WO2018107543A1 - Application of additive, electrode slurry, additive slurry, cathode or anode of lithium ion battery, preparation method for cathode or anode of lithium ion battery, and lithium ion battery - Google Patents

Application of additive, electrode slurry, additive slurry, cathode or anode of lithium ion battery, preparation method for cathode or anode of lithium ion battery, and lithium ion battery Download PDF

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Publication number
WO2018107543A1
WO2018107543A1 PCT/CN2016/113704 CN2016113704W WO2018107543A1 WO 2018107543 A1 WO2018107543 A1 WO 2018107543A1 CN 2016113704 W CN2016113704 W CN 2016113704W WO 2018107543 A1 WO2018107543 A1 WO 2018107543A1
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group
metal element
additive
lithium
ion battery
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PCT/CN2016/113704
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French (fr)
Chinese (zh)
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先雪峰
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先雪峰
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Publication of WO2018107543A1 publication Critical patent/WO2018107543A1/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the invention relates to the technical field of lithium ion batteries, in particular to an application of an additive in preparing a positive electrode and/or a negative electrode of a lithium ion battery, a lithium ion battery electrode slurry, an additive slurry, and a lithium ion battery.
  • Lithium-ion battery is a new generation of green high-energy battery, with many advantages such as high voltage, high energy density, long life, small self-discharge, no memory effect, wide operating temperature range, etc., in the field of small mobile energy (such as mobile phones, digital cameras, etc. ), large mobile energy fields (such as plug-in hybrid vehicles, pure electric vehicles, etc.) and fixed energy fields (such as energy storage power stations, UPS, etc.) have broad application prospects.
  • small mobile energy such as mobile phones, digital cameras, etc.
  • large mobile energy fields such as plug-in hybrid vehicles, pure electric vehicles, etc.
  • fixed energy fields such as energy storage power stations, UPS, etc.
  • the high voltage of the lithium ion battery also means that in the state of charge, the positive and negative electrodes of the battery have a large potential difference, which means that the negative electrode is more reductive, the positive electrode is more oxidized, and the thermal stability is worse.
  • high-voltage positive electrode materials such as lithium cobaltate, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, etc., in the case of overcharging, acupuncture, extrusion, etc., it is often caused by heat runaway and even fire. Explosion, there are serious security risks.
  • the object of the present invention is to overcome the defects of low safety and serious safety hazards of the lithium ion battery in the prior art, and to provide an additive for preparing a positive electrode and/or a negative electrode of a lithium ion battery, and a lithium ion battery electrode slurry.
  • Material, an additive slurry, a positive or negative electrode of a lithium ion battery, a preparation method thereof, and a lithium ion battery is to overcome the defects of low safety and serious safety hazards of the lithium ion battery in the prior art, and to provide an additive for preparing a positive electrode and/or a negative electrode of a lithium ion battery, and a lithium ion battery electrode slurry.
  • the present invention provides an additive for use in preparing a positive electrode and/or a negative electrode of a lithium ion battery, the additive being M(OH) a , wherein M is a Group IIA metal element, IB Group metal element, Group IIB metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, Group IVA metal element, VA At least one of a group metal element, silicon and boron, a>0.
  • the present invention provides a lithium ion battery electrode slurry, the electrode paste comprising an active material, a binder, a conductive agent, an additive, a solvent, and optionally a thickener,
  • the additive is in an amount of 0.05 to 42% by weight based on the weight;
  • the additive is M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, At least one of a group IVB metal element, a VB group metal element, a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IIIA metal element, a group IVA metal element, a group VA metal element, silicon and boron, a>0.
  • the present invention provides an additive slurry comprising a binder, an additive, a solvent, and an optional conductive agent, the binder being dried based on the weight of the additive
  • the content of the base is 0.5 to 11% by weight
  • the content of the solvent is 90 to 410% by weight
  • the content of the conductive agent is 0 to 11% by weight
  • the additive is M(OH) a , wherein M is Group IIA metal element, Group IB metal element, Group IIB metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, At least one of an IVA group metal element, a VA group metal element, silicon and boron, a>0.
  • the present invention provides a positive electrode or a negative electrode of a lithium ion battery, the positive electrode or the negative electrode of the lithium ion battery comprising a current collector and an electrode dressing on the current collector, the electrode dressing containing an active material, a binder, and a conductive material a filler, an additive and an optional thickener, wherein the additive is M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element, At least one of a group VB metal element, a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IIIA metal element, a group IVA metal element, a group VA metal element, silicon and boron, a>0.
  • M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element
  • the present invention provides a method for preparing a positive electrode or a negative electrode of a lithium ion battery, the method comprising: coating the lithium ion battery electrode slurry of the present invention on a current collector, drying; or comprising:
  • an active material slurry comprising an active material, a binder, a conductive agent, a solvent, and an optional thickener, and then coating the active material slurry in step (1) Drying on the obtained additive-coated current collector; or including:
  • an active material slurry comprising an active material, a binder, a conductive agent, a solvent, and an optional thickener, and then coating the active material slurry on a current collector, Drying to obtain an electrode pole piece;
  • the present invention provides a positive electrode or a negative electrode of a lithium ion battery prepared by the above method of the present invention.
  • the present invention provides a lithium ion battery including a battery case and a cell assembly and an electrolyte located inside the battery case, the cell assembly including a positive electrode, a negative electrode, and a diaphragm, and
  • the positive electrode is the positive electrode of the lithium ion battery according to the present invention
  • the negative electrode is the negative electrode of the lithium ion battery according to the present invention.
  • the inventors of the present invention have found in the research that the additive of the present invention is used for preparing a positive electrode and/or a negative electrode of a lithium ion battery, and the safety of the lithium ion battery thus prepared can be remarkably improved, and the lithium ion is almost There is no adverse effect on the conductivity and cycle performance of the battery.
  • the present invention provides an additive for use in preparing a positive electrode and/or a negative electrode of a lithium ion battery, the additive being M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, IIB Group metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, Group IVA metal element, Group VA metal element, silicon And at least one element of boron, a>0.
  • M is a Group IIA metal element, a Group IB metal element, IIB Group metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, Group IVA metal element, Group VA metal element, silicon And at least one element of boron, a>0.
  • the Group IIA metal element is Be and/or Mg
  • the Group IB metal element is Cu
  • the Group IIB metal element is Zn
  • the Group IIIB metal element Is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er
  • the Group IVB metal element is Ti and/or Zr
  • the Group VB metal element is V and/or Nb
  • the Group VIB metal element is Cr and/or Mo
  • the Group VIIB metal element is Mn
  • the Group VIII metal element is at least one of Fe, Co and Ni
  • the Group IIIA metal element is Al
  • the IVA The group metal element is Sn
  • the VA group metal element is Bi and/or Sb.
  • the additive may be one or more of the foregoing various hydroxides, and may be crystalline or amorphous.
  • the additive is at least one of aluminum hydroxide, ortho silicic acid, and titanium hydroxide.
  • the specific application mode or introduction manner of the foregoing additive is not particularly limited as long as it is applied in the process of preparing the positive electrode and/or the negative electrode of the lithium ion battery.
  • the additive according to the invention belongs to the use of the corresponding additive in the preparation of a positive electrode and/or a negative electrode of a lithium ion battery.
  • the content of the additive is 0.05 to 25% by weight based on the dry weight of the electrode dressing, and further preferably 2 to 14% by weight in view of battery energy density and overall battery performance. More preferably, it is 5-9 weight%.
  • the dry weight of the electrode dressing refers to the weight of the material obtained after drying all of the slurry coated on the current collector.
  • the size of the additive is preferably 300 ⁇ m or less, more preferably 30 ⁇ m or less, from the viewpoint of facilitating dispersion.
  • the present invention provides a lithium ion battery electrode slurry, the electrode paste comprising an active material, a binder, a conductive agent, an additive, a solvent, and optionally a thickener,
  • the additive is in an amount of 0.05 to 42% by weight based on the weight;
  • the additive is M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, At least one of a group IVB metal element, a VB group metal element, a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IIIA metal element, a group IVA metal element, a group VA metal element, silicon and boron, a>0.
  • the content of the additive is from 2 to 18% by weight, further preferably from 6 to 11% by weight, based on the weight of the active material.
  • the Group IIA metal element is Be and/or Mg
  • the Group IB metal element is Cu
  • the Group IIB metal element is Zn.
  • the Group IIIB metal element is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er
  • the Group IVB metal element is Ti and/or Zr
  • the Group VB metal element is V and / Or Nb
  • the Group VIB metal element is Cr and/or Mo
  • the Group VIIB metal element is Mn
  • the Group VIII metal element is at least one of Fe, Co and Ni
  • the Group IIIA metal element is Al
  • the Group IVA metal element is Sn
  • the VA group metal element is Bi and/or Sb.
  • the additive is at least one of aluminum hydroxide, ortho silicic acid, and titanium hydroxide.
  • the size of the additive is preferably 300 ⁇ m or less, more preferably 30 ⁇ m or less from the viewpoint of facilitating dispersion.
  • the lithium ion battery electrode slurry of the present invention may be a lithium ion battery positive electrode slurry or a lithium ion battery negative electrode slurry.
  • the selection and amount of the active material, the binder, the conductive agent, the solvent and the thickener are not particularly limited, and may be respectively the corresponding components in the field.
  • Conventional type selection and dosage preferably based on the weight of the active material, based on the weight of the active material, the binder is 0.5-5.5 by weight on a dry basis.
  • the conductive agent is contained in an amount of 0.5 to 5.5% by weight
  • the solvent is contained in an amount of 50 to 210% by weight
  • the thickener is contained in an amount of 0 to 3% by weight.
  • the thickener is generally not used in the lithium ion battery positive electrode slurry, but is used in the lithium ion battery negative electrode slurry in an amount of 0.5 to 3% by weight based on the weight of the active material.
  • the positive electrode active material is lithium cobaltate, lithium nickel oxide, lithium nickel cobalt oxide.
  • Lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, lithium manganate, lithium vanadate, lithium iron phosphate, lithium manganese phosphate, lithium manganese iron phosphate, lithium manganese iron phosphate, manganese iron cobalt cobalt At least one of lithium manganese iron cobalt phosphate, lithium vanadium phosphate, and lithium iron silicate.
  • the negative electrode active material of the lithium ion battery is not particularly selected for the negative electrode active material, and may be various negative electrode active materials conventionally used in the art.
  • the negative electrode active material is graphite, lithium titanate, silicon, hard carbon, tin. And at least one of tin oxide.
  • the binder is polyacrylamide, poly At least one of vinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, fluorinated rubber, and polyurethane, the cellulose-based polymer may be selected from methyl cellulose One or more of ethyl cellulose, hydroxypropyl methyl cellulose, and hydroxypropyl ethyl cellulose.
  • the binder is a polymer, the number average molecular weight of each polymer is generally from 3 to 1.5 million.
  • the conductive agent is Ketjen black, acetylene black, and graphite. At least one of an olefin, a carbon nanotube, a carbon fiber (VGCF), microcrystalline graphite, and conductive carbon black (Super-P).
  • the solvent is N-methylpyrrolidone (NMP), deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol and isopropanol. At least one of them.
  • NMP N-methylpyrrolidone
  • the solvent is N-methylpyrrolidone
  • the solvent is deionized water and/or N-methylpyrrolidone.
  • the thickener is mostly used in the negative electrode slurry of the lithium ion battery, and whether or not the thickener is added to the positive electrode slurry of the lithium ion battery can be selected according to the actual application, and the specific selection is well known to those skilled in the art, and preferably,
  • the thickener is at least one of sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.
  • the method for preparing the lithium ion battery electrode slurry of the present invention is not particularly limited, and various methods commonly used in the art may be used as long as the slurry containing the above components can be uniformly mixed, for example, containing an activity.
  • a slurry of a substance, a binder, a conductive agent, an additive, a solvent, and an optional thickener may be obtained by first mixing a binder and a solvent to obtain a mixed solution, and then an active material, a conductive agent, an additive, and optionally
  • the thickener is mixed with the mixed solution, or may be mixed by adding a thickener or a binder and a solvent to obtain a mixed solution, and then the active material, the conductive agent, the additive, and the binder or the thickener are mixed with the mixed solution. .
  • the present invention provides an additive slurry comprising a binder, an additive, a solvent, and an optional conductive agent, the binder being dried based on the weight of the additive
  • the content of the base is 0.5 to 11% by weight
  • the content of the solvent is 90 to 410% by weight
  • the content of the conductive agent is 0 to 11% by weight
  • the additive is M(OH) a , wherein M is Group IIA metal element, Group IB metal element, Group IIB metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, At least one of an IVA group metal element, a VA group metal element, silicon and boron, a>0.
  • the Group IIA metal element is Be and/or Mg
  • the Group IB metal element is Cu
  • the Group IIB metal element is Zn
  • the metal element is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er
  • the Group IVB metal element is Ti and/or Zr
  • the VB group metal element is V and/or Nb
  • the Group VIB metal element is Cr and/or Mo
  • the Group VIIB metal element is Mn
  • the Group VIII metal element is at least one of Fe, Co and Ni
  • the Group IIIA metal element is Al
  • the Group IVA metal element is Sn
  • the Group VA metal element is Bi and/or Sb.
  • the additive in order to further improve the safety of the prepared lithium ion battery, it is preferred that the additive be at least one of aluminum hydroxide, ortho silicic acid, and titanium hydroxide.
  • the size of the additive is preferably 300 ⁇ m or less, more preferably 30 ⁇ m or less from the viewpoint of facilitating dispersion.
  • the type of the binder, the solvent, and the optional conductive agent are not particularly limited, and may be selected from the conventional types of the respective components in the field, and preferably, the binder is polypropylene. At least one of an amide, polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, fluorinated rubber, and polyurethane, the cellulose-based polymer may be selected from the group consisting of One or more of cellulose, ethyl cellulose, hydroxypropyl methylcellulose, and hydroxypropylethylcellulose. When the binder is a polymer, the number average molecular weight of each polymer is generally from 3 to 1.5 million.
  • the solvent is at least one of N-methylpyrrolidone, deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol, and isopropyl alcohol. Among them, it is further preferred that the solvent is N-methylpyrrolidone and/or deionized water.
  • a conductive agent may be added to improve the conductivity of the coating.
  • the conductive agent is in Ketjen black, acetylene black, graphene, carbon nanotubes, carbon fiber, microcrystalline graphite, and conductive carbon black. At least one.
  • the method for preparing the additive slurry of the present invention is not particularly limited, and various methods commonly used in the art may be used as long as the slurry containing the above components can be uniformly mixed, for example, containing a binder,
  • the slurry of the additive, the solvent, and the optional conductive agent may be mixed by first mixing the binder and the solvent to obtain a mixed solution, and then mixing the additive, the optional conductive agent, and the mixed solution.
  • the present invention provides a positive electrode or a negative electrode of a lithium ion battery, the positive electrode or the negative electrode of the lithium ion battery comprising a current collector and an electrode dressing on the current collector, the electrode dressing containing an active material, a binder, and a conductive material a filler, an additive and an optional thickener, wherein the additive is M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element, At least one of a group VB metal element, a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IIIA metal element, a group IVA metal element, a group VA metal element, silicon and boron, a>0.
  • M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element
  • the Group IIA metal element is Be and/or Mg
  • the Group IB metal element is Cu
  • the Group IIB metal element is Zn.
  • the Group IIIB metal element is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er
  • the Group IVB metal element is Ti and/or Zr
  • the Group VB metal element is V and / Or Nb
  • the Group VIB metal element is Cr and/or Mo
  • the Group VIIB metal element is Mn
  • the Group VIII metal element is at least one of Fe, Co and Ni
  • the Group IIIA metal element is Al
  • the Group IVA metal element is Sn
  • the VA group metal element is Bi and/or Sb.
  • the additive is at least one of aluminum hydroxide, ortho silicic acid, and titanium hydroxide.
  • the active material is not particularly selected, and various active materials conventionally used in the art may be used.
  • the active material is a positive electrode active material or a negative electrode active material.
  • the positive electrode active materials are lithium cobaltate, lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, lithium manganate, lithium vanadate, lithium iron phosphate, lithium manganese phosphate, At least one of lithium manganese iron phosphate, lithium manganese iron phosphate, lithium manganese iron cobalt cobalt, lithium manganese iron nickel cobalt, lithium vanadium phosphate, and lithium iron silicate.
  • the negative active material is graphite or lithium titanate. At least one of silicon, hard carbon, tin, and tin oxide.
  • the binder is polyacrylamide or polyvinylidene fluoride. At least one of polytetrafluoroethylene, styrene-butadiene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, fluorinated rubber, and polyurethane.
  • the conductive agent is Ketjen black, acetylene black, graphene, carbon nanometer. At least one of a tube, carbon fiber, microcrystalline graphite, and conductive carbon black.
  • the negative electrode of the lithium ion battery generally contains a thickener, and preferably, the thickener is sodium carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycol, and At least one of polyvinyl alcohol.
  • the content of the additive is based on the dry weight of the electrode dressing. It is 0.05 to 25% by weight, further preferably 2 to 14% by weight, still more preferably 5 to 9% by weight.
  • the present invention provides a method for preparing a positive electrode or a negative electrode of a lithium ion battery, the method comprising: coating the lithium ion battery electrode slurry of the present invention on a current collector, drying; or comprising:
  • an active material slurry comprising an active material, a binder, a conductive agent, a solvent, and an optional thickener, and then coating the active material slurry in step (1) Drying on the obtained additive-coated current collector; or including:
  • an active material slurry comprising an active material, a binder, a conductive agent, a solvent, and an optional thickener, and then coating the active material slurry on a current collector, Drying to obtain an electrode pole piece;
  • the current collector is not particularly limited, and various positive electrode current collectors commonly used in the art may be used.
  • the positive electrode current collector may be aluminum foil.
  • the current collector is not particularly limited, and various negative electrode current collectors commonly used in the art may be used.
  • the negative electrode current collector may be a copper foil.
  • the method of coating in each step is not particularly limited, and various methods commonly used in the art can be used, which are well known to those skilled in the art and will not be described herein.
  • the slurry in the active material slurry for a positive electrode of a lithium ion battery, includes a positive electrode active material, a binder, a conductive agent, and a solvent, and the viscosity is based on the weight of the active material.
  • the content of the binder on a dry basis is from 0.5 to 5.5% by weight
  • the content of the conductive agent is from 0.5 to 5.5% by weight
  • the content of the solvent is from 50 to 210% by weight.
  • the slurry includes a negative electrode active material, a binder, a conductive agent, a solvent, and a thickener, based on the weight of the active material,
  • the binder is contained in an amount of 0.5 to 5.5% by weight on a dry basis
  • the content of the conductive agent is 0.5 to 5.5% by weight
  • the content of the thickener is 0.5 to 3% by weight
  • the content of the solvent is 50. -210% by weight.
  • the method for drying is not particularly limited and may be various methods commonly used in the art.
  • the drying conditions include: a temperature of 80-180 ° C.
  • the present invention provides a positive or negative electrode of a lithium ion battery prepared by the method.
  • the present invention provides a lithium ion battery including a battery case and a cell assembly and an electrolyte located inside the battery case, the cell assembly including a positive electrode, a negative electrode, and a diaphragm, and
  • the positive electrode is the lithium ion of the present invention
  • the positive electrode of the battery, and/or the negative electrode is the negative electrode of the lithium ion battery of the present invention.
  • the positive electrode and the negative electrode is a positive electrode or a negative electrode prepared by adding the additive of the present invention, that is, the positive electrode is the present invention.
  • the positive electrode of the lithium ion battery, or the negative electrode is the negative electrode of the lithium ion battery according to the present invention, or the positive electrode and the negative electrode are respectively the positive electrode and the negative electrode of the lithium ion battery according to the present invention.
  • the separator and the electrolytic solution forming the lithium ion battery may be a separator and a nonaqueous electrolyte which are conventionally used in the art.
  • the separator is disposed between the positive electrode and the negative electrode, and has electrical insulating properties and liquid retaining properties, and the cell assembly and the non-aqueous electrolyte are housed together in the battery can.
  • the separator may be various separators commonly used in the art, such as a polymer microporous film, including a polypropylene microporous film and a multilayer composite microporous film of polypropylene and polyethylene. The position, nature and type of the separator are well known to those skilled in the art and will not be described herein.
  • the nonaqueous electrolytic solution is a mixed solution of an electrolyte lithium salt and a nonaqueous solvent, and it is not particularly limited, and a conventional nonaqueous electrolytic solution in the art can be used.
  • the electrolyte lithium salt is selected from one or more of lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium halide, lithium chloroaluminate, and lithium fluorocarbon sulfonate.
  • the non-aqueous solvent is a mixed solution of a chain acid ester and a cyclic acid ester, wherein the chain acid ester may be dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and methyl propylene carbonate.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • methyl propylene carbonate At least one of ester (MPC), dipropyl carbonate (DPC) and other fluorine-containing, sulfur-containing or unsaturated chain-containing chain organic esters
  • the cyclic acid ester may be ethylene carbonate (EC) or carbonic acid.
  • the injection amount of the electrolyte is generally 5-8 g/amperes, and the concentration of the electrolyte is generally 0.8-1.2 mol/liter.
  • the battery case is not particularly limited, and various battery cases commonly used in the art can be used, which are well known to those skilled in the art and will not be described herein.
  • the method for preparing the battery is a common method in the art.
  • the positive electrode and the negative electrode and the separator form a cell assembly, and the obtained cell assembly and non-aqueous electrolyte are sealed in the battery case.
  • the specific methods are well known to those skilled in the art and will not be described herein.
  • Lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 was purchased from Shanghai Shanshan Technology Co., Ltd.
  • Lithium cobaltate LiCoO 2 was purchased from Tianjin Bamo Technology Co., Ltd.
  • Lithium nickel cobalt aluminum oxide LiNi 0.8 Co 0.15 Al 0.05 O 2 was purchased from Toda Industry Co., Ltd., Japan.
  • the Pvdf binder HSV900 was purchased from Arkema, France.
  • the PTFE emulsion binder D210 had a solid content of 60% and was purchased from Daikin Industries Co., Ltd., Japan.
  • the conductive agent Super-P was purchased from the Swiss company Temco.
  • Natural graphite was purchased from Shenzhen Beitray New Energy Materials Co., Ltd.
  • the thickener CMC was purchased from Japan Daiichi Pharmaceutical Co., Ltd.
  • the styrene-butadiene rubber latex binder has a solid content of 50% and was purchased from Japan Rayon Co., Ltd.
  • the preparation method of aluminum hydroxide comprises: dissolving 37.5 kg of aluminum nitrate nonahydrate in 100 kg of deionized water to prepare an aluminum nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the aluminum nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time of adding ammonia was controlled to be 2 hours. After the reaction was completed, aluminum hydroxide was precipitated. The precipitate was washed with deionized water to remove nitrate therein, and finally dried to obtain the dried aluminum hydroxide (Al (OH) 3) by spraying the particles, wherein the particle size D50 was measured 120nm.
  • the preparation method of silicon hydroxide comprises: adding 21.2 kg of sodium metasilicate pentahydrate into 200 kg of deionized water and stirring and dissolving to obtain a sodium metasilicate solution. Under vigorous stirring at 280 rpm, 15% by weight of dilute nitric acid was quickly added to the sodium metasilicate solution until the pH of the reaction system was 7.3. After the reaction, precipitation of ortho silicic acid (silicon hydroxide) was obtained. The precipitate was washed with deionized water to remove sodium nitrate therein, and water was replaced with isopropyl alcohol, and finally dried ortho silicic acid (Si(OH) 4 ) powder was obtained by spray drying, and the particle diameter D50 was found to be 100 nm.
