WO2018098882A1

WO2018098882A1 - Application of additive, electrode slurry, additive slurry, positive electrode or negative electrode of lithium ion battery and preparation method thereof, and lithium ion battery

Info

Publication number: WO2018098882A1
Application number: PCT/CN2016/112930
Authority: WO
Inventors: 先雪峰
Original assignee: 先雪峰
Priority date: 2016-11-29
Filing date: 2016-12-29
Publication date: 2018-06-07
Also published as: CN106654277A

Abstract

An application of an additive, as well as an electrode slurry, additive slurry, a positive electrode or a negative electrode of a lithium ion battery and preparation methods thereof, and a lithium ion battery in the technical field of lithium ion batteries. An additive is applied in the preparation of a positive electrode and/or a negative electrode of a lithium ion battery, and the additive is MO_a(OH)_bCH₂O, in which M is at least one element of 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 IIIA metal element, a group IVA metal element¸ a group VA metal element, boron, and silicon, a > 0, b > 0, and c ≥ 0. The additive is used for preparation of a positive electrode and/or a negative electrode of a lithium ion battery, and can significantly improve the safety of the lithium ion battery obtained by the preparation.

Description

Application of additive, electrode slurry, additive slurry, positive or negative electrode of lithium ion battery, preparation method thereof and lithium ion battery

Technical field

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.

Background technique

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.

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.

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.

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.

Summary of the invention

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.

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 MO _a (OH) _b · cH ₂ O, wherein M is IIA Group 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, IVA At least one of a group metal element, a group VA metal element, boron and silicon, a>0, b>0, c≥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 contained in an amount of 0.05 to 51% by weight based on the weight; the additive is MO _a (OH) _b · cH ₂ O, wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, 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, boron and silicon At least one element, a>0, b>0, c≥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 10% by weight, the content of the solvent is 100 to 400% by weight, the content of the conductive agent is 0 to 10% by weight; and the additive is MO _a (OH) _b · cH ₂ O , 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, a Group VIB metal element, a Group VIIB metal element, a Group VIII metal element, At least one of a Group IIIA metal element, a Group IVA metal element, a Group VA metal element, boron and silicon, a>0, b>0, c≥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 MO _a (OH) _b · cH ₂ O, 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, boron and silicon, a>0, b>0, c≥0.

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 a lithium ion battery electrode slurry of the present invention on a current collector, and drying; or

(1) coating the additive slurry of the present invention on a current collector, and drying to obtain an additive-coated current collector;

(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 resulting additive-coated current collector; or

(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) The additive slurry of the present invention is coated on the electrode pole piece obtained in the step (1) and dried.

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.

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.

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.

Other features and advantages of the invention will be described in detail in the detailed description which follows.

detailed description

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.

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.

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 MO _a (OH) _b · cH ₂ O, 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, boron and silicon, a>0, b>0, c≥0.

Among them, it should be understood by those skilled in the art that in MO _a (OH) _b · cH ₂ O, the choice of a and b conforms to the stoichiometric principle of the corresponding substance.

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.

In the application of the present invention, the additive may be one or more of the foregoing various oxyhydroxides, 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 oxyhydroxide, metasilicate, and titanium oxyhydroxide.

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 30% by weight based on the dry weight of the electrode dressing, and further preferably 3 to 15% by weight in view of battery energy density and overall battery performance. More preferably, it is 6-10% by 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.

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.

Preferably, the content of the additive is from 3 to 19% by weight, further preferably from 7 to 12% by weight, based on the weight of the active material.

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.

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 oxyhydroxide, metasilicate, and titanium oxyhydroxide.

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.

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 by weight on a dry basis. The content of the conductive agent is from 0.5 to 5% by weight, the content of the solvent is from 55 to 200% by weight, and the content of the thickener is from 0 to 2.5% 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 2.5% by weight based on the weight of the active material.

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.

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.

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.

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).

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.

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.

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. .

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 10% by weight, the content of the solvent is 100 to 400% by weight, the content of the conductive agent is 0 to 10% by weight; and the additive is MO _a (OH) _b · cH ₂ O 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, a Group VIB metal element, a Group VIIB metal element, a Group VIII metal element, At least one of a Group IIIA metal element, a Group IVA metal element, a Group VA metal element, boron and silicon, a>0, b>0, c≥0.

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.

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 oxyhydroxide, metasilicate, and titanium oxyhydroxide.

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.

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.

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.

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.

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.

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.

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, it is preferable that the additive is at least one of aluminum oxyhydroxide, metasilicate, and titanium oxyhydroxide.

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.

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.

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.

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.

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 30% by weight, further preferably 3 to 15% by weight, still more preferably 6 to 10% by weight.

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.

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.

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.

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% by weight, the content of the conductive agent is from 0.5 to 5% by weight, and the content of the solvent is from 55 to 200% by weight.

