the rest are the same as those in Example 21.
  • the mass ratio of lithium iron manganese phosphate to the binder obtained in step (1) is 80.6:18, the rest are the same as those in Example 21.
  • the mass ratio of lithium iron manganese phosphate to the binder obtained in step (1) is 78.6:20, the rest are the same as in Example 21.
  • the leveling agent is selected from polypropylene alcohol, and the mass ratio of lithium iron phosphate to polypropylene alcohol is 80.8:15, the rest are the same as in Example 1.
  • lithium cobalt oxide is selected as the positive electrode active material, the rest is the same as that of Example 21.
  • the positive electrode active material is selected from lithium iron phosphate
  • the conductive agent is selected from nano-particle conductive carbon
  • the mass ratio of lithium iron phosphate to nano-particle conductive carbon is 70.6:25. 21 is the same.
  • the lithium ion battery with the positive electrode piece of the present application has a significantly higher 90° vertical side nail penetration rate than the lithium ion battery provided by the comparative example, It shows that the safety and reliability of the lithium ion battery provided by the present application is significantly improved.
  • the lithium-ion battery with the positive pole piece of the present application has a significantly higher 90° vertical side piercing pass rate than the lithium-ion battery provided by the comparative example, which may be It is because the full charge resistance of lithium iron phosphate, lithium iron manganese phosphate and lithium manganate is greater than that of lithium cobalt oxide, and it is less likely to catch fire or explode at the moment when the steel nail passes through, thus indicating that the lithium ion battery provided by this application is safe and reliable. Sex has been improved.
  • the positive electrode plate provided by the present application has high thickness uniformity and strong adhesion between the current collector and the second material layer and the first material layer. When applied to a lithium ion battery, it can effectively reduce the amount of damage caused by external forces. The probability of safety accidents caused by impacts or punctures, thereby improving the safety and reliability of lithium-ion batteries.

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Abstract

本申请提供了一种电化学装置、电子装置及电化学装置的制备方法，包括正极，所述正极包含集流体、第一材料层和第二材料层，所述第二材料层设置在所述集流体的至少一个表面上，所述第一材料层设置在所述集流体和所述第二材料层之间，其中，所述第一材料层包括流平剂，所述第一材料层的厚度最大值与最小值之差不大于3μm。得到的正极厚度均匀性高，集流体和第二材料层与第一材料层之间的粘结力强，将其应用于电化学装置或者电子装置，能够有效降低由于外力撞击或穿刺等原因造成的安全事故发生概率，从而提高电化学装置或电子装置的安全可靠性。

