CN112531173A - Metal foil treatment process, electrode plate and electrochemical device - Google Patents

Metal foil treatment process, electrode plate and electrochemical device Download PDF

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Publication number
CN112531173A
CN112531173A CN201910877261.4A CN201910877261A CN112531173A CN 112531173 A CN112531173 A CN 112531173A CN 201910877261 A CN201910877261 A CN 201910877261A CN 112531173 A CN112531173 A CN 112531173A
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Prior art keywords
metal foil
lithium
foil
aluminum foil
treatment process
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刘晓欠
王可飞
刘胜奇
张青文
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Ningde Amperex Technology Ltd
Dongguan Amperex Technology Ltd
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Ningde Amperex Technology Ltd
Dongguan Amperex Technology Ltd
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Priority to CN201910877261.4A priority Critical patent/CN112531173A/en
Publication of CN112531173A publication Critical patent/CN112531173A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A metal foil treatment process comprising the steps of: carrying out plasma treatment on the surface of the metal foil; coiling the metal foil after the plasma treatment into a coil shape, and baking the coil-shaped metal foil; and cooling the rolled metal foil. The metal foil treatment process can remove the peculiar smell caused by the plasma treatment. The application also provides an electrode plate and an electrochemical device.

Description

Metal foil treatment process, electrode plate and electrochemical device
Technical Field
The application relates to a metal foil treatment process, an electrode plate and an electrochemical device.
Background
The lithium ion battery has the advantages of large specific energy, high working voltage, low self-discharge rate, small volume, light weight and the like, and has wide application in the field of consumer electronics. In order to increase the surface tension of a current collector metal foil in a lithium ion battery and facilitate spreading of a slurry (e.g., an active material), a plasma treatment (e.g., corona) is generally performed on the surface of the current collector metal foil. However, the treated metal foil often has serious odor, which affects the use of the metal foil and is not good for the health of operators.
Disclosure of Invention
In view of the above, it is desirable to provide a treatment process for removing the odor caused by plasma treatment of metal foil, an electrode sheet using the treatment process, and an electrochemical device using the electrode sheet.
The application provides a metal foil treatment process, which comprises the following steps:
carrying out plasma treatment on the surface of the metal foil;
coiling the metal foil after the plasma treatment into a coil shape, and baking the coil metal foil to remove the peculiar smell caused by the plasma treatment; and
and cooling the rolled metal foil.
Further, the metal foil includes at least one of an aluminum foil, a copper foil, a tin foil, a lithium foil, and a nickel foil.
Further, the baking temperature is 50 ℃ to 150 ℃; or from 60 ℃ to 90 ℃.
Further, the baking time is 10min to 180 min; or 20min to 120 min.
Further, the baking comprises the steps of:
heating the rolled metal foil to a preset temperature at a heating rate of 0.1-20 ℃/min or a heating rate of 0.5-5 ℃/min, and maintaining the preset temperature for 10-180 min, wherein the preset temperature is selected from 50-150 ℃.
Further, the step of "cooling the rolled metal foil" is specifically:
and (3) placing the rolled metal foil in air, nitrogen or inert gas for cooling to room temperature.
Further, the step of "cooling the rolled metal foil" is specifically:
and cooling the rolled metal foil to room temperature at a cooling rate of 0.1-5 ℃/min or 0.5-5 ℃/min.
Furthermore, the cooling comprises cooling and heat preservation stages, and each cooling and heat preservation stage comprises cooling to a preset temperature and preserving heat at the preset temperature.
Further, the cooling step further comprises the step of cooling the metal foil to room temperature in air, nitrogen or inert gas after the temperature reduction and preservation step.
An electrode sheet, comprising:
an active material layer including an active material, a binder, and a conductive agent; and a metal foil treated according to the metal foil treatment process as described above.
Further, the active material includes at least one selected from the group consisting of lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium iron phosphate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium rich manganese based material, and lithium titanate.
Further, the binder includes at least one selected from the group consisting of polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinyl pyrrolidone, polyamide, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, and styrene butadiene rubber.
Further, the conductive agent includes at least one selected from the group consisting of conductive carbon black, acetylene black, carbon nanotubes, carbon fibers, ketjen black, and graphene.
An electrochemical device comprising an electrode sheet as described above.