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 content of the binder on a dry basis is from 0.5 to 5% by weight, the content of the conductive agent is from 0.5 to 5% by weight, the content of the thickener is from 0.5 to 2.5% by weight, and the content of the solvent is 55. -200% by weight.

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.

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.

In a sixth aspect, the present invention provides a positive or negative electrode of a lithium ion battery prepared by the method.

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.

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.

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.

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.

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.

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.

Example

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.

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.

Boehmite (AlOOH) powder was purchased from Xuancheng Jingrui New Material Co., Ltd., and the medium particle diameter D50 was 800 nm.

The silicic acid (SiO _0.95 (OH) _2.1 ) powder was purchased from Sinopharm Chemical Reagent Co., Ltd., and the water was used as a dispersing agent. The medium particle size D50 was adjusted to 1 μm by wet bead milling, and then dried by spray drying. The water was removed to finally obtain a dried metasilicate (SiO _0.95 (OH) _2.1 ) powder having a medium particle diameter D50 of 1 μm.

The titanium oxyhydroxide TiO(OH) ₂ powder was purchased from Hangzhou Wanjing New Material Co., Ltd., and the medium particle diameter D50 was 150 nm.

The preparation method of bismuth oxyhydroxide 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 of adding ammonia was controlled to be 2 hours. After the reaction was completed, a cerium hydroxide precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and then water was added to the precursor to prepare a 50% by weight suspension, which was added to the hydrothermal reaction vessel and maintained at 200 ° C. After hours, yttrium oxyhydroxide (YOOH·0.12H ₂ O) was obtained, and finally, dried cerium oxyhydroxide (YOOH·0.12H ₂ O) particles were obtained by spray drying, and the particle diameter D50 was found to be 150 nm.

The preparation method of bismuth oxyhydroxide 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 of adding ammonia was controlled to be 2 hours. After the reaction was completed, a cerium hydroxide precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and then water was added to the precursor to prepare a 50% by weight suspension, which was added to the hydrothermal reaction vessel and maintained at 220 ° C. After hours, cerium oxyhydroxide (ScOOH) was obtained, and finally, dried cerium oxyhydroxide (ScOOH) particles were obtained by spray drying, and the particle diameter D50 was found to be 180 nm.

Zirconium oxyhydroxide (ZrO(OH) ₂ ) powder was purchased from Xuancheng Jingrui New Material Co., Ltd., and the medium particle diameter D50 was 25 nm.

The preparation method of vanadium oxyhydroxide comprises: dissolving 12.2 kg of anhydrous sodium metavanadate in 100 kg of deionized water to prepare a sodium metavanadate solution, and gradually adding a mass fraction of 98 to the sodium metavanadate solution under stirring. % concentrated sulfuric acid until the pH of the reaction system was 1.7, and the time for controlling the concentrated sulfuric acid was 5 minutes. The solution was then heated to boiling and maintained for 3 hours to give a vanadium oxyhydroxide precipitate. The vanadium oxyhydroxide precipitate was washed with deionized water to remove sodium sulfate therefrom, and finally dried vanadium oxyhydroxide (VO _2.3 (OH) _0.4 ) particles were obtained by spray drying, and the particle diameter D50 was found to be 320 nm.

The preparation method of bismuth oxyhydroxide comprises: dissolving 58.5 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 of adding ammonia was controlled to be 2 hours. After the reaction was completed, a cerium hydroxide precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therefrom, and then water was added to the precursor to prepare a 50% by weight suspension, and the suspension was added to a hydrothermal reaction kettle to maintain 8 at 200 ° C. After hours, bismuth oxyhydroxide (LaOOH·0.38H ₂ O) was obtained, and finally, dried cerium oxyhydroxide (LaOOH·0.38H ₂ O) particles were obtained by spray drying, and the particle diameter D50 was found to be 410 nm.

The preparation method of bismuth oxyhydroxide 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 System pH is 7.3, control The time of adding ammonia was 2 hours, and after completion of the reaction, a cerium hydroxide precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and then water was added to the precursor to prepare a 50% by weight suspension, and the suspension was added to the hydrothermal reaction vessel to maintain 10 at 220 ° C. After hours, cerium oxyhydroxide (CeOOH) was obtained, and finally dried cerium oxyhydroxide (CeOOH) particles were obtained by spray drying, and the particle diameter D50 was found to be 730 nm.

The preparation method of bismuth oxyhydroxide 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 of adding ammonia was controlled to be 2 hours. After the reaction was completed, a cerium hydroxide precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and then water was added to the precursor to prepare a 50% by weight suspension, and the suspension was added to the hydrothermal reaction vessel to maintain 10 at 220 ° C. After hours, hydroxy cerium oxide (NdOOH) was obtained, and finally dried cerium oxyhydroxide (NdOOH) particles were obtained by spray drying, and the particle diameter D50 was found to be 650 nm.