  • the preparation method of the titanium hydroxide comprises: dissolving 16 kg of sodium hydroxide in 200 kg of deionized water to obtain a sodium hydroxide solution, and slowly adding 19 kg of titanium tetrachloride liquid to the sodium hydroxide in a water bath at 0 ° C and vigorous stirring at 300 rpm.
  • the time of adding titanium tetrachloride was controlled to be 2 hours, and after the reaction was completed, titanium hydroxide precipitation was obtained.
  • the precipitate was washed with deionized water to remove sodium chloride therein, and isopropyl alcohol was added to replace the water, and finally dried titanium hydroxide (Ti(OH) 4 ) particles were obtained by spray drying, and the particle diameter D50 was measured. 60nm.
  • the preparation method of barium hydroxide comprises: dissolving 38.3 kg of cerium nitrate hexahydrate in 100 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therefrom, and finally dried yttrium hydroxide (Y(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 130 nm.
  • Y(OH) 3 yttrium hydroxide
  • the preparation method of cerium hydroxide comprises: dissolving 33.9 kg of cerium nitrate hexahydrate in 100 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried cerium hydroxide (Sc(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 150 nm.
  • the preparation method of zirconium hydroxide comprises: dissolving 16 kg of sodium hydroxide in 200 kg of deionized water to obtain a sodium hydroxide solution, and slowly adding 23.3 kg of zirconium tetrachloride powder to the hydroxide under a water bath of 0 ° C and vigorous stirring at 320 rpm. In the sodium solution, the addition of zirconium tetrachloride powder was controlled for 2 hours, and after completion of the reaction, zirconium hydroxide was precipitated.
  • the precipitate was washed with deionized water to remove sodium chloride therein, and isopropyl alcohol was added to replace the water, and finally dried zirconium hydroxide (Zr(OH) 4 ) particles were obtained by spray drying, and the particle diameter D50 was measured. 230 nm.
  • the preparation method of vanadium hydroxide comprises: dissolving 12 kg of sodium hydroxide in 200 kg of deionized water to obtain a sodium hydroxide solution, and slowly drying 15.7 kg of vanadium trichloride powder under the condition of 0 ° C water bath, nitrogen protection, and 350 rpm vigorous stirring. Adding sodium hydroxide solution, controlling the addition of vanadium trichloride powder for 2 hours, after the end of the reaction, vanadium hydroxide precipitation was obtained. The precipitate was washed with deionized water under nitrogen to remove sodium chloride therein, and isopropyl alcohol was added to replace the water, and finally dried vanadium hydroxide (V(OH) 3 ) particles were obtained by spray drying. Wherein the particle diameter D50 is 360 nm.
  • the preparation method of barium hydroxide comprises: dissolving 43.3 kg of cerium nitrate hexahydrate in 200 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried yttrium hydroxide (La(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was measured to be 390 nm.
  • the preparation method of cerium hydroxide comprises: dissolving 43.4 kg of cerium nitrate hexahydrate in 150 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried cerium hydroxide (Ce(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was measured to be 680 nm.
  • the preparation method of cerium hydroxide comprises: dissolving 43.8 kg of cerium nitrate hexahydrate in 150 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried cerium hydroxide (Nd(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was measured to be 600 nm.
  • the preparation method of cerium hydroxide comprises: dissolving 44.4 kg of cerium nitrate hexahydrate in 150 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried cerium hydroxide (Sm(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 510 nm.
  • the preparation method of cerium hydroxide comprises: dissolving 45.1 kg of cerium nitrate hexahydrate in 150 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried yttrium hydroxide (Gd(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 450 nm.
  • the preparation method of cerium hydroxide comprises: dissolving 44.3 kg of cerium nitrate pentahydrate in 150 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried cerium hydroxide (Er(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 220 nm.
  • the preparation method of barium hydroxide comprises: dissolving 9.29 kg of metal cerium in a mixed solution consisting of 32 kg of concentrated nitric acid having a mass fraction of 65% and 50 kg of hydrofluoric acid having a mass fraction of 40% to prepare a mash, under stirring conditions. Next, ammonia water having a mass fraction of 25% was gradually added to the mash, until the pH of the reaction system was 7.3, and the time for controlling the addition of ammonia was 2 hours, and the precipitation of cesium hydroxide was obtained after the completion of the reaction.
  • the precipitate was washed with deionized water to remove nitric acid and hydrofluoric acid, and the free water was removed by spray drying to finally obtain a dried cerium hydroxide (Nb(OH) 5 ) powder having a medium particle diameter D50 of 1.1 ⁇ m. .
  • the preparation method of the chromium hydroxide comprises: dissolving 40.0 kg of chromium nitrate nonahydrate in 150 kg of deionized water to prepare a chromium nitrate solution, and gradually adding a mass fraction of 25% ammonia water to the chromium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, chromium hydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried chromium hydroxide (Cr(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 100 nm.
  • the preparation method of molybdenum oxyhydroxide comprises: dissolving 25.6 kg of molybdenum trichloride trihydrate in 250 kg of absolute ethanol under stirring to obtain a clear solution, and gradually adding 21.5 kg of mass fraction to the clarified solution under stirring. For 25% ammonia water, the time for adding ammonia was controlled to 2 hours, and after the reaction was completed, a precipitate of molybdenum hydroxide was obtained. The precipitate was washed with deionized water to remove ammonium chloride therein, and water was replaced with isopropyl alcohol, and finally dried molybdenum hydroxide (Mo(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was measured to be 190 nm. .
  • the preparation method of manganese hydroxide comprises: diluting 35.8 kg of a 50 wt% aqueous solution of manganese nitrate with 150 kg of deionized water to prepare a manganese nitrate solution, and gradually adding to the manganese nitrate solution under stirring and nitrogen protection conditions.
  • Ammonia water having a mass fraction of 25% was added until the pH of the reaction system was 7.3, and the time for adding ammonia was controlled to be 2 hours, and the precipitation of manganese hydroxide was obtained after the completion of the reaction.
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and dried manganese hydroxide (Mn(OH) 2 ) powder was obtained by spray drying, and the particle diameter D50 was found to be 840 nm.
  • the preparation method of the iron hydroxide comprises: dissolving 40.4 kg of ferric nitrate non-aqueous water in 150 kg of deionized water to prepare a ferric nitrate solution, and rapidly adding a mass fraction of 25% ammonia water to the ferric nitrate solution under the condition of vigorous stirring at 260 rpm. Until the pH of the reaction system was 11, a precipitate was obtained after completion of the reaction. The precipitate was quickly washed with deionized water to remove ammonium nitrate and ammonia water therein, and water was replaced with isopropyl alcohol, and iron hydroxide (Fe(OH) 3 ) powder was obtained by spray drying, and the particle diameter D50 was found to be 190 nm.
  • the preparation method of cobalt hydroxide comprises: dissolving 29.1 kg of cobalt hexahydrate in 150 kg of deionized water to prepare a cobaltous cobalt nitrate solution, and gradually adding a mass fraction to the cobaltous cobalt nitrate solution under stirring and nitrogen protection conditions. 25% ammonia water until the pH value of the reaction system was 7.3, and the time for controlling the addition of ammonia was 2 hours. After the reaction was completed, cobalt oxyhydroxide was precipitated.
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and dried cobalt oxyhydroxide (Co(OH) 2 ) powder was obtained by spray drying, and the particle diameter D50 was found to be 640 nm.
  • the preparation method of nickel hydroxide comprises: dissolving 29.1 kg of nickel nitrate hexahydrate in 150 kg of deionized water to prepare a nickel nitrate solution, and gradually adding a mass fraction to the nickel nitrate solution under stirring and nitrogen protection conditions. 25% ammonia water until the pH value of the reaction system was 7.3, and the time for controlling the addition of ammonia was 2 hours. After the reaction was completed, nickel hydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried nickel hydroxide (Ni(OH) 2 ) was obtained by spray drying, and the particle diameter D50 was found to be 550 nm.
  • the preparation method of the tin hydroxide comprises: dissolving 35.1 kg of tin tetrachloride pentahydrate in 200 kg of absolute ethanol to obtain a clear solution, and gradually adding 28.6 kg of ammonia water having a mass fraction of 25% to the clear solution under stirring.
  • the time for controlling the addition of ammonia was 2 hours, and after the reaction was completed, tin hydroxide was precipitated.
  • the precipitate was washed with deionized water to remove ammonium chloride therein, and water was replaced with isopropyl alcohol, and finally dried tin hydroxide (Sn(OH) 4 ) particles were obtained by spray drying, and the particle diameter D50 was determined to be 80 nm. .
  • the preparation method of barium hydroxide comprises: dissolving 48.5 kg of barium nitrate pentahydrate into 200 kg of dilute nitric acid aqueous solution having a mass fraction of 2% to prepare a barium nitrate solution, and rapidly adding a barium nitrate solution to 26 kg under vigorous stirring at 320 rpm.
  • ammonia water having a mass fraction of 25% a precipitate of barium hydroxide was obtained after the completion of the reaction.
  • the precipitate was washed with deionized water to remove ammonium nitrate and ammonia water therein, and dried cerium hydroxide (Bi(OH) 3 ) was obtained by spray drying, and the particle diameter D50 was found to be 3.7 ⁇ m.
  • the preparation method of cerium hydroxide comprises: dissolving 22.8 kg of antimony trichloride in 250 kg of absolute ethanol under stirring to obtain a clear solution, and gradually adding 21.5 kg of mass fraction to the clarified solution under stirring. % ammonia water, the time for controlling the addition of ammonia was 2 hours, and the precipitation of barium hydroxide was obtained after the reaction. The precipitate was washed with deionized water to remove ammonium chloride therein, and water was replaced with isopropyl alcohol, and finally dried cerium hydroxide (Sb(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was measured to be 80 nm. .
  • Boron hydroxide was prepared as follows: The 150kg added 6.18kg of boric acid was dissolved in deionized water to prepare a boric acid solution, the solution was spray-dried to obtain dry boric acid (B (OH) 3) powder, wherein the particle size D50 was measured 12.4 Mm.
  • the preparation method of barium hydroxide comprises: dissolving 18.7 kg of barium nitrate trihydrate with 100 kg of deionized water to prepare a barium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the barium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried cerium hydroxide (Be(OH) 2 ) was obtained by spray drying, and the particle diameter D50 was found to be 3.5 ⁇ m.
  • the preparation method of magnesium hydroxide comprises: dissolving 25.6 kg of magnesium nitrate hexahydrate in 100 kg of deionized water to prepare a magnesium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the magnesium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, magnesium hydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried magnesium hydroxide (Mg(OH) 2 ) was obtained by spray drying, and the particle diameter D50 was found to be 2.8 ⁇ m.
  • the preparation method of copper hydroxide comprises: dissolving 24.2 kg of copper nitrate trihydrate in 100 kg of deionized water to prepare a copper nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the copper nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time of adding ammonia was controlled to be 2 hours. After the reaction was completed, copper hydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried copper hydroxide (Cu(OH) 2 ) was obtained by spray drying, and the particle diameter D50 was found to be 3.2 ⁇ m.
  • the preparation method of zinc hydroxide comprises: dissolving 29.7 kg of zinc nitrate hexahydrate in 100 kg of deionized water to prepare a zinc nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the zinc nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time of adding ammonia was controlled to be 2 hours. After the reaction was completed, zinc hydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried zinc hydroxide (Zn(OH) 2 ) was obtained by spray drying, and the particle diameter D50 was found to be 3.9 ⁇ m.
  • the positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 ⁇ m, the coating width was 160 mm, and the double-sided surface density of the dressing was 335.4 g/m 2 (the double-sided surface density of the dressing was measured by the weight after drying, the same below, The content of the additive was 7% by weight based on the dry weight of the electrode dressing, and then dried at 110 ° C to obtain a positive electrode tab.
  • the specific method is: first dissolve the thickener CMC with 12500g deionized water as solvent And stirring, respectively, the styrene-butadiene rubber latex binder, the conductive agent Super-P, the natural graphite anode material and the above thickener solution are mixed, and then stirred to form a uniform anode slurry;
  • the negative electrode slurry was uniformly coated on a copper foil having a thickness of 18 ⁇ m, the coating width was 164 mm, and the double-sided surface density of the dressing was 164.1 g/m 2 (based on the weight after drying, the same below), and then at 100 Drying at ° C to obtain a negative electrode tab.
  • the positive electrode piece is cut into a size of 120 mm ⁇ 160 mm as a positive electrode
  • the negative electrode piece is cut into a size of 125 mm ⁇ 164 mm as a negative electrode
  • a polypropylene film is used as a separator, assembled into a battery core assembly, and placed in a soft aluminum-plastic film battery case.
  • the positive and negative poles are respectively welded with the aluminum plastic film, and the insulation between the polar ear and the battery case is ensured in the process.
  • the positive active material lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 The weight is about 191 g, the weight of the negative active material natural graphite is about 104 g, and the nominal capacity of the battery is 30 Ah.
  • the battery was aged at 45 ° C for 48 hours, then charged to 4.00 V with a current of 0.6 A, and then aged for another 48 hours at 45 ° C. Finally, the battery was produced under the protection of a nitrogen atmosphere. The gas was taken out and the battery was sealed twice to obtain a lithium ion battery A1.
  • a lithium ion battery A2 was prepared according to the method of Example 1, except that in the step (1), the preparation method of the battery positive electrode tab was as follows:
  • 21750g lithium nickel cobalt aluminum oxide LiNi 0.8 Co 0.15 Al 0.05 O 2 cathode material, 1250g PTFE emulsion binder D210, 750g conductive agent acetylene black are mixed by: 25000g deionized water as solvent, PTFE emulsion is glued The agent D210 is dispersed to obtain an emulsion, and the lithium nickel cobalt aluminum oxide LiNi 0.8 Co 0.15 Al 0.05 O 2 positive electrode material and the conductive agent acetylene black are respectively mixed with the emulsion of the above binder under stirring, and then stirred to form a uniform slurry. ;
  • the slurry was uniformly coated on an aluminum foil having a thickness of 25 ⁇ m, a coating width of 160 mm, a double-sided surface density of the dressing of 311.9 g/m 2 (based on the weight after drying), and then dried at 100 ° C. Obtaining a positive electrode tab;
  • 1000g of orthosilicate Si(OH) 4 powder additive and 75g of PTFE emulsion binder D210 are mixed by dispersing PTFE emulsion binder D210 with 2500g of deionized water as solvent, and obtaining the emulsion.
  • the original silicic acid Si(OH) 4 powder additive is mixed with the emulsion of the above binder, and then stirred to form a uniform additive slurry;
  • the additive slurry was uniformly coated on the surface of the above positive electrode tab with a coating width of 162 mm to cover the active material, and the double-sided surface density of the dressing was 24.6 g/m 2 (based on the dry weight of the electrode dressing, the additive The content was 7% by weight), and then dried at 100 ° C to obtain a positive electrode tab coated with an additive.
  • a lithium ion battery A3 was prepared according to the method of Example 1, except that in the step (1), the preparation method of the battery positive electrode tab was as follows:
  • 1000g of titanium hydroxide Ti(OH) 4 powder additive, 45g of conductive agent Super-P, 45g of binder HSV900 are mixed by: dissolving the binder HSV900 with 2500g of NMP as solvent, and stirring a titanium hydroxide Ti(OH) 4 powder additive, a conductive agent Super-P mixed with a solution of the above binder, and then stirred to form a uniform additive slurry;
  • the additive slurry was uniformly coated on an aluminum foil having a thickness of 25 ⁇ m, a coating width of 162 mm, a double-sided surface density of the dressing of 25.8 g/m 2 (based on the weight after drying), and then dried at 120 ° C. Obtaining an additive-coated aluminum foil;
  • 21750g lithium cobalt oxide LiCoO 2 cathode material, 750g binder HSV900, 750g conductive carbon nanotubes are mixed by the method of dissolving the binder HSV900 with 25000g NMP as solvent, and respectively adding cobalt acid under stirring a lithium LiCoO 2 positive electrode material, a conductive agent carbon nanotube is mixed with a solution of the above binder, and then stirred to form a uniform active material slurry;
  • the active material slurry was uniformly coated on the surface of the additive-coated aluminum foil, the coating width was 160 mm, and the double-sided surface density of the dressing was 311.9 g/m 2 (based on the dry weight of the electrode dressing, the additive content was 7 weight) %), and then dried at 120 ° C to obtain a positive electrode tab coated with an additive of aluminum foil.
  • 21750g lithium nickel cobalt manganese oxygen LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode material, 750g binder HSV900, 750g conductive agent Super-P are mixed, the specific method is: first, using 25000g NMP as a solvent, the binder HSV900 is dissolved, And stirring, respectively, a lithium nickel cobalt manganese oxygen LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, a conductive agent Super-P and a solution of the above binder are mixed, and then stirred to form a uniform positive electrode slurry;
  • the positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 ⁇ m, a coating width of 160 mm, a double-sided surface density of the dressing of 311.9 g/m 2 (based on the weight after drying), and then dried at 110 ° C. , the positive electrode piece is obtained.
  • 11725g natural graphite anode material, 181g thickener CMC, 121g conductive agent Super-P, 725g styrene-butadiene rubber latex binder and 910g aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by: 13500g deionized water is used as solvent, the thickener CMC is dissolved, and the styrene-butadiene rubber latex binder, the conductive agent Super-P, the natural graphite anode material, the aluminum hydroxide powder additive and the above thickener are respectively stirred under stirring. The solution is mixed, and then stirred to form a uniform negative electrode slurry;
  • the negative electrode slurry was uniformly coated on a copper foil having a thickness of 18 ⁇ m, the coating width was 164 mm, and the double-sided surface density of the dressing was 176.5 g/m 2 (based on the dry weight of the electrode dressing, the additive content was 7 weight). %), and then dried at 100 ° C to obtain a negative electrode tab.
  • the positive electrode piece is cut into a size of 120 mm ⁇ 160 mm as a positive electrode
  • the negative electrode piece is cut into a size of 125 mm ⁇ 164 mm as a negative electrode
  • a polypropylene film is used as a separator, assembled into a battery core assembly, and placed in a soft aluminum-plastic film battery case.
  • the positive and negative poles are respectively welded with the aluminum plastic film, and the insulation between the polar ear and the battery case is ensured in the process.
  • the positive active material lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 The weight is about 191 g, the weight of the negative active material natural graphite is about 104 g, and the nominal capacity of the battery is 30 Ah.
  • the battery was aged at 45 ° C for 48 hours, then charged to 4.00 V with a current of 0.6 A, and then aged for another 48 hours at 45 ° C. Finally, the battery was produced under the protection of a nitrogen atmosphere. The gas was taken out and the battery was sealed twice to obtain a lithium ion battery A4.
  • a lithium ion battery A5 was prepared according to the method of Example 1, except that in the step (1), 22220 g of lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, 765 g of a binder HSV 900, and 765 g of a conductive agent Super were used.
  • Al(OH) 3 -P and 1250g aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by: dissolving the binder HSV900 with 25000g NMP as solvent, and respectively dispersing lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode material, conductive agent Super-P, aluminum hydroxide (Al(OH) 3 ) powder additive mixed with the above binder solution, and then stirred to form a uniform positive electrode slurry;
  • the positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 ⁇ m, the coating width was 160 mm, and the double-sided surface density of the dressing was 328.3 g/m 2 (based on the dry weight of the electrode dressing, the additive content was 5% by weight). Then, it was dried at 110 ° C to obtain a positive electrode tab.
  • a lithium ion battery A6 was prepared according to the method of Example 1, except that in the step (1), 21282 g of lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, 734 g of a binder HSV 900, and 734 g of a conductive agent Super were used.
  • Al(OH) 3 -P and 2250g of aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by: dissolving the binder HSV900 with 25000g NMP as solvent, and respectively dispersing lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode material, conductive agent Super-P, aluminum hydroxide (Al(OH) 3 ) powder additive mixed with the above binder solution, and then stirred to form a uniform positive electrode slurry;
  • the positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 ⁇ m, a coating width of 160 mm, and a double-sided surface density of the dressing of 342.8 g/m 2 (based on the dry weight of the electrode dressing, the additive content was 9% by weight) Then, it was dried at 110 ° C to obtain a positive electrode tab.
  • the lithium ion battery A7 was prepared according to the method of Example 2, except that in the step (1), the additive slurry was prepared by dispersing 30 g of the PTFE emulsion binder D210 with 1500 g of deionized water as a solvent. The emulsion was mixed with 1000 g of orthosilicate Si(OH) 4 powder with an emulsion of the above binder under stirring, followed by stirring to form a uniform additive slurry.
  • the additive slurry was uniformly coated on the surface of the above positive electrode tab with a coating width of 162 mm to cover the active material, and the double-sided surface density of the dressing was 16.7 g/m 2 (based on the dry weight of the electrode dressing, the additive The content was 5% by weight), and then dried at 100 ° C to obtain a positive electrode tab coated with an additive.
  • the lithium ion battery A8 was prepared according to the method of Example 2, except that in the step (1), the additive slurry was prepared by dispersing 160 g of the PTFE emulsion binder D210 with 3500 g of deionized water as a solvent to obtain an emulsion. And 1000 g of the orthosilicate Si(OH) 4 powder was mixed with the emulsion of the above binder under stirring, and then stirred to form a uniform additive slurry.
  • the additive slurry was uniformly coated on the surface of the above positive electrode tab with a coating width of 162 mm to cover the active material, and the double-sided surface density of the dressing was 34.1 g/m 2 (based on the dry weight of the electrode dressing, the additive The content was 9% by weight), and then dried at 100 ° C to obtain a positive electrode tab coated with an additive.
  • a lithium ion battery A9 was prepared according to the method of Example 1, except that in the step (1), 22,920 g of lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, 790 g of a binder HSV 900, and 790 g of a conductive agent Super were used.
  • Al(OH) 3 -P and 500g of aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by dissolving the binder HSV900 with 25000g of NMP as solvent and stirring lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode material, conductive agent Super-P, aluminum hydroxide (Al(OH) 3 ) additive mixed with the above binder solution, and then stirred to form a uniform positive electrode slurry;
  • the positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 ⁇ m, the coating width was 160 mm, and the double-sided surface density of the dressing was 318.3 g/m 2 (based on the dry weight of the electrode dressing, the content of the additive was 2% by weight). Then, it was dried at 110 ° C to obtain a positive electrode tab.
  • a lithium ion battery A10 was prepared according to the method of Example 1, except that in the step (1), 23154 g of lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, 798 g of a binder HSV900, and 798 g of a conductive agent Super were used.
  • Al(OH) 3 powder additive 250g aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by: dissolving the binder HSV900 with 25000g NMP as solvent, and respectively dissolving lithium nickel cobalt manganese oxide LiNi 0.5 Co under stirring 0.2 Mn 0.3 O 2 cathode material, conductive agent Super-P, aluminum hydroxide (Al(OH) 3 ) additive mixed with the above binder solution, and then stirred to form a uniform positive electrode slurry;
  • the positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 ⁇ m, the coating width was 160 mm, and the double-sided surface density of the dressing was 315.1 g/m 2 (based on the dry weight of the electrode dressing, the content of the additive was 1% by weight). Then, it was dried at 110 ° C to obtain a positive electrode tab.