According to the metal foil treatment process, the surface tension of the metal foil is improved through plasma treatment, then the peculiar smell caused by the plasma treatment is eliminated through baking, the surface tension of the metal foil is stabilized, and the mechanical property of the metal foil is maintained.
Further, the metal foil is cooled by cooling at a specific speed or the cooling comprises a cooling and heat preservation stage, so that the influence on the mechanical property of the metal foil can be reduced.
Furthermore, the metal foil can be prevented from being oxidized during cooling by cooling in nitrogen or inert gas, so that the influence on the conductivity and mechanical property of the metal foil is reduced.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Some embodiments of the present application are described in detail below. The embodiments described below and the features of the embodiments can be combined with each other without conflict.
The embodiment of the application provides a metal foil treatment process, which comprises the following steps:
in step S1, the surface of the metal foil is subjected to plasma treatment.
In this embodiment, the metal foil may include at least one of an aluminum foil, a copper foil, a tin foil, a lithium foil, and a nickel foil.
The surface tension of the metal foil after the plasma treatment is improved.
In some embodiments, the surface of the metal foil may be plasma treated multiple times, wherein the specific process parameters of each plasma treatment may be the same or different. For example, the distance from the plasma emission source to the surface of the metal foil at the first plasma treatment may be 0.5cm to 25cm, the power of the first plasma treatment may be 30kW to 50kW, and the transfer speed of the metal foil may be 100m/min to 150 m/min; the distance between the plasma emission source and the surface of the metal foil during the second plasma treatment can be 0.5 cm-15 cm, the power of the second plasma treatment can be 10 kW-15 kW, and the conveying speed of the metal foil can be 150 m/min-200 m/min.
And step S2, rolling the metal foil after the plasma treatment into a roll shape, and baking the roll-shaped metal foil to remove the peculiar smell caused by the plasma treatment.
In the present embodiment, the baking of the rolled metal foil may be specifically: and (3) placing the rolled metal foil in a baking oven to bake at a preset temperature, wherein the preset temperature is selected from 50 ℃ to 150 ℃, and preferably, the preset temperature is selected from 60 ℃ to 90 ℃. The time for baking at the preset temperature can be 10min to 180min, and preferably, the time for baking at the preset temperature can be 20min to 120 min.
In some embodiments, the baking step of the rolled metal foil may be: heating the rolled metal foil to a preset temperature at a heating rate of 0.1-20 ℃/min, wherein the preset temperature is selected from 50-150 ℃. Preferably, the heating rate is 0.5 ℃/min to 5 ℃/min.
Furthermore, the preset temperature can be maintained for 10min to 180min after the rolled metal foil is heated to the preset temperature.
Since the metal foil is plasma-treated for a short time, the conveying speed is fast and continuous in-line treatment is preferable. The speed of eliminating the peculiar smell of the metal foil caused by the plasma treatment is low, if the metal foil is kept in a flat state and is directly baked after the plasma treatment to remove the peculiar smell, the production efficiency is low, and the metal foil is rolled, so that the baking of the metal foil is not influenced, and the production efficiency can be obviously improved. In addition, the metal foil is put into the baking oven for baking after being rolled into a roll, so that impurities brought into the baking step during plasma processing can be reduced, the roll metal foil is more conveniently placed in the baking oven, the metal foil can be prevented from being scratched, the scratching area can be reduced, and the generation of scratches on the surface of the metal foil can be reduced.
In step S3, the metal foil after the plasma treatment is cooled.
In the present embodiment, the cooling is natural cooling in air.
Further, the metal foil after removing the odor can be placed in nitrogen or inert gas to be cooled to room temperature.
In some embodiments, the cooling of the metal foil after removing the odor may specifically be: and cooling the rolled metal foil to room temperature at a cooling rate of 0.1-5 ℃/min. Preferably, the cooling rate is 0.5 ℃/min to 5 ℃/min.
In other embodiments, the cooling may include cooling and holding stages, each of which includes cooling to a predetermined temperature and holding at the predetermined temperature.
In some embodiments, after the metal foil is baked to 50 ℃ to 150 ℃, the temperature is reduced to any temperature at any rate and is kept for a certain time, so that the temperature of the metal foil is reduced in a stepped manner until the temperature is reduced to room temperature. Wherein, the metal foil can be firstly insulated and then cooled after being baked to 50 ℃ to 150 ℃.