The preparation method of bismuth oxyhydroxide 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 of adding ammonia was controlled to be 2 hours. After the reaction was completed, a cerium hydroxide precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and then water was added to the precursor to prepare a 50% by weight suspension, and the suspension was added to the hydrothermal reaction vessel to maintain 10 at 220 ° C. After hours, bismuth oxyhydroxide (SmOOH) was obtained, and finally dried cerium oxyhydroxide (SmOOH) particles were obtained by spray drying, and the particle diameter D50 was found to be 540 nm.

The preparation method of bismuth oxyhydroxide 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 of adding ammonia was controlled to be 2 hours. After the reaction was completed, a cerium hydroxide precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and then water was added to the precursor to prepare a 50% by weight suspension, and the suspension was added to the hydrothermal reaction vessel to maintain 10 at 220 ° C. After hours, bismuth oxyhydroxide (GdOOH) was obtained, and finally dried cerium oxyhydroxide (GdOOH) particles were obtained by spray drying, and the particle diameter D50 was found to be 500 nm.

The preparation method of bismuth oxyhydroxide 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 of adding ammonia was controlled to be 2 hours. After the reaction was completed, a cerium hydroxide precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and then water was added to the precursor to prepare a 50% by weight suspension, and the suspension was added to the hydrothermal reaction vessel to maintain 10 at 220 ° C. After hours, cerium oxyhydroxide (ErOOH) was obtained, and finally, dried cerium oxyhydroxide (ErOOH) particles were obtained by spray drying, and the particle diameter D50 was found to be 250 nm.

The preparation method of bismuth oxyhydroxide comprises: heat-treating yttrium hydroxide (Nb(OH) ₅ ) powder (purchased from Beijing Haoke Technology Co., Ltd.) at 200 ° C for 3 hours under an air atmosphere to obtain bismuth oxyhydroxide (NbO (OH) ₃ ), and using water as a dispersant, the medium particle size D50 is adjusted to 1.2 μm by wet bead milling, and the free water is removed by spray drying to finally obtain a dried hydroxyl group having a medium particle diameter D50 of 1.2 μm. Yttrium oxide (NbO(OH) ₃ ) powder.

The preparation method of chromium oxyhydroxide comprises: dissolving 40.0 kg of chromium nitrate non-hydrate in 150 kg of deionized water to prepare a chromium nitrate solution, and gradually adding ammonia water having a mass fraction of 25% 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, a chromium hydroxide precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and then water was added to the precursor to prepare a 50% by weight suspension, and the suspension was added to a hydrothermal reaction vessel to maintain 10 at 150 ° C. After hours, chromium oxyhydroxide (CrO _0.5 (OH) ₂ ) was obtained, and finally, dried chromium oxyhydroxide (CrO _0.5 (OH) ₂ ) particles were obtained by spray drying, and the particle diameter D50 was found to be 120 nm.

Molybdenum oxyhydroxide (MoO ₂ (OH) ₂ ) powder was purchased from Hidaka Co., Ltd., and water was used as a dispersant. The medium particle size D50 was adjusted to 1.5 μm by wet bead milling, and then free water was spray dried. After removal, a dried powder of molybdenum oxyhydroxide (MoO ₂ (OH) ₂ ) having a medium particle diameter D50 of 1.5 μm was finally obtained.

The preparation method of manganese oxyhydroxide 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. The mass fraction was 25% ammonia until the pH of the reaction system was 7.3, and the time for controlling the addition of ammonia was 2 hours. After the reaction was completed, a manganese oxyhydroxide (Mn(OH) ₂ ) precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and dried to obtain a dried manganese oxyhydroxide (Mn(OH) ₂ ) precursor by spray drying. The precursor was heat-treated at 180 ° C for 12 hours in an air atmosphere to finally obtain a manganese oxyhydroxide (MnOOH) powder, and the particle diameter D50 was found to be 850 nm.

The preparation method of iron oxyhydroxide comprises: dissolving 40.4 kg of ferric nitrate non-aqueous water in 150 kg of deionized water to prepare a ferric nitrate solution, and gradually adding ammonia water having a mass fraction of 25% to the ferric 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, and a precipitate was obtained after the reaction was completed. The precipitate was washed with deionized water to remove ammonium nitrate therein, and iron oxyhydroxide (FeO _0.45 (OH) _2.1 ) powder was obtained by spray drying, and the particle diameter D50 was found to be 220 nm.

The preparation method of cobalt oxyhydroxide 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 of the reaction system was 7.3, and the time for controlling the addition of ammonia was 2 hours. After the reaction, a cobalt oxyhydroxide (Co(OH) ₂ ) precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and dried by spray drying to obtain a dried cobalt (Co(OH) ₂ ) precursor. The precursor was heat-treated at 180 ° C for 12 hours in an air atmosphere to finally obtain a cobalt oxyhydroxide (CoOOH) powder, and the particle diameter D50 was found to be 670 nm.