  • a lithium ion battery A11 was prepared according to the method of Example 1, except that in the step (1), 20112 g of lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, 694 g of a binder HSV 900, and 694 g of a conductive agent Super were used.
  • Al(OH) 3 powder additive 3500g aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by: dissolving the binder HSV900 with 25000g NMP as solvent, and respectively adding lithium nickel cobalt manganese oxide LiNi 0.5 Co under stirring 0.2 Mn 0.3 O 2 cathode material, conductive agent Super-P, aluminum hydroxide (Al(OH) 3 ) additive mixed with the above binder solution, and then stirred to form a uniform positive electrode slurry;
  • the positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 ⁇ m, the coating width was 160 mm, and the double-sided surface density of the dressing was 362.7 g/m 2 (the content of the additive was 14% by weight based on the dry weight of the electrode dressing). Then, it was dried at 110 ° C to obtain a positive electrode tab.
  • a lithium ion battery A12 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with yttrium hydroxide (Y(OH) 3 ) powder.
  • a lithium ion battery A13 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with strontium hydroxide (Sc(OH) 3 ) powder.
  • a lithium ion battery A14 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with zirconium hydroxide (Zr(OH) 4 ) powder.
  • a lithium ion battery A15 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with vanadium hydroxide (V(OH) 3 ) powder.
  • a lithium ion battery A16 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with lanthanum hydroxide (La(OH) 3 ) powder.
  • a lithium ion battery A17 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with a cerium hydroxide (Ce(OH) 3 ) powder.
  • a lithium ion battery A18 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with a cerium hydroxide (Nd(OH) 3 ) powder.
  • a lithium ion battery A19 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with barium hydroxide (Sm(OH) 3 ) powder.
  • a lithium ion battery A20 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with a barium hydroxide (Gd(OH) 3 ) powder.
  • a lithium ion battery A21 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with strontium hydroxide (Er(OH) 3 ) powder.
  • a lithium ion battery A22 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with a cerium hydroxide (Nb(OH) 5 ) powder.
  • a lithium ion battery A23 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with chromium (Cr(OH) 3 ) powder.
  • a lithium ion battery A24 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with a molybdenum hydroxide (Mo(OH) 3 ) powder.
  • a lithium ion battery A25 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with manganese hydroxide (Mn(OH) 2 ) powder.
  • a lithium ion battery A26 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with iron hydroxide (Fe(OH) 3 ) powder.
  • a lithium ion battery A27 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with cobalt oxychloride (Co(OH) 2 ) powder.
  • a lithium ion battery A28 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with nickel oxyhydroxide (Ni(OH) 2 ) powder.
  • a lithium ion battery A29 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with tin (Sn(OH) 4 ) powder.
  • a lithium ion battery A30 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with bismuth hydroxide (Bi(OH) 3 ) powder.
  • a lithium ion battery A31 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with strontium hydroxide (Sb(OH) 3 ) powder.
  • a lithium ion battery A32 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with a boric acid (B(OH) 3 ) powder.
  • a lithium ion battery A33 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with barium hydroxide (Be(OH) 2 ) powder.
  • a lithium ion battery A34 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with magnesium hydroxide (Mg(OH) 2 ) powder.
  • a lithium ion battery A35 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with copper hydroxide (Cu(OH) 2 ) powder.
  • a lithium ion battery A36 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with zinc hydroxide (Zn(OH) 2 ) powder.
  • a lithium ion battery D1 was prepared according to the method of Example 1, except that in the step (1), the aluminum hydroxide powder additive was not added to obtain a positive electrode active material slurry, and the positive electrode active material slurry was uniformly coated to a thickness of On a 25 ⁇ m aluminum foil, the coating width was 160 mm, the double-sided surface density of the dressing was 311.9 g/m 2 (based on the weight after drying), and then dried at 110 ° C to obtain a positive electrode tab.
  • the lithium ion battery D2 was prepared according to the method of Example 2, except that in the step (1), after the positive electrode tab was obtained, the original silicic acid Si(OH) 4 powder additive was not added in the preparation of the additive slurry, specifically, First, the PTFE emulsion binder D210 was dispersed in 2500 g of deionized water as a solvent to obtain an emulsion of the binder, and the emulsion was uniformly coated on the surface of the above positive electrode sheet to have a coating width of 162 mm to cover the active material. The double side density of the dressing was 24.6 g/m 2 (based on the weight after drying) and then dried at 100 °C.
  • a lithium ion battery D3 was prepared according to the method of Example 3, except that in the step (1), the titanium hydroxide Ti(OH) 4 powder additive was not added in the preparation of the additive slurry, specifically, 2500 g of NMP was used as a solvent. Dissolving 45 g of the binder HSV900 to obtain a solution of the binder, and then mixing 45 g of the conductive agent Super-P with the solution of the above binder, followed by stirring to form a uniform slurry;
  • the above slurry was uniformly coated on an aluminum foil having a thickness of 25 ⁇ m to a coating width of 162 mm, and the obtained dressing had a double-sided surface density of 25.8 g/m 2 (based on the weight after drying), and then baked at 120 ° C. Dry, obtained treated aluminum foil;
  • 21750g lithium cobalt oxide LiCoO 2 cathode material, 750g binder HSV900, 750g conductive carbon nanotubes are mixed by the method of dissolving the binder HSV900 with 25000g NMP as solvent, and respectively adding cobalt acid under stirring a lithium LiCoO 2 positive electrode material, a conductive agent carbon nanotube is mixed with a solution of the above binder, and then stirred to form a uniform active material slurry;
  • the active material slurry was uniformly coated on the surface of the treated aluminum foil, the coating width was 160 mm, the double-sided surface density of the dressing was 311.9 g/m 2 , and then dried at 120 ° C to obtain an aluminum foil-treated positive electrode sheet. .
  • the single cells (including the lithium ion batteries A1-A36 prepared in Examples 1-36 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 8.5 V, and at 8.5 V. The constant pressure was maintained for 1 hour under voltage, and the phenomenon during the process was observed and recorded. Each of the 30 single cells was tested in parallel. The results are shown in Table 1.
  • the single cells (including the lithium ion batteries A1-A36 prepared in Examples 1-36 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A. Extend the battery from the end face of the semi-cylindrical body with a radius of 75 mm from the direction perpendicular to the pole piece of the battery. The extrusion speed is 5 mm/s until the deformation of the battery reaches 30%. After the extrusion is completed, stay for one hour, observe and record. The phenomenon in the process. Each of the 30 single cells was tested in parallel. The results are shown in Table 2.
  • the single cells (including the lithium ion batteries A1-A36 prepared in Examples 1-36 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A. Extend the battery from the end face of the semi-cylindrical body with a radius of 75 mm from the direction perpendicular to the pole piece of the battery. The extrusion speed is 5 mm/s until the deformation of the battery reaches 50%. After the extrusion is completed, it is allowed to stand for one hour, observe and record. The phenomenon in the process. Each of the 30 single cells was tested in parallel. The results are shown in Table 3.
  • the single cells (including the lithium ion batteries A1-A36 prepared in Examples 1-36 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A.
  • a 6 mm diameter nail was passed through the battery at a rate of 25 mm/s in a direction perpendicular to the long and wide faces of the battery, and allowed to stand for one hour to observe and record the phenomenon during the process.
  • Each of the 30 single cells was tested in parallel. The results are shown in Table 4.
  • the positive electrode or the negative electrode can be further improved by the content of the additive in the range of 5 to 9 % by weight based on the dry weight of the electrode dressing.
  • the safety of the prepared lithium ion battery can further improve the safety of the prepared lithium ion battery under extremely severe conditions when the amount of the additive is further increased.

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Abstract

The present invention relates to the technical field of lithium ion batteries, and provides an application of an additive, an electrode slurry, an additive slurry, a cathode or anode of a lithium ion battery, a preparation method for the cathode or anode of a lithium ion battery, and a lithium ion battery. Specifically disclosed is an application of the additive in preparation of the cathode and/or anode of the lithium ion battery. The additive is M(OH)a, wherein M is at least one of the following elements: a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element, a Group VB metal element, a Group VIB metal element, a Group VIIB metal element, a Group VIII metal element, a Group IIIV metal element, a Group IVA metal element, a Group VA metal element, silicon, and boron, and a>0. By applying the additive to prepare the cathode and/or anode of the lithium ion battery, the safety of the prepared lithium ion battery can be significantly improved.

Description

添加剂的应用、电极浆料、添加剂浆料、锂离子电池正极或负极及其制备方法和锂离子电池Application of additive, electrode slurry, additive slurry, positive or negative electrode of lithium ion battery, preparation method thereof and lithium ion battery 技术领域Technical field
本发明涉及锂离子电池技术领域,具体地,涉及一种添加剂在制备锂离子电池正极和/或负极中的应用、一种锂离子电池电极浆料、一种添加剂浆料、一种锂离子电池正极或负极及其制备方法和一种锂离子电池。The invention relates to the technical field of lithium ion batteries, in particular to an application of an additive in preparing a positive electrode and/or a negative electrode of a lithium ion battery, a lithium ion battery electrode slurry, an additive slurry, and a lithium ion battery. A positive electrode or a negative electrode, a preparation method thereof, and a lithium ion battery.
背景技术Background technique
锂离子电池是新一代的绿色高能电池,具有电压高、能量密度大、寿命长、自放电小、无记忆效应、工作温度范围宽等众多优点,在小型移动能源领域(例如手机、数码相机等)、大型移动能源领域(例如插电式混合动力车、纯电动车等)和固定能源领域(例如储能电站、UPS等),都有着广泛的应用前景。Lithium-ion battery is a new generation of green high-energy battery, with many advantages such as high voltage, high energy density, long life, small self-discharge, no memory effect, wide operating temperature range, etc., in the field of small mobile energy (such as mobile phones, digital cameras, etc. ), large mobile energy fields (such as plug-in hybrid vehicles, pure electric vehicles, etc.) and fixed energy fields (such as energy storage power stations, UPS, etc.) have broad application prospects.
锂离子电池电压高也意味着在荷电状态下,电池的正、负极具有较大的电势差,也就意味着负极还原性更强,正极氧化性更强,热稳定性更差。特别是对于采用钴酸锂、锂镍钴铝氧、锂镍钴锰氧等高电压正极材料的电池而言,在过充、针刺、挤压等滥用情况下常常会因为热失控引起起火甚至爆炸,存在着严重的安全隐患。The high voltage of the lithium ion battery also means that in the state of charge, the positive and negative electrodes of the battery have a large potential difference, which means that the negative electrode is more reductive, the positive electrode is more oxidized, and the thermal stability is worse. Especially for batteries using high-voltage positive electrode materials such as lithium cobaltate, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, etc., in the case of overcharging, acupuncture, extrusion, etc., it is often caused by heat runaway and even fire. Explosion, there are serious security risks.
除此之外,与采用不可燃且具有阻燃作用的水做电解液溶剂的传统的铅酸、碱性电池相比,商用锂离子电池通常采用可燃的碳酸酯类有机溶剂做电解液溶剂,或凝胶类聚合物做电解质,在滥用条件下,会进一步扩大安全事故的后果。In addition, compared with conventional lead-acid and alkaline batteries that use non-flammable and flame-retardant water as the electrolyte solvent, commercial lithium-ion batteries usually use a combustible carbonate-based organic solvent as the electrolyte solvent. Or gel-like polymers as electrolytes, under the abuse conditions, will further expand the consequences of safety accidents.
现有的锂离子电池的安全隐患阻碍了对锂离子电池的大规模应用,因此,研发一种安全性大幅提高的锂离子电池,具有重要的现实意义。The safety hazards of existing lithium-ion batteries hinder the large-scale application of lithium-ion batteries. Therefore, it is of great practical significance to develop a lithium-ion battery with greatly improved safety.
发明内容Summary of the invention
本发明的目的是为了克服现有技术中锂离子电池安全性低、存在严重安全隐患的缺陷,提供一种添加剂在制备锂离子电池正极和/或负极中的应用、一种锂离子电池电极浆料、一种添加剂浆料、一种锂离子电池正极或负极及其制备方法和一种锂离子电池。The object of the present invention is to overcome the defects of low safety and serious safety hazards of the lithium ion battery in the prior art, and to provide an additive for preparing a positive electrode and/or a negative electrode of a lithium ion battery, and a lithium ion battery electrode slurry. Material, an additive slurry, a positive or negative electrode of a lithium ion battery, a preparation method thereof, and a lithium ion battery.
为了实现上述目的,第一方面,本发明提供了一种添加剂在制备锂离子电池正极和/或负极中的应用,所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0。In order to achieve the above object, in a first aspect, the present invention provides an additive for use in preparing a positive electrode and/or a negative electrode of a lithium ion battery, the additive being M(OH) a , wherein M is a Group IIA metal element, IB Group metal element, Group IIB metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, Group IVA metal element, VA At least one of a group metal element, silicon and boron, a>0.
第二方面,本发明提供了一种锂离子电池电极浆料,所述电极浆料包括活性物质、粘结剂、导电剂、添加剂、溶剂和任选的增稠剂,以所述活性物质的重量为基准,所述添加剂的含量为0.05-42重量%;所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0。In a second aspect, the present invention provides a lithium ion battery electrode slurry, the electrode paste comprising an active material, a binder, a conductive agent, an additive, a solvent, and optionally a thickener, The additive is in an amount of 0.05 to 42% by weight based on the weight; the additive is M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, At least one of a group IVB metal element, a VB group metal element, a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IIIA metal element, a group IVA metal element, a group VA metal element, silicon and boron, a>0.
第三方面,本发明提供了一种添加剂浆料,所述添加剂浆料包括粘结剂、添加剂、溶剂和任选的导电剂,以所述添加剂的重量为基准,所述粘结剂以干基计的含量为0.5-11重量%,所述溶剂的含量为90-410重量%,所述导电剂的含量为0-11重量%;所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0。In a third aspect, the present invention provides an additive slurry comprising a binder, an additive, a solvent, and an optional conductive agent, the binder being dried based on the weight of the additive The content of the base is 0.5 to 11% by weight, the content of the solvent is 90 to 410% by weight, the content of the conductive agent is 0 to 11% by weight; the additive is M(OH) a , wherein M is Group IIA metal element, Group IB metal element, Group IIB metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, At least one of an IVA group metal element, a VA group metal element, silicon and boron, a>0.
第四方面,本发明提供了一种锂离子电池正极或负极,所述锂离子电池正极或负极包括集流体及位于集流体上的电极敷料,所述电极敷料含有活性物质、粘结剂、导电剂、添加剂和任选的增稠剂,所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0。 In a fourth aspect, the present invention provides a positive electrode or a negative electrode of a lithium ion battery, the positive electrode or the negative electrode of the lithium ion battery comprising a current collector and an electrode dressing on the current collector, the electrode dressing containing an active material, a binder, and a conductive material a filler, an additive and an optional thickener, wherein the additive is M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element, At least one of a group VB metal element, a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IIIA metal element, a group IVA metal element, a group VA metal element, silicon and boron, a>0.
第五方面,本发明提供了一种制备锂离子电池正极或负极的方法,所述方法包括:将本发明所述的锂离子电池电极浆料涂覆在集流体上,烘干;或者包括:In a fifth aspect, the present invention provides a method for preparing a positive electrode or a negative electrode of a lithium ion battery, the method comprising: coating the lithium ion battery electrode slurry of the present invention on a current collector, drying; or comprising:
(1)将本发明所述的添加剂浆料涂覆在集流体上,烘干,得到添加剂涂覆的集流体;(1) coating the additive slurry of the present invention on a current collector, and drying to obtain an additive-coated current collector;
(2)配制活性物质浆料,所述活性物质浆料包括活性物质、粘结剂、导电剂、溶剂和任选的增稠剂,然后将所述活性物质浆料涂覆在步骤(1)得到的添加剂涂覆的集流体上,烘干;或者包括:(2) formulating an active material slurry comprising an active material, a binder, a conductive agent, a solvent, and an optional thickener, and then coating the active material slurry in step (1) Drying on the obtained additive-coated current collector; or including:
(1)配制活性物质浆料,所述活性物质浆料包括活性物质、粘结剂、导电剂、溶剂和任选的增稠剂,然后将所述活性物质浆料涂覆在集流体上,烘干,得到电极极片;(1) formulating an active material slurry comprising an active material, a binder, a conductive agent, a solvent, and an optional thickener, and then coating the active material slurry on a current collector, Drying to obtain an electrode pole piece;
(2)将本发明所述的添加剂浆料涂覆在步骤(1)得到的电极极片上,烘干。(2) The additive slurry of the present invention is coated on the electrode pole piece obtained in the step (1) and dried.
第六方面,本发明提供了本发明上述的方法制备得到的锂离子电池正极或负极。In a sixth aspect, the present invention provides a positive electrode or a negative electrode of a lithium ion battery prepared by the above method of the present invention.
第七方面,本发明提供了一种锂离子电池,所述锂离子电池包括电池壳体以及位于电池壳体内部的电芯组件和电解液,所述电芯组件包括正极、负极和隔膜,且所述正极为本发明所述的锂离子电池正极,和/或所述负极为本发明所述的锂离子电池负极。In a seventh aspect, the present invention provides a lithium ion battery including a battery case and a cell assembly and an electrolyte located inside the battery case, the cell assembly including a positive electrode, a negative electrode, and a diaphragm, and The positive electrode is the positive electrode of the lithium ion battery according to the present invention, and/or the negative electrode is the negative electrode of the lithium ion battery according to the present invention.
本发明的发明人在研究中创造性发现,将本发明所述的添加剂用于制备锂离子电池正极和/或负极,能够明显提高由此制备得到的锂离子电池的安全性,且几乎对锂离子电池的导电性能和循环性能等性能无不良影响。The inventors of the present invention have found in the research that the additive of the present invention is used for preparing a positive electrode and/or a negative electrode of a lithium ion battery, and the safety of the lithium ion battery thus prepared can be remarkably improved, and the lithium ion is almost There is no adverse effect on the conductivity and cycle performance of the battery.
本发明的其它特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the invention will be described in detail in the detailed description which follows.
具体实施方式detailed description
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It is to be understood that the specific embodiments described herein are merely illustrative and not restrictive.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to include values that are close to the ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and the individual point values, and the individual point values can be combined with one another to yield one or more new ranges of values. The scope should be considered as specifically disclosed herein.
第一方面,本发明提供了一种添加剂在制备锂离子电池正极和/或负极中的应用,所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0。In a first aspect, the present invention provides an additive for use in preparing a positive electrode and/or a negative electrode of a lithium ion battery, the additive being M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, IIB Group metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, Group IVA metal element, Group VA metal element, silicon And at least one element of boron, a>0.
其中,本领域技术人员应该理解的是,M(OH)a中,a的选择符合相应物质的化学计量比原则。Among them, it should be understood by those skilled in the art that in M(OH) a , the choice of a conforms to the stoichiometric principle of the corresponding substance.
本发明的应用中,优选情况下,添加剂中,所述IIA族金属元素为Be和/或Mg,所述IB族金属元素为Cu,所述IIB族金属元素为Zn,所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种,所述IVB族金属元素为Ti和/或Zr,所述VB族金属元素为V和/或Nb,所述VIB族金属元素为Cr和/或Mo,所述VIIB族金属元素为Mn,所述VIII族金属元素为Fe、Co和Ni中的至少一种,所述IIIA族金属元素为Al,所述IVA族金属元素为Sn,所述VA族金属元素为Bi和/或Sb。In the application of the present invention, preferably, in the additive, the Group IIA metal element is Be and/or Mg, the Group IB metal element is Cu, the Group IIB metal element is Zn, and the Group IIIB metal element Is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er, the Group IVB metal element is Ti and/or Zr, and the Group VB metal element is V and/or Nb, The Group VIB metal element is Cr and/or Mo, the Group VIIB metal element is Mn, the Group VIII metal element is at least one of Fe, Co and Ni, and the Group IIIA metal element is Al, the IVA The group metal element is Sn, and the VA group metal element is Bi and/or Sb.
本发明的应用中,添加剂可以为前述各种氢氧化物中一种或多种,可以是晶态,也可以是非晶态。为了进一步提高制备得到的锂离子电池的安全性,优选地,添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种。In the application of the present invention, the additive may be one or more of the foregoing various hydroxides, and may be crystalline or amorphous. In order to further improve the safety of the prepared lithium ion battery, preferably, the additive is at least one of aluminum hydroxide, ortho silicic acid, and titanium hydroxide.
本发明的应用中,在制备锂离子电池正极和/或负极的方法中,对于前述添加剂的具体应用方式或引入方式没有特别的限定,只要在制备锂离子电池正极和/或负极的过程中应用了本发明所述的添加剂即属于该相应添加剂在制备锂离子电池正极和/或负极中的应用。其中,优选情况下,在正极或负极中,以电极敷料的干重为基准,添加剂的含量为0.05-25重量%,鉴于电池能量密度和电池综合性能考虑,进一步优选为2-14重量%,更优选为5-9重量%。本领域技术人员应该理解的是,电极敷料的干重是指涂覆在集流体上的所有浆料烘干后得到的物质的重量。In the application of the present invention, in the method for preparing the positive electrode and/or the negative electrode of the lithium ion battery, the specific application mode or introduction manner of the foregoing additive is not particularly limited as long as it is applied in the process of preparing the positive electrode and/or the negative electrode of the lithium ion battery. The additive according to the invention belongs to the use of the corresponding additive in the preparation of a positive electrode and/or a negative electrode of a lithium ion battery. Wherein, in the positive electrode or the negative electrode, the content of the additive is 0.05 to 25% by weight based on the dry weight of the electrode dressing, and further preferably 2 to 14% by weight in view of battery energy density and overall battery performance. More preferably, it is 5-9 weight%. It will be understood by those skilled in the art that the dry weight of the electrode dressing refers to the weight of the material obtained after drying all of the slurry coated on the current collector.
本发明的应用中,对于添加剂的单个颗粒或团聚体尺寸没有特别要求,但从便于分散的角度来说,添加剂的尺寸优选为300微米以下,更优选为30微米以下。 In the application of the present invention, there is no particular requirement for the individual particle or agglomerate size of the additive, but the size of the additive is preferably 300 μm or less, more preferably 30 μm or less, from the viewpoint of facilitating dispersion.
第二方面,本发明提供了一种锂离子电池电极浆料,所述电极浆料包括活性物质、粘结剂、导电剂、添加剂、溶剂和任选的增稠剂,以所述活性物质的重量为基准,所述添加剂的含量为0.05-42重量%;所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0。In a second aspect, the present invention provides a lithium ion battery electrode slurry, the electrode paste comprising an active material, a binder, a conductive agent, an additive, a solvent, and optionally a thickener, The additive is in an amount of 0.05 to 42% by weight based on the weight; the additive is M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, At least one of a group IVB metal element, a VB group metal element, a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IIIA metal element, a group IVA metal element, a group VA metal element, silicon and boron, a>0.
优选地,以所述活性物质的重量为基准,所述添加剂的含量为2-18重量%,进一步优选为6-11重量%。Preferably, the content of the additive is from 2 to 18% by weight, further preferably from 6 to 11% by weight, based on the weight of the active material.