Specifically, the cooling may include a plurality of cooling and heat-preserving stages until the temperature is finally reduced to room temperature. And the metal foil can be naturally cooled or placed in nitrogen or inert gas for cooling to room temperature after the cooling and heat preservation stage.
According to the metal foil treatment process, the surface tension of the metal foil is improved through plasma treatment, then the peculiar smell caused by the plasma treatment is eliminated through baking, the surface tension of the metal foil is stabilized, and the mechanical property of the metal foil is maintained. The metal foil treated by the metal foil treatment process can also be used as a current collector to be applied to electrode plates of batteries and other electrochemical devices.
In the present application, the lithium ion battery is merely an exemplary embodiment of the electrochemical device, and the electrochemical device may be other suitable devices. The lithium ion battery comprises a positive pole piece, a negative pole piece, an isolating membrane and electrolyte, wherein the isolating membrane is positioned between the positive pole piece and the negative pole piece. The positive pole piece includes the anodal mass flow body, and the negative pole piece includes the negative current collection body, and the anodal mass flow body includes the metal foil, the metal foil can be but not only is limited to aluminium foil or nickel foil, and the negative current collection body includes the metal foil, the metal foil can be but not only is limited to copper foil or nickel foil.
Positive pole piece
The positive electrode sheet further includes a positive active material layer disposed on the positive current collector, the positive active material layer including a positive active material including a positive electrode material capable of absorbing and releasing lithium (Li) (hereinafter, sometimes referred to as "a positive electrode material capable of absorbing/releasing lithium Li"), a binder, and a conductive agent. Examples of the positive electrode material capable of absorbing/releasing lithium (Li) may include at least one of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganate, lithium nickelate, lithium manganese phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium iron phosphate, lithium titanate, and a lithium-rich manganese-based material.
Specifically, the chemical formula of lithium cobaltate may be as shown in chemical formula 1:
LixCoaM1bO2-cchemical formula 1
Wherein M1 represents at least one selected from the group consisting of nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), yttrium (Y), lanthanum (La), zirconium (Zr), and silicon (Si), and x, a, B, and c values are respectively in the following ranges: x is more than or equal to 0.8 and less than or equal to 1.2, a is more than or equal to 0.8 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, and c is more than or equal to-0.1 and less than or equal to 0.2;
the chemical formula of lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate can be as shown in chemical formula 2:
LiyNidCoiNjM2eO2-fchemical formula 2
Wherein N represents one or two selected from manganese (Mn) or aluminum (Al), and M2 may be further selected from at least one of magnesium (Mg), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), zirconium (Zr), and silicon (Si), and y, d, e, f, i, and j values are respectively in the following ranges: y is more than or equal to 0.8 and less than or equal to 1.2, d is more than or equal to 0.3 and less than or equal to 0.98, e is more than or equal to 0.02 and less than or equal to 0.7, f is more than or equal to 0.1 and less than or equal to 0.2, i is more than or equal to 0.05 and less than or equal to 0.33, and f is more than or equal to 0.05;
the chemical formula of lithium manganate can be as chemical formula 3:
LizMn2-gM3gO4-hchemical formula 3
Wherein M3 represents at least one selected from the group consisting of cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), and z, g, and h values are respectively in the following ranges: z is more than or equal to 0.8 and less than or equal to 1.2, g is more than or equal to 0 and less than or equal to 1.0, and h is more than or equal to-0.2 and less than or equal to 0.2.
The binder includes at least one selected from the group consisting of polyvinylidene fluoride, copolymers of vinylidene fluoride-hexafluoropropylene, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethylcellulose, polyvinylpyrrolidone, polyamide, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, and styrene butadiene rubber.
The conductive agent includes at least one selected from the group consisting of conductive carbon black, acetylene black, carbon nanotubes, carbon fibers, ketjen black, and graphene.
Negative pole piece
The negative electrode tab further includes a negative electrode active material layer disposed on the negative electrode current collector, the negative electrode active material layer including a negative electrode material capable of absorbing and releasing lithium (Li) (hereinafter, sometimes referred to as "a negative electrode material capable of absorbing/releasing lithium Li"), a binder, and a conductive agent. Examples of the negative electrode material capable of absorbing/releasing lithium (Li) may include carbon materials, metal compounds, oxides, sulfides, nitrides of lithium such as LiN3Lithium metal, metals that form alloys with lithium, and polymeric materials.