The preparation method of nickel oxyhydroxide 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 of the reaction system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, a nickel oxyhydroxide (Ni(OH) ₂ ) precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and dried by spray drying to obtain a dried nickel oxyhydroxide (Ni(OH) ₂ ) precursor. The precursor was heat-treated at 180 ° C for 18 hours in an air atmosphere to finally obtain a nickel oxyhydroxide (NiOOH) powder, and the particle diameter D50 was found to be 580 nm.

The preparation method of the tin oxyhydroxide comprises: dissolving 35.1 kg of tin tetrachloride pentahydrate in 150 kg of deionized water to prepare a tin tetrachloride solution, and gradually adding a mass fraction of 25 to the tin tetrachloride solution under stirring. % ammonia water until the pH of the reaction system is 7.3, and the time for controlling the addition of ammonia is 2 hours. After the reaction is completed, a tin hydroxide precursor is obtained. The precursor was washed with deionized water to remove ammonium chloride therein, and then water was added to the precursor to prepare a 50% by weight suspension, which was added to the hydrothermal reaction vessel and maintained at 160 ° C. After 10 hours, tin oxyhydroxide (SnO(OH) ₂ ) was obtained, and finally, dried tin oxyhydroxide (SnO(OH) ₂ ) particles were obtained by spray drying, and the particle diameter D50 was found to be 100 nm.

The bismuth oxyhydroxide was prepared by heat-treating bismuth hydroxide (Bi(OH) ₃ ) powder (purchased from Xi'an Wanjie Chemical Co., Ltd.) at 110 ° C for 15 hours under an air atmosphere to obtain bismuth oxyhydroxide (BiOOH) powder. The particle diameter D50 was measured to be 1.4 μm.

The preparation method of bismuth oxyhydroxide comprises: slowly adding 22.8 kg of antimony trichloride powder to 150 kg of deionized water under stirring to obtain a suspension, and then gradually adding ammonia water having a mass fraction of 25% to the suspension 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, a cerium hydroxide precursor was obtained. The precursor was washed with deionized water to remove ammonium chloride therein, and then water was added to the precursor to prepare a 50% by weight suspension, which was added to the hydrothermal reaction vessel and maintained at 160 ° C. After 10 hours, bismuth oxyhydroxide (SbOOH) was obtained, and finally dried cerium oxyhydroxide (SbOOH) particles were obtained by spray drying, and the particle diameter D50 was measured to be 90 nm.

Boron oxyhydroxide was prepared as follows: Boric acid (B(OH) ₃ ) powder was purchased from Tianjin Zhonghe Shengtai Chemical Co., Ltd., using isopropanol as dispersant, and the medium particle size D50 was adjusted to 1.5 by wet bead milling. The isopropyl alcohol was removed by spray drying to obtain a dried boric acid powder having a medium particle diameter D50 of 1.5 μm. This was heat-treated at 110 ° C for 5 hours in an air atmosphere to obtain a dried boron oxyhydroxide (BO _1.2 (OH) _0.6 ) powder having a medium particle diameter D50 of 1.5 μm.

The preparation method of bismuth oxyhydroxide comprises: dissolving 18.7 kg of lanthanum nitrate trihydrate 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, a bismuth hydroxide (Be(OH) ₂ ) precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and dried by spray drying to obtain a dried bismuth hydroxide (Be(OH) ₂ ) precursor. The precursor was heat-treated at 450 ° C for 1 hour in an air atmosphere to finally obtain a bismuth oxyhydroxide (BeO _0.4 (OH) _1.2 ) powder, and the particle diameter D50 was found to be 3.3 μm.

The preparation method of magnesium oxyhydroxide 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 completion of the reaction, a magnesium hydroxide (Mg(OH) ₂ ) precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and dried by spray drying to obtain a dried magnesium hydroxide (Mg(OH) ₂ ) precursor. The precursor was heat-treated at 430 ° C for 2 hours in an air atmosphere to finally obtain a magnesium oxyhydroxide (MgO _0.5 OH) powder, and the particle diameter D50 was found to be 2.6 μm.

The preparation method of copper oxyhydroxide 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 completion of the reaction, a copper hydroxide (Cu(OH) ₂ ) precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and a dried copper hydroxide (Cu(OH) ₂ ) precursor was obtained by spray drying. The precursor was heat-treated at 430 ° C for 2 hours in an air atmosphere to finally obtain a copper oxyhydroxide (CuO _0.6 (OH) _0.8 ) powder, and the particle diameter D50 was found to be 3.0 μm.