本发明的锂离子电池电极浆料中,优选情况下,添加剂中,所述IIA族金属元素为Be和/或Mg,所述IB族金属元素为Cu,所述IIB族金属元素为Zn,所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种,所述IVB族金属元素为Ti和/或Zr,所述VB族金属元素为V和/或Nb,所述VIB族金属元素为Cr和/或Mo,所述VIIB族金属元素为Mn,所述VIII族金属元素为Fe、Co和Ni中的至少一种,所述IIIA族金属元素为Al,所述IVA族金属元素为Sn,所述VA族金属元素为Bi和/或Sb。In the lithium ion battery electrode slurry of the present invention, preferably, in the additive, the Group IIA metal element is Be and/or Mg, the Group IB metal element is Cu, and the Group IIB metal element is Zn. The Group IIIB metal element is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er, the Group IVB metal element is Ti and/or Zr, and the Group VB metal element is V and / Or Nb, the Group VIB metal element is Cr and/or Mo, the Group VIIB metal element is Mn, and the Group VIII metal element is at least one of Fe, Co and Ni, and the Group IIIA metal element is Al, the Group IVA metal element is Sn, and the VA group metal element is Bi and/or Sb.
本发明的锂离子电池电极浆料中,为了进一步提高制备得到的锂离子电池的安全性,优选地,所述添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种。In the lithium ion battery electrode slurry of the present invention, in order to further improve the safety of the prepared lithium ion battery, it is preferable that the additive is at least one of aluminum hydroxide, ortho silicic acid, and titanium hydroxide.
本发明的锂离子电池电极浆料中,对于添加剂的单个颗粒或团聚体尺寸没有特别要求,但从便于分散的角度来说,添加剂的尺寸优选为300微米以下,更优选为30微米以下。In the lithium ion battery electrode slurry of the present invention, there is no particular requirement for the individual particle or agglomerate size of the additive, but the size of the additive is preferably 300 μm or less, more preferably 30 μm or less from the viewpoint of facilitating dispersion.
其中,本领域技术人员应该理解的是,本发明所述的锂离子电池电极浆料可以为锂离子电池正极浆料,也可以为锂离子电池负极浆料。在锂离子电池正极浆料或锂离子电池负极浆料中,对于活性物质、粘结剂、导电剂、溶剂和增稠剂的种类选择和用量没有特别的限定,可以分别为本领域相应组分的常规的种类选择和用量,出于电池能量密度和电池综合性能的考虑,优选情况下,以所述活性物质的重量为基准,所述粘结剂以干基计的含量为0.5-5.5重量%,所述导电剂的含量为0.5-5.5重量%,所述溶剂的含量为50-210重量%,所述增稠剂的含量为0-3重量%。增稠剂一般在锂离子电池正极浆料中不使用,而在锂离子电池负极浆料中使用,以活性物质的重量为基准,含量为0.5-3重量%。It should be understood by those skilled in the art that the lithium ion battery electrode slurry of the present invention may be a lithium ion battery positive electrode slurry or a lithium ion battery negative electrode slurry. In the lithium ion battery positive electrode slurry or the lithium ion battery negative electrode slurry, the selection and amount of the active material, the binder, the conductive agent, the solvent and the thickener are not particularly limited, and may be respectively the corresponding components in the field. Conventional type selection and dosage, preferably based on the weight of the active material, based on the weight of the active material, the binder is 0.5-5.5 by weight on a dry basis. %, the conductive agent is contained in an amount of 0.5 to 5.5% by weight, the solvent is contained in an amount of 50 to 210% by weight, and the thickener is contained in an amount of 0 to 3% by weight. The thickener is generally not used in the lithium ion battery positive electrode slurry, but is used in the lithium ion battery negative electrode slurry in an amount of 0.5 to 3% by weight based on the weight of the active material.
锂离子电池正极浆料中,对于正极活性物质没有特别的选择,可以为本领域常规使用的各种正极活性物质,优选情况下,正极活性物质为钴酸锂、锂镍氧、锂镍钴氧、锂镍钴铝氧、锂镍钴锰氧、锂镍锰氧、锰酸锂、钒酸锂、磷酸铁锂、磷酸锰锂、磷酸锰铁锂、磷酸锰铁镍锂、磷酸锰铁钴锂、磷酸锰铁镍钴锂、磷酸钒锂和硅酸铁锂中的至少一种。In the positive electrode slurry of a lithium ion battery, there is no particular choice for the positive electrode active material, and various positive electrode active materials conventionally used in the art may be used. Preferably, the positive electrode active material is lithium cobaltate, lithium nickel oxide, lithium nickel cobalt oxide. Lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, lithium manganate, lithium vanadate, lithium iron phosphate, lithium manganese phosphate, lithium manganese iron phosphate, lithium manganese iron phosphate, manganese iron cobalt cobalt At least one of lithium manganese iron cobalt phosphate, lithium vanadium phosphate, and lithium iron silicate.
锂离子电池负极浆料中,对于负极活性物质没有特别的选择,可以为本领域常规使用的各种负极活性物质,优选情况下,负极活性物质为石墨、钛酸锂、硅、硬碳、锡和氧化锡中的至少一种。The negative electrode active material of the lithium ion battery is not particularly selected for the negative electrode active material, and may be various negative electrode active materials conventionally used in the art. Preferably, the negative electrode active material is graphite, lithium titanate, silicon, hard carbon, tin. And at least one of tin oxide.
锂离子电池正极浆料和锂离子电池负极浆料中,对于粘结剂没有特别的选择,可以为本领域常规使用的各种粘结剂,优选情况下,粘结剂为聚丙烯酰胺、聚偏二氟乙烯、聚四氟乙烯、丁苯橡胶、纤维素基聚合物、聚乙烯醇、聚烯烃、氟化橡胶和聚胺酯中的至少一种,纤维素基聚合物可以选自甲基纤维素、乙基纤维素、羟丙基甲基纤维素和羟丙基乙基纤维素中的一种或几种。前述粘结剂为聚合物时,各聚合物的数均分子量一般为30-150万。In the lithium ion battery positive electrode slurry and the lithium ion battery negative electrode slurry, there is no particular choice for the binder, and various binders conventionally used in the art may be used. Preferably, the binder is polyacrylamide, poly At least one of vinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, fluorinated rubber, and polyurethane, the cellulose-based polymer may be selected from methyl cellulose One or more of ethyl cellulose, hydroxypropyl methyl cellulose, and hydroxypropyl ethyl cellulose. When the binder is a polymer, the number average molecular weight of each polymer is generally from 3 to 1.5 million.
锂离子电池正极浆料和锂离子电池负极浆料中,对于导电剂没有特别的选择,可以为本领域常规使用的各种导电剂,优选情况下,导电剂为科琴黑、乙炔黑、石墨烯、碳纳米管、碳纤维(VGCF)、微晶石墨和导电碳黑(Super-P)中的至少一种。In the lithium ion battery positive electrode slurry and the lithium ion battery negative electrode slurry, there is no particular choice for the conductive agent, and various conductive agents conventionally used in the art may be used. Preferably, the conductive agent is Ketjen black, acetylene black, and graphite. At least one of an olefin, a carbon nanotube, a carbon fiber (VGCF), microcrystalline graphite, and conductive carbon black (Super-P).
对于溶剂没有特别的选择,可以为本领域常规使用的各种溶剂,优选情况下,溶剂为N-甲基吡咯烷酮(NMP)、去离子水、四氢呋喃、二甲基亚砜、乙醇和异丙醇中的至少一种。其中,进一步优选地,在锂离子电池正极浆料中,溶剂为N-甲基吡咯烷酮;在锂离子电池负极浆料中,溶剂为去离子水和/或N-甲基吡咯烷酮。There is no particular choice for the solvent, and various solvents conventionally used in the art may be used. Preferably, the solvent is N-methylpyrrolidone (NMP), deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol and isopropanol. At least one of them. Further, it is further preferred that in the lithium ion battery positive electrode slurry, the solvent is N-methylpyrrolidone; and in the lithium ion battery negative electrode slurry, the solvent is deionized water and/or N-methylpyrrolidone.
其中,增稠剂多应用于锂离子电池负极浆料中,在锂离子电池正极浆料中是否添加增稠剂可以根据实际应用情况进行选择,具体选择为本领域技术人员所熟知,优选情况下,增稠剂为羧甲基纤维素钠(CMC)、聚乙烯吡咯烷酮、聚乙二醇和聚乙烯醇中的至少一种。 Among them, the thickener is mostly used in the negative electrode slurry of the lithium ion battery, and whether or not the thickener is added to the positive electrode slurry of the lithium ion battery can be selected according to the actual application, and the specific selection is well known to those skilled in the art, and preferably, The thickener is at least one of sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.
其中,对于本发明的锂离子电池电极浆料的制备方法,没有特别的限定,可以为本领域常用的各种方法,只要能够将含有前述组分的浆料混合均匀即可,例如,含有活性物质、粘结剂、导电剂、添加剂、溶剂和任选的增稠剂的浆料可以通过先将粘结剂和溶剂混合,得到混合液,然后将活性物质、导电剂、添加剂和任选的增稠剂与混合液进行混合,或者可以通过将增稠剂或粘结剂和溶剂混合,得到混合液,然后将活性物质、导电剂、添加剂和粘结剂或增稠剂与混合液进行混合。The method for preparing the lithium ion battery electrode slurry of the present invention is not particularly limited, and various methods commonly used in the art may be used as long as the slurry containing the above components can be uniformly mixed, for example, containing an activity. A slurry of a substance, a binder, a conductive agent, an additive, a solvent, and an optional thickener may be obtained by first mixing a binder and a solvent to obtain a mixed solution, and then an active material, a conductive agent, an additive, and optionally The thickener is mixed with the mixed solution, or may be mixed by adding a thickener or a binder and a solvent to obtain a mixed solution, and then the active material, the conductive agent, the additive, and the binder or the thickener are mixed with the mixed solution. .
第三方面,本发明提供了一种添加剂浆料,所述添加剂浆料包括粘结剂、添加剂、溶剂和任选的导电剂,以所述添加剂的重量为基准,所述粘结剂以干基计的含量为0.5-11重量%,所述溶剂的含量为90-410重量%,所述导电剂的含量为0-11重量%;所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0。In a third aspect, the present invention provides an additive slurry comprising a binder, an additive, a solvent, and an optional conductive agent, the binder being dried based on the weight of the additive The content of the base is 0.5 to 11% by weight, the content of the solvent is 90 to 410% by weight, the content of the conductive agent is 0 to 11% by weight; the additive is M(OH) a , wherein M is Group IIA metal element, Group IB metal element, Group IIB metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, At least one of an IVA group metal element, a VA group metal element, silicon and boron, a>0.
本发明的添加剂浆料中,优选情况下,添加剂中,所述IIA族金属元素为Be和/或Mg,所述IB族金属元素为Cu,所述IIB族金属元素为Zn,所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种,所述IVB族金属元素为Ti和/或Zr,所述VB族金属元素为V和/或Nb,所述VIB族金属元素为Cr和/或Mo,所述VIIB族金属元素为Mn,所述VIII族金属元素为Fe、Co和Ni中的至少一种,所述IIIA族金属元素为Al,所述IVA族金属元素为Sn,所述VA族金属元素为Bi和/或Sb。In the additive slurry of the present invention, preferably, in the additive, the Group IIA metal element is Be and/or Mg, the Group IB metal element is Cu, and the Group IIB metal element is Zn, the Group IIIB The metal element is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er, the Group IVB metal element is Ti and/or Zr, and the VB group metal element is V and/or Nb, The Group VIB metal element is Cr and/or Mo, the Group VIIB metal element is Mn, the Group VIII metal element is at least one of Fe, Co and Ni, and the Group IIIA metal element is Al, The Group IVA metal element is Sn, and the Group VA metal element is Bi and/or Sb.
本发明的添加剂浆料中,为了进一步提高制备得到的锂离子电池的安全性,优选地,添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种。In the additive slurry of the present invention, in order to further improve the safety of the prepared lithium ion battery, it is preferred that the additive be at least one of aluminum hydroxide, ortho silicic acid, and titanium hydroxide.
本发明的添加剂浆料中,对于添加剂的单个颗粒或团聚体尺寸没有特别要求,但从便于分散的角度来说,添加剂的尺寸优选为300微米以下,更优选为30微米以下。In the additive slurry of the present invention, there is no particular requirement for the individual particle or agglomerate size of the additive, but the size of the additive is preferably 300 μm or less, more preferably 30 μm or less from the viewpoint of facilitating dispersion.
在添加剂浆料中,对于粘结剂、溶剂和任选的导电剂的种类选择没有特别的限定,可以分别为本领域相应组分的常规的种类选择,优选情况下,粘结剂为聚丙烯酰胺、聚偏二氟乙烯、聚四氟乙烯、丁苯橡胶、纤维素基聚合物、聚乙烯醇、聚烯烃、氟化橡胶和聚胺酯中的至少一种,纤维素基聚合物可以选自甲基纤维素、乙基纤维素、羟丙基甲基纤维素和羟丙基乙基纤维素中的一种或几种。前述粘结剂为聚合物时,各聚合物的数均分子量一般为30-150万。In the additive slurry, the type of the binder, the solvent, and the optional conductive agent are not particularly limited, and may be selected from the conventional types of the respective components in the field, and preferably, the binder is polypropylene. At least one of an amide, polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, fluorinated rubber, and polyurethane, the cellulose-based polymer may be selected from the group consisting of One or more of cellulose, ethyl cellulose, hydroxypropyl methylcellulose, and hydroxypropylethylcellulose. When the binder is a polymer, the number average molecular weight of each polymer is generally from 3 to 1.5 million.
添加剂浆料中,优选情况下,溶剂为N-甲基吡咯烷酮、去离子水、四氢呋喃、二甲基亚砜、乙醇和异丙醇中的至少一种。其中,进一步优选地,溶剂为N-甲基吡咯烷酮和/或去离子水。In the additive slurry, preferably, the solvent is at least one of N-methylpyrrolidone, deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol, and isopropyl alcohol. Among them, it is further preferred that the solvent is N-methylpyrrolidone and/or deionized water.
添加剂浆料中,加入导电剂可以用来提高涂层的导电性,优选情况下,导电剂为科琴黑、乙炔黑、石墨烯、碳纳米管、碳纤维、微晶石墨和导电碳黑中的至少一种。In the additive slurry, a conductive agent may be added to improve the conductivity of the coating. Preferably, the conductive agent is in Ketjen black, acetylene black, graphene, carbon nanotubes, carbon fiber, microcrystalline graphite, and conductive carbon black. At least one.
其中,对于本发明的添加剂浆料的制备方法,没有特别的限定,可以为本领域常用的各种方法,只要能够将含有前述组分的浆料混合均匀即可,例如,含有粘结剂、添加剂、溶剂和任选的导电剂的浆料可以通过先将粘结剂和溶剂混合,得到混合液,然后将添加剂、任选的导电剂与混合液进行混合。The method for preparing the additive slurry of the present invention is not particularly limited, and various methods commonly used in the art may be used as long as the slurry containing the above components can be uniformly mixed, for example, containing a binder, The slurry of the additive, the solvent, and the optional conductive agent may be mixed by first mixing the binder and the solvent to obtain a mixed solution, and then mixing the additive, the optional conductive agent, and the mixed solution.
第四方面,本发明提供了一种锂离子电池正极或负极,所述锂离子电池正极或负极包括集流体及位于集流体上的电极敷料,所述电极敷料含有活性物质、粘结剂、导电剂、添加剂和任选的增稠剂,所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0。In a fourth aspect, the present invention provides a positive electrode or a negative electrode of a lithium ion battery, the positive electrode or the negative electrode of the lithium ion battery comprising a current collector and an electrode dressing on the current collector, the electrode dressing containing an active material, a binder, and a conductive material a filler, an additive and an optional thickener, wherein the additive is M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element, At least one of a group VB metal element, a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IIIA metal element, a group IVA metal element, a group VA metal element, silicon and boron, a>0.
本发明的锂离子电池正极或负极中,优选情况下,添加剂中,所述IIA族金属元素为Be和/或Mg,所述IB族金属元素为Cu,所述IIB族金属元素为Zn,所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种,所述IVB族金属元素为Ti和/或Zr,所述VB族金属元素为V和/或Nb,所述VIB族金属元素为Cr和/或Mo,所述VIIB族金属元素为Mn,所述VIII族金属元素为Fe、Co和Ni中的至少一种,所述IIIA族金属元素为Al,所述IVA族金属元素为Sn,所述VA族金属元素为Bi和/或Sb。In the positive electrode or the negative electrode of the lithium ion battery of the present invention, preferably, in the additive, the Group IIA metal element is Be and/or Mg, the Group IB metal element is Cu, and the Group IIB metal element is Zn. The Group IIIB metal element is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er, the Group IVB metal element is Ti and/or Zr, and the Group VB metal element is V and / Or Nb, the Group VIB metal element is Cr and/or Mo, the Group VIIB metal element is Mn, and the Group VIII metal element is at least one of Fe, Co and Ni, and the Group IIIA metal element is Al, the Group IVA metal element is Sn, and the VA group metal element is Bi and/or Sb.
本发明的锂离子电池正极或负极中,为了进一步提高制备得到的锂离子电池的安全性,优选地, 所述添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种。In the positive electrode or the negative electrode of the lithium ion battery of the present invention, in order to further improve the safety of the prepared lithium ion battery, preferably, The additive is at least one of aluminum hydroxide, ortho silicic acid, and titanium hydroxide.
本发明的锂离子电池正极或负极中,对于活性物质没有特别的选择,可以为本领域常规使用的各种活性物质,优选情况下,所述活性物质为正极活性物质或负极活性物质,所述正极活性物质为钴酸锂、锂镍氧、锂镍钴氧、锂镍钴铝氧、锂镍钴锰氧、锂镍锰氧、锰酸锂、钒酸锂、磷酸铁锂、磷酸锰锂、磷酸锰铁锂、磷酸锰铁镍锂、磷酸锰铁钴锂、磷酸锰铁镍钴锂、磷酸钒锂和硅酸铁锂中的至少一种,所述负极活性物质为石墨、钛酸锂、硅、硬碳、锡和氧化锡中的至少一种。In the positive electrode or the negative electrode of the lithium ion battery of the present invention, the active material is not particularly selected, and various active materials conventionally used in the art may be used. Preferably, the active material is a positive electrode active material or a negative electrode active material. The positive electrode active materials are lithium cobaltate, lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, lithium manganate, lithium vanadate, lithium iron phosphate, lithium manganese phosphate, At least one of lithium manganese iron phosphate, lithium manganese iron phosphate, lithium manganese iron cobalt cobalt, lithium manganese iron nickel cobalt, lithium vanadium phosphate, and lithium iron silicate. The negative active material is graphite or lithium titanate. At least one of silicon, hard carbon, tin, and tin oxide.
本发明的锂离子电池正极或负极中,对于粘结剂没有特别的选择,可以为本领域常规使用的各种粘结剂,优选情况下,粘结剂为聚丙烯酰胺、聚偏二氟乙烯、聚四氟乙烯、丁苯橡胶、纤维素基聚合物、聚乙烯醇、聚烯烃、氟化橡胶和聚胺酯中的至少一种。In the positive electrode or the negative electrode of the lithium ion battery of the present invention, there is no particular choice for the binder, and various binders conventionally used in the art may be used. Preferably, the binder is polyacrylamide or polyvinylidene fluoride. At least one of polytetrafluoroethylene, styrene-butadiene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, fluorinated rubber, and polyurethane.
本发明的锂离子电池正极或负极中,对于导电剂没有特别的选择,可以为本领域常规使用的各种导电剂,优选情况下,导电剂为科琴黑、乙炔黑、石墨烯、碳纳米管、碳纤维、微晶石墨和导电碳黑中的至少一种。In the positive electrode or the negative electrode of the lithium ion battery of the present invention, there is no particular choice for the conductive agent, and various conductive agents conventionally used in the art may be used. Preferably, the conductive agent is Ketjen black, acetylene black, graphene, carbon nanometer. At least one of a tube, carbon fiber, microcrystalline graphite, and conductive carbon black.
本发明的锂离子电池正极或负极中,如前所述,锂离子电池负极中一般含有增稠剂,优选情况下,增稠剂为羧甲基纤维素钠、聚乙烯吡咯烷酮、聚乙二醇和聚乙烯醇中的至少一种。In the positive electrode or the negative electrode of the lithium ion battery of the present invention, as described above, the negative electrode of the lithium ion battery generally contains a thickener, and preferably, the thickener is sodium carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycol, and At least one of polyvinyl alcohol.
本发明的锂离子电池正极或负极中,为了进一步提高制备得到的锂离子电池的安全性同时兼顾电池能量密度和电池综合性能,优选地,以电极敷料的干重为基准,所述添加剂的含量为0.05-25重量%,进一步优选为2-14重量%,更进一步优选为5-9重量%。In the positive electrode or the negative electrode of the lithium ion battery of the present invention, in order to further improve the safety of the prepared lithium ion battery while taking into consideration the battery energy density and the overall performance of the battery, preferably, the content of the additive is based on the dry weight of the electrode dressing. It is 0.05 to 25% by weight, further preferably 2 to 14% by weight, still more preferably 5 to 9% by weight.
第五方面,本发明提供了一种制备锂离子电池正极或负极的方法,所述方法包括:将本发明所述的锂离子电池电极浆料涂覆在集流体上,烘干;或者包括:In a fifth aspect, the present invention provides a method for preparing a positive electrode or a negative electrode of a lithium ion battery, the method comprising: coating the lithium ion battery electrode slurry of the present invention on a current collector, drying; or comprising:
(1)将本发明所述的添加剂浆料涂覆在集流体上,烘干,得到添加剂涂覆的集流体;(1) coating the additive slurry of the present invention on a current collector, and drying to obtain an additive-coated current collector;
(2)配制活性物质浆料,所述活性物质浆料包括活性物质、粘结剂、导电剂、溶剂和任选的增稠剂,然后将所述活性物质浆料涂覆在步骤(1)得到的添加剂涂覆的集流体上,烘干;或者包括:(2) formulating an active material slurry comprising an active material, a binder, a conductive agent, a solvent, and an optional thickener, and then coating the active material slurry in step (1) Drying on the obtained additive-coated current collector; or including:
(1)配制活性物质浆料,所述活性物质浆料包括活性物质、粘结剂、导电剂、溶剂和任选的增稠剂,然后将所述活性物质浆料涂覆在集流体上,烘干,得到电极极片;(1) formulating an active material slurry comprising an active material, a binder, a conductive agent, a solvent, and an optional thickener, and then coating the active material slurry on a current collector, Drying to obtain an electrode pole piece;
(2)将本发明所述的添加剂浆料涂覆在步骤(1)得到的电极极片上,烘干。(2) The additive slurry of the present invention is coated on the electrode pole piece obtained in the step (1) and dried.
其中,锂离子电池正极中,对于集流体没有特别的限定,可以为本领域常用的各种正极集流体,例如正极集流体可以为铝箔。In the positive electrode of the lithium ion battery, the current collector is not particularly limited, and various positive electrode current collectors commonly used in the art may be used. For example, the positive electrode current collector may be aluminum foil.
其中,锂离子电池负极中,对于集流体没有特别的限定,可以为本领域常用的各种负极集流体,例如负极集流体可以为铜箔。In the negative electrode of the lithium ion battery, the current collector is not particularly limited, and various negative electrode current collectors commonly used in the art may be used. For example, the negative electrode current collector may be a copper foil.
其中,对于各步骤中涂覆的方法没有特别的限定,可以为本领域常用的各种方法,此为本领域技术人所熟知,在此不再赘述。The method of coating in each step is not particularly limited, and various methods commonly used in the art can be used, which are well known to those skilled in the art and will not be described herein.