Description

电化学装置、电子装置及电化学装置的制备方法 技术领域
本申请涉及电化学领域，具体涉及一种电化学装置、电子装置及电化学装置的制备方法。
背景技术
锂离子电池具有储能密度大、开路电压高、自放电率低、循环寿命长、安全性能好等优点，广泛应用于电能储存、移动电子设备、电动汽车和航天航空设备等各个领域。随着移动电子设备和电动汽车进入高速发展阶段，市场对锂离子二次电池的能量密度、安全性能、循环性能和使用寿命等都提出了越来越高的要求，其中，安全性能尤为重要。
目前，锂离子电池在使用过程中，仍然存在由于外力撞击或穿刺等原因引起火灾，对人体生命健康或环境造成威胁，有待提高的安全可靠性阻碍了锂离子电池的应用领域和应用范围的拓展。因此，亟需开发一种安全可靠性高的锂离子电池。
发明内容
本申请的目的在于提供一种电化学装置、电子装置及电化学装置的制备方法，以提高电化学装置的安全可靠性。
需要说明的是，以下内容中，以锂离子电池作为电化学装置的例子来解释本申请，但是本申请的电化学装置并不仅限于锂离子电池。
具体技术方案如下：
本申请的第一方面提供了一种电化学装置，其包括正极，正极包含集流体、第一材料层和第二材料层，所述第二材料层设置在所述集流体的至少一个表面上，所述第一材料层设置在所述集流体和所述第二材料层之间，其中，所述第一材料层包括流平剂，所述第一材料层的厚度最大值与最小值之差不大于3μm。
不限于任何理论，当第一材料层的厚度最大值与最小值的差值过大时，例如大于3μm，第一材料层的厚度均匀性较差，易使涂层存在厚度较薄的区域，从而使电化学装置的结构可靠性降低。
在本申请的一种实施方案中，流平剂为重均分子量不高于50000的聚合物。例如重均 分子量不高于50000的烯烃类衍生物的聚合物、硅氧烷聚合物、烯酸酯聚合物、醇聚合物或醚聚合物。通过控制流平剂的分子量在上述范围内，能够使流平剂与粘结剂相互作用，提高第一材料层浆料的流平性，从而使第一材料层的厚度更均匀。
在本申请的一种实施方案中，流平剂可以包含烯烃类衍生物的聚合物、羧酸盐类聚合物、硅氧烷类聚合物、烯酸酯类聚合物、醇类聚合物或醚类聚合物中的至少一种，上述流平剂的重均分子量也可以不高于50000。
在本申请的一种实施方案中，流平剂包含羧酸钠聚合物、含氧丙烯烃类衍生物的聚合物或聚硅氧烷中的至少一种，优选地，流平剂包含聚乙氧基丙氧基丙烯烃。上述流平剂的重均分子量也可以不高于50000。
在本申请的一种实施方案中，第一材料层还包括活性材料、粘结剂、导电剂，基于第一材料层的总质量，活性材料的质量百分含量为50％至98.89％，粘结剂的质量百分含量为1％至20％，导电剂的质量百分含量为0.1％至20％，流平剂的质量百分含量为0.01％至10％。不限于任何理论，通过控制活性材料、粘结剂、导电剂和流平剂的含量在上述范围内，能够使得到的第一材料层厚度更均匀，使各处的性能一致，当受到外力撞击或穿刺时，不易从局部被损坏。此外，提高了集流体和第二材料层与第一材料层之间的粘结力，从而提高了电化学装置的安全可靠性。
本申请的电化学装置中，集流体包括依次设置于集流体的至少一个表面上的第一材料层和第二材料层，可以是设置在集流体的一个表面上，也可以设置在集流体的两个表面上。
在本申请的一种实施方案中，粘结剂包括丙烯烃类衍生物的共聚物、聚丙烯酸酯类、丙烯腈多元共聚物、羧甲基纤维素盐中的至少一种。优选地，粘结剂包括由丙烯酸腈、丙烯酸盐、丙烯酰胺、丙烯酸酯中的至少一种单体聚合而成的聚合物。
本申请的粘结剂可以是一种水性粘结剂，其中，丙烯酸盐中的金属离子能够取代部分氢离子，从而增加粘结剂的亲水性，使粘结剂在电解液中溶胀减小，保持较高的粘结力。另外，由于氢离子易得电子而形成氢气，因此当氢离子减少后，还可防止产生因氢离子过多而导致的锂离子电池胀气问题。
在本申请的一种实施方案中，基于聚合物的总质量，丙烯腈的质量百分含量为25％至70％，丙烯酸盐的质量百分含量为10％至60％，丙烯酰胺的质量百分含量为10％至60％，丙烯酸酯的质量百分含量为0％至10％。不限于任何理论，通过控制丙烯腈、丙烯酸盐、丙烯酰胺和丙烯酸酯的质量百分含量在上述范围内，能够得到粘结性良好的粘结剂，从而 提高第一材料层与集流体之间的粘结力。
在本申请的一种实施方案中，粘结剂的重均分子量为100000至2000000，优选为300000至800000。不限于任何理论，粘结剂的重均分子量过大，粘结剂的增稠作用过强，导致浆料粘度过高、流动性变差，易导致第一材料层浆料漏涂；粘结剂的重均分子量过小，导致浆料粘度过低，浆料成膜性差，也会导致第一材料层浆料漏涂。不限于任何理论，通过控制粘结剂的重均分子量在上述范围内，能够使第一材料层的材料在集流体表面形成厚度均匀的膜层，能够提高第一材料层与集流体和第二材料层之间粘结力。
在本申请的一种实施方案中，第一材料层单层厚度为0.05μm至20μm，优选为0.1μm至15μm。不限于任何理论，当第一材料层的厚度过低时，例如低于0.05μm，降低电化学装置的安全可靠性，且在制备过程中很难保证第一材料层整体的均匀性，同时制备难度和成本增加；当第一材料层的厚度过高时，例如高于20μm，正极中活性材料相对含量下降，影响锂离子电池的能量密度。
在本申请的一种实施方案中，正极满充后的电阻为10Ω以上，优选30Ω至100Ω。通过控制正极电阻在上述范围内，能够增大锂离子电池短路时的内阻，降低短路电流，降低温升，从而提高锂离子电池的安全性。
在本申请的一种实施方案中，活性材料的Dv99为0.01μm至19.9μm，优选为0.01μm至10μm。不限于任何理论，通过控制活性材料的Dv99在上述范围内，能够提高第一材料层的平整度。以活性材料的Dv99不超过第一材料层的厚度为宜，否则在冷压过程中易刺伤铝箔。
在本申请的一种实施方案中，对导电剂没有特别限定，只要能实现本申请目的即可。不限于任何理论，第一材料层中的导电剂的含量过高，第一材料层的导电性过高，在穿钉测试中更容易起火或者爆炸；导电剂含量过低，则影响锂离子电池的电化学性能。本申请对导电剂的形状没有特别限制，例如，导电剂可以包含片层状、网状、线状或零维导电剂中的至少一种。优选地，导电剂可以包含石墨烯、网状石墨纤维、碳纳米管、科琴黑、石墨纤维或纳米颗粒导电碳中的至少一种。