The preparation method of zinc oxyhydroxide comprises: dissolving 29.7 kg of zinc nitrate hexahydrate in 100 kg of deionized water to obtain 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, a zinc hydroxide (Zn(OH) ₂ ) precursor was obtained. The precursor was washed with deionized water to remove ammonium nitrate therein, and dried by spray drying to obtain a dried zinc hydroxide (Zn(OH) ₂ ) precursor. The precursor was heat-treated at 450 ° C for 4 hours in an air atmosphere to finally obtain a zinc oxyhydroxide (ZnO _0.7 (OH) _0.6 ) powder, and the particle diameter D50 was found to be 3.7 μm.

Example 1

(1) Preparation of battery positive electrode sheets

Mixing 21850g lithium nickel cobalt manganese oxide LiNi _0.5 Co _0.2 Mn _0.3 O ₂ cathode material, 460g binder HSV900, 690g conductive agent Super-P and 2000g boehmite (AlOOH) powder additive, the specific method is: first 25000g NMP As a solvent, the binder HSV900 is dissolved, and the lithium nickel cobalt manganese oxide LiNi _0.5 Co _0.2 Mn _0.3 O ₂ cathode material, the conductive agent Super-P, the boehmite (AlOOH) powder additive are bonded to the above, respectively, under stirring. The solution of the agent is 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 μm, the coating width was 160 mm, and the double-sided surface density of the dressing was 333.9 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 8% by weight based on the dry weight of the electrode dressing, and then dried at 110 ° C to obtain a positive electrode tab.

(2) Preparation of battery negative pole piece

12220g natural graphite anode material, 195g thickener CMC, 195g 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;

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 165 g/m ² (based on the weight after drying, the same below), and then at 100 ° C. Drying is carried out to obtain a negative electrode tab.

(3) Assembly of single cells

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.

Example 2

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:

21850g of lithium nickel cobalt aluminum oxide LiNi _0.8 Co _0.15 Al _0.05 O ₂ cathode material, 767g PTFE emulsion binder D210, 690g 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 μm, a coating width of 160 mm, a double-sided surface density of the coating of 307.2 g/m ² (based on the weight after drying), and then dried at 100 ° C. Obtaining a positive electrode tab;

1000g of SiO _0.95 (OH) _2.1 powder additive of metasilicate and 83g of PTFE emulsion binder D210 are mixed by dispersing PTFE emulsion binder D210 with 2500g deionized water as solvent, and obtaining emulsion Mixing the metasilicate SiO _0.95 (OH) _2.1 powder additive with the emulsion of the above binder under stirring, and then 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 28.2 g/m ² (based on the dry weight of the electrode dressing, the additive The content was 8 wt%), and then dried at 100 ° C to obtain a positive electrode tab coated with an additive.

Example 3

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 titanium hydroxide TiO(OH) ₂ powder additive, 50g conductive agent Super-P, 50g binder HSV900 are mixed by: dissolving the binder HSV900 with 2500g NMP as solvent, and stirring The titanium oxyhydroxide TiO(OH) ₂ powder additive and the conductive agent Super-P are mixed with the 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 μm, a coating width of 162 mm, a double-sided surface density of the dressing of 29.6 g/m ² (based on the weight after drying), and then dried at 120 ° C. Obtaining an additive-coated aluminum foil;

21850g of lithium cobaltate LiCoO ₂ cathode material, 460g of binder HSV900, 690g of conductive carbon nanotubes are mixed by the method of dissolving the binder HSV900 with 25000g of 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 with a coating width of 160 mm, and the double-sided surface density of the dressing was 307.2 g/m ² (based on the dry weight of the electrode dressing, the additive content was 8 weights). %), and then dried at 120 ° C to obtain a positive electrode tab coated with an additive of aluminum foil.

Example 4

(1) Preparation of battery positive electrode sheets

22800g lithium nickel cobalt manganese oxide LiNi _0.5 Co _0.2 Mn _0.3 O ₂ cathode material, 480g binder HSV900, 720g 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 μm, a coating width of 160 mm, a double-sided surface density of the dressing of 307.2 g/m ² (based on the weight after drying), and then dried at 110 ° C. , the positive electrode piece is obtained.

(2) Preparation of battery negative pole piece

12220g natural graphite anode material, 195g thickener CMC, 195g conductive agent Super-P, 780g styrene-butadiene rubber latex binder and 1130g boehmite (AlOOH) powder additive are mixed, the specific method is: first 13500g deionized water As a solvent, the thickener CMC is dissolved, and the styrene-butadiene rubber latex binder, the conductive agent Super-P, the natural graphite anode material, the boehmite powder additive and the above thickener solution are respectively mixed under stirring, and then Stirring to form a uniform negative electrode slurry;

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 179.3 g/m ² (based on the dry weight of the electrode dressing, the additive content was 8 weights). %), and then dried at 100 ° C to obtain a negative electrode tab.

(3) Assembly of single cells

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.