其中,优选情况下,用于锂离子电池正极的活性物质浆料中,所述浆料包括正极活性物质、粘结剂、导电剂和溶剂,以所述活性物质的重量为基准,所述粘结剂以干基计的含量为0.5-5.5重量%,所述导电剂的含量为0.5-5.5重量%,所述溶剂的含量为50-210重量%。Wherein, in the active material slurry for a positive electrode of a lithium ion battery, the slurry includes a positive electrode active material, a binder, a conductive agent, and a solvent, and the viscosity is based on the weight of the active material. The content of the binder on a dry basis is from 0.5 to 5.5% by weight, the content of the conductive agent is from 0.5 to 5.5% by weight, and the content of the solvent is from 50 to 210% by weight.
优选情况下,用于锂离子电池负极的活性物质浆料中,所述浆料包括负极活性物质、粘结剂、导电剂、溶剂和增稠剂,以所述活性物质的重量为基准,所述粘结剂以干基计的含量为0.5-5.5重量%,所述导电剂的含量为0.5-5.5重量%,所述增稠剂含量为0.5-3重量%,所述溶剂的含量为50-210重量%。Preferably, in the active material slurry for a negative electrode of a lithium ion battery, the slurry includes a negative electrode active material, a binder, a conductive agent, a solvent, and a thickener, based on the weight of the active material, The binder is contained in an amount of 0.5 to 5.5% by weight on a dry basis, the content of the conductive agent is 0.5 to 5.5% by weight, the content of the thickener is 0.5 to 3% by weight, and the content of the solvent is 50. -210% by weight.
其中,前述各种正极活性物质、负极活性物质、粘结剂、导电剂、溶剂和增稠剂的具体种类选择,均可参见前文相应内容,在此不再赘述。且本领域技术人员应该理解的是,在制备锂离子电池正极或负极时,使用各自对应的集流体和活性物质浆料。The specific types of the above-mentioned various positive electrode active materials, negative electrode active materials, binders, conductive agents, solvents, and thickeners can be referred to the corresponding contents, and are not described herein again. And it should be understood by those skilled in the art that in preparing a positive electrode or a negative electrode of a lithium ion battery, respective corresponding current collectors and active material slurry are used.
其中,对于烘干的方法没有特别的限定,可以为本领域常用的各种方法,优选情况下,烘干的条件包括:温度为80-180℃。The method for drying is not particularly limited and may be various methods commonly used in the art. Preferably, the drying conditions include: a temperature of 80-180 ° C.
第六方面,本发明提供了所述方法制备得到的锂离子电池正极或负极。In a sixth aspect, the present invention provides a positive or negative electrode of a lithium ion battery prepared by the method.
第七方面,本发明提供了一种锂离子电池,所述锂离子电池包括电池壳体以及位于电池壳体内部的电芯组件和电解液,所述电芯组件包括正极、负极和隔膜,且所述正极为本发明所述的锂离子 电池正极,和/或所述负极为本发明所述的锂离子电池负极。In a seventh aspect, the present invention provides a lithium ion battery including a battery case and a cell assembly and an electrolyte located inside the battery case, the cell assembly including a positive electrode, a negative electrode, and a diaphragm, and The positive electrode is the lithium ion of the present invention The positive electrode of the battery, and/or the negative electrode is the negative electrode of the lithium ion battery of the present invention.
本发明的锂离子电池中,本领域技术人员应该理解的是,正极和负极中的至少一个电极为添加有本发明所述添加剂后制备得到的正极或负极,即,正极为本发明所述的锂离子电池正极,或者负极为本发明所述的锂离子电池负极,或者,正极和负极同时分别为本发明所述的锂离子电池正极和负极。In the lithium ion battery of the present invention, it should be understood by those skilled in the art that at least one of the positive electrode and the negative electrode is a positive electrode or a negative electrode prepared by adding the additive of the present invention, that is, the positive electrode is the present invention. The positive electrode of the lithium ion battery, or the negative electrode is the negative electrode of the lithium ion battery according to the present invention, or the positive electrode and the negative electrode are respectively the positive electrode and the negative electrode of the lithium ion battery according to the present invention.
本发明的锂离子电池中,形成锂离子电池的隔膜和电解液可以为本领域常规使用的隔膜和非水电解液。In the lithium ion battery of the present invention, the separator and the electrolytic solution forming the lithium ion battery may be a separator and a nonaqueous electrolyte which are conventionally used in the art.
其中,隔膜设置于正极和负极之间,它具有电绝缘性能和液体保持性能,并使电芯组件和非水电解液一起容纳在电池壳中。隔膜可以为本领域常用的各种隔膜,如高分子聚合物微孔薄膜,包括聚丙稀微孔薄膜和聚丙稀与聚乙烯的多层复合微孔薄膜。隔膜的位置、性质和种类为本领域技术人员所熟知,在此不再赘述。Wherein the separator is disposed between the positive electrode and the negative electrode, and has electrical insulating properties and liquid retaining properties, and the cell assembly and the non-aqueous electrolyte are housed together in the battery can. The separator may be various separators commonly used in the art, such as a polymer microporous film, including a polypropylene microporous film and a multilayer composite microporous film of polypropylene and polyethylene. The position, nature and type of the separator are well known to those skilled in the art and will not be described herein.
其中,非水电解液为电解质锂盐和非水溶剂的混合溶液,对它没有特别限定,可以使用本领域常规的非水电解液。比如电解质锂盐选自六氟磷酸锂(LiPF6)、高氯酸锂、四氟硼酸锂、六氟砷酸锂、卤化锂、氯铝酸锂及氟烃基磺酸锂中的一种或几种。非水溶剂选用链状酸酯和环状酸酯混合溶液,其中链状酸酯可以为碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)、碳酸二丙酯(DPC)以及其它含氟、含硫或含不饱和键的链状有机酯类中的至少一种,环状酸酯可以为碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸亚乙烯酯(VC)、γ-丁内酯(γ-BL)、磺内酯以及其它含氟、含硫或含不饱和键的环状有机酯类中的至少一种。电解液的注入量一般为5-8克/安时,电解液的浓度一般为0.8-1.2摩尔/升。Among them, the nonaqueous electrolytic solution is a mixed solution of an electrolyte lithium salt and a nonaqueous solvent, and it is not particularly limited, and a conventional nonaqueous electrolytic solution in the art can be used. For example, the electrolyte lithium salt is selected from one or more of lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium halide, lithium chloroaluminate, and lithium fluorocarbon sulfonate. The non-aqueous solvent is a mixed solution of a chain acid ester and a cyclic acid ester, wherein the chain acid ester may be dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and methyl propylene carbonate. At least one of ester (MPC), dipropyl carbonate (DPC) and other fluorine-containing, sulfur-containing or unsaturated chain-containing chain organic esters, and the cyclic acid ester may be ethylene carbonate (EC) or carbonic acid. At least one of propylene ester (PC), vinylene carbonate (VC), γ-butyrolactone (γ-BL), sultone and other fluorine-containing, sulfur-containing or unsaturated bond-containing cyclic organic esters Kind. The injection amount of the electrolyte is generally 5-8 g/amperes, and the concentration of the electrolyte is generally 0.8-1.2 mol/liter.
本发明的锂离子电池中,对于电池壳体没有特别的限定,可以为本领域常用的各种电池壳体,此为本领域技术人员所熟知,在此不再赘述。In the lithium ion battery of the present invention, the battery case is not particularly limited, and various battery cases commonly used in the art can be used, which are well known to those skilled in the art and will not be described herein.
本发明的锂离子电池中,制备电池的方法为本领域的常用方法,一般来说,将正极和负极与隔膜构成一个电芯组件,将得到的电芯组件和非水电解液密封在电池壳中,即可得到锂离子电池。具体方法为本领域技术人员所熟知,在此不再赘述。In the lithium ion battery of the present invention, the method for preparing the battery is a common method in the art. Generally, the positive electrode and the negative electrode and the separator form a cell assembly, and the obtained cell assembly and non-aqueous electrolyte are sealed in the battery case. In the middle, you can get a lithium-ion battery. The specific methods are well known to those skilled in the art and will not be described herein.
实施例Example
以下将通过实施例对本发明进行详细描述,但并不因此限制本发明,如无特别说明,所用的材料均可通过商购获得,所用的方法均为本领域的常规方法。The invention is described in detail below by way of examples, without restricting the invention, unless otherwise specified, the materials used are commercially available, and the methods used are all conventional methods in the art.
锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2购自上海杉杉科技有限公司。Lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 was purchased from Shanghai Shanshan Technology Co., Ltd.
钴酸锂LiCoO2购自天津巴莫科技股份有限公司。Lithium cobaltate LiCoO 2 was purchased from Tianjin Bamo Technology Co., Ltd.
锂镍钴铝氧LiNi0.8Co0.15Al0.05O2购自日本户田工业株式会社。Lithium nickel cobalt aluminum oxide LiNi 0.8 Co 0.15 Al 0.05 O 2 was purchased from Toda Industry Co., Ltd., Japan.
Pvdf粘结剂HSV900购自法国阿科玛公司。The Pvdf binder HSV900 was purchased from Arkema, France.
PTFE乳液粘结剂D210固含量为60%,购自日本大金工业株式会社。The PTFE emulsion binder D210 had a solid content of 60% and was purchased from Daikin Industries Co., Ltd., Japan.
导电剂Super-P购自瑞士特密高公司。The conductive agent Super-P was purchased from the Swiss company Temco.
天然石墨购自深圳贝特瑞新能源材料股份有限公司。Natural graphite was purchased from Shenzhen Beitray New Energy Materials Co., Ltd.
增稠剂CMC购自日本第一工业制药株式会社。The thickener CMC was purchased from Japan Daiichi Pharmaceutical Co., Ltd.
丁苯橡胶乳胶粘结剂固含量为50%,购自日本瑞翁株式会社。The styrene-butadiene rubber latex binder has a solid content of 50% and was purchased from Japan Rayon Co., Ltd.
氢氧化铝的制备方法包括:将37.5kg九水硝酸铝溶解在100kg去离子水中,制得硝酸铝溶液,在搅拌条件下,向硝酸铝溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化铝沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,最后通过喷雾干燥得到干燥的氢氧化铝(Al(OH)3)颗粒,测得其中粒径D50为120nm。The preparation method of aluminum hydroxide comprises: dissolving 37.5 kg of aluminum nitrate nonahydrate in 100 kg of deionized water to prepare an aluminum nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the aluminum nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time of adding ammonia was controlled to be 2 hours. After the reaction was completed, aluminum hydroxide was precipitated. The precipitate was washed with deionized water to remove nitrate therein, and finally dried to obtain the dried aluminum hydroxide (Al (OH) 3) by spraying the particles, wherein the particle size D50 was measured 120nm.
氢氧化硅的制备方法包括:将21.2kg五水偏硅酸钠加入200kg去离子水中搅拌溶解,得到偏硅酸钠溶液。在280rpm强力搅拌下,向偏硅酸钠溶液中快速加入15重量%的稀硝酸,直至反应体系pH值为7.3,反应结束后得到原硅酸(氢氧化硅)沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸钠,并用异丙醇置换水,最后通过喷雾干燥得到干燥的原硅酸(Si(OH)4)粉末,测得其中粒径D50为100nm。 The preparation method of silicon hydroxide comprises: adding 21.2 kg of sodium metasilicate pentahydrate into 200 kg of deionized water and stirring and dissolving to obtain a sodium metasilicate solution. Under vigorous stirring at 280 rpm, 15% by weight of dilute nitric acid was quickly added to the sodium metasilicate solution until the pH of the reaction system was 7.3. After the reaction, precipitation of ortho silicic acid (silicon hydroxide) was obtained. The precipitate was washed with deionized water to remove sodium nitrate therein, and water was replaced with isopropyl alcohol, and finally dried ortho silicic acid (Si(OH) 4 ) powder was obtained by spray drying, and the particle diameter D50 was found to be 100 nm.
氢氧化钛的制备方法包括:将16kg氢氧化钠加入200kg去离子水中溶解,得到氢氧化钠溶液,在0℃水浴、300rpm强力搅拌的条件下,将19kg四氯化钛液体缓慢加入氢氧化钠溶液中,控制加四氯化钛时间为2小时,反应结束后得到氢氧化钛沉淀。将该沉淀用去离子水洗涤以去除其中的氯化钠,并加入异丙醇置换水,最后通过喷雾干燥得到干燥的氢氧化钛(Ti(OH)4)颗粒,测得其中粒径D50为60nm。The preparation method of the titanium hydroxide comprises: dissolving 16 kg of sodium hydroxide in 200 kg of deionized water to obtain a sodium hydroxide solution, and slowly adding 19 kg of titanium tetrachloride liquid to the sodium hydroxide in a water bath at 0 ° C and vigorous stirring at 300 rpm. In the solution, the time of adding titanium tetrachloride was controlled to be 2 hours, and after the reaction was completed, titanium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove sodium chloride therein, and isopropyl alcohol was added to replace the water, and finally dried titanium hydroxide (Ti(OH) 4 ) particles were obtained by spray drying, and the particle diameter D50 was measured. 60nm.
氢氧化钇的制备方法包括:将38.3kg六水硝酸钇溶解在100kg去离子水中,制得硝酸钇溶液,在搅拌条件下,向硝酸钇溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化钇沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,最后通过喷雾干燥得到干燥的氢氧化钇(Y(OH)3)颗粒,测得其中粒径D50为130nm。The preparation method of barium hydroxide comprises: dissolving 38.3 kg of cerium nitrate hexahydrate in 100 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therefrom, and finally dried yttrium hydroxide (Y(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 130 nm.
氢氧化钪的制备方法包括:将33.9kg六水硝酸钪溶解在100kg去离子水中,制得硝酸钪溶液,在搅拌条件下,向硝酸钪溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化钪沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,最后通过喷雾干燥得到干燥的氢氧化钪(Sc(OH)3)颗粒,测得其中粒径D50为150nm。The preparation method of cerium hydroxide comprises: dissolving 33.9 kg of cerium nitrate hexahydrate in 100 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried cerium hydroxide (Sc(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 150 nm.
氢氧化锆的制备方法包括:将16kg氢氧化钠加入200kg去离子水中溶解,得到氢氧化钠溶液,在0℃水浴、320rpm强力搅拌的条件下,将23.3kg四氯化锆粉末缓慢加入氢氧化钠溶液中,控制加四氯化锆粉末时间为2小时,反应结束后得到氢氧化锆沉淀。将该沉淀用去离子水洗涤以去除其中的氯化钠,并加入异丙醇置换水,最后通过喷雾干燥得到干燥的氢氧化锆(Zr(OH)4)颗粒,测得其中粒径D50为230nm。The preparation method of zirconium hydroxide comprises: dissolving 16 kg of sodium hydroxide in 200 kg of deionized water to obtain a sodium hydroxide solution, and slowly adding 23.3 kg of zirconium tetrachloride powder to the hydroxide under a water bath of 0 ° C and vigorous stirring at 320 rpm. In the sodium solution, the addition of zirconium tetrachloride powder was controlled for 2 hours, and after completion of the reaction, zirconium hydroxide was precipitated. The precipitate was washed with deionized water to remove sodium chloride therein, and isopropyl alcohol was added to replace the water, and finally dried zirconium hydroxide (Zr(OH) 4 ) particles were obtained by spray drying, and the particle diameter D50 was measured. 230 nm.
氢氧化钒的制备方法包括:将12kg氢氧化钠加入200kg去离子水中溶解,得到氢氧化钠溶液,在0℃水浴、氮气保护、350rpm强力搅拌的条件下,将15.7kg三氯化钒粉末缓慢加入氢氧化钠溶液中,控制加三氯化钒粉末时间为2小时,反应结束后得到氢氧化钒沉淀。在氮气保护下,将该沉淀用去离子水洗涤以去除其中的氯化钠,并加入异丙醇置换水,最后通过喷雾干燥得到干燥的氢氧化钒(V(OH)3)颗粒,测得其中粒径D50为360nm。The preparation method of vanadium hydroxide comprises: dissolving 12 kg of sodium hydroxide in 200 kg of deionized water to obtain a sodium hydroxide solution, and slowly drying 15.7 kg of vanadium trichloride powder under the condition of 0 ° C water bath, nitrogen protection, and 350 rpm vigorous stirring. Adding sodium hydroxide solution, controlling the addition of vanadium trichloride powder for 2 hours, after the end of the reaction, vanadium hydroxide precipitation was obtained. The precipitate was washed with deionized water under nitrogen to remove sodium chloride therein, and isopropyl alcohol was added to replace the water, and finally dried vanadium hydroxide (V(OH) 3 ) particles were obtained by spray drying. Wherein the particle diameter D50 is 360 nm.
氢氧化镧的制备方法包括:将43.3kg六水硝酸镧溶解在200kg去离子水中,制得硝酸镧溶液,在搅拌条件下,向硝酸镧溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化镧沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,最后通过喷雾干燥得到干燥的氢氧化镧(La(OH)3)颗粒,测得其中粒径D50为390nm。The preparation method of barium hydroxide comprises: dissolving 43.3 kg of cerium nitrate hexahydrate in 200 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried yttrium hydroxide (La(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was measured to be 390 nm.
氢氧化铈的制备方法包括:将43.4kg六水硝酸铈溶解在150kg去离子水中,制得硝酸铈溶液,在搅拌条件下,向硝酸铈溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化铈沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,最后通过喷雾干燥得到干燥的氢氧化铈(Ce(OH)3)颗粒,测得其中粒径D50为680nm。The preparation method of cerium hydroxide comprises: dissolving 43.4 kg of cerium nitrate hexahydrate in 150 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried cerium hydroxide (Ce(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was measured to be 680 nm.
氢氧化钕的制备方法包括:将43.8kg六水硝酸钕溶解在150kg去离子水中,制得硝酸钕溶液,在搅拌条件下,向硝酸钕溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化钕沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,最后通过喷雾干燥得到干燥的氢氧化钕(Nd(OH)3)颗粒,测得其中粒径D50为600nm。The preparation method of cerium hydroxide comprises: dissolving 43.8 kg of cerium nitrate hexahydrate in 150 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried cerium hydroxide (Nd(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was measured to be 600 nm.
氢氧化钐的制备方法包括:将44.4kg六水硝酸钐溶解在150kg去离子水中,制得硝酸钐溶液,在搅拌条件下,向硝酸钐溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化钐沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,最后通过喷雾干燥得到干燥的氢氧化钐(Sm(OH)3)颗粒,测得其中粒径D50为510nm。The preparation method of cerium hydroxide comprises: dissolving 44.4 kg of cerium nitrate hexahydrate in 150 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried cerium hydroxide (Sm(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 510 nm.
氢氧化钆的制备方法包括:将45.1kg六水硝酸钆溶解在150kg去离子水中,制得硝酸钆溶液,在搅拌条件下,向硝酸钆溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化钆沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,最后通过喷雾干燥得到干燥的氢氧化钆(Gd(OH)3)颗粒,测得其中粒径D50为450nm。The preparation method of cerium hydroxide comprises: dissolving 45.1 kg of cerium nitrate hexahydrate in 150 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried yttrium hydroxide (Gd(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 450 nm.
氢氧化铒的制备方法包括:将44.3kg五水硝酸铒溶解在150kg去离子水中,制得硝酸铒溶液,在搅拌条件下,向硝酸铒溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化铒沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸 铵,最后通过喷雾干燥得到干燥的氢氧化铒(Er(OH)3)颗粒,测得其中粒径D50为220nm。The preparation method of cerium hydroxide comprises: dissolving 44.3 kg of cerium nitrate pentahydrate in 150 kg of deionized water to prepare a cerium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the cerium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried cerium hydroxide (Er(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 220 nm.
氢氧化铌的制备方法包括:将9.29kg金属铌溶解于由32kg质量分数为65%的浓硝酸和50kg质量分数为40%的氢氟酸组成的混合溶液中,制得铌液,在搅拌条件下,向铌液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化铌沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸和氢氟酸,再通过喷雾干燥将游离水去除,最终得到干燥的中粒径D50为1.1μm的氢氧化铌(Nb(OH)5)粉末。The preparation method of barium hydroxide comprises: dissolving 9.29 kg of metal cerium in a mixed solution consisting of 32 kg of concentrated nitric acid having a mass fraction of 65% and 50 kg of hydrofluoric acid having a mass fraction of 40% to prepare a mash, under stirring conditions. Next, ammonia water having a mass fraction of 25% was gradually added to the mash, until the pH of the reaction system was 7.3, and the time for controlling the addition of ammonia was 2 hours, and the precipitation of cesium hydroxide was obtained after the completion of the reaction. The precipitate was washed with deionized water to remove nitric acid and hydrofluoric acid, and the free water was removed by spray drying to finally obtain a dried cerium hydroxide (Nb(OH) 5 ) powder having a medium particle diameter D50 of 1.1 μm. .
氢氧化铬的制备方法包括:将40.0kg九水硝酸铬溶解在150kg去离子水中,制得硝酸铬溶液,在搅拌条件下,向硝酸铬溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化铬沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,最后通过喷雾干燥得到干燥的氢氧化铬(Cr(OH)3)颗粒,测得其中粒径D50为100nm。The preparation method of the chromium hydroxide comprises: dissolving 40.0 kg of chromium nitrate nonahydrate in 150 kg of deionized water to prepare a chromium nitrate solution, and gradually adding a mass fraction of 25% ammonia water to the chromium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, chromium hydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium nitrate therein, and finally dried chromium hydroxide (Cr(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 100 nm.
氢氧化钼的制备方法包括:在搅拌条件下,将25.6kg三水三氯化钼溶解在250kg无水乙醇中,得到澄清溶液,在搅拌条件下,向该澄清溶液中逐步加入21.5kg质量分数为25%的氨水,控制加氨水时间为2小时,反应结束后得到氢氧化钼沉淀。将该沉淀用去离子水洗涤以去除其中的氯化铵,并用异丙醇置换水,最后通过喷雾干燥得到干燥的氢氧化钼(Mo(OH)3)颗粒,测得其中粒径D50为190nm。The preparation method of molybdenum oxyhydroxide comprises: dissolving 25.6 kg of molybdenum trichloride trihydrate in 250 kg of absolute ethanol under stirring to obtain a clear solution, and gradually adding 21.5 kg of mass fraction to the clarified solution under stirring. For 25% ammonia water, the time for adding ammonia was controlled to 2 hours, and after the reaction was completed, a precipitate of molybdenum hydroxide was obtained. The precipitate was washed with deionized water to remove ammonium chloride therein, and water was replaced with isopropyl alcohol, and finally dried molybdenum hydroxide (Mo(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was measured to be 190 nm. .
氢氧化亚锰的制备方法包括:将35.8kg的50重量%硝酸亚锰水溶液用150kg去离子水稀释,制得硝酸亚锰溶液,在搅拌及氮气保护的条件下,向硝酸亚锰溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化亚锰沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,并通过喷雾干燥得到干燥的氢氧化亚锰(Mn(OH)2)粉末,测得其中粒径D50为840nm。The preparation method of manganese hydroxide comprises: diluting 35.8 kg of a 50 wt% aqueous solution of manganese nitrate with 150 kg of deionized water to prepare a manganese nitrate solution, and gradually adding to the manganese nitrate solution under stirring and nitrogen protection conditions. Ammonia water having a mass fraction of 25% was added until the pH of the reaction system was 7.3, and the time for adding ammonia was controlled to be 2 hours, and the precipitation of manganese hydroxide was obtained after the completion of the reaction. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried manganese hydroxide (Mn(OH) 2 ) powder was obtained by spray drying, and the particle diameter D50 was found to be 840 nm.