在本申请的一种实施方案中，第二材料层的单层厚度为20μm至200μm。不限于任何理论，当第二材料层的厚度过低时，例如低于20μm，影响电芯能量密度，并且不易加工；当第二材料层的厚度过高时，例如高于200μm，影响锂离子的传输速率，从而影响锂离子电池的电化学性能。
在本申请的一种实施方案中，第二材料层包括第二活性材料。在本申请中，第一材料层中的活性材料和第二活性材料可以相同，也可以不同。
在本申请的锂离子电池中，第一材料层中活性材料和第二活性材料没有特别限制，例如，可以各自独立地包括镍钴锰酸锂(811、622、523、111)、镍钴铝酸锂、磷酸铁锂、富锂锰基材料、锰酸锂、磷酸锰铁锂或钛酸锂中的至少一种。采用上述活性材料制得的锂离子电池，其安全可靠性更高。
本申请的正极中，集流体没有特别限制，例如铝箔、铝合金箔或复合集流体等。在本申请中，正极集流体的厚度没有特别限制，只要能够实现本申请目的即可，例如，正极集流体的厚度为8μm至15μm。
本申请中的负极没有特别限制，只要能够实现本申请目的即可。例如，负极通常包含负极集流体和负极活性材料层。其中，负极集流体没有特别限制，例如铜箔、铜合金箔以及复合集流体等。负极活性材料层包括负极活性材料，负极活性材料没有特别限制，例如，可以包括人造石墨、天然石墨、中间相碳微球、软碳、硬碳、硅、硅碳、钛酸锂等中的至少一种。在本申请中，负极集流体和负极活性材料层的厚度没有特别限制，只要能够实现本申请目的即可。例如，负极集流体的厚度为4μm至10μm，负极活性材料层的厚度为30μm至120μm。
任选地，所述负极还可以包含导电层，所述导电层位于负极集流体和负极活性材料层之间。所述导电层包括导电剂和粘结剂。上述所述导电剂没有特别限制，只要能实现本申请目的即可。例如，导电剂可以包括导电炭黑(Super P)、碳纳米管(CNTs)、碳纤维或石墨烯等中的至少一种。上述所述粘结剂没有特别限制，只要能实现本申请目的即可。例如，粘结剂可以包括丁苯橡胶(SBR)、聚乙烯醇(PVA)、聚四氟乙烯(PTFE)或羧甲基纤维素钠(CMC-Na)等中的至少一种。例如，粘结剂可选用丁苯橡胶(SBR)。
本领域技术人员应当理解，本申请的负极可以使其一个表面具有负极活性材料层，也可以使其两个表面均具有负极活性材料层。
本申请的锂离子电池还包括隔离膜，用以分隔正极和负极，防止锂离子电池内部短路，允许电解质离子自由通过，完成电化学充放电过程的作用。在本申请中，隔离膜没有特别限制，只要能够实现本申请目的即可。
例如，聚乙烯(PE)、聚丙烯(PP)为主的聚烯烃(PO)类隔离膜，聚酯膜(例如聚对苯二甲酸二乙酯(PET)膜)、纤维素膜、聚酰亚胺膜(PI)、聚酰胺膜(PA)，氨纶或芳 纶膜、织造膜、非织造膜(无纺布)、微孔膜、复合膜、隔膜纸、碾压膜、纺丝膜等中的至少一种。
例如，隔离膜可以包括基材层和表面处理层。基材层可以为具有多孔结构的无纺布、膜或复合膜，基材层的材料可以包括聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯和聚酰亚胺等中的至少一种。任选地，可以使用聚丙烯多孔膜、聚乙烯多孔膜、聚丙烯无纺布、聚乙烯无纺布或聚丙烯-聚乙烯-聚丙烯多孔复合膜。任选地，基材层的至少一个表面上设置有表面处理层，表面处理层可以是聚合物层或无机物层，也可以是混合聚合物与无机物所形成的层。
例如，无机物层包括无机颗粒和粘结剂，所述无机颗粒没有特别限制，例如可以选自氧化铝、氧化硅、氧化镁、氧化钛、二氧化铪、氧化锡、二氧化铈、氧化镍、氧化锌、氧化钙、氧化锆、氧化钇、碳化硅、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙和硫酸钡等中的至少一种。所述粘结剂没有特别限制，例如可以选自聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯和聚六氟丙烯中的一种或几种的组合。聚合物层中包含聚合物，聚合物的材料包括聚酰胺、聚丙烯腈、丙烯酸酯聚合物、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚偏氟乙烯或聚(偏氟乙烯-六氟丙烯)等中的至少一种。
本申请的锂离子电池还包括电解质，电解质可以是凝胶电解质、固态电解质和电解液中的一种或多种，电解液包括锂盐和非水溶剂。
在本申请一些实施方案中，锂盐选自LiPF 6、LiBF 4、LiAsF 6、LiClO 4、LiB(C 6H 5) 4、LiCH 3SO 3、LiCF 3SO 3、LiN(SO 2CF 3) 2、LiC(SO 2CF 3) 3、LiSiF 6、LiBOB和二氟硼酸锂中的一种或多种。举例来说，锂盐可以选用LiPF 6，因为它可以给出高的离子导电率并改善循环特性。
非水溶剂可为碳酸酯化合物、羧酸酯化合物、醚化合物、其它有机溶剂或它们的组合。
上述碳酸酯化合物可为链状碳酸酯化合物、环状碳酸酯化合物、氟代碳酸酯化合物或其组合。
上述链状碳酸酯化合物的实例为碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(MEC)及其组合。 环状碳酸酯化合物的实例为碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸乙烯基亚乙酯(VEC)及其组合。氟代碳酸酯化合物的实例为碳酸氟代亚乙酯(FEC)、碳酸1,2-二氟亚乙酯、碳酸1,1-二氟亚乙酯、碳酸1,1,2-三氟亚乙酯、碳酸1,1,2,2-四氟亚乙酯、碳酸1-氟-2-甲基亚乙酯、碳酸1-氟-1-甲基亚乙酯、碳酸1,2-二氟-1-甲基亚乙酯、碳酸1,1,2-三氟-2-甲基亚乙酯、碳酸三氟甲基亚乙酯及其组合。
上述羧酸酯化合物的实例为甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、癸内酯、戊内酯、甲瓦龙酸内酯、己内酯及其组合。
上述醚化合物的实例为二丁醚、四甘醇二甲醚、二甘醇二甲醚、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、2-甲基四氢呋喃、四氢呋喃及其组合。