Example 5

A lithium ion battery A5 was prepared according to the method of Example 1, except that in the step (1), 22325 g of lithium nickel cobalt manganese oxide LiNi _0.5 Co _0.2 Mn _0.3 O ₂ positive electrode material, 470 g of a binder HSV 900, and 705 g of a conductive agent Super were used. -P and 1500g Boehmite (AlOOH) 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 _0.2 Mn _0.3 O under stirring ₂ cathode material, conductive agent Super-P, boehmite (AlOOH) powder additive mixed with the solution of the above binder, 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 μm, the coating width was 160 mm, and the double-sided surface density of the dressing was 326.8 g/m ² (based on the dry weight of the electrode dressing, the content of the additive was 6% by weight). Then, it was dried at 110 ° C to obtain a positive electrode tab.

Example 6

A lithium ion battery A6 was prepared according to the method of Example 1, except that in the step (1), 21375 g of lithium nickel cobalt manganese oxide LiNi _0.5 Co _0.2 Mn _0.3 O ₂ positive electrode material, 450 g of a binder HSV 900, and 675 g of a conductive agent Super were used. -P and 2500g boehmite (AlOOH) 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 _0.2 Mn _0.3 O under stirring ₂ cathode material, conductive agent Super-P, boehmite (AlOOH) powder additive mixed with the solution of the above binder, 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 μm, a coating width of 160 mm, and a double-sided surface density of the dressing of 341.3 g/m ² (based on the dry weight of the electrode dressing, the additive content was 10% by weight) Then, it was dried at 110 ° C to obtain a positive electrode tab.

Example 7

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 25 g of the PTFE emulsion binder D210 with 1500 g of deionized water as a solvent. The emulsion was mixed with 1000 g of metasilicate SiO _0.95 (OH) _2.1 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 19.9 g/m ² (based on the dry weight of the electrode dressing, the additive The content was 6% by weight), and then dried at 100 ° C to obtain a positive electrode tab coated with an additive.

Example 8

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 150 g of the PTFE emulsion binder D210 with 3500 g of deionized water as a solvent to obtain an emulsion. And 1000 g of metasilicate SiO _0.95 (OH) _2.1 powder was mixed with the 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 37.6 g/m ² (based on the dry weight of the electrode dressing, the additive The content was 10% by weight), and then dried at 100 ° C to obtain a positive electrode tab coated with an additive.

Example 9

A lithium ion battery A9 was prepared according to the method of Example 1, except that in the step (1), 23038 g of lithium nickel cobalt manganese oxide LiNi _0.5 Co _0.2 Mn _0.3 O ₂ positive electrode material, 485 g of a binder HSV 900, and 727 g of a conductive agent Super were used. -P and 750g Boehmite (AlOOH) 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 a} positive electrode material, a conductive agent Super-P, a boehmite (AlOOH) additive mixed with a solution of the above binder, 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 μm, the coating width was 160 mm, and the double-sided surface density of the dressing was 316.7 g/m ² (based on the dry weight of the electrode dressing, the additive content was 3% by weight). Then, it was dried at 110 ° C to obtain a positive electrode tab.

Example 10

A lithium ion battery A10 was prepared according to the method of Example 1, except that in the step (1), 23513 g of lithium nickel cobalt manganese oxide LiNi _0.5 Co _0.2 Mn _0.3 O ₂ positive electrode material, 495 g of a binder HSV 900, and 742 g of a conductive agent Super were used. -P and 250g boehmite (AlOOH) 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 _0.2 Mn _0.3 O under stirring _{2 a} positive electrode material, a conductive agent Super-P, a boehmite (AlOOH) additive mixed with a solution of the above binder, 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 μm, the coating width was 160 mm, and the double-sided surface density of the dressing was 310.3 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.

Example 11

A lithium ion battery A11 was prepared according to the method of Example 1, except that in the step (1), 20188 g of lithium nickel cobalt manganese oxide LiNi _0.5 Co _0.2 Mn _0.3 O ₂ positive electrode material, 425 g of a binder HSV900, and 637 g of a conductive agent Super were used. -P and 3750g Boehmite (AlOOH) 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 _0.2 Mn _0.3 O under stirring _{2 a} positive electrode material, a conductive agent Super-P, a boehmite (AlOOH) additive mixed with a solution of the above binder, 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 μm, the coating width was 160 mm, and the double-sided surface density of the dressing was 361.4 g/m ² (the content of the additive was 15% by weight based on the dry weight of the electrode dressing). Then, it was dried at 110 ° C to obtain a positive electrode tab.

Example 12

A lithium ion battery A12 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a ytterbium oxyhydroxide (YOOH·0.12H ₂ O) powder.

Example 13

A lithium ion battery A13 was prepared in accordance with the method of Example 1, except that in the step (1), the boehmite powder was replaced with a hydroxyl group. Cerium oxide (ScOOH) powder.

Example 14

A lithium ion battery A14 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a zirconium oxyhydroxide (ZrO(OH) ₂ ) powder.