氢氧化铁的制备方法包括:将40.4kg九水硝酸铁用150kg去离子水溶解,制得硝酸铁溶液,在260rpm强力搅拌的条件下,向硝酸铁溶液中快速加入质量分数为25%的氨水,直至反应体系pH值为11,反应结束后得到沉淀。将该沉淀用去离子水快速洗涤以去除其中的硝酸铵和氨水,并用异丙醇置换水,通过喷雾干燥得到氢氧化铁(Fe(OH)3)粉末,测得其中粒径D50为190nm。The preparation method of the iron hydroxide comprises: dissolving 40.4 kg of ferric nitrate non-aqueous water in 150 kg of deionized water to prepare a ferric nitrate solution, and rapidly adding a mass fraction of 25% ammonia water to the ferric nitrate solution under the condition of vigorous stirring at 260 rpm. Until the pH of the reaction system was 11, a precipitate was obtained after completion of the reaction. The precipitate was quickly washed with deionized water to remove ammonium nitrate and ammonia water therein, and water was replaced with isopropyl alcohol, and iron hydroxide (Fe(OH) 3 ) powder was obtained by spray drying, and the particle diameter D50 was found to be 190 nm.
氢氧化钴的制备方法包括:将29.1kg六水硝酸亚钴用150kg去离子水溶解,制得硝酸亚钴溶液,在搅拌及氮气保护的条件下,向硝酸亚钴溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化亚钴沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,并通过喷雾干燥得到干燥的氢氧化亚钴(Co(OH)2)粉末,测得其中粒径D50为640nm。The preparation method of cobalt hydroxide comprises: dissolving 29.1 kg of cobalt hexahydrate in 150 kg of deionized water to prepare a cobaltous cobalt nitrate solution, and gradually adding a mass fraction to the cobaltous cobalt nitrate solution under stirring and nitrogen protection conditions. 25% ammonia water until the pH value of the reaction system was 7.3, and the time for controlling the addition of ammonia was 2 hours. After the reaction was completed, cobalt oxyhydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried cobalt oxyhydroxide (Co(OH) 2 ) powder was obtained by spray drying, and the particle diameter D50 was found to be 640 nm.
氢氧化镍的制备方法包括:将29.1kg六水硝酸亚镍用150kg去离子水溶解,制得硝酸亚镍溶液,在搅拌及氮气保护的条件下,向硝酸亚镍溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化亚镍沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,并通过喷雾干燥得到干燥的氢氧化亚镍(Ni(OH)2),测得其中粒径D50为550nm。The preparation method of nickel hydroxide comprises: dissolving 29.1 kg of nickel nitrate hexahydrate in 150 kg of deionized water to prepare a nickel nitrate solution, and gradually adding a mass fraction to the nickel nitrate solution under stirring and nitrogen protection conditions. 25% ammonia water until the pH value of the reaction system was 7.3, and the time for controlling the addition of ammonia was 2 hours. After the reaction was completed, nickel hydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried nickel hydroxide (Ni(OH) 2 ) was obtained by spray drying, and the particle diameter D50 was found to be 550 nm.
氢氧化锡的制备方法包括:将35.1kg五水四氯化锡溶解在200kg无水乙醇中,得到澄清溶液,在搅拌条件下,向该澄清溶液中逐步加入28.6kg质量分数为25%的氨水,控制加氨水时间为2小时,反应结束后得到氢氧化锡沉淀。将该沉淀用去离子水洗涤以去除其中的氯化铵,并用异丙醇置换水,最后通过喷雾干燥得到干燥的氢氧化锡(Sn(OH)4)颗粒,测得其中粒径D50为80nm。The preparation method of the tin hydroxide comprises: dissolving 35.1 kg of tin tetrachloride pentahydrate in 200 kg of absolute ethanol to obtain a clear solution, and gradually adding 28.6 kg of ammonia water having a mass fraction of 25% to the clear solution under stirring. The time for controlling the addition of ammonia was 2 hours, and after the reaction was completed, tin hydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium chloride therein, and water was replaced with isopropyl alcohol, and finally dried tin hydroxide (Sn(OH) 4 ) particles were obtained by spray drying, and the particle diameter D50 was determined to be 80 nm. .
氢氧化铋的制备方法包括:将48.5kg五水硝酸铋加入质量分数为2%的200kg稀硝酸水溶液中溶解,制得硝酸铋溶液,在320rpm强力搅拌条件下,将硝酸铋溶液快速加入至26kg质量分数为25%的氨水中,反应结束后得到氢氧化铋沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵和氨水,并通过喷雾干燥得到干燥的氢氧化铋(Bi(OH)3),测得其中粒径D50为3.7μm。The preparation method of barium hydroxide comprises: dissolving 48.5 kg of barium nitrate pentahydrate into 200 kg of dilute nitric acid aqueous solution having a mass fraction of 2% to prepare a barium nitrate solution, and rapidly adding a barium nitrate solution to 26 kg under vigorous stirring at 320 rpm. In the ammonia water having a mass fraction of 25%, a precipitate of barium hydroxide was obtained after the completion of the reaction. The precipitate was washed with deionized water to remove ammonium nitrate and ammonia water therein, and dried cerium hydroxide (Bi(OH) 3 ) was obtained by spray drying, and the particle diameter D50 was found to be 3.7 μm.
氢氧化锑的制备方法包括:在搅拌条件下,将22.8kg三氯化锑溶解在250kg无水乙醇中,得到澄清溶液,在搅拌条件下,向该澄清溶液中逐步加入21.5kg质量分数为25%的氨水,控制加氨水时间为2小时,反应结束后得到氢氧化锑沉淀。将该沉淀用去离子水洗涤以去除其中的氯化铵,并用异丙醇置换水,最后通过喷雾干燥得到干燥的氢氧化锑(Sb(OH)3)颗粒,测得其中粒径D50为80nm。The preparation method of cerium hydroxide comprises: dissolving 22.8 kg of antimony trichloride in 250 kg of absolute ethanol under stirring to obtain a clear solution, and gradually adding 21.5 kg of mass fraction to the clarified solution under stirring. % ammonia water, the time for controlling the addition of ammonia was 2 hours, and the precipitation of barium hydroxide was obtained after the reaction. The precipitate was washed with deionized water to remove ammonium chloride therein, and water was replaced with isopropyl alcohol, and finally dried cerium hydroxide (Sb(OH) 3 ) particles were obtained by spray drying, and the particle diameter D50 was measured to be 80 nm. .
氢氧化硼按如下方法制备:将6.18kg硼酸加入150kg去离子水中溶解,制得硼酸溶液,将该溶 液喷雾干燥得到干燥的硼酸(B(OH)3)粉末,测得其中粒径D50为12.4μm。Boron hydroxide was prepared as follows: The 150kg added 6.18kg of boric acid was dissolved in deionized water to prepare a boric acid solution, the solution was spray-dried to obtain dry boric acid (B (OH) 3) powder, wherein the particle size D50 was measured 12.4 Mm.
氢氧化铍的制备方法包括:将18.7kg三水硝酸铍用100kg去离子水溶解,制得硝酸铍溶液,在搅拌条件下,向硝酸铍溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化铍沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,并通过喷雾干燥得到干燥的氢氧化铍(Be(OH)2),测得其中粒径D50为3.5μm。The preparation method of barium hydroxide comprises: dissolving 18.7 kg of barium nitrate trihydrate with 100 kg of deionized water to prepare a barium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the barium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, barium hydroxide precipitation was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried cerium hydroxide (Be(OH) 2 ) was obtained by spray drying, and the particle diameter D50 was found to be 3.5 μm.
氢氧化镁的制备方法包括:将25.6kg六水硝酸镁用100kg去离子水溶解,制得硝酸镁溶液,在搅拌条件下,向硝酸镁溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化镁沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,并通过喷雾干燥得到干燥的氢氧化镁(Mg(OH)2),测得其中粒径D50为2.8μm。The preparation method of magnesium hydroxide comprises: dissolving 25.6 kg of magnesium nitrate hexahydrate in 100 kg of deionized water to prepare a magnesium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the magnesium nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, magnesium hydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried magnesium hydroxide (Mg(OH) 2 ) was obtained by spray drying, and the particle diameter D50 was found to be 2.8 μm.
氢氧化铜的制备方法包括:将24.2kg三水硝酸铜用100kg去离子水溶解,制得硝酸铜溶液,在搅拌条件下,向硝酸铜溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化铜沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,并通过喷雾干燥得到干燥的氢氧化铜(Cu(OH)2),测得其中粒径D50为3.2μm。The preparation method of copper hydroxide comprises: dissolving 24.2 kg of copper nitrate trihydrate in 100 kg of deionized water to prepare a copper nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the copper nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time of adding ammonia was controlled to be 2 hours. After the reaction was completed, copper hydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried copper hydroxide (Cu(OH) 2 ) was obtained by spray drying, and the particle diameter D50 was found to be 3.2 μm.
氢氧化锌的制备方法包括:将29.7kg六水硝酸锌用100kg去离子水溶解,制得硝酸锌溶液,在搅拌条件下,向硝酸锌溶液中逐步加入质量分数为25%的氨水,直至反应体系pH值为7.3,控制加氨水时间为2小时,反应结束后得到氢氧化锌沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵,并通过喷雾干燥得到干燥的氢氧化锌(Zn(OH)2),测得其中粒径D50为3.9μm。The preparation method of zinc hydroxide comprises: dissolving 29.7 kg of zinc nitrate hexahydrate in 100 kg of deionized water to prepare a zinc nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the zinc nitrate solution under stirring, until the reaction The pH of the system was 7.3, and the time of adding ammonia was controlled to be 2 hours. After the reaction was completed, zinc hydroxide was precipitated. The precipitate was washed with deionized water to remove ammonium nitrate therein, and dried zinc hydroxide (Zn(OH) 2 ) was obtained by spray drying, and the particle diameter D50 was found to be 3.9 μm.
实施例1Example 1
(1)电池正极极片制备(1) Preparation of battery positive electrode sheets
将21750g锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、750g粘结剂HSV900、750g导电剂Super-P和1750g氢氧化铝(Al(OH)3)粉末添加剂混合,具体方法为:先以25000g NMP为溶剂,将粘结剂HSV900溶解,并在搅拌下分别将锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、导电剂Super-P、氢氧化铝(Al(OH)3)粉末添加剂与上述粘结剂的溶液混合,之后搅拌形成均匀的正极浆料;21750g lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode material, 750g binder HSV900, 750g conductive agent Super-P and 1750g aluminum hydroxide (Al(OH) 3 ) powder additive are mixed, the specific method is: The binder HSV900 was first dissolved in 25000 g of NMP as a solvent, and lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode material, conductive agent Super-P, aluminum hydroxide (Al(OH)) were respectively stirred under stirring. 3 ) mixing the powder additive with the solution of the above binder, and then stirring to form a uniform positive electrode slurry;
将该正极浆料均匀涂覆在厚度为25μm的铝箔上,涂覆宽度为160mm,敷料双面面密度为335.4g/m2(敷料双面面密度以烘干后的重量计,下同,且以电极敷料的干重为基准,添加剂的含量为7重量%),然后在110℃下烘干,得到正极极片。The positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 μm, the coating width was 160 mm, and the double-sided surface density of the dressing was 335.4 g/m 2 (the double-sided surface density of the dressing was measured by the weight after drying, the same below, The content of the additive was 7% by weight based on the dry weight of the electrode dressing, and then dried at 110 ° C to obtain a positive electrode tab.
(2)电池负极极片制备(2) Preparation of battery negative pole piece
将12285g天然石墨负极材料、195g增稠剂CMC、130g导电剂Super-P和780g丁苯橡胶乳胶粘结剂混合,具体方法为:先以12500g去离子水为溶剂,将增稠剂CMC溶解,并在搅拌下分别将丁苯橡胶乳胶粘结剂、导电剂Super-P、天然石墨负极材料与上述增稠剂的溶液混合,之后搅拌形成均匀的负极浆料;12285g natural graphite anode material, 195g thickener CMC, 130g conductive agent Super-P and 780g styrene-butadiene rubber latex binder are mixed, the specific method is: first dissolve the thickener CMC with 12500g deionized water as solvent And stirring, respectively, the styrene-butadiene rubber latex binder, the conductive agent Super-P, the natural graphite anode material and the above thickener solution are mixed, and then stirred to form a uniform anode slurry;
将该负极浆料均匀涂覆在厚度为18μm的铜箔上,涂覆宽度为164mm,敷料双面面密度为164.1g/m2(以烘干后的重量计,下同),然后在100℃下烘干,得到负极极片。The negative electrode slurry was uniformly coated on a copper foil having a thickness of 18 μm, the coating width was 164 mm, and the double-sided surface density of the dressing was 164.1 g/m 2 (based on the weight after drying, the same below), and then at 100 Drying at ° C to obtain a negative electrode tab.
(3)单体电池的装配(3) Assembly of single cells
将正极极片裁剪成120mm×160mm的尺寸作为正极,将负极极片裁剪成125mm×164mm的尺寸作为负极,以聚丙烯膜为隔膜,组装成电芯组件,放入软包铝塑膜电池壳体中,并将正负极极耳分别与铝塑膜焊接在一起,过程中保证极耳与电池壳体的绝缘,经过核算,正极活性物质锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2的重量约为191g,负极活性物质天然石墨的重量约为104g,电池的标称容量为30Ah。随后将LiPF6按1摩尔/升的浓度溶解在EC/DMC=1:1(体积比)的混合溶剂中形成非水电解液,在氮气气氛保护下将160g此电解液注入上述电池半成品中,并将电池封口。将该电池在45℃的条件下陈化48小时,之后以0.6A的电流充电至4.00V,再在45℃的条件下二次陈化48小时,最后在氮气气氛保护下将电池中产生的气体抽出并将电池二次封口,得到锂离子电池A1。The positive electrode piece is cut into a size of 120 mm×160 mm as a positive electrode, the negative electrode piece is cut into a size of 125 mm×164 mm as a negative electrode, and a polypropylene film is used as a separator, assembled into a battery core assembly, and placed in a soft aluminum-plastic film battery case. In the body, the positive and negative poles are respectively welded with the aluminum plastic film, and the insulation between the polar ear and the battery case is ensured in the process. After calculation, the positive active material lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 The weight is about 191 g, the weight of the negative active material natural graphite is about 104 g, and the nominal capacity of the battery is 30 Ah. Subsequently, LiPF 6 was dissolved in a mixed solvent of EC/DMC=1:1 (volume ratio) at a concentration of 1 mol/liter to form a non-aqueous electrolyte, and 160 g of this electrolyte was injected into the above-mentioned battery semi-finished product under the protection of a nitrogen atmosphere. And seal the battery. The battery was aged at 45 ° C for 48 hours, then charged to 4.00 V with a current of 0.6 A, and then aged for another 48 hours at 45 ° C. Finally, the battery was produced under the protection of a nitrogen atmosphere. The gas was taken out and the battery was sealed twice to obtain a lithium ion battery A1.
实施例2Example 2
按照实施例1的方法制备锂离子电池A2,不同的是,步骤(1)中,电池正极极片的制备方法如下: A lithium ion battery A2 was prepared according to the method of Example 1, except that in the step (1), the preparation method of the battery positive electrode tab was as follows:
将21750g锂镍钴铝氧LiNi0.8Co0.15Al0.05O2正极材料、1250g PTFE乳液粘结剂D210、750g导电剂乙炔黑混合,具体方法为:先以25000g去离子水为溶剂,将PTFE乳液粘结剂D210分散,得到乳液,并在搅拌下分别将锂镍钴铝氧LiNi0.8Co0.15Al0.05O2正极材料、导电剂乙炔黑与上述粘结剂的乳液混合,之后搅拌形成均匀的浆料;21750g lithium nickel cobalt aluminum oxide LiNi 0.8 Co 0.15 Al 0.05 O 2 cathode material, 1250g PTFE emulsion binder D210, 750g conductive agent acetylene black are mixed by: 25000g deionized water as solvent, PTFE emulsion is glued The agent D210 is dispersed to obtain an emulsion, and the lithium nickel cobalt aluminum oxide LiNi 0.8 Co 0.15 Al 0.05 O 2 positive electrode material and the conductive agent acetylene black are respectively mixed with the emulsion of the above binder under stirring, and then stirred to form a uniform slurry. ;
将该浆料均匀涂覆在厚度为25μm的铝箔上,涂覆宽度为160mm,敷料双面面密度为311.9g/m2(以烘干后的重量计),然后在100℃下烘干,得到正极极片;The slurry was uniformly coated on an aluminum foil having a thickness of 25 μm, a coating width of 160 mm, a double-sided surface density of the dressing of 311.9 g/m 2 (based on the weight after drying), and then dried at 100 ° C. Obtaining a positive electrode tab;
将1000g原硅酸Si(OH)4粉末添加剂、75g PTFE乳液粘结剂D210混合,具体方法为:先以2500g去离子水为溶剂,将PTFE乳液粘结剂D210分散,得到乳液,并在搅拌下将原硅酸Si(OH)4粉末添加剂与上述粘结剂的乳液混合,之后搅拌形成均匀的添加剂浆料;1000g of orthosilicate Si(OH) 4 powder additive and 75g of PTFE emulsion binder D210 are mixed by dispersing PTFE emulsion binder D210 with 2500g of deionized water as solvent, and obtaining the emulsion. The original silicic acid Si(OH) 4 powder additive is mixed with the emulsion of the above binder, and then stirred to form a uniform additive slurry;
将该添加剂浆料均匀涂覆在上述正极极片表面,涂覆宽度为162mm,以覆盖住活性物质,敷料双面面密度为24.6g/m2(以电极敷料的干重为基准,添加剂的含量7重量%),然后在100℃下烘干,得到表面涂覆有添加剂的正极极片。The additive slurry was uniformly coated on the surface of the above positive electrode tab with a coating width of 162 mm to cover the active material, and the double-sided surface density of the dressing was 24.6 g/m 2 (based on the dry weight of the electrode dressing, the additive The content was 7% by weight), and then dried at 100 ° C to obtain a positive electrode tab coated with an additive.
实施例3Example 3
按照实施例1的方法制备锂离子电池A3,不同的是,步骤(1)中,电池正极极片的制备方法如下:A lithium ion battery A3 was prepared according to the method of Example 1, except that in the step (1), the preparation method of the battery positive electrode tab was as follows:
将1000g氢氧化钛Ti(OH)4粉末添加剂、45g导电剂Super-P、45g粘结剂HSV900混合,具体方法为:先以2500g NMP为溶剂,将粘结剂HSV900溶解,并在搅拌下将氢氧化钛Ti(OH)4粉末添加剂、导电剂Super-P与上述粘结剂的溶液混合,之后搅拌形成均匀的添加剂浆料;1000g of titanium hydroxide Ti(OH) 4 powder additive, 45g of conductive agent Super-P, 45g of binder HSV900 are mixed by: dissolving the binder HSV900 with 2500g of NMP as solvent, and stirring a titanium hydroxide Ti(OH) 4 powder additive, a conductive agent Super-P mixed with a solution of the above binder, and then stirred to form a uniform additive slurry;
将该添加剂浆料均匀涂覆在厚度为25μm的铝箔上,涂覆宽度为162mm,敷料双面面密度为25.8g/m2(以烘干后的重量计),然后在120℃下烘干,得到添加剂涂覆的铝箔;The additive slurry was uniformly coated on an aluminum foil having a thickness of 25 μm, a coating width of 162 mm, a double-sided surface density of the dressing of 25.8 g/m 2 (based on the weight after drying), and then dried at 120 ° C. Obtaining an additive-coated aluminum foil;
将21750g钴酸锂LiCoO2正极材料、750g粘结剂HSV900、750g导电剂碳纳米管混合,具体方法为:先以25000g NMP为溶剂,将粘结剂HSV900溶解,并在搅拌下分别将钴酸锂LiCoO2正极材料、导电剂碳纳米管与上述粘结剂的溶液混合,之后搅拌形成均匀的活性物质浆料;21750g lithium cobalt oxide LiCoO 2 cathode material, 750g binder HSV900, 750g conductive carbon nanotubes are mixed by the method of dissolving the binder HSV900 with 25000g NMP as solvent, and respectively adding cobalt acid under stirring a lithium LiCoO 2 positive electrode material, a conductive agent carbon nanotube is mixed with a solution of the above binder, and then stirred to form a uniform active material slurry;
将该活性物质浆料均匀涂覆在添加剂涂覆的铝箔表面,涂覆宽度为160mm,敷料双面面密度为311.9g/m2(以电极敷料的干重为基准,添加剂的含量为7重量%),然后在120℃下烘干,得到铝箔经过添加剂涂覆的正极极片。The active material slurry was uniformly coated on the surface of the additive-coated aluminum foil, the coating width was 160 mm, and the double-sided surface density of the dressing was 311.9 g/m 2 (based on the dry weight of the electrode dressing, the additive content was 7 weight) %), and then dried at 120 ° C to obtain a positive electrode tab coated with an additive of aluminum foil.
实施例4Example 4
(1)电池正极极片制备(1) Preparation of battery positive electrode sheets
将21750g锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、750g粘结剂HSV900、750g导电剂Super-P混合,具体方法为:先以25000g NMP为溶剂,将粘结剂HSV900溶解,并在搅拌下分别将锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、导电剂Super-P与上述粘结剂的溶液混合,之后搅拌形成均匀的正极浆料;21750g lithium nickel cobalt manganese oxygen LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode material, 750g binder HSV900, 750g conductive agent Super-P are mixed, the specific method is: first, using 25000g NMP as a solvent, the binder HSV900 is dissolved, And stirring, respectively, a lithium nickel cobalt manganese oxygen LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, a conductive agent Super-P and a solution of the above binder are mixed, and then stirred to form a uniform positive electrode slurry;
将该正极浆料均匀涂覆在厚度为25μm的铝箔上,涂覆宽度为160mm,敷料双面面密度为311.9g/m2(以烘干后的重量计),然后在110℃下烘干,得到正极极片。The positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 μm, a coating width of 160 mm, a double-sided surface density of the dressing of 311.9 g/m 2 (based on the weight after drying), and then dried at 110 ° C. , the positive electrode piece is obtained.
(2)电池负极极片制备(2) Preparation of battery negative pole piece
将11425g天然石墨负极材料、181g增稠剂CMC、121g导电剂Super-P、725g丁苯橡胶乳胶粘结剂和910g氢氧化铝(Al(OH)3)粉末添加剂混合,具体方法为:先以13500g去离子水为溶剂,将增稠剂CMC溶解,并在搅拌下分别将丁苯橡胶乳胶粘结剂、导电剂Super-P、天然石墨负极材料、氢氧化铝粉末添加剂与上述增稠剂的溶液混合,之后搅拌形成均匀的负极浆料;11725g natural graphite anode material, 181g thickener CMC, 121g conductive agent Super-P, 725g styrene-butadiene rubber latex binder and 910g aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by: 13500g deionized water is used as solvent, the thickener CMC is dissolved, and the styrene-butadiene rubber latex binder, the conductive agent Super-P, the natural graphite anode material, the aluminum hydroxide powder additive and the above thickener are respectively stirred under stirring. The solution is mixed, and then stirred to form a uniform negative electrode slurry;
将该负极浆料均匀涂覆在厚度为18μm的铜箔上,涂覆宽度为164mm,敷料双面面密度为176.5g/m2(以电极敷料的干重为基准,添加剂的含量为7重量%),然后在100℃下烘干,得到负极极片。The negative electrode slurry was uniformly coated on a copper foil having a thickness of 18 μm, the coating width was 164 mm, and the double-sided surface density of the dressing was 176.5 g/m 2 (based on the dry weight of the electrode dressing, the additive content was 7 weight). %), and then dried at 100 ° C to obtain a negative electrode tab.