上述其它有机溶剂的实例为二甲亚砜、1,2-二氧戊环、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯、和磷酸酯及其组合。
本申请的粘结剂的制备方法没有特别限制，例如可以采用如下制备方法：
在反应釜中加入蒸馏水，启动搅拌，通入氮气除氧后，按不同质量比加入丙烯腈、丙烯酸盐、丙烯酰胺和丙烯酸酯等上述组分中的至少一种，在惰性气氛下加热至65℃左右并恒温，然后加入引发剂引发反应，至反应20小时左右后结束。
本申请对引发剂没有特别限制，只要能引发单体聚合即可，例如可以为20％的过硫酸铵溶液。本申请对蒸馏水和引发剂的添加量没有特别限制，只要能保证加入的单体发生聚合反应即可。在反应后，向反应的沉淀物中加入碱液已进行中和，使pH值为6.5至9，对反应产物进行过滤、洗涤、烘干、粉碎、过筛等处理。
本申请的第二方面提供了一种上述第一方面所述的电化学装置的制备方法，包括：在集流体的至少一个表面上依次形成第一材料层和第二材料层，其中，所述第一材料层的厚度最大值与最小值之差不大于3μm。
在本申请中，在集流体的至少一个表面上依次形成第一材料层和第二材料层，可以是在集流体的一个表面上依次形成第一材料层和第二材料层，也可以是在集流体的两个表面上依次形成第一材料层和第二材料层。对形成第一材料层和第二材料层的方法没有特别限制，只要能实现本申请的目的即可。例如，涂覆法。
本申请的第三方面提供了一种电子装置，包括上述第一方面所述的电化学装置。
本申请的电子装置没有特别限定，其可以是用于现有技术中已知的任何电子装置。在一些实施例中，电子装置可以包括，但不限于，笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
电化学装置的制备过程为本领域技术人员所熟知的，本申请没有特别的限制。例如电化学装置可以通过以下过程制造：将正极和负极经由隔离膜重叠，并根据需要将其卷绕、折叠等操作后放入壳体内，将电解液注入壳体并封口，其中所用的隔离膜为本申请提供的上述隔离膜。此外，也可以根据需要将防过电流元件、导板等置于壳体中，从而防止电化学装置内部的压力上升、过充放电。
本申请提供一种电化学装置，包括正极，所述正极包含集流体、第一材料层和第二材料层，所述第二材料层设置在所述集流体的至少一个表面上，所述第一材料层设置在所述集流体和所述第二材料层之间，其中，所述第一材料层包括流平剂，所述第一材料层的厚度最大值与最小值之差不大于3μm。得到的正极厚度均匀性高，集流体和第二材料层与第一材料层之间的粘结力强，将其应用于电化学装置或者电子装置，能够有效避免由于外力撞击或穿刺等原因造成的安全事故发生，从而提高电化学装置或电子装置的安全可靠性。
附图说明
为了更清楚地说明本申请和现有技术的技术方案，下面对实施例和现有技术中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例。
图1为本申请的一种实施方案的正极极片的结构示意图；
图2为本申请的另一种实施方案的正极极片的结构示意图；
图3为本申请的一种实施方案的正极极片的俯视图；
图4为本申请的另一种实施方案的正极极片的俯视图；
图5为本申请的再一种实施方案的正极极片的俯视图。
具体实施方式
为使本申请的目的、技术方案、及优点更加清楚明白，以下参照附图和实施例，对本申请进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的 实施例。
需要说明的是，本申请的具体实施方式中，以锂离子电池作为电化学装置的例子来解释本申请，但是本申请的电化学装置并不仅限于锂离子电池。
图1为本申请的一种实施方案的正极极片的结构示意图，第一材料层20和第二材料层30依次设置在正极集流体10的表面，且仅涂覆在正极集流体10的一个表面上。第一材料层20和第二材料层30的涂覆区域的面积小于等于正极集流体10的面积。
图2为本申请的另一种实施方案的正极极片的结构示意图，第一材料层20和第二材料层30依次设置在正极集流体10的表面，涂覆在正极集流体10的两个表面上。
图3至图5为本申请的一些实施方案的正极极片的俯视图，第一材料层20和第二材料层30在正极集流体上涂覆区域50小于等于正极集流体的表面积。如图3所示，未涂覆区域40可以将涂覆区域50包围环绕，且上侧、下侧、左侧和右侧的未涂覆区域40的宽度可以相同或者不相同。也可以是如图4所示的情况，未涂覆区域40位于沿集流体长度方向的两侧，且左侧和右侧的未涂覆区域40的宽度可以相同或者不相同。也可以是如图5所示的情况，未涂覆区域40位于沿垂直于集流体长度方向的两侧，且上侧和下侧的未涂覆区域40的长度可以相同或者不相同。
以下，举出实施例及对比例来对本申请的实施方式进行更具体地说明。各种的试验及评价按照下述的方法进行。另外，只要无特别说明，“份”、“％”为质量基准。
测试方法和设备：
第一材料层厚度差测试：
1)在(25±3)℃的环境下，将涂有第一材料层的极片从成品电芯中拆出。用无尘纸拭去极片表面残留的电解液；
2)涂有第一材料层的极片在等离子体下切割，得到其横截面；
3)在SEM下观察2)中得到的极片横截面，并测试单面第一材料层的厚度，相邻测试点间隔2mm至3mm，至少测试15个不同点，记所有测试点的均值为第一材料层的厚度。
重均分子量测试：
采用凝胶渗透色谱法(GPC)测试流平剂和粘结剂的重均分子量。本申请中，重均分子量是指按质量统计平均的分子量。
粘结力测试：
使用高铁拉力机、90°角法测试第一材料层与集流体之间的粘结力：将成品锂离子电池中设置有第一材料层部分的极片裁切为20mm×60mm的条状试样，其长宽值可根据实际情况适当调整。沿试样的长度方向，将试样一端的第一材料层面通过双面胶粘附在钢板上，其中粘附长度不低于40mm；然后将钢板固定在高铁拉力机的相应位置，拉起试样的未被粘附在钢板上的另一端，通过连接物或直接将极片样品放入夹头内夹紧，其中被拉起的试样部分与钢板在空间上夹角为90°。夹头以5mm/min的速度拉动极片，使第一材料层与集流体分离，最终测得平稳区域的拉力平均值记为第一材料层与集流体之间的粘结力。如图6所示，要求上述平稳区域的粘结力数据的标准差与平均值的比值不超过10％。