Example 15

A lithium ion battery A15 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a vanadium oxyhydroxide (VO _2.3 (OH) _0.4 ) powder.

Example 16

A lithium ion battery A16 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a cerium oxyhydroxide (LaOOH·0.38H ₂ O) powder.

Example 17

A lithium ion battery A17 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a cerium oxyhydroxide (CeOOH) powder.

Example 18

A lithium ion battery A18 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a cerium oxyhydroxide (NdOOH) powder.

Example 19

A lithium ion battery A19 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a bismuth oxyhydroxide (SmOOH) powder.

Example 20

A lithium ion battery A20 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a cerium oxyhydroxide (GdOOH) powder.

Example 21

A lithium ion battery A21 was prepared in the same manner as in Example 1 except that in the step (1), the boehmite powder was replaced with erbium oxyhydroxide (ErOOH) powder.

Example 22

A lithium ion battery A22 was prepared in the same manner as in Example 1 except that in the step (1), the boehmite powder was replaced with a cerium oxyhydroxide (NbO(OH) ₃ ) powder.

Example 23

A lithium ion battery A23 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a chromium oxyhydroxide (CrO _0.5 (OH) ₂ ) powder.

Example 24

A lithium ion battery A24 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a molybdenum oxyhydroxide (MoO ₂ (OH) ₂ ) powder.

Example 25

A lithium ion battery A25 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with manganese oxyhydroxide (MnOOH) powder.

Example 26

A lithium ion battery A26 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with iron oxyhydroxide (FeO _0.45 (OH) _2.1 ) powder.

Example 27

A lithium ion battery A27 was prepared in the same manner as in Example 1 except that in the step (1), the boehmite powder was replaced with a cobalt oxyhydroxide (CoOOH) powder.

Example 28

A lithium ion battery A28 was prepared in accordance with the method of Example 1, except that in the step (1), the boehmite powder was replaced with a nickel oxyhydroxide (NiOOH) powder.

Example 29

A lithium ion battery A29 was prepared in accordance with the method of Example 1, except that in the step (1), the boehmite powder was replaced with a tin oxyhydroxide (SnO(OH) ₂ ) powder.

Example 30

A lithium ion battery A30 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a bismuth oxyhydroxide (BiOOH) powder.

Example 31

A lithium ion battery A31 was prepared in accordance with the method of Example 1, except that in the step (1), the boehmite powder was replaced with a bismuth oxyhydroxide (SbOOH) powder.

Example 32

A lithium ion battery A32 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a boron oxyhydroxide (BO _1.2 (OH) _0.6 ) powder.

Example 33

A lithium ion battery A33 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a cerium oxyhydroxide (BeO _0.4 (OH) _1.2 ) powder.

Example 34

A lithium ion battery A34 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with a magnesium oxyhydroxide (MgO _0.5 OH) powder.

Example 35

A lithium ion battery A35 was prepared in the same manner as in Example 1 except that in the step (1), the boehmite powder was replaced with copper oxyhydroxide (CuO _0.6 (OH) _0.8 ) powder.

Example 36

A lithium ion battery A36 was prepared in the same manner as in Example 1, except that in the step (1), the boehmite powder was replaced with zinc oxyhydroxide (ZnO _0.7 (OH) _0.6 ) powder.

Comparative example 1

A lithium ion battery D1 was prepared according to the method of Example 1, except that in the step (1), the boehmite 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 307.2 g/m ² (based on the weight after drying), and then dried at 110 ° C to obtain a positive electrode tab.

Comparative example 2

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 silicic acid SiO _0.95 (OH) _2.1 powder additive was not added in the preparation of the additive slurry, specifically First, the PTFE emulsion binder D210 is dispersed in 2500 g of water as a solvent to obtain an emulsion of the binder, and the emulsion is uniformly coated on the surface of the above positive electrode sheet, and the coating width is 162 mm to cover the active material, the dressing The double-sided surface density was 28.2 g/m ² (based on the weight after drying) and then dried at 100 °C.

Comparative example 3

The lithium ion battery D3 was prepared according to the method of Example 3, except that in the step (1), the titanium hydroxide TiO(OH) ₂ powder additive was not added in the preparation of the additive slurry, that is, 50 g of the conductive agent Super-P, 50 g. The binder HSV900 is mixed. Specifically, the binder HSV900 is first dissolved in 2500 g of NMP as a solvent to obtain a solution of the binder, and then the conductive agent Super-P is mixed with the solution of the binder, followed by stirring to form a uniformity. Slurry

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 29.6 g/m ² (based on the weight after drying), and then baked at 120 ° C. Dry, obtain treated aluminum foil;

The active material slurry was uniformly coated on the surface of the additive-coated aluminum foil with a coating width of 160 mm, the double-sided surface density of the dressing was 307.2 g/m ² (based on the weight after drying), and then baked at 120 ° C. Dry, a positive electrode tab coated with an aluminum foil through an additive was obtained.

