CN112349902A - Ternary cathode material of lithium ion battery, preparation method of ternary cathode material, cathode and lithium ion battery - Google Patents

Ternary cathode material of lithium ion battery, preparation method of ternary cathode material, cathode and lithium ion battery Download PDF

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CN112349902A
CN112349902A CN202011032176.7A CN202011032176A CN112349902A CN 112349902 A CN112349902 A CN 112349902A CN 202011032176 A CN202011032176 A CN 202011032176A CN 112349902 A CN112349902 A CN 112349902A
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ion battery
lithium ion
cathode material
ternary
lithium
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刘少军
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Jiangsu Union Energy Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of a ternary cathode material of a lithium ion battery, which comprises the following steps: carrying out low-temperature solid phase reaction on + 2-valent solid nickel acetate, cobalt acetate, manganese acetate and solid organic acid to obtain a ternary precursor; and calcining the mixture obtained by mixing the ternary precursor and a lithium source at high temperature to obtain the cathode material. The invention also relates to a ternary cathode material and a cathode of the lithium ion battery and the lithium ion battery.

Description

Ternary cathode material of lithium ion battery, preparation method of ternary cathode material, cathode and lithium ion battery
Technical Field
The invention relates to the field of electrochemical battery materials, in particular to a ternary cathode material of a lithium ion battery, a preparation method of the ternary cathode material, a cathode and the lithium ion battery.
Background
The lithium ion battery has the advantages of high voltage, high capacity, high energy density, good cycle performance, environmental friendliness and the like. The performance of lithium ion batteries is highly dependent on the positive electrode material. The positive electrode material restricts the comprehensive performance of the battery.
The traditional preparation method of the lithium ion battery anode material adopts a codeposition-high temperature solid phase method, namely, firstly, a precursor is prepared by the coprecipitation method, then lithium mixing and sintering are carried out to prepare the corresponding anode material, but due to the reaction in a liquid phase, impurity ions such as Na in a reaction system+、SO4 2-、Cl-The removal of (a) requires repeated washing of the co-precipitated material resulting in loss of material, which results in inaccurate control of the stoichiometry of the material. Meanwhile, a large amount of wastewater is generated in the production process, so that the mass production and the popularization and the use of the material are limited. The low-heat solid phase reaction method developed recently overcomes the defects of liquid phase reaction, effectively shortens the preparation process of materials and obviously lowers the synthesis temperature compared with the traditional solid phase method. However, the cathode material prepared by the existing low-heat solid phase reaction method still has the problems of poor particle dispersibility and poor uniformity, so that the finally prepared cathode material has poor cycle performance in the battery charging and discharging process.
Disclosure of Invention
Based on the above, it is necessary to provide a ternary cathode material for a lithium ion battery, a preparation method thereof, a cathode and a lithium ion battery aiming at the problem that the prepared cathode material particles are poor in dispersibility and uniformity.
The invention provides a preparation method of a ternary cathode material of a lithium ion battery, which comprises the following steps:
carrying out low-temperature solid phase reaction on + 2-valent solid nickel acetate, cobalt acetate, manganese acetate and solid organic acid to obtain a ternary precursor; and
and calcining the mixture obtained by mixing the ternary precursor and a lithium source at high temperature to obtain the cathode material.
In one embodiment, at least one of the solid nickel acetate, cobalt acetate, and manganese acetate contains water of crystallization.
In one embodiment, the solid organic acid comprises one or more of oxalic acid, adipic acid, succinic acid, citric acid, tartaric acid.
In one embodiment, the lithium source is any one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium chloride, and lithium sulfate.
In one embodiment, the reaction temperature of the low-heat solid phase reaction is 20-30 ℃, and the reaction time is 20-40 min.
In one embodiment, the ratio of the total molar mass of the solid nickel acetate, cobalt acetate and manganese acetate to the molar mass of the solid organic acid is (0.8-1): 1.
in one embodiment, before mixing the ternary precursor with the lithium source, the method further comprises a step of vacuum drying the ternary precursor.
In one embodiment, the temperature of the vacuum drying step is 110-150 ℃, and the drying time is 12-24 h.
In one embodiment, the high-temperature calcination temperature is 600-950 ℃, and the calcination time is 4-10 hours.
In one embodiment, the calcination process is conducted in an atmosphere containing oxygen.
In one embodiment, the calcination process is conducted under oxygen conditions.
In one embodiment, the high temperature calcination step comprises:
a pre-sintering step, in which the mixture is calcined for 4 to 6 hours at the temperature of 600 to 750 ℃ in the atmosphere containing oxygen;
an impurity removing step, namely washing the product obtained in the pre-burning step to remove impurities, and drying in vacuum to obtain dry powder;
and a secondary sintering step, calcining the dry powder for 4 to 6 hours at the temperature of between 750 and 950 ℃ in an atmosphere containing oxygen.
The invention also provides a lithium ion battery ternary cathode material prepared by the preparation method, wherein the chemical formula of the ternary cathode material is LiNixCoyMn1-x-yO2Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1.