无机颗粒Dv99测试：
使用激光粒度仪测试无机颗粒的Dv99。Dv99表示无机颗粒在体积基准的粒度分布中，从小粒径侧起，达到体积累积99％的粒径。
穿钉通过率测试：
将待测的锂离子电池以0.05C的倍率恒流充电至电压为4.45V(即满充电压)，随后以4.45V恒压充电至电流为0.025C(截止电流)，使锂离子电池达到满充状态，记录测试前锂离子电池外观。在25±3℃环境中对电池进行穿钉测试，钢钉直径4mm，穿刺速度30mm/s，穿钉位置位于锂离子电池侧面，测试进行3.5min或电极组件表面温度降到50℃以后停止测试，以10个锂离子电池为一组，观察测试过程中锂离子电池状态，以锂离子电池不燃烧、不爆炸为判定标准。
实施例1
(1)粘结剂的制备
在反应釜中加入蒸馏水并启动搅拌，通入氮气除氧2h后，按质量比45︰45︰10向反应釜加入以下单体：丙烯腈、丙烯酸钠和丙烯酰胺，在惰性气氛下加热至在惰性气氛下加热至65℃并保持恒温，然后加入20％的过硫酸铵溶液作为引发剂开始反应，至反应22小时后取出沉淀物，加入碱液中和pH至6.5。其中，蒸馏水、单体、引发剂之间的质量比为89.5︰10︰0.5。反应后对反应产物进行过滤、洗涤、烘干、粉碎、过筛等处理，得到粘结剂。
(2)正极极片的制备
将正极活性材料磷酸铁锂、步骤(1)中得到的粘结剂、导电剂纳米颗粒导电碳、导电剂碳纳米管和流平剂聚乙氧基丙氧基丙烯烃按质量比95.5∶3∶0.7∶0.5∶0.3混合，然后加入N-甲基吡咯烷酮(NMP)作为溶剂，调配成固含量为30％的浆料，并搅拌均匀。将浆料均匀涂覆在厚度为10μm的正极集流体铝箔上，90℃条件下烘干，得到厚度为5μm的第一材料层；其中，磷酸铁锂的Dv99为4μm；聚乙氧基丙氧基丙烯烃的重均分子量为20000；
将正极活性材料钴酸锂(LCO)、粘结剂聚偏二氟乙烯(PVDF)、导电剂导电炭黑、导电剂碳纳米管按质量比97.7∶1.3∶0.5∶0.5混合，然后加入N-甲基吡咯烷酮(NMP)作为溶剂，调配成固含量为75％的浆料，并搅拌均匀。将浆料均匀涂覆在第一材料层上，90℃条件下烘干，得到厚度为85μm的第二材料层；
在该正极极片的另一个表面上重复以上步骤，即得到双面涂布完成的正极极片。涂布完成后，将正极极片裁切成规格为74mm×867mm的片材并焊接极耳待用。
(3)负极极片的制备
将负极活性材料石墨、苯乙烯-丁二烯聚合物和羧甲基纤维素钠按照重量比97.5︰1.3︰1.2进行混合，加入去离子水作为溶剂，调配成为固含量为70％的浆料，并搅拌均匀。将浆料均匀涂覆在厚度为10μm的负极集流体铜箔上，110℃条件下烘干，冷压后得到负极活性材料层厚度为150μm的单面涂覆负极活性材料层的负极极片。
在该负极极片的另一个表面上重复以上步骤，即得到双面涂布完成的负极极片。涂布完成后，将负极极片裁切成规格为76mm×851mm的片材并焊接极耳待用。
(4)电解液的制备
在干燥氩气气氛中，将有机溶剂碳酸乙烯酯、碳酸甲乙酯和碳酸二乙酯以质量比EC︰EMC︰DEC＝30︰50︰20混合得到有机溶液，然后向有机溶剂中加入锂盐六氟磷酸锂溶解并混合均匀，得到锂盐的浓度为1.15Mol/L的电解液。
(5)隔离膜的制备
将氧化铝与聚偏氟乙烯依照质量比90∶10混合并将其溶入到去离子水中以形成固含量为50％的陶瓷浆料。随后采用微凹涂布法将陶瓷浆料均匀涂布到多孔基材(聚乙烯，厚度7μm，平均孔径为0.073μm，孔隙率为26％)的其中一面上，经过干燥处理以获得陶瓷涂层与多孔基材的双层结构，陶瓷涂层的厚度为50μm。
将聚偏二氟乙烯(PVDF)与聚丙烯酸酯依照质量比96∶4混合并将其溶入到去离子水中以形成固含量为50％的聚合物浆料。随后采用微凹涂布法将聚合物浆料均匀涂布到上述陶瓷涂层与多孔基材双层结构的两个表面上，经过干燥处理以获得隔离膜，其中聚合物浆料形成的单层涂层厚度为2μm。
(6)锂离子电池的制备
将上述制备的正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正负极极片中间起到隔离的作用，并卷绕得到电极组件。将电极组件装入铝塑膜包装袋中，并在80℃下脱去水分，注入配好的电解液，经过真空封装、静置、化成、整形等工序得到锂离子电池。
实施例2
除了在步骤(2)正极极片的制备中，流平剂选用聚羧酸钠，磷酸铁锂与聚羧酸钠的质量比为94.8∶1以外，其余与实施例1相同。
实施例3
除了在步骤(2)正极极片的制备中，流平剂选用聚硅氧烷，磷酸铁锂与聚硅氧烷的质量比为95.6∶0.2以外，其余与实施例1相同。
实施例4
除了在步骤(2)正极极片的制备中，流平剂选用聚丙烯酸甲酯，磷酸铁锂与聚丙烯酸甲酯的质量比为95.5∶0.3以外，其余与实施例1相同。
实施例5
除了在步骤(2)正极极片的制备中，流平剂选用聚丙烯醇，磷酸铁锂与聚丙烯醇的质量比为96.8∶2以外，其余与实施例1相同。
实施例6
除了在步骤(2)正极极片的制备中，流平剂选用聚乙二醚，磷酸铁锂与聚乙二醚的质量比为87.8∶8以外，其余与实施例1相同。
实施例7
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚乙氧基丙氧基丙烯烃的质量比为95.79∶0.01以外，其余与实施例1相同。
实施例8
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚乙氧基丙氧基丙烯烃的质量比为 95.75∶0.05以外，其余与实施例1相同。
实施例9
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚乙氧基丙氧基丙烯烃的质量比为95.7∶0.1以外，其余与实施例1相同。
实施例10
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚乙氧基丙氧基丙烯烃的质量比为95.5∶0.4以外，其余与实施例1相同。
实施例11