Examples of the carbon material may include at least one of low-graphitizable carbon, artificial graphite, natural graphite, mesocarbon microbeads, soft carbon, hard carbon, pyrolytic carbon, coke, glassy carbon, an organic polymer compound sintered body, carbon fibers, activated carbon, and the like. The coke may include at least one of pitch coke, needle coke, and petroleum coke, among others. The organic polymer compound sintered body refers to a material obtained by calcining a polymer material such as a phenol plastic or furan resin at an appropriate temperature to carbonize it, and dividing the material into low-graphitizable carbon or easily graphitizable carbon. Examples of the polymer material may include at least one of polyacetylene and polypyrrole.
Among these anode materials capable of absorbing/releasing lithium (Li), further, a material having a charge and discharge voltage close to that of lithium metal is selected. This is because the lower the charge and discharge voltage of the negative electrode material, the easier it is for an electrochemical device (e.g., a lithium ion battery) to have a higher energy density. Among them, the negative electrode material may be selected from carbon materials because their crystal structures are only slightly changed upon charge and discharge, and therefore, good cycle characteristics and large charge and discharge capacities can be obtained. Graphite is particularly preferred because it gives a large electrochemical equivalent and a high energy density.
In addition, the anode material capable of absorbing/releasing lithium (Li) may include elemental lithium metal, metal elements and semimetal elements capable of forming an alloy with lithium (Li), alloys and compounds including such elements, and the like. In particular, they are used together with a carbon material because in this case, good cycle characteristics and high energy density can be obtained. Alloys as used herein include, in addition to alloys comprising two or more metallic elements, alloys comprising one or more metallic elements and one or more semi-metallic elements. The alloy may be in the following states solid solution, eutectic crystal (eutectic mixture), intermetallic compound and mixtures thereof.
Examples of the metallic element and the semi-metallic element may include tin (Sn), lead (Pb), aluminum (Al), indium (In), silicon (Si), zinc (Zn), antimony (Sb), bismuth (Bi), cadmium (Cd), magnesium (Mg), boron (B), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), zirconium (Zr), yttrium (Y), and hafnium (Hf). Examples of the above alloys and compounds may include those having the formula: masMbtLiuAnd a material having the formula: mapMcqMdrThe material of (1). In these chemical formulae, Ma represents at least one of a metal element and a semimetal element capable of forming an alloy together with lithium; mb represents at least one of a metal element and a semimetal element other than lithium and Ma; mc represents at least one element of non-metallic elements; md represents at least one element of metal elements other than Ma and semimetal elements; and s, t, u, p, q and r satisfy s > 0, t ≧ 0, u ≧ 0, p > 0, q > 0 and r ≧ 0.
In addition, an inorganic compound excluding lithium (Li), such as MnO, may be used in the negative electrode2、V2O5、V6O13NiS, and MoS.
Electrolyte
The lithium ion battery also comprises an electrolyte, wherein the electrolyte can be one or more of a gel electrolyte, a solid electrolyte and an electrolyte solution, and the electrolyte solution comprises a lithium salt and a non-aqueous solvent.
The lithium salt is selected from LiPF6、LiBF4、LiAsF6、LiClO4、LiB(C6H5)4、LiCH3SO3、LiCF3SO3、LiN(SO2CF3)2、LiC(SO2CF3)3、LiSiF6One or more of LiBOB and lithium difluoroborate. For example, LiPF is selected as lithium salt6Since 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 solvent, or a combination thereof.
The carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluoro carbonate compound, or a combination thereof.
Examples of the chain carbonate compound are diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC), Methyl Ethyl Carbonate (MEC), and combinations thereof. Examples of the cyclic carbonate compound are Ethylene Carbonate (EC), Propylene Carbonate (PC), Butylene Carbonate (BC), Vinyl Ethylene Carbonate (VEC), and combinations thereof. Examples of the fluoro carbonate compound are fluoroethylene carbonate (FEC), 1, 2-difluoroethylene carbonate, 1, 2-trifluoroethylene carbonate, 1,2, 2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1, 2-difluoro-1-methylethylene carbonate, 1, 2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, and combinations thereof.
Examples of carboxylate compounds are methyl acetate, ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ -butyrolactone, decalactone, valerolactone, mevalonic lactone, caprolactone, methyl formate, and combinations thereof.
Examples of ether compounds are dibutyl ether, tetraglyme, diglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and combinations thereof.