Test case

Single cell abuse test

1, overcharge test

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% extrusion test

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% extrusion test

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, acupuncture test

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.

Table 1

Table 2

table 3

Table 4

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.

Comparing the results of Example 1 and Example 9-11 in Tables 1-4, it can be seen that in the positive electrode or the negative electrode, when the content of the additive is 6 to 10% by weight based on the dry weight of the electrode dressing, it can be further improved. 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.

Comparing the results of Examples 1-4 in Tables 1-4 with those of Examples 12-36, it can be seen that when the additive is at least one of aluminum oxyhydroxide, metasilicate, and titanium oxyhydroxide, the prepared product can be further improved. The safety of lithium-ion batteries.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.

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.

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

The use of an additive for preparing a positive electrode and/or a negative electrode of a lithium ion battery, characterized in that the additive is MO a (OH) b · cH 2 O, wherein M is a metal element of Group IIA, a metal element of Group IB, 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, Group VA metal element, At least one element of boron and silicon, a>0, b>0, c≥0.
The use according to claim 1, wherein, 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 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 oxyhydroxide, metasilicate, and titanium oxyhydroxide.
The use according to claim 1 or 2, wherein in the positive electrode or the negative electrode, the content of the additive is from 0.05 to 30% by weight, preferably from 3 to 15% by weight, based on the dry weight of the electrode dressing, further preferably It is 6-10% by weight.
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 content of the additive is 0.05 to 51% by weight, preferably 3 to 19% by weight, further preferably 7 to 12% by weight; the additive is MO a (OH) b · cH 2 O, wherein M is a 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, Group IVA At least one of a metal element, a VA group metal element, boron and silicon, a>0, b>0, c≥0;

Preferably, the binder is contained in an amount of 0.5 to 5% by weight on a dry basis, and the content of the conductive agent is 0.5 to 5% by weight based on the weight of the active material, and the content of the solvent is 55-200% by weight, the thickener is present in an amount of from 0 to 2.5% by weight.
The lithium ion battery electrode slurry according to claim 4, wherein, 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 / 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, and the Group VA metal element is Bi and/or Sb; preferably, the additive is at least one of aluminum oxyhydroxide, metasilicate, and titanium oxyhydroxide; /or

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

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

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

The solvent is at least one of N-methylpyrrolidone, deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol, and isopropanol; and/or

The thickener is at least one of sodium carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.
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. The content of the solvent is from 100 to 400% by weight, the content of the conductive agent is from 0 to 10% by weight, and the additive is MO a (OH) b · cH 2 O, wherein M It 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, a Group VIB metal element, a Group VIIB metal element, a Group VIII metal element, a Group IIIA metal element. At least one of a Group IVA metal element, a Group VA metal element, boron and silicon, a>0, b>0, c≥0.
The additive slurry according to claim 6, wherein, 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 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 oxyhydroxide, metasilicate, and titanium oxyhydroxide; and/or

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

The solvent is at least one of N-methylpyrrolidone, deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol, and isopropanol; and/or

The conductive agent is at least one of Ketchen Black, acetylene black, graphene, carbon nanotubes, carbon fibers, microcrystalline graphite, and conductive carbon black.
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 MO a (OH) b · cH 2 O, 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, boron and silicon, a>0, b>0, c≥0.
The positive electrode or the negative electrode of a lithium ion battery according to claim 8, wherein, 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 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, and the Group VIII metal element is at least one of Fe, Co and Ni, the Group IIIA The metal element is Al, the Group IVA metal element is Sn, and the VA group metal element is Bi and/or Sb; preferably, the additive is at least one of aluminum oxyhydroxide, metasilicate, and titanium oxyhydroxide. ;and / or

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

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

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

The thickener is at least one of sodium carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.
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 30% by weight, preferably from 3 to 15% by weight, based on the dry weight of the electrode dressing, further preferably 6-10% by weight.
A method for preparing a positive electrode or a negative electrode of a lithium ion battery, characterized in that the method comprises: coating the lithium ion battery electrode slurry according to claim 4 or 5 on a current collector, and drying; or

(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) 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 resulting additive-coated current collector; or

(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) The additive slurry according to claim 6 or 7 is coated on the electrode pad obtained in the step (1) and dried.
A positive electrode or a negative electrode of a lithium ion battery prepared by the method of claim 11.
A lithium ion battery, characterized in that the lithium ion battery comprises a battery case and electricity inside the battery case a core assembly and an electrolyte, the battery assembly including a positive electrode, a negative electrode, and a separator, and the positive electrode is the positive electrode of the lithium ion battery according to claim 8, 9, 10 or 12, and/or the negative electrode is claim 8. The lithium ion battery negative electrode according to 9, 9 or 12.