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚乙氧基丙氧基丙烯烃的质量比为95.3∶0.5以外，其余与实施例1相同。
实施例12
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚乙氧基丙氧基丙烯烃的质量比为95∶0.8以外，其余与实施例1相同。
实施例13
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚羧酸钠的质量比为92.8∶3以外，其余与实施例2相同。
实施例14
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚羧酸钠的质量比为90.8∶5以外，其余与实施例2相同。
实施例15
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚羧酸钠的质量比为87.8∶8以外，其余与实施例2相同。
实施例16
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚羧酸钠的质量比为85.8∶10以外，其余与实施例2相同。
实施例17
除了在步骤(2)正极极片的制备中，流平剂聚乙氧基丙氧基丙烯烃的重均分子量为5000以外，其余与实施例1相同。
实施例18
除了在步骤(2)正极极片的制备中，流平剂聚乙氧基丙氧基丙烯烃的重均分子量为30000以外，其余与实施例1相同。
实施例19
除了在步骤(2)正极极片的制备中，流平剂聚乙氧基丙氧基丙烯烃的重均分子量为50000以外，其余与实施例1相同。
实施例20
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚乙氧基丙氧基丙烯烃的质量比为95.6∶0.2以外，其余与实施例1相同。
实施例21
除了在步骤(2)正极极片的制备中，正极活性材料选用磷酸铁锰锂以外，其余与实施例20相同。
实施例22
除了在步骤(2)正极极片的制备中，正极活性材料选用锰酸锂以外，其余与实施例20相同。
实施例23
除了在步骤(2)中正极极片的制备为：将磷酸铁锰锂、步骤(1)中得到的粘结剂、碳纳米管和聚乙氧基丙氧基丙烯烃按质量比96.6∶3∶0.2∶0.2混合，然后加入N-甲基吡咯烷酮(NMP)作为溶剂，调配成固含量为30％的浆料，并搅拌均匀。将浆料均匀涂覆在厚度10μm的正极集流体铝箔上，90℃条件下烘干，得到厚度为0.06μm的第一材料层；其中，磷酸铁锂的Dv99为0.02μm；其余与实施例1相同。
实施例24
除了在步骤(2)正极极片的制备中，磷酸铁锂的Dv99为0.06μm、第一材料层的厚度为0.15μm以外，其余与实施例23相同。
实施例25
除了在步骤(2)正极极片的制备中，正极活性材料选用磷酸铁锰锂，步骤(1)中得到的粘结剂、磷酸铁锰锂、纳米颗粒导电碳、碳纳米管、聚乙氧基丙氧基丙烯烃的质量比为96：3：0.3：0.5：0.2，第一材料层的厚度为2μm，磷酸铁锰锂的Dv99为0.5μm以外，其余与实施例1相同。
实施例26
除了在步骤(2)正极极片的制备中，第一材料层的厚度为3μm，磷酸铁锰锂的Dv99为1μm以外，其余与实施例25相同。
实施例27
除了在步骤(2)正极极片的制备中，第一材料层的厚度为5μm，磷酸铁锰锂的Dv99为3μm以外，其余与实施例21相同。
实施例28
除了在步骤(2)正极极片的制备中，第一材料层的厚度为9μm，磷酸铁锰锂的Dv99为7μm以外，其余与实施例21相同。
实施例29
除了在步骤(2)正极极片的制备中，第一材料层的厚度为13μm，磷酸铁锰锂的Dv99为11μm以外，其余与实施例21相同。
实施例30
除了在步骤(2)正极极片的制备中，第一材料层的厚度为17μm，磷酸铁锰锂的Dv99为15μm以外，其余与实施例21相同。
实施例31
除了在步骤(2)正极极片的制备中，第一材料层的厚度为19.5μm，磷酸铁锰锂的Dv99为18μm以外，其余与实施例21相同。
实施例32
除了在步骤(2)正极极片的制备中，第一材料层的厚度为20μm，磷酸铁锰锂的Dv99为19.9μm以外，其余与实施例21相同。
实施例33
除了在步骤(2)正极极片的制备中，导电剂选用石墨烯以外，其余与实施例21相同。
实施例34
除了在步骤(2)正极极片的制备中，导电剂选用网状石墨纤维以外，其余与实施例21相同。
实施例35
除了在步骤(2)正极极片的制备中，导电剂选用科琴黑以外，其余与实施例21相同。
实施例36
除了在步骤(2)正极极片的制备中，导电剂选用石墨纤维以外，其余与实施例21相 同。
实施例37
除了在将步骤(2)正极极片的制备中，将碳纳米管替换成网状石墨纤维以外，其余与实施例21相同。
实施例38
除了在步骤(2)正极极片的制备中，导电剂选用网状石墨纤维，磷酸铁锰锂、步骤(1)中得到的粘结剂、网状石墨纤维、聚乙氧基丙氧基丙烯烃的质量比为98.7∶1∶0.1∶0.2以外，其余与实施例21相同。
实施例39
除了在步骤(2)正极极片的制备中导电剂选用碳纳米管，磷酸铁锰锂、步骤(1)中得到的粘结剂、碳纳米管、聚乙氧基丙氧基丙烯烃的质量比为98.3∶1∶0.5∶0.2以外，其余与实施例21相同。
实施例40
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管的质量比为96.2∶0.1∶0.5以外，其余与实施例21相同。
实施例41
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管的质量比为96∶0.3∶0.5以外，其余与实施例21相同。
实施例42
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管的质量比为95.4∶0.9∶0.5以外，其余与实施例21相同。
实施例43
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管的质量比为95.2∶1.1∶0.5以外，其余与实施例21相同。
实施例44
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管的质量比为95∶1.3∶0.5以外，其余与实施例21相同。