Examples of other organic solvents are dimethylsulfoxide, 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.
Isolation film
The separator includes, but is not limited to, at least one selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, polyimide, and aramid. For example, the polyethylene includes at least one component selected from the group consisting of high density polyethylene, low density polyethylene, and ultra high molecular weight polyethylene. Particularly polyethylene and polypropylene, which have a good effect on preventing short circuits and can improve the stability of the battery through a shutdown effect.
The surface of the separator may further include a porous layer disposed on at least one surface of the separator, the porous layer including one or both of inorganic particles selected from alumina (Al) and a binder2O3) Silicon oxide (SiO)2) Magnesium oxide (MgO), titanium oxide (T)iO2) Hafnium oxide (HfO)2) Tin oxide (SnO)2) Cerium oxide (CeO)2) Nickel oxide (NiO), zinc oxide (ZnO), calcium oxide (CaO), zirconium oxide (ZrO)2) Yttrium oxide (Y)2O3) Silicon carbide (SiC), boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate. The binder is selected from one or more of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethylcellulose, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.
The porous layer can improve the heat resistance, the oxidation resistance and the electrolyte infiltration performance of the isolating membrane, and enhance the adhesion between the isolating membrane and the positive pole piece or the negative pole piece.
Although a lithium ion battery is exemplified above, after reading the present application, one skilled in the art can appreciate that the present solution can be applied to other suitable electrochemical devices. Such an electrochemical device includes any device in which electrochemical reactions occur, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors.
The following examples and comparative examples further illustrate the present invention.
Comparative example 1
And (2) feeding the aluminum foil into a plasma processing chamber by a conveyor belt for carrying out plasma processing twice, wherein a plasma emission source is 2cm away from the surface of the aluminum foil, the power of each plasma processing is 15kW, the conveying speed of each aluminum foil is 120m/min, and the aluminum foil after the plasma processing is naturally cooled to room temperature in the air. The aluminum foil after plasma treatment emits foul smell, so that a user generates a dizziness condition.
Lithium ion battery preparation
And (2) fully stirring and uniformly mixing the positive active material lithium cobaltate, the conductive agent acetylene black and the binder polyvinylidene fluoride in an N-methyl pyrrolidone solvent system according to the mass ratio of 94:3:3, coating the mixture on a positive current collector (the prepared aluminum foil), and drying, cold pressing and slitting to obtain the positive pole piece.
The method comprises the steps of fully stirring and uniformly mixing the negative active material artificial graphite, the conductive agent acetylene black, the binder styrene butadiene rubber and the thickener carboxymethylcellulose sodium in a deionized water solvent system according to the mass ratio of 96:1:1.5:1.5, coating the mixture on a negative current collector Cu foil, and drying, cold pressing and splitting to obtain a negative pole piece.
Dissolving polyvinylidene fluoride in water, forming uniform slurry through mechanical stirring, coating the slurry on the two side surfaces of a porous base material (polyethylene) coated with ceramic coatings on the two sides, and drying to form an isolating membrane.
Lithium salt LiPF6And a nonaqueous organic solvent (ethylene carbonate (EC): diethyl carbonate (DEC): Propylene Carbonate (PC): Propyl Propionate (PP): Vinylene Carbonate (VC)) (20: 30:20:28: 2) in a mass ratio of 8: 92 as the electrolyte of the lithium ion battery.
And (3) stacking the positive pole piece, the isolating film and the negative pole piece in sequence, enabling the isolating film to be positioned between the positive pole piece and the negative pole piece to play a role of safety isolation, winding to obtain an electrode assembly, placing the electrode assembly in a packaging shell, injecting electrolyte and packaging to obtain the lithium ion battery.
Comparative example 2
The aluminum foil enters a plasma processing chamber by a conveyor belt for plasma processing, and is directly conveyed to an air atmosphere at 70 ℃ for baking in the conveying process, wherein a plasma emission source is 2cm away from the surface of the aluminum foil, the plasma processing power is 15kW, the conveying speed of the aluminum foil is 120m/min, and the time for passing through the air atmosphere at 70 ℃ is 20 s. The aluminum foil treated by the steps emits slight odor, so that a user generates a dizziness condition, and meanwhile, partial scratches are formed on the surface of the aluminum foil.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in comparative example 2.