The invention also provides a positive electrode containing the ternary positive electrode material of the lithium ion battery.
The invention further provides a lithium ion battery which comprises the positive electrode.
The preparation method of the ternary anode material of the lithium ion battery provided by the invention comprises the steps of firstly carrying out low-heat solid phase reaction on acetate of nickel, cobalt and manganese and solid organic acid, then carrying out lithium mixing and calcination, and finally forming a substance, namely a ternary precursor containing nickel, cobalt and manganese, by carrying out processes of diffusion, reaction, nucleation and grain growth on reactant molecules of the three acetates in the low-heat solid phase reaction. The ternary precursor is a secondary particle consisting of a plurality of nanoscale primary particles, so that lithium ions are easier to be embedded in the high-temperature calcination process, the size of the primary particles is small, the reaction process of the high-temperature calcination is further shortened, the agglomeration of materials is avoided, and the finally formed anode material has better particle dispersibility and uniformity. On the other hand, compared with the existing method for preparing the cathode material by low-heat solid phase reaction, the method for preparing the ternary cathode material of the lithium ion battery provided by the invention is wider in applicable lithium source variety range.
Drawings
FIG. 1 is a flow chart of a method for preparing a ternary cathode material for a lithium ion battery according to the present invention;
FIG. 2 is a micrograph of a ternary precursor prepared according to example 1 of the present invention;
FIG. 3 is a LiNi prepared in example 1 of the present invention0.5Co0.2Mn0.3O2A microscopic topography of the powder;
FIG. 4 is a LiNi prepared in comparative example 1 of the present invention0.5Co0.2Mn0.3O2A microscopic topography of the powder;
FIG. 5 is a LiNi prepared in comparative example 2 of the present invention0.5Co0.2Mn0.3O2A microscopic topography of the powder;
FIG. 6 is a LiNi prepared in example 1, comparative example 1 and comparative example 2 of the present invention0.5Co0.2Mn0.3O2The specific discharge capacity of the battery prepared by using the positive electrode active material is tested by a curve.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 6 includes 1, 2, 3, 4, 5, 6, and the like.
The term "low heat solid phase reaction" as used herein refers to a chemical reaction between solid compounds at or near room temperature (. ltoreq.100 ℃). Compared with liquid phase reaction, the method has the biggest advantages of full reaction, no side reaction, 100 percent conversion rate, no pollution and no solvent residue.
The +2 valence state in the invention refers to the valence state of the metal element in the acetate.
The embodiment of the invention provides a preparation method of a ternary cathode material of a lithium ion battery, which comprises the following steps:
s10, carrying out low-heat solid phase reaction on the solid nickel acetate with the valence of +2, cobalt acetate, manganese acetate and solid organic acid to obtain a ternary precursor; and
and S20, calcining the mixture obtained by mixing the ternary precursor and a lithium source at high temperature to obtain the cathode material.
According to the preparation method of the ternary cathode material of the lithium ion battery, provided by the embodiment of the invention, acetate of nickel, cobalt and manganese and solid organic acid are subjected to low-heat solid phase reaction, then lithium mixing and calcination are carried out, and reactant molecules of the three acetate in the low-heat solid phase reaction are subjected to processes of diffusion, reaction, nucleation and grain growth to finally form a substance, namely a ternary precursor containing nickel, cobalt and manganese. The ternary precursor is a secondary particle consisting of a plurality of nanoscale primary particles, so that lithium ions are easier to be embedded in the high-temperature calcination process, the size of the primary particles is small, the reaction process of the high-temperature calcination is further shortened, the agglomeration of materials is avoided, and the finally formed anode material has better particle dispersibility and uniformity. On the other hand, compared with the existing method for preparing the cathode material by the low-heat solid phase reaction, the method for preparing the ternary cathode material of the lithium ion battery provided by the embodiment of the invention is more applicable to a wider range of lithium sources.
In step S10, the solid nickel acetate, cobalt acetate, manganese acetate can easily react with the solid organic acid in a low heat solid phase reaction.
The low heat solid phase reaction of the reaction system containing water of crystallization can easily occur. Preferably, at least one of the solid nickel acetate, cobalt acetate and manganese acetate contains crystal water. More preferably, the solid nickel acetate, cobalt acetate and manganese acetate all contain crystal water. For example, the solid nickel acetate, cobalt acetate, manganese acetate may be Ni (CH)3COO)2·4H2O、Co(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O。
The solid organic acid may comprise one or more of oxalic acid, adipic acid, succinic acid, citric acid, tartaric acid. Preferably oxalic acid and/or citric acid.
In one embodiment, the low thermal solid phase reaction may be carried out by mechanically milling the reactant particles. Forming a cold-melt layer on the surface of a reactant when a reaction system containing crystal water is mixed, diffusing reactant molecules in the cold-melt layer and carrying out chemical reaction to generate a target product, wherein each cold-melt layer is equivalent to a micro-reaction zone, and continuously updating the particle surface through mechanical grinding to continuously form a new cold-melt layer; meanwhile, the generated product nucleates and grows up to form a new product phase. Preferably, in step S10, solid nickel acetate, cobalt acetate, and manganese acetate may be mixed and ground to fine particles, and then mixed and ground with the solid organic acid.