实施例45
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管的质 量比为94.8∶1.5∶0.5以外，其余与实施例21相同。
实施例46
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管的质量比为96∶0.5∶0.3以外，其余与实施例21相同。
实施例47
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管的质量比为95.8∶0.5∶0.5以外，其余与实施例21相同。
实施例48
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管的质量比为95.6∶0.5∶0.7以外，其余与实施例21相同。
实施例49
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管的质量比为95.4∶0.5∶0.9以外，其余与实施例21相同。
实施例50
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管的质量比为95.2∶0.5∶1.1以外，其余与实施例21相同。
实施例51
除了去掉在步骤(2)正极极片的制备中的碳纳米管，磷酸铁锰锂和纳米颗粒导电碳的质量比为95.3：1.5以外，其余与实施例21相同。
实施例52
除了在步骤(2)正极极片的制备中，磷酸铁锰锂和纳米颗粒导电碳的质量比为94.8：2以外，其余与实施例51相同。
实施例53
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、粘结剂的质量比为86.8：5：8以外，其余与实施例51相同。
实施例54
除了在步骤(2)正极极片的制备中，磷酸铁锰锂和纳米颗粒导电碳、粘结剂的质量比为79.8：10：10以外，其余与实施例51相同。
实施例55
除了在步骤(2)正极极片的制备中，磷酸铁锰锂和纳米颗粒导电碳、粘结剂的质量比为71.8：15：13以外，其余与实施例51相同。
实施例56
除了在步骤(2)正极极片的制备中，磷酸铁锰锂、纳米颗粒导电碳、碳纳米管、粘结剂的质量比59.8∶15∶5：20以外，其余与实施例21相同。
实施例57
除了在步骤(1)粘结剂的制备中，粘结剂选用聚丙烯酸钠以外，其余与实施例21相同。
实施例58
除了在步骤(1)粘结剂的制备中，粘结剂选用聚丙烯酸胺以外，其余与实施例21相同。
实施例59
除了在步骤(1)粘结剂的制备中，丙烯腈、丙烯酸钠和丙烯酰胺的质量比为30︰60︰10以外，其余与实施例21相同。
实施例60
除了在步骤(1)粘结剂的制备中，丙烯腈、丙烯酸钠和丙烯酰胺的质量比为30︰10︰60以外，其余与实施例21相同。
实施例61
除了在步骤(1)粘结剂的制备中，丙烯腈、丙烯酸钠和丙烯酰胺的质量比为55︰35︰10以外，其余与实施例21相同。
实施例62
除了在步骤(1)粘结剂的制备中，丙烯腈、丙烯酸钠和丙烯酰胺的质量比为55︰10︰35以外，其余与实施例21相同。
实施例63
除了在步骤(1)粘结剂的制备中，丙烯腈、丙烯酸钠和丙烯酰胺的质量比为70︰20︰10以外，其余与实施例21相同。
实施例64
除了在步骤(1)粘结剂的制备中，按质量比为42︰45︰10：3向反应釜加入以下单体：丙烯腈、丙烯酸钠、丙烯酰胺和丙烯酸酯制备粘结剂以外，其余与实施例18相同。
实施例65
除了在步骤(2)正极极片的制备中，磷酸铁锰锂与步骤(1)中得到的粘结剂质量比为97.6∶1以外，其余与实施例21相同。
实施例66
除了在步骤(2)正极极片的制备中，磷酸铁锰锂与步骤(1)中得到的粘结剂质量比为96.6∶2以外，其余与实施例21相同。
实施例67
除了在步骤(2)正极极片的制备中，磷酸铁锰锂与步骤(1)中得到的粘结剂质量比为94.6∶4以外，其余与实施例21相同。
实施例68
除了在步骤(2)正极极片的制备中，磷酸铁锰锂与步骤(1)中得到的粘结剂质量比为93.6∶5以外，其余与实施例21相同。
实施例69
除了在步骤(2)正极极片的制备中，磷酸铁锰锂与步骤(1)中得到的粘结剂质量比为90.6∶8以外，其余与实施例21相同。
实施例70
除了在步骤(2)正极极片的制备中，磷酸铁锰锂与步骤(1)中得到的粘结剂质量比为88.6∶10以外，其余与实施例21相同。
实施例71
除了在步骤(2)正极极片的制备中，磷酸铁锰锂与步骤(1)中得到的粘结剂质量比为86.6∶12以外，其余与实施例21相同。
实施例72
除了在步骤(2)正极极片的制备中，磷酸铁锰锂与步骤(1)中得到的粘结剂质量比为83.6∶15以外，其余与实施例21相同。
实施例73
除了在步骤(2)正极极片的制备中，磷酸铁锰锂与步骤(1)中得到的粘结剂质量比为80.6∶18以外，其余与实施例21相同。
实施例74
除了在步骤(2)正极极片的制备中，磷酸铁锰锂与步骤(1)中得到的粘结剂质量比 为78.6∶20以外，其余与实施例21相同。
对比例1
除了在步骤(2)正极极片的制备中，不含流平剂聚乙氧基丙氧基丙烯烃，磷酸铁锂、步骤(1)中得到的粘结剂、纳米颗粒导电碳、碳纳米管的质量比为95.8∶3∶0.7∶0.5以外，其余与实施例1相同。
对比例2
除了在步骤(2)正极极片的制备中，磷酸铁锂与聚乙氧基丙氧基丙烯烃的质量比为95.795∶0.005以外，其余与实施例1相同。
对比例3
除了在步骤(2)正极极片的制备中，流平剂选用聚丙烯醇，磷酸铁锂与聚丙烯醇的质量比为80.8∶15以外，其余与实施例1相同。
对比例4
除了在步骤(2)正极极片的制备中，正极活性材料选用钴酸锂以外，其余与实施例21相同。
对比例5
除了在步骤(2)正极极片的制备中，正极活性材料选用磷酸铁锂、导电剂选用纳米颗粒导电碳，磷酸铁锂与纳米颗粒导电碳的质量比为70.6：25以外，其余与实施例21相同。
对比例6
除了在步骤(2)正极极片的制备中，磷酸铁锂与步骤(1)中得到的粘结剂的质量比为75.6∶23以外，其余与实施例21相同。