Example 1
The aluminum foil enters the plasma processing chamber by the way of a conveyor belt to be processed by plasma, and then is wound into a roll shape. Wherein the distance between the plasma emission source and the surface of the aluminum foil is 2cm, the plasma treatment power is 55kW, and the conveying speed of the aluminum foil is 120 m/min. And placing the aluminum foil coil subjected to the plasma treatment in a baking furnace, standing, heating from room temperature to 120 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 20min, taking out, and naturally cooling to room temperature in the air, wherein the cooled aluminum foil has no peculiar smell and no scratch.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in example 1.
Example 2
The aluminum foil enters the plasma processing chamber by a conveyor belt for plasma processing twice and then is wound into a roll. Wherein, the distance between the plasma emission source and the surface of the aluminum foil is 2cm, the power of plasma treatment is 50kW, and the conveying speed of the aluminum foil is 160 m/min. And placing the aluminum foil coil subjected to the plasma treatment in a baking furnace, standing, heating from room temperature to 90 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 30min, taking out, and naturally cooling to room temperature in the air, wherein the cooled aluminum foil has no peculiar smell and no scratch.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in example 2.
Example 3
The aluminum foil enters the plasma processing chamber by the way of a conveyor belt to be processed by plasma, and then is wound into a roll shape. Wherein the distance between the plasma emission source and the surface of the aluminum foil is 2cm, the plasma treatment power is 50kW, and the conveying speed of the aluminum foil is 120 m/min. And placing the aluminum foil coil subjected to the plasma treatment in a baking furnace, standing, heating from room temperature to 80 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 90min, taking out, and naturally cooling to room temperature in the air, wherein the cooled aluminum foil has no peculiar smell and no scratch.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in example 3.
Example 4
The aluminum foil enters the plasma processing chamber by the way of a conveyor belt to be processed by three times of plasma processing and then is wound into a roll shape. Wherein, the distance between the plasma emission source and the surface of the aluminum foil is 2cm, the power of plasma treatment is 15kW, and the conveying speed of the aluminum foil is 120 m/min. And placing the aluminum foil coil subjected to the plasma treatment in a baking furnace, standing, heating from room temperature to 75 ℃ at the heating rate of 2.5 ℃/min, keeping the temperature for 120min, taking out, and naturally cooling to room temperature in the air, wherein the cooled aluminum foil has no peculiar smell and no scratch.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in example 4.
Example 5
The aluminum foil enters the plasma processing chamber by a conveyor belt for plasma processing twice and then is wound into a roll. Wherein, the distance between the plasma emission source and the surface of the aluminum foil is 2cm, the power of plasma treatment is 15kW, and the conveying speed of the aluminum foil is 100 m/min. And (3) placing the aluminum foil roll after the plasma treatment in a baking furnace at 60 ℃ for standing and baking for 180min, taking out the aluminum foil roll and naturally cooling the aluminum foil roll to room temperature in the air, wherein the cooled aluminum foil has no peculiar smell and no scratch.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in example 5.
Example 6
The aluminum foil enters the plasma processing chamber by a conveyor belt for plasma processing twice and then is wound into a roll. Wherein, the distance between the plasma emission source and the surface of the aluminum foil is 2cm, the power of plasma treatment is 15kW, and the conveying speed of the aluminum foil is 100 m/min. And (3) placing the aluminum foil roll after the plasma treatment in a baking furnace at 65 ℃ for standing and baking for 150min, taking out the aluminum foil roll and naturally cooling the aluminum foil roll to room temperature in the air, wherein the cooled aluminum foil has no peculiar smell and no scratch.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in example 6.
Example 7
The aluminum foil enters the plasma processing chamber by a conveyor belt for plasma processing twice and then is wound into a roll. Wherein, the distance between the plasma emission source and the surface of the aluminum foil is 2cm, the power of plasma treatment is 15kW, and the conveying speed of the aluminum foil is 80 m/min. And (3) placing the aluminum foil roll after the plasma treatment in a baking furnace at 70 ℃ for standing and baking for 100min, then opening a furnace door, cooling the aluminum foil roll to room temperature along with the baking furnace, and taking out the aluminum foil roll, wherein the cooled aluminum foil has no peculiar smell and no scratch.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in example 7.