(3)单体电池的装配(3) Assembly of single cells
将正极极片裁剪成120mm×160mm的尺寸作为正极,将负极极片裁剪成125mm×164mm的尺寸作为负极,以聚丙烯膜为隔膜,组装成电芯组件,放入软包铝塑膜电池壳体中,并将正负极极耳分 别与铝塑膜焊接在一起,过程中保证极耳与电池壳体的绝缘,经过核算,正极活性物质锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2的重量约为191g,负极活性物质天然石墨的重量约为104g,电池的标称容量为30Ah。随后将LiPF6按1摩尔/升的浓度溶解在EC/DMC=1:1(体积比)的混合溶剂中形成非水电解液,在氮气气氛保护下将160g此电解液注入上述电池半成品中,并将电池封口。将该电池在45℃的条件下陈化48小时,之后以0.6A的电流充电至4.00V,再在45℃的条件下二次陈化48小时,最后在氮气气氛保护下将电池中产生的气体抽出并将电池二次封口,得到锂离子电池A4。The positive electrode piece is cut into a size of 120 mm×160 mm as a positive electrode, the negative electrode piece is cut into a size of 125 mm×164 mm as a negative electrode, and a polypropylene film is used as a separator, assembled into a battery core assembly, and placed in a soft aluminum-plastic film battery case. In the body, the positive and negative poles are respectively welded with the aluminum plastic film, and the insulation between the polar ear and the battery case is ensured in the process. After calculation, the positive active material lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 The weight is about 191 g, the weight of the negative active material natural graphite is about 104 g, and the nominal capacity of the battery is 30 Ah. Subsequently, LiPF 6 was dissolved in a mixed solvent of EC/DMC=1:1 (volume ratio) at a concentration of 1 mol/liter to form a non-aqueous electrolyte, and 160 g of this electrolyte was injected into the above-mentioned battery semi-finished product under the protection of a nitrogen atmosphere. And seal the battery. The battery was aged at 45 ° C for 48 hours, then charged to 4.00 V with a current of 0.6 A, and then aged for another 48 hours at 45 ° C. Finally, the battery was produced under the protection of a nitrogen atmosphere. The gas was taken out and the battery was sealed twice to obtain a lithium ion battery A4.
实施例5Example 5
按照实施例1的方法制备锂离子电池A5,不同的是,步骤(1)中,将22220g锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、765g粘结剂HSV900、765g导电剂Super-P和1250g氢氧化铝(Al(OH)3)粉末添加剂混合,具体方法为:先以25000g NMP为溶剂,将粘结剂HSV900溶解,并在搅拌下分别将锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、导电剂Super-P、氢氧化铝(Al(OH)3)粉末添加剂与上述粘结剂的溶液混合,之后搅拌形成均匀的正极浆料;A lithium ion battery A5 was prepared according to the method of Example 1, except that in the step (1), 22220 g of lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, 765 g of a binder HSV 900, and 765 g of a conductive agent Super were used. -P and 1250g aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by: dissolving the binder HSV900 with 25000g NMP as solvent, and respectively dispersing lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode material, conductive agent Super-P, aluminum hydroxide (Al(OH) 3 ) powder additive mixed with the above binder solution, and then stirred to form a uniform positive electrode slurry;
将该正极浆料均匀涂覆在厚度为25μm的铝箔上,涂覆宽度为160mm,敷料双面面密度为328.3g/m2(以电极敷料的干重为基准,添加剂的含量为5重量%),然后在110℃下烘干,得到正极极片。The positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 μm, the coating width was 160 mm, and the double-sided surface density of the dressing was 328.3 g/m 2 (based on the dry weight of the electrode dressing, the additive content was 5% by weight). Then, it was dried at 110 ° C to obtain a positive electrode tab.
实施例6Example 6
按照实施例1的方法制备锂离子电池A6,不同的是,步骤(1)中,将21282g锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、734g粘结剂HSV900、734g导电剂Super-P和2250g氢氧化铝(Al(OH)3)粉末添加剂混合,具体方法为:先以25000g NMP为溶剂,将粘结剂HSV900溶解,并在搅拌下分别将锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、导电剂Super-P、氢氧化铝(Al(OH)3)粉末添加剂与上述粘结剂的溶液混合,之后搅拌形成均匀的正极浆料;A lithium ion battery A6 was prepared according to the method of Example 1, except that in the step (1), 21282 g of lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, 734 g of a binder HSV 900, and 734 g of a conductive agent Super were used. -P and 2250g of aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by: dissolving the binder HSV900 with 25000g NMP as solvent, and respectively dispersing lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode material, conductive agent Super-P, aluminum hydroxide (Al(OH) 3 ) powder additive mixed with the above binder solution, and then stirred to form a uniform positive electrode slurry;
该正极浆料均匀涂覆在厚度为25μm的铝箔上,涂覆宽度为160mm,敷料双面面密度为342.8g/m2(以电极敷料的干重为基准,添加剂的含量为9重量%),然后在110℃下烘干,得到正极极片。The positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 μm, a coating width of 160 mm, and a double-sided surface density of the dressing of 342.8 g/m 2 (based on the dry weight of the electrode dressing, the additive content was 9% by weight) Then, it was dried at 110 ° C to obtain a positive electrode tab.
实施例7Example 7
按照实施例2的方法制备锂离子电池A7,不同的是,步骤(1)中,添加剂浆料的制备方法为:先以1500g去离子水为溶剂,将30g PTFE乳液粘结剂D210分散,得到乳液,并在搅拌下将1000g原硅酸Si(OH)4粉末与上述粘结剂的乳液混合,之后搅拌形成均匀的添加剂浆料。The lithium ion battery A7 was prepared according to the method of Example 2, except that in the step (1), the additive slurry was prepared by dispersing 30 g of the PTFE emulsion binder D210 with 1500 g of deionized water as a solvent. The emulsion was mixed with 1000 g of orthosilicate Si(OH) 4 powder with an emulsion of the above binder under stirring, followed by stirring to form a uniform additive slurry.
将该添加剂浆料均匀涂覆在上述正极极片表面,涂覆宽度为162mm,以覆盖住活性物质,敷料双面面密度为16.7g/m2(以电极敷料的干重为基准,添加剂的含量为5重量%),然后在100℃下烘干,得到表面涂覆有添加剂的正极极片。The additive slurry was uniformly coated on the surface of the above positive electrode tab with a coating width of 162 mm to cover the active material, and the double-sided surface density of the dressing was 16.7 g/m 2 (based on the dry weight of the electrode dressing, the additive The content was 5% by weight), and then dried at 100 ° C to obtain a positive electrode tab coated with an additive.
实施例8Example 8
按照实施例2的方法制备锂离子电池A8,不同的是,步骤(1)中,添加剂浆料的制备方法为:先以3500g去离子水为溶剂,将160gPTFE乳液粘结剂D210分散,得到乳液,并在搅拌下将1000g原硅酸Si(OH)4粉末与上述粘结剂的乳液混合,之后搅拌形成均匀的添加剂浆料。The lithium ion battery A8 was prepared according to the method of Example 2, except that in the step (1), the additive slurry was prepared by dispersing 160 g of the PTFE emulsion binder D210 with 3500 g of deionized water as a solvent to obtain an emulsion. And 1000 g of the orthosilicate Si(OH) 4 powder was mixed with the emulsion of the above binder under stirring, and then stirred to form a uniform additive slurry.
将该添加剂浆料均匀涂覆在上述正极极片表面,涂覆宽度为162mm,以覆盖住活性物质,敷料双面面密度为34.1g/m2(以电极敷料的干重为基准,添加剂的含量为9重量%),然后在100℃下烘干,得到表面涂覆有添加剂的正极极片。The additive slurry was uniformly coated on the surface of the above positive electrode tab with a coating width of 162 mm to cover the active material, and the double-sided surface density of the dressing was 34.1 g/m 2 (based on the dry weight of the electrode dressing, the additive The content was 9% by weight), and then dried at 100 ° C to obtain a positive electrode tab coated with an additive.
实施例9Example 9
按照实施例1的方法制备锂离子电池A9,不同的是,步骤(1)中,将22920g锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、790g粘结剂HSV900、790g导电剂Super-P和500g氢氧化铝(Al(OH)3)粉末添加剂混合,具体方法为:先以25000g NMP为溶剂,将粘结剂HSV900溶解,并在搅拌下分 别将锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、导电剂Super-P、氢氧化铝(Al(OH)3)添加剂与上述粘结剂的溶液混合,之后搅拌形成均匀的正极浆料;A lithium ion battery A9 was prepared according to the method of Example 1, except that in the step (1), 22,920 g of lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, 790 g of a binder HSV 900, and 790 g of a conductive agent Super were used. -P and 500g of aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by dissolving the binder HSV900 with 25000g of NMP as solvent and stirring lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode material, conductive agent Super-P, aluminum hydroxide (Al(OH) 3 ) additive mixed with the above binder solution, and then stirred to form a uniform positive electrode slurry;
将该正极浆料均匀涂覆在厚度为25μm的铝箔上,涂覆宽度为160mm,敷料双面面密度为318.3g/m2(以电极敷料的干重为基准,添加剂的含量为2重量%),然后在110℃下烘干,得到正极极片。The positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 μm, the coating width was 160 mm, and the double-sided surface density of the dressing was 318.3 g/m 2 (based on the dry weight of the electrode dressing, the content of the additive was 2% by weight). Then, it was dried at 110 ° C to obtain a positive electrode tab.
实施例10Example 10
按照实施例1的方法制备锂离子电池A10,不同的是,步骤(1)中,将23154g锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、798g粘结剂HSV900、798g导电剂Super-P和250g氢氧化铝(Al(OH)3)粉末添加剂混合,具体方法为:先以25000g NMP为溶剂,将粘结剂HSV900溶解,并在搅拌下分别将锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、导电剂Super-P、氢氧化铝(Al(OH)3)添加剂与上述粘结剂的溶液混合,之后搅拌形成均匀的正极浆料;A lithium ion battery A10 was prepared according to the method of Example 1, except that in the step (1), 23154 g of lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, 798 g of a binder HSV900, and 798 g of a conductive agent Super were used. -P and 250g aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by: dissolving the binder HSV900 with 25000g NMP as solvent, and respectively dissolving lithium nickel cobalt manganese oxide LiNi 0.5 Co under stirring 0.2 Mn 0.3 O 2 cathode material, conductive agent Super-P, aluminum hydroxide (Al(OH) 3 ) additive mixed with the above binder solution, and then stirred to form a uniform positive electrode slurry;
将该正极浆料均匀涂覆在厚度为25μm的铝箔上,涂覆宽度为160mm,敷料双面面密度为315.1g/m2(以电极敷料的干重为基准,添加剂的含量为1重量%),然后在110℃下烘干,得到正极极片。The positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 μm, the coating width was 160 mm, and the double-sided surface density of the dressing was 315.1 g/m 2 (based on the dry weight of the electrode dressing, the content of the additive was 1% by weight). Then, it was dried at 110 ° C to obtain a positive electrode tab.
实施例11Example 11
按照实施例1的方法制备锂离子电池A11,不同的是,步骤(1)中,将20112g锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、694g粘结剂HSV900、694g导电剂Super-P和3500g氢氧化铝(Al(OH)3)粉末添加剂混合,具体方法为:先以25000g NMP为溶剂,将粘结剂HSV900溶解,并在搅拌下分别将锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2正极材料、导电剂Super-P、氢氧化铝(Al(OH)3)添加剂与上述粘结剂的溶液混合,之后搅拌形成均匀的正极浆料;A lithium ion battery A11 was prepared according to the method of Example 1, except that in the step (1), 20112 g of lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode material, 694 g of a binder HSV 900, and 694 g of a conductive agent Super were used. -P and 3500g aluminum hydroxide (Al(OH) 3 ) powder additive are mixed by: dissolving the binder HSV900 with 25000g NMP as solvent, and respectively adding lithium nickel cobalt manganese oxide LiNi 0.5 Co under stirring 0.2 Mn 0.3 O 2 cathode material, conductive agent Super-P, aluminum hydroxide (Al(OH) 3 ) additive mixed with the above binder solution, and then stirred to form a uniform positive electrode slurry;
将该正极浆料均匀涂覆在厚度为25μm的铝箔上,涂覆宽度为160mm,敷料双面面密度为362.7g/m2(以电极敷料的干重为基准,添加剂的含量为14重量%),然后在110℃下烘干,得到正极极片。The positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 μm, the coating width was 160 mm, and the double-sided surface density of the dressing was 362.7 g/m 2 (the content of the additive was 14% by weight based on the dry weight of the electrode dressing). Then, it was dried at 110 ° C to obtain a positive electrode tab.
实施例12Example 12
按照实施例1的方法制备锂离子电池A12,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化钇(Y(OH)3)粉末。A lithium ion battery A12 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with yttrium hydroxide (Y(OH) 3 ) powder.
实施例13Example 13
按照实施例1的方法制备锂离子电池A13,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化钪(Sc(OH)3)粉末。A lithium ion battery A13 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with strontium hydroxide (Sc(OH) 3 ) powder.
实施例14Example 14
按照实施例1的方法制备锂离子电池A14,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化锆(Zr(OH)4)粉末。A lithium ion battery A14 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with zirconium hydroxide (Zr(OH) 4 ) powder.
实施例15Example 15
按照实施例1的方法制备锂离子电池A15,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化钒(V(OH)3)粉末。A lithium ion battery A15 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with vanadium hydroxide (V(OH) 3 ) powder.
实施例16Example 16
按照实施例1的方法制备锂离子电池A16,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化镧(La(OH)3)粉末。A lithium ion battery A16 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with lanthanum hydroxide (La(OH) 3 ) powder.
实施例17 Example 17
按照实施例1的方法制备锂离子电池A17,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化铈(Ce(OH)3)粉末。A lithium ion battery A17 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with a cerium hydroxide (Ce(OH) 3 ) powder.
实施例18Example 18
按照实施例1的方法制备锂离子电池A18,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化钕(Nd(OH)3)粉末。A lithium ion battery A18 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with a cerium hydroxide (Nd(OH) 3 ) powder.
实施例19Example 19
按照实施例1的方法制备锂离子电池A19,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化钐(Sm(OH)3)粉末。A lithium ion battery A19 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with barium hydroxide (Sm(OH) 3 ) powder.
实施例20Example 20
按照实施例1的方法制备锂离子电池A20,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化钆(Gd(OH)3)粉末。A lithium ion battery A20 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with a barium hydroxide (Gd(OH) 3 ) powder.
实施例21Example 21
按照实施例1的方法制备锂离子电池A21,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化铒(Er(OH)3)粉末。A lithium ion battery A21 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with strontium hydroxide (Er(OH) 3 ) powder.
实施例22Example 22
按照实施例1的方法制备锂离子电池A22,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化铌(Nb(OH)5)粉末。A lithium ion battery A22 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with a cerium hydroxide (Nb(OH) 5 ) powder.
实施例23Example 23
按照实施例1的方法制备锂离子电池A23,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化铬(Cr(OH)3)粉末。A lithium ion battery A23 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with chromium (Cr(OH) 3 ) powder.
实施例24Example 24
按照实施例1的方法制备锂离子电池A24,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化钼(Mo(OH)3)粉末。A lithium ion battery A24 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with a molybdenum hydroxide (Mo(OH) 3 ) powder.
实施例25Example 25
按照实施例1的方法制备锂离子电池A25,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化亚锰(Mn(OH)2)粉末。A lithium ion battery A25 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with manganese hydroxide (Mn(OH) 2 ) powder.
实施例26Example 26
按照实施例1的方法制备锂离子电池A26,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化铁(Fe(OH)3)粉末。A lithium ion battery A26 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with iron hydroxide (Fe(OH) 3 ) powder.
实施例27Example 27
按照实施例1的方法制备锂离子电池A27,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化亚钴(Co(OH)2)粉末。A lithium ion battery A27 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with cobalt oxychloride (Co(OH) 2 ) powder.
实施例28Example 28
按照实施例1的方法制备锂离子电池A28,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化亚镍(Ni(OH)2)粉末。A lithium ion battery A28 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with nickel oxyhydroxide (Ni(OH) 2 ) powder.
实施例29 Example 29
按照实施例1的方法制备锂离子电池A29,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化锡(Sn(OH)4)粉末。A lithium ion battery A29 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with tin (Sn(OH) 4 ) powder.
实施例30Example 30
按照实施例1的方法制备锂离子电池A30,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化铋(Bi(OH)3)粉末。A lithium ion battery A30 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with bismuth hydroxide (Bi(OH) 3 ) powder.
实施例31Example 31
按照实施例1的方法制备锂离子电池A31,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化锑(Sb(OH)3)粉末。A lithium ion battery A31 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with strontium hydroxide (Sb(OH) 3 ) powder.
实施例32Example 32
按照实施例1的方法制备锂离子电池A32,不同的是,步骤(1)中,将氢氧化铝粉末替换为硼酸(B(OH)3)粉末。A lithium ion battery A32 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with a boric acid (B(OH) 3 ) powder.
实施例33Example 33
按照实施例1的方法制备锂离子电池A33,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化铍(Be(OH)2)粉末。A lithium ion battery A33 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with barium hydroxide (Be(OH) 2 ) powder.
实施例34Example 34
按照实施例1的方法制备锂离子电池A34,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化镁(Mg(OH)2)粉末。A lithium ion battery A34 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with magnesium hydroxide (Mg(OH) 2 ) powder.
实施例35Example 35
按照实施例1的方法制备锂离子电池A35,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化铜(Cu(OH)2)粉末。A lithium ion battery A35 was prepared in the same manner as in Example 1, except that in the step (1), the aluminum hydroxide powder was replaced with copper hydroxide (Cu(OH) 2 ) powder.
实施例36Example 36
按照实施例1的方法制备锂离子电池A36,不同的是,步骤(1)中,将氢氧化铝粉末替换为氢氧化锌(Zn(OH)2)粉末。A lithium ion battery A36 was prepared in the same manner as in Example 1 except that in the step (1), the aluminum hydroxide powder was replaced with zinc hydroxide (Zn(OH) 2 ) powder.
对比例1Comparative example 1
按照实施例1的方法制备锂离子电池D1,不同的是,步骤(1)中,未添加氢氧化铝粉末添加剂,得到正极活性物质浆料,将该正极活性物质浆料均匀涂覆在厚度为25μm的铝箔上,涂覆宽度为160mm,敷料双面面密度为311.9g/m2(以烘干后的重量计),然后在110℃下烘干,得到正极极片。A lithium ion battery D1 was prepared according to the method of Example 1, except that in the step (1), the aluminum hydroxide powder additive was not added to obtain a positive electrode active material slurry, and the positive electrode active material slurry was uniformly coated to a thickness of On a 25 μm aluminum foil, the coating width was 160 mm, the double-sided surface density of the dressing was 311.9 g/m 2 (based on the weight after drying), and then dried at 110 ° C to obtain a positive electrode tab.
对比例2Comparative example 2
按照实施例2的方法制备锂离子电池D2,不同的是,步骤(1)中,得到正极极片之后,在制备添加剂浆料时未加入原硅酸Si(OH)4粉末添加剂,具体地,先以2500g去离子水为溶剂,将PTFE乳液粘结剂D210分散,得到粘结剂的乳液,将该乳液均匀涂覆在上述正极极片表面,涂覆宽度为162mm,以覆盖住活性物质,敷料双面面密度为24.6g/m2(以烘干后的重量计),然后在100℃下烘干。The lithium ion battery D2 was prepared according to the method of Example 2, except that in the step (1), after the positive electrode tab was obtained, the original silicic acid Si(OH) 4 powder additive was not added in the preparation of the additive slurry, specifically, First, the PTFE emulsion binder D210 was dispersed in 2500 g of deionized water as a solvent to obtain an emulsion of the binder, and the emulsion was uniformly coated on the surface of the above positive electrode sheet to have a coating width of 162 mm to cover the active material. The double side density of the dressing was 24.6 g/m 2 (based on the weight after drying) and then dried at 100 °C.
对比例3Comparative example 3
按照实施例3的方法制备锂离子电池D3,不同的是,步骤(1)中,在制备添加剂浆料时未加入氢氧化钛Ti(OH)4粉末添加剂,具体地,先以2500g NMP为溶剂,将45g粘结剂HSV900溶解, 得到粘结剂的溶液,然后将45g导电剂Super-P与上述粘结剂的溶液混合,之后搅拌形成均匀的浆料;A lithium ion battery D3 was prepared according to the method of Example 3, except that in the step (1), the titanium hydroxide Ti(OH) 4 powder additive was not added in the preparation of the additive slurry, specifically, 2500 g of NMP was used as a solvent. Dissolving 45 g of the binder HSV900 to obtain a solution of the binder, and then mixing 45 g of the conductive agent Super-P with the solution of the above binder, followed by stirring to form a uniform slurry;
将上述浆料均匀涂覆在厚度为25μm的铝箔上,涂覆宽度为162mm,得到的敷料双面面密度为25.8g/m2(以烘干后的重量计),然后在120℃下烘干,得到处理过的铝箔;The above slurry was uniformly coated on an aluminum foil having a thickness of 25 μm to a coating width of 162 mm, and the obtained dressing had a double-sided surface density of 25.8 g/m 2 (based on the weight after drying), and then baked at 120 ° C. Dry, obtained treated aluminum foil;
将21750g钴酸锂LiCoO2正极材料、750g粘结剂HSV900、750g导电剂碳纳米管混合,具体方法为:先以25000g NMP为溶剂,将粘结剂HSV900溶解,并在搅拌下分别将钴酸锂LiCoO2正极材料、导电剂碳纳米管与上述粘结剂的溶液混合,之后搅拌形成均匀的活性物质浆料;21750g lithium cobalt oxide LiCoO 2 cathode material, 750g binder HSV900, 750g conductive carbon nanotubes are mixed by the method of dissolving the binder HSV900 with 25000g NMP as solvent, and respectively adding cobalt acid under stirring a lithium LiCoO 2 positive electrode material, a conductive agent carbon nanotube is mixed with a solution of the above binder, and then stirred to form a uniform active material slurry;
将该活性物质浆料均匀涂覆在处理过的铝箔表面,涂覆宽度为160mm,敷料双面面密度为311.9g/m2,然后在120℃下烘干,得到铝箔处理过的正极极片。The active material slurry was uniformly coated on the surface of the treated aluminum foil, the coating width was 160 mm, the double-sided surface density of the dressing was 311.9 g/m 2 , and then dried at 120 ° C to obtain an aluminum foil-treated positive electrode sheet. .
试验例Test case
单体电池的滥用测试Single cell abuse test
1、过充测试1, overcharge test
将单体电池(包括实施例1-36制得的锂离子电池A1-A36以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至8.5V,并在8.5V的电压下恒压保持1小时,观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表1。The single cells (including the lithium ion batteries A1-A36 prepared in Examples 1-36 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 8.5 V, and at 8.5 V. The constant pressure was maintained for 1 hour under voltage, and the phenomenon during the process was observed and recorded. Each of the 30 single cells was tested in parallel. The results are shown in Table 1.