表1 实施例1-19和对比例1-3的制备参数及测试结果
Figure PCTCN2020142272-appb-000001
Figure PCTCN2020142272-appb-000002
表2 实施例20-74和对比例4-6的制备参数及测试结果
Figure PCTCN2020142272-appb-000003
Figure PCTCN2020142272-appb-000004
Figure PCTCN2020142272-appb-000005
Figure PCTCN2020142272-appb-000006
Figure PCTCN2020142272-appb-000007
Figure PCTCN2020142272-appb-000008
Figure PCTCN2020142272-appb-000009
Figure PCTCN2020142272-appb-000010
Figure PCTCN2020142272-appb-000011
从表1实施例1-19和对比例1-3可以看出，具有本申请正极极片的锂离子电池，其90°垂直侧边穿钉通过率明显高于对比例提供的锂离子电池，表明本申请提供的锂离子电池的安全可靠性明显提高。
从表1实施例1-19和对比例1-3还可以看出，本申请提供的正极极片，其中第一材料层的厚度最大值与最小值之差均小于对比例提供的正极极片，表明本申请提供的正极极片上的第一材料层的厚度均匀性更好。
从表1实施例1-19和对比例1-3还可以看出，本申请提供的正极极片，只要使得满充电阻在本申请保护的范围内，就能够提高本申请锂离子电池的安全可靠性。
从表2实施例20-74和对比例4可以看出，具有本申请正极极片的锂离子电池，其90°垂直侧边穿钉通过率明显高于对比例提供的锂离子电池，这可能是由于磷酸铁锂、磷酸铁锰锂和锰酸锂的满充电阻均大于钴酸锂，在钢钉穿过的瞬间更不容易起火或爆炸，从而表明本申请提供的锂离子电池的安全可靠性得到了提高。
从表2实施例23-32可以看出，随着第一材料层中的活性材料的Dv99增大，锂离子电池具有高的穿钉通过率。表明只要使得活性材料的Dv99在本申请保护的范围内，就能够得到安全性能良好的锂离子电池。
从表2实施例65-74和对比例6可以看出，具有本申请正极极片，只要使得第一材料层中粘结剂的含量在本申请的保护范围内，得到的锂离子电池的安全则具有高的穿钉通过率，从而提高锂离子电池的安全可靠性。
从表2实施例20-74和对比例4-5可以看出，本申请提供的正极极片，其满充电阻在本申请保护的范围内，而对比例4和5在本申请的保护范围之外，这可能是由于对比例4中钴酸锂的电阻较小、对比例5中导电剂的含量偏高，从而导致对比例4和5的穿钉测试通过率为0。表明本申请提供的正极极片其满充电阻在本申请保护的范围内，可以提高锂离子电池的穿钉测试通过率，从而提高锂离子电池的安全可靠性。
综上所述，本申请提供的正极极片厚度均匀性高，集流体和第二材料层与第一材料层之间的粘结力强，将其应用于锂离子电池，能够有效降低由于外力撞击或穿刺等原因造成的安全事故发生概率，从而提高锂离子电池的安全可靠性。
以上所述仅为本申请的较佳实施例，并不用以限制本申请，凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请保护的范围之内。

Claims (15)

  1. 一种电化学装置，包括正极，所述正极包含集流体、第一材料层和第二材料层，所述第二材料层设置在所述集流体的至少一个表面上，所述第一材料层设置在所述集流体和所述第二材料层之间，其中，所述第一材料层的厚度最大值与最小值之差不大于3μm。
  2. 根据权利要求1所述的电化学装置，其中，所述第一材料层包括流平剂，所述流平剂为重均分子量不高于50000的聚合物。
  3. 根据权利要求2所述的电化学装置，其中，所述流平剂包括烯烃类衍生物的聚合物、羧酸盐类聚合物、硅氧烷类聚合物、烯酸酯类聚合物、醇类聚合物或醚类聚合物中的至少一种。
  4. 根据权利要求2所述的电化学装置，其中，所述流平剂包括羧酸钠聚合物、含氧丙烯烃类衍生物的聚合物或聚硅氧烷中的至少一种。
  5. 根据权利要求2所述的电化学装置，所述第一材料层还包括活性材料、粘结剂和导电剂，基于所述第一材料层的总质量，所述活性材料的质量百分含量为50％至98.89％，所述粘结剂的质量百分含量为1％至20％，所述导电剂的质量百分含量为0.1％至20％，所述流平剂的质量百分含量为0.01％至10％。
  6. 根据权利要求5所述的电化学装置，其中，所述粘结剂包括丙烯烃类衍生物的共聚物、聚丙烯酸酯类、丙烯腈多元共聚物、羧甲基纤维素盐中的至少一种。
  7. 根据权利要求6所述的电化学装置，其中，所述粘结剂包括由丙烯酸腈、丙烯酸盐、丙烯酰胺、丙烯酸酯中的至少一种单体聚合而成的聚合物。
  8. 根据权利要求1所述的电化学装置，其中，所述第一材料层单层厚度为0.05μm至20μm。
  9. 根据权利要求1所述的电化学装置，其中，所述正极满充后的电阻为10Ω以上。
  10. 根据权利要求5所述的电化学装置，其中，所述活性材料的平均粒径Dv99为0.01μm至19.9μm。
  11. 根据权利要求5所述的电化学装置，其中，所述导电剂包含片层状、网状、线状或零维导电剂中的至少一种。
  12. 根据权利要求1所述的电化学装置，其中，所述第二材料层的单层厚度为20μm 至200μm。
  13. 根据权利要求1或5所述的电化学装置，其中，所述正极满足以下特征中的至少一者：
    (a)所述流平剂包含聚乙氧基丙氧基丙烯烃；
    (b)所述导电剂包含石墨烯、网状石墨纤维、碳纳米管、科琴黑、石墨纤维或纳米颗粒导电碳中的至少一种。
  14. 一种如权利要求1-13中任意一项所述的电化学装置的制备方法，包括：
    在集流体的至少一个表面上依次形成第一材料层和第二材料层，其中，所述第一材料层的厚度最大值与最小值之差不大于3μm。
  15. 一种电子装置，其包含权利要求1-13中任意一项所述的电化学装置。
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