Example 8
The aluminum foil enters the plasma processing chamber by a conveyor belt for plasma processing twice and then is wound into a roll. Wherein, the distance between a plasma emission source and the surface of the aluminum foil is 2cm during the first plasma treatment, the power of the first plasma treatment is 50kW, and the conveying speed of the first aluminum foil is 120 m/min; and during the second plasma treatment, the distance between a plasma emission source and the surface of the aluminum foil is 1cm, the power of the second plasma treatment is 15kW, and the conveying speed of the second aluminum foil is 180 m/min. And placing the aluminum foil coil subjected to the plasma treatment in a baking furnace, standing, heating from room temperature to 150 ℃ at the heating rate of 6 ℃/min, keeping the temperature for 15min, taking out, and naturally cooling to room temperature in the air, wherein the cooled aluminum foil has no peculiar smell and no scratch.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in example 8.
Example 9
The aluminum foil enters the plasma processing chamber by the way of a conveyor belt to be processed by plasma, and then is wound into a roll shape. Wherein the distance between the plasma emission source and the surface of the aluminum foil is 2cm, the plasma treatment power is 20kW, and the conveying speed of the aluminum foil is 120 m/min. And placing the aluminum foil coil subjected to the plasma treatment in a baking furnace, standing, heating from room temperature to 100 ℃ at a heating rate of 10 ℃/min, then cooling to room temperature at a cooling rate of 0.8 ℃/min, and taking out, wherein the cooled aluminum foil has no peculiar smell and no scratch.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in example 9.
Example 10
The aluminum foil enters the plasma processing chamber by the way of a conveyor belt to be processed by plasma, and then is wound into a roll shape. Wherein, the distance between the plasma emission source and the surface of the aluminum foil is 2cm, the power of plasma treatment is 20kW, and the conveying speed of the aluminum foil is 120 m/min. And placing the aluminum foil coil subjected to the plasma treatment in a baking furnace, standing, heating from room temperature to 150 ℃ at a heating rate of 10 ℃/min, preserving heat for 10min, then cooling to 70 ℃ at a cooling rate of 3 ℃/min, preserving heat for 20min, taking out, and naturally cooling to room temperature in the air, wherein the cooled aluminum foil has no peculiar smell and no scratch.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in example 10.
Example 11
The aluminum foil enters the plasma processing chamber by the way of a conveyor belt to be processed by plasma, and then is wound into a roll shape. Wherein, the distance between the plasma emission source and the surface of the aluminum foil is 2cm, the power of plasma treatment is 15kW, and the conveying speed of the aluminum foil is 80 m/min. And placing the aluminum foil coil subjected to the plasma treatment in a baking furnace, standing, heating from room temperature to 85 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 60min, taking out, and naturally cooling to room temperature in nitrogen, wherein the cooled aluminum foil has no peculiar smell and no scratch.
Preparing a lithium ion battery: the difference from comparative example 1 is that the aluminum foil in comparative example 1 was replaced with the aluminum foil prepared in example 11.
The following performance tests were performed on the electrode sheets and lithium ion batteries prepared in comparative examples 1 to 2 and examples 1 to 11 as described above:
1. resistance test of positive active material layer after cold pressing
Under the pressure of 5kgf, the contact area of the test needle and the diaphragm is 15mm2Under the condition of (1), starting the test in the middle area more than 25mm away from the edge of the pole piece and the uncoated area by using a diaphragm resistance meter, taking a point every 2cm for 10 values in total, and taking the average value as the resistance of the diaphragm.
2. Bonding force test of formed positive active material layer and aluminum foil
Taking a pole piece to be tested, cutting a sample with the width of 20mm and the length of 200mm by using a blade, pasting a double-sided adhesive tape with the width of 20mm and the length of 80mm on a steel plate, and pasting the test surface of the cut pole piece sample on the double-sided adhesive tape downwards. And fixing one end of the steel plate, which is not attached with the pole piece, by using a lower clamp of a tensile machine, fixing the end, which is not attached with the glue, of the pole piece by using an upper clamp, and moving an upper chuck upwards by 60mm at the speed of 40mm/min by using an operating system of the tensile machine to measure the bonding force of the pole piece.