2、30%挤压测试2, 30% extrusion test
将单体电池(包括实施例1-36制得的锂离子电池A1-A36以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至4.25V,并在4.25V的电压下恒压充电直至电流小于1.5A。用两块半径为75mm的半圆柱体的端面从垂直于电池极片方向挤压电池,挤压速度为5mm/s,直至电池变形量达到30%,挤压完成后停留一小时,观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表2。The single cells (including the lithium ion batteries A1-A36 prepared in Examples 1-36 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A. Extend the battery from the end face of the semi-cylindrical body with a radius of 75 mm from the direction perpendicular to the pole piece of the battery. The extrusion speed is 5 mm/s until the deformation of the battery reaches 30%. After the extrusion is completed, stay for one hour, observe and record. The phenomenon in the process. Each of the 30 single cells was tested in parallel. The results are shown in Table 2.
3、50%挤压测试3, 50% extrusion test
将单体电池(包括实施例1-36制得的锂离子电池A1-A36以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至4.25V,并在4.25V的电压下恒压充电直至电流小于1.5A。用两块半径为75mm的半圆柱体的端面从垂直于电池极片方向挤压电池,挤压速度为5mm/s,直至电池变形量达到50%,挤压完成后停留一小时,观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表3。The single cells (including the lithium ion batteries A1-A36 prepared in Examples 1-36 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A. Extend the battery from the end face of the semi-cylindrical body with a radius of 75 mm from the direction perpendicular to the pole piece of the battery. The extrusion speed is 5 mm/s until the deformation of the battery reaches 50%. After the extrusion is completed, it is allowed to stand for one hour, observe and record. The phenomenon in the process. Each of the 30 single cells was tested in parallel. The results are shown in Table 3.
4、针刺测试4, acupuncture test
将单体电池(包括实施例1-36制得的锂离子电池A1-A36以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至4.25V,并在4.25V的电压下恒压充电直至电流小于1.5A。用直径为6毫米的钉子沿垂直于电池长宽面的方向,以25mm/s的速度匀速穿过电池,并停留一小时,观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表4。The single cells (including the lithium ion batteries A1-A36 prepared in Examples 1-36 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A. A 6 mm diameter nail was passed through the battery at a rate of 25 mm/s in a direction perpendicular to the long and wide faces of the battery, and allowed to stand for one hour to observe and record the phenomenon during the process. Each of the 30 single cells was tested in parallel. The results are shown in Table 4.
表1Table 1
Figure PCTCN2016113704-appb-000001
Figure PCTCN2016113704-appb-000001
Figure PCTCN2016113704-appb-000002
Figure PCTCN2016113704-appb-000002
表2Table 2
Figure PCTCN2016113704-appb-000003
Figure PCTCN2016113704-appb-000003
Figure PCTCN2016113704-appb-000004
Figure PCTCN2016113704-appb-000004
表3table 3
Figure PCTCN2016113704-appb-000005
Figure PCTCN2016113704-appb-000005
Figure PCTCN2016113704-appb-000006
Figure PCTCN2016113704-appb-000006
表4Table 4
Figure PCTCN2016113704-appb-000007
Figure PCTCN2016113704-appb-000007
Figure PCTCN2016113704-appb-000008
Figure PCTCN2016113704-appb-000008
将表1-4中各实施例和对比例的数据比较可知,在制备正极或负极时引入本发明的添加剂,能够明显提高由此制备得到的锂离子电池的安全性。Comparing the data of the respective examples and comparative examples in Tables 1-4, it is understood that the introduction of the additive of the present invention in the preparation of the positive electrode or the negative electrode can significantly improve the safety of the lithium ion battery thus prepared.
将表1-4中实施例1与实施例9-11的结果比较可知,在正极或负极中,以电极敷料的干重为基准,添加剂的含量为5-9重量%时,能够进一步提高由此制备得到的锂离子电池的安全性,而当添加剂用量进一步增加时还能够进一步提高制备得到的锂离子电池在极苛刻条件下的安全性。Comparing the results of Example 1 and Example 9-11 in Tables 1-4, it can be seen that the positive electrode or the negative electrode can be further improved by the content of the additive in the range of 5 to 9 % by weight based on the dry weight of the electrode dressing. The safety of the prepared lithium ion battery can further improve the safety of the prepared lithium ion battery under extremely severe conditions when the amount of the additive is further increased.
将表1-4中实施例1-4与实施例12-36的结果比较可知,所述添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种时,能够进一步提高制备得到的锂离子电池的安全性。Comparing the results of Examples 1-4 in Tables 1-4 with Examples 12-36, it can be seen that when the additive is at least one of aluminum hydroxide, ortho silicic acid and titanium hydroxide, the prepared preparation can be further improved. The safety of lithium-ion batteries.
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节, 在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical idea of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications are all within the scope of the present invention.
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。It should be further noted that the specific technical features described in the above specific embodiments may be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention has various possibilities. The combination method will not be described separately.
此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。 In addition, any combination of various embodiments of the invention may be made as long as it does not deviate from the idea of the invention, and it should be regarded as the disclosure of the invention.

Claims (13)

  1. 一种添加剂在制备锂离子电池正极和/或负极中的应用,其特征在于,所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0。The use of an additive for preparing a positive electrode and/or a negative electrode of a lithium ion battery, wherein the additive is M(OH) a , wherein M is a metal element of group IIA, a metal element of group IB, a metal element of group IIB, Group IIIB metal elements, Group IVB metal elements, Group VB metal elements, Group VIB metal elements, Group VIIB metal elements, Group VIII metal elements, Group IIIA metal elements, Group IVA metal elements, Group VA metal elements, silicon and boron At least one element, a>0.
  2. 根据权利要求1所述的应用,其中,所述IIA族金属元素为Be和/或Mg,所述IB族金属元素为Cu,所述IIB族金属元素为Zn,所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种,所述IVB族金属元素为Ti和/或Zr,所述VB族金属元素为V和/或Nb,所述VIB族金属元素为Cr和/或Mo,所述VIIB族金属元素为Mn,所述VIII族金属元素为Fe、Co和Ni中的至少一种,所述IIIA族金属元素为Al,所述IVA族金属元素为Sn,所述VA族金属元素为Bi和/或Sb;The use according to claim 1, wherein the Group IIA metal element is Be and/or Mg, the Group IB metal element is Cu, the Group IIB metal element is Zn, and the Group IIIB metal element is Y. At least one of Sc, La, Ce, Nd, Sm, Gd, and Er, the Group IVB metal element is Ti and/or Zr, and the Group VB metal element is V and/or Nb, the VIB family The metal element is Cr and/or Mo, the Group VIIB metal element is Mn, the Group VIII metal element is at least one of Fe, Co and Ni, the Group IIIA metal element is Al, the Group IVA metal The element is Sn, and the VA group metal element is Bi and/or Sb;
    优选地,所述添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种。Preferably, the additive is at least one of aluminum hydroxide, ortho silicic acid and titanium hydroxide.
  3. 根据权利要求1或2所述的应用,其中,在正极或负极中,以电极敷料的干重为基准,所述添加剂的含量为0.05-25重量%,优选为2-14重量%,进一步优选为5-9重量%。The use according to claim 1 or 2, wherein in the positive electrode or the negative electrode, the content of the additive is 0.05 to 25% by weight, preferably 2 to 14% by weight, based on the dry weight of the electrode dressing, further preferably It is 5-9 wt%.
  4. 一种锂离子电池电极浆料,其特征在于,所述电极浆料包括活性物质、粘结剂、导电剂、添加剂、溶剂和任选的增稠剂,以所述活性物质的重量为基准,所述添加剂的含量为0.05-42重量%,优选为2-18重量%,进一步优选为6-11重量%;所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0;A lithium ion battery electrode slurry, characterized in that the electrode paste comprises an active material, a binder, a conductive agent, an additive, a solvent and an optional thickener, based on the weight of the active material, The additive is contained in an amount of 0.05 to 42% by weight, preferably 2 to 18% by weight, further preferably 6 to 11% by weight; the additive is M(OH) a , wherein M is a Group IIA metal element, IB group Metal element, Group IIB metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, Group IVA metal element, VA group At least one of a metal element, silicon and boron, a>0;
    优选地,以所述活性物质的重量为基准,所述粘结剂以干基计的含量为0.5-5.5重量%,所述导电剂的含量为0.5-5.5重量%,所述溶剂的含量为50-210重量%,所述增稠剂的含量为0-3重量%。Preferably, the binder is contained in an amount of 0.5 to 5.5% by weight on a dry basis, and the content of the conductive agent is 0.5 to 5.5% by weight based on the weight of the active material, and the content of the solvent is 50-210% by weight, the thickener is present in an amount of from 0 to 3% by weight.
  5. 根据权利要求4所述的锂离子电池电极浆料,其中,所述IIA族金属元素为Be和/或Mg,所述IB族金属元素为Cu,所述IIB族金属元素为Zn,所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种,所述IVB族金属元素为Ti和/或Zr,所述VB族金属元素为V和/或Nb,所述VIB族金属元素为Cr和/或Mo,所述VIIB族金属元素为Mn,所述VIII族金属元素为Fe、Co和Ni中的至少一种,所述IIIA族金属元素为Al,所述IVA族金属元素为Sn,所述VA族金属元素为Bi和/或Sb;优选地,所述添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种;和/或The lithium ion battery electrode slurry according to claim 4, wherein the Group IIA metal element is Be and/or Mg, the Group IB metal element is Cu, and the Group IIB metal element is Zn, the IIIB The group metal element is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er, the Group IVB metal element is Ti and/or Zr, and the VB group metal element is V and/or Nb The Group VIB metal element is Cr and/or Mo, the Group VIIB metal element is Mn, the Group VIII metal element is at least one of Fe, Co and Ni, and the Group IIIA metal element is Al, The Group IVA metal element is Sn, and the Group VA metal element is Bi and/or Sb; preferably, the additive is at least one of aluminum hydroxide, ortho silicic acid and titanium hydroxide; and/or
    所述活性物质为正极活性物质或负极活性物质,所述正极活性物质为钴酸锂、锂镍氧、锂镍钴氧、锂镍钴铝氧、锂镍钴锰氧、锂镍锰氧、锰酸锂、钒酸锂、磷酸铁锂、磷酸锰锂、磷酸锰铁锂、磷酸锰铁镍锂、磷酸锰铁钴锂、磷酸锰铁镍钴锂、磷酸钒锂和硅酸铁锂中的至少一种,所述负极活性物质为石墨、钛酸锂、硅、硬碳、锡和氧化锡中的至少一种;和/或The active material is a positive electrode active material or a negative electrode active material, and the positive electrode active material is lithium cobaltate, lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, manganese. At least one of lithium acid, lithium vanadate, lithium iron phosphate, lithium manganese phosphate, lithium iron phosphate, lithium manganese iron iron phosphate, lithium manganese iron cobalt cobalt, lithium manganese iron cobalt cobalt, lithium vanadium phosphate and lithium iron silicate In one aspect, the anode active material is at least one of graphite, lithium titanate, silicon, hard carbon, tin, and tin oxide; and/or
    所述粘结剂为聚丙烯酰胺、聚偏二氟乙烯、聚四氟乙烯、丁苯橡胶、纤维素基聚合物、聚乙烯醇、聚烯烃、氟化橡胶和聚胺酯中的至少一种;和/或The binder is at least one of polyacrylamide, polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, fluorinated rubber, and polyurethane; /or
    所述导电剂为科琴黑、乙炔黑、石墨烯、碳纳米管、碳纤维、微晶石墨和导电碳黑中的至少一种;和/或The conductive agent is at least one of Ketchen Black, acetylene black, graphene, carbon nanotubes, carbon fiber, microcrystalline graphite, and conductive carbon black; and/or
    所述溶剂为N-甲基吡咯烷酮、去离子水、四氢呋喃、二甲基亚砜、乙醇和异丙醇中的至少一种;和/或The solvent is at least one of N-methylpyrrolidone, deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol, and isopropanol; and/or
    所述增稠剂为羧甲基纤维素钠、聚乙烯吡咯烷酮、聚乙二醇和聚乙烯醇中的至少一种。The thickener is at least one of sodium carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.
  6. 一种添加剂浆料,其特征在于,所述添加剂浆料包括粘结剂、添加剂、溶剂和任选的导电剂,以所述添加剂的重量为基准,所述粘结剂以干基计的含量为0.5-11重量%,所述溶剂的含量为90-410 重量%,所述导电剂的含量为0-11重量%;所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0。An additive slurry, characterized in that the additive slurry comprises a binder, an additive, a solvent and an optional conductive agent, the binder being content on a dry basis based on the weight of the additive. It is 0.5 to 11% by weight, the solvent is contained in an amount of 90 to 410% by weight, the conductive agent is contained in an amount of 0 to 11% by weight; the additive is M(OH) a , wherein M is a Group IIA metal element , Group IB metal elements, Group IIB metal elements, Group IIIB metal elements, Group IVB metal elements, Group VB metal elements, Group VIB metal elements, Group VIIB metal elements, Group VIII metal elements, Group IIIA metal elements, Group IVA metal elements At least one of a group VA metal element, silicon and boron, a>0.
  7. 根据权利要求6所述的添加剂浆料,其中,所述IIA族金属元素为Be和/或Mg,所述IB族金属元素为Cu,所述IIB族金属元素为Zn,所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种,所述IVB族金属元素为Ti和/或Zr,所述VB族金属元素为V和/或Nb,所述VIB族金属元素为Cr和/或Mo,所述VIIB族金属元素为Mn,所述VIII族金属元素为Fe、Co和Ni中的至少一种,所述IIIA族金属元素为Al,所述IVA族金属元素为Sn,所述VA族金属元素为Bi和/或Sb;优选地,所述添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种;和/或The additive slurry according to claim 6, wherein the Group IIA metal element is Be and/or Mg, the Group IB metal element is Cu, the Group IIB metal element is Zn, and the Group IIIB metal element Is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er, the Group IVB metal element is Ti and/or Zr, and the Group VB metal element is V and/or Nb, The Group VIB metal element is Cr and/or Mo, the Group VIIB metal element is Mn, the Group VIII metal element is at least one of Fe, Co and Ni, and the Group IIIA metal element is Al, the IVA The group metal element is Sn, and the VA group metal element is Bi and/or Sb; preferably, the additive is at least one of aluminum hydroxide, ortho silicic acid and titanium hydroxide; and/or
    所述粘结剂为聚丙烯酰胺、聚偏二氟乙烯、聚四氟乙烯、丁苯橡胶、纤维素基聚合物、聚乙烯醇、聚烯烃、氟化橡胶和聚胺酯中的至少一种;和/或The binder is at least one of polyacrylamide, polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, fluorinated rubber, and polyurethane; /or
    所述溶剂为N-甲基吡咯烷酮、去离子水、四氢呋喃、二甲基亚砜、乙醇和异丙醇中的至少一种;和/或The solvent is at least one of N-methylpyrrolidone, deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol, and isopropanol; and/or
    所述导电剂为科琴黑、乙炔黑、石墨烯、碳纳米管、碳纤维、微晶石墨和导电碳黑中的至少一种。The conductive agent is at least one of Ketchen Black, acetylene black, graphene, carbon nanotubes, carbon fibers, microcrystalline graphite, and conductive carbon black.
  8. 一种锂离子电池正极或负极,其特征在于,所述锂离子电池正极或负极包括集流体及位于集流体上的电极敷料,所述电极敷料含有活性物质、粘结剂、导电剂、添加剂和任选的增稠剂,所述添加剂为M(OH)a,其中,M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硅和硼中的至少一种元素,a>0。A positive electrode or a negative electrode of a lithium ion battery, characterized in that the positive electrode or the negative electrode of the lithium ion battery comprises a current collector and an electrode dressing on the current collector, the electrode dressing containing an active substance, a binder, a conductive agent, an additive and An optional thickener, wherein the additive is M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element, a VB group metal element At least one of a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IIIA metal element, a group IVA metal element, a group VA metal element, silicon and boron, a>0.
  9. 根据权利要求8所述的锂离子电池正极或负极,其中,所述IIA族金属元素为Be和/或Mg,所述IB族金属元素为Cu,所述IIB族金属元素为Zn,所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种,所述IVB族金属元素为Ti和/或Zr,所述VB族金属元素为V和/或Nb,所述VIB族金属元素为Cr和/或Mo,所述VIIB族金属元素为Mn,所述VIII族金属元素为Fe、Co和Ni中的至少一种,所述IIIA族金属元素为Al,所述IVA族金属元素为Sn,所述VA族金属元素为Bi和/或Sb;优选地,所述添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种;和/或The positive electrode or negative electrode of a lithium ion battery according to claim 8, wherein the Group IIA metal element is Be and/or Mg, the Group IB metal element is Cu, and the Group IIB metal element is Zn, the IIIB The group metal element is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er, the Group IVB metal element is Ti and/or Zr, and the VB group metal element is V and/or Nb The Group VIB metal element is Cr and/or Mo, the Group VIIB metal element is Mn, the Group VIII metal element is at least one of Fe, Co and Ni, and the Group IIIA metal element is Al, The Group IVA metal element is Sn, and the Group VA metal element is Bi and/or Sb; preferably, the additive is at least one of aluminum hydroxide, ortho silicic acid and titanium hydroxide; and/or
    所述活性物质为正极活性物质或负极活性物质,所述正极活性物质为钴酸锂、锂镍氧、锂镍钴氧、锂镍钴铝氧、锂镍钴锰氧、锂镍锰氧、锰酸锂、钒酸锂、磷酸铁锂、磷酸锰锂、磷酸锰铁锂、磷酸锰铁镍锂、磷酸锰铁钴锂、磷酸锰铁镍钴锂、磷酸钒锂和硅酸铁锂中的至少一种,所述负极活性物质为石墨、钛酸锂、硅、硬碳、锡和氧化锡中的至少一种;和/或The active material is a positive electrode active material or a negative electrode active material, and the positive electrode active material is lithium cobaltate, lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, manganese. At least one of lithium acid, lithium vanadate, lithium iron phosphate, lithium manganese phosphate, lithium iron phosphate, lithium manganese iron iron phosphate, lithium manganese iron cobalt cobalt, lithium manganese iron cobalt cobalt, lithium vanadium phosphate and lithium iron silicate In one aspect, the anode active material is at least one of graphite, lithium titanate, silicon, hard carbon, tin, and tin oxide; and/or
    所述粘结剂为聚丙烯酰胺、聚偏二氟乙烯、聚四氟乙烯、丁苯橡胶、纤维素基聚合物、聚乙烯醇、聚烯烃、氟化橡胶和聚胺酯中的至少一种;和/或The binder is at least one of polyacrylamide, polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, fluorinated rubber, and polyurethane; /or
    所述导电剂为科琴黑、乙炔黑、石墨烯、碳纳米管、碳纤维、微晶石墨和导电碳黑中的至少一种;和/或The conductive agent is at least one of Ketchen Black, acetylene black, graphene, carbon nanotubes, carbon fiber, microcrystalline graphite, and conductive carbon black; and/or
    所述增稠剂为羧甲基纤维素钠、聚乙烯吡咯烷酮、聚乙二醇和聚乙烯醇中的至少一种。The thickener is at least one of sodium carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.
  10. 根据权利要求8或9所述的锂离子电池正极或负极,其中,以电极敷料的干重为基准,所述添加剂的含量为0.05-25重量%,优选为2-14重量%,进一步优选为5-9重量%。The positive electrode or the negative electrode of a lithium ion battery according to claim 8 or 9, wherein the content of the additive is from 0.05 to 25% by weight, preferably from 2 to 14% by weight, based on the dry weight of the electrode dressing, further preferably 5-9 wt%.
  11. 一种制备锂离子电池正极或负极的方法,其特征在于,所述方法包括:将权利要求4或5所述的锂离子电池电极浆料涂覆在集流体上,烘干;或者包括:A method for preparing a positive electrode or a negative electrode of a lithium ion battery, the method comprising: coating the lithium ion battery electrode slurry according to claim 4 or 5 on a current collector, drying; or comprising:
    (1)将权利要求6或7所述的添加剂浆料涂覆在集流体上,烘干,得到添加剂涂覆的集流体;(1) coating the additive slurry according to claim 6 or 7 on a current collector, and drying to obtain an additive-coated current collector;
    (2)配制活性物质浆料,所述活性物质浆料包括活性物质、粘结剂、导电剂、溶剂和任选的增 稠剂,然后将所述活性物质浆料涂覆在步骤(1)得到的添加剂涂覆的集流体上,烘干;或者包括:(2) formulating an active material slurry comprising an active material, a binder, a conductive agent, a solvent, and optionally an increase a thickener, which is then coated on the additive-coated current collector obtained in the step (1), and dried; or includes:
    (1)配制活性物质浆料,所述活性物质浆料包括活性物质、粘结剂、导电剂、溶剂和任选的增稠剂,然后将所述活性物质浆料涂覆在集流体上,烘干,得到电极极片;(1) formulating an active material slurry comprising an active material, a binder, a conductive agent, a solvent, and an optional thickener, and then coating the active material slurry on a current collector, Drying to obtain an electrode pole piece;
    (2)将权利要求6或7所述的添加剂浆料涂覆在步骤(1)得到的电极极片上,烘干。(2) The additive slurry according to claim 6 or 7 is coated on the electrode pad obtained in the step (1) and dried.
  12. 权利要求11所述的方法制备得到的锂离子电池正极或负极。A positive electrode or a negative electrode of a lithium ion battery prepared by the method of claim 11.
  13. 一种锂离子电池,其特征在于,所述锂离子电池包括电池壳体以及位于电池壳体内部的电芯组件和电解液,所述电芯组件包括正极、负极和隔膜,且所述正极为权利要求8、9、10或12所述的锂离子电池正极,和/或所述负极为权利要求8、9、10或12所述的锂离子电池负极。 A lithium ion battery, comprising: a battery case; and a cell assembly and an electrolyte located inside the battery case, the cell assembly including a positive electrode, a negative electrode and a diaphragm, and the positive electrode is The lithium ion battery positive electrode according to claim 8, 9, 10 or 12, and/or the negative electrode is the lithium ion battery negative electrode according to claim 8, 9, 10 or 12.
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CN110931786A (en) * 2019-12-11 2020-03-27 河南创力新能源科技股份有限公司 Preparation method of iron-nickel battery cathode silicate crystal material
CN111477846A (en) * 2020-03-27 2020-07-31 深圳市量能科技有限公司 High-rate nickel-metal hydride battery positive electrode and manufacturing method thereof
CN115832299A (en) * 2021-10-29 2023-03-21 宁德时代新能源科技股份有限公司 Slurry, positive pole piece, secondary battery, battery module, battery pack and electric device
CN115832207A (en) * 2022-01-05 2023-03-21 宁德时代新能源科技股份有限公司 Pole piece slurry, pole piece, preparation method of pole piece, lithium ion secondary battery, battery module, battery pack and electric device
CN115490866A (en) * 2022-10-11 2022-12-20 深圳市皓飞实业有限公司 Dispersant for polycarboxylate lithium battery
CN115490866B (en) * 2022-10-11 2024-03-22 深圳市皓飞实业有限公司 Dispersing agent for polycarboxylate lithium battery

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