In another embodiment, the low heat solid phase reaction may also be carried out by a high speed agitation process. The energy provided by high-speed stirring can apply a force to the solid substance, so that the constraint energy barrier of the surrounding mass points on the solid substance is reduced, and the thermal motion energy of the mass points at normal temperature can overcome the constraint energy barrier. For compounds containing water of crystallization, the water of crystallization is generally removed and then melted when heated. The water of crystallization molecules in a compound are generally more easily released against its confinement by surrounding particles. The released water molecules form a trace amount of solvent which can further react with the compound molecules to form a critical state between the solution state and the molten state. The crystal water contained in the compound is released to form a trace solvent at the temperature lower than the dehydration temperature through an external acting force, and although the trace solvent cannot completely solvate the reactant, a layer of molten film can be formed on the surface of the reactant, so that the chemical reaction is promoted.
The reaction temperature of the low-heat solid phase reaction can be 20-100 ℃, and the reaction time can be 20-40 min.
The ratio of the total molar mass of the solid nickel acetate, cobalt acetate, manganese acetate to the molar mass of the solid organic acid may be (0.8 to 1): 1, preferably (0.8-0.9): 1.
the molar mass ratio of the nickel acetate to the cobalt acetate to the manganese acetate can be (1-9): (0.5-3): (0.5 to 3). In one embodiment, the molar mass ratio of the nickel acetate, the cobalt acetate and the manganese acetate is 5:2: 3. In another embodiment, the molar mass ratio of nickel acetate, cobalt acetate and manganese acetate is 6:2: 2. In yet another embodiment, the molar mass ratio of nickel acetate, cobalt acetate, manganese acetate is 8:1: 1.
According to the preparation method of the ternary cathode material of the lithium ion battery, the material loss is avoided in the preparation process of the ternary precursor, and the stoichiometric ratio of the raw materials of the three elements of nickel, cobalt and manganese can be accurately controlled.
Further, between the step S10 and the step S20, a step S12 is further included, and the ternary precursor is vacuum-dried. The vacuum drying step serves to remove excess solid organic acid.
Preferably, the temperature of the vacuum drying step is 110-150 ℃, and the drying time is 12-24 h.
Further, the ternary precursor is a secondary particle composed of a plurality of primary particles with the particle size of nanometer level, and the particle size of the secondary particle can be 2-3 μm. The particle size distribution can satisfy D95-D5Less than or equal to 1 mu m, namely, has narrower particle size distribution.
The chemical formula of the ternary precursor is NixCoyMn(1-x-y)C2O4Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1.
In step S20, the lithium source may be at least one selected from lithium hydroxide and lithium salt, and the lithium salt may be one or more selected from but not limited to lithium carbonate, lithium nitrate, lithium chloride, and lithium sulfate. The method of the embodiment has relatively loose requirements on the types of the lithium sources, and is applicable to a wider range of types of the lithium sources.
The molar mass of the lithium source is 3-10% excess relative to the total molar mass of the solid nickel acetate, cobalt acetate and manganese acetate, because the lithium salt is volatilized and lost after being melted in the high-temperature calcination process
In order to uniformly mix the lithium source and the ternary precursor, the mixing process may include step S22:
and adding a solvent into the mixture of the lithium source and the ternary precursor for grinding.
The solvent can be an organic solvent or a mixture of an organic solvent and water in any proportion, and the organic solvent can be ethanol. The amount of the solvent is only used to enable convenient milling to mix the lithium source and the ternary precursor uniformly.
The lithium source and the ternary precursor grinding step only have the function of uniformly mixing the lithium source and the ternary precursor, and do not initiate the reaction of the lithium source and the ternary precursor.
And in the high-temperature calcination step, lithium ions are inserted into the ternary precursor, and the ternary precursor is pyrolyzed to form an oxide.
Preferably, the high-temperature calcination is carried out at a temperature of 600-950 ℃ for 4-10 hours, and the calcination is carried out in an oxygen-containing atmosphere. The atmosphere containing oxygen may be an air atmosphere or a pure oxygen atmosphere. When the ternary cathode material of the lithium ion battery is a high nickel material, such as high nickel 811, or the nickel content is higher than high nickel 811, the calcination process is performed in a pure oxygen atmosphere.
In a preferred embodiment, the high temperature calcination step comprises:
a pre-sintering step, in which the mixture is calcined for 4 to 6 hours at the temperature of 600 to 750 ℃ in the atmosphere containing oxygen;
an impurity removing step, namely washing the product obtained in the pre-burning step to remove impurities, and drying in vacuum to obtain dry powder;
and a secondary sintering step, calcining the dry powder for 4 to 6 hours at the temperature of between 750 and 950 ℃ in an atmosphere containing oxygen.
The high-temperature calcination step is used for presintering to form crystals, impurities on the surfaces of the crystals are removed through washing treatment, then secondary sintering is carried out, the morphology of the obtained material is