3. Direct current resistance testing of lithium ion batteries
Discharging the fully charged lithium ion battery at 25 ℃ by current 2 times the capacity until 70% of the electricity quantity of the lithium ion battery remains, recording the termination voltage as v0 and the termination current as I0; then, the discharge was carried out for 1s at a current 1 times the capacity, and the termination voltage and termination current were expressed as vx and Ix, respectively. The direct current internal resistance of the lithium ion battery under the condition is as follows:
Figure BDA0002204756950000151
4. resistance value increase rate test after 800 cycles of lithium ion battery cycle
At 25 ℃, fully charged lithium ion batteries are discharged at a current of 0.025 times of capacity, voltage is measured every 1h, the voltage of the lithium ion battery is recorded as v1 when 8h (namely the lithium ion battery is 80% of the electricity), and the current is I1. The lithium ion battery is charged to 100% of electric quantity by the current with 0.5 time of capacity, the current with 0.2 times of capacity is discharged until the electric quantity is consumed, when the cycle is 800 times, the voltage of the lithium ion battery is measured to be v800 and the current is I800 under the condition that the lithium ion battery is discharged to 80% of electric quantity, and the resistance value increase rate of the lithium ion battery is recorded as follows:
Figure BDA0002204756950000152
the aluminum foils of examples 1 to 11 were subjected to surface tension measurement before plasma treatment, after plasma treatment, and after baking and cooling, and the measurement results are shown in table 1 below.
TABLE 1
Figure BDA0002204756950000161
According to the metal foil treatment process, the surface tension of the metal foil is improved through plasma treatment, then the peculiar smell caused by the plasma treatment is eliminated through standing and baking, the surface tension of the metal foil is stabilized, and the mechanical property of the metal foil is maintained. Further, the metal foil is cooled by cooling at a specific speed or the cooling comprises a cooling and heat preservation stage, so that the influence on the mechanical property of the metal foil can be reduced. Furthermore, the metal foil can be prevented from being oxidized during cooling by cooling in nitrogen or inert gas, so that the influence on the conductivity and mechanical property of the metal foil is reduced.
The positive pole piece adopts the metal foil of this application metal foil processing technology as the mass flow body, compares in the metal foil of conventional method processing, and the resistance of cold pressing back positive pole active material layer is littleer, becomes back positive pole active material layer stronger with the adhesive force of aluminium foil, makes into lithium ion battery after, and lithium ion battery's direct current resistance is littleer, circulates resistance growth rate after 800 circles and reduces, has effectively promoted lithium ion battery's performance.
In addition, it is obvious to those skilled in the art that other various corresponding changes and modifications can be made according to the technical idea of the present application, and all such changes and modifications should fall within the protective scope of the claims of the present application.

Claims (10)

1. A metal foil treatment process comprising the steps of:
carrying out plasma treatment on the surface of the metal foil;
coiling the metal foil after the plasma treatment into a coil shape, and baking the coil-shaped metal foil; and
and cooling the rolled metal foil.
2. The metal foil treatment process of claim 1, wherein the metal foil comprises at least one of an aluminum foil, a copper foil, a tin foil, a lithium foil, and a nickel foil.
3. The metal foil treatment process according to claim 1, wherein the baking temperature is 50 ℃ to 150 ℃; or from 60 ℃ to 90 ℃.
4. The metal foil treatment process according to claim 3, wherein the baking time is 10 to 180 min; or 20min to 120 min.
5. The metal foil treatment process of claim 1, wherein the baking comprises the steps of: heating the rolled metal foil to a preset temperature at a heating rate of 0.1-20 ℃/min or a heating rate of 0.5-5 ℃/min, and maintaining the preset temperature for 10-180 min, wherein the preset temperature is selected from 50-150 ℃.
6. An electrode sheet, comprising:
an active material layer including an active material, a binder, and a conductive agent; and
a metal foil treated by the metal foil treatment process according to any one of claims 1 to 5.
7. The electrode pad according to claim 6, wherein the active material includes at least one selected from the group consisting of lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium rich manganese based material, and lithium titanate.
8. The electrode tab of claim 6, wherein the binder comprises at least one selected from the group consisting of polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethylcellulose, polyvinylpyrrolidone, polyamide, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, and styrene butadiene rubber.
9. The electrode sheet according to claim 6, wherein the conductive agent includes at least one selected from the group consisting of conductive carbon black, acetylene black, carbon nanotubes, carbon fibers, Ketjen black, and graphene.
10. An electrochemical device comprising an electrode sheet according to any one of claims 6 to 9.
CN201910877261.4A 2019-09-17 2019-09-17 Metal foil treatment process, electrode plate and electrochemical device Pending CN112531173A (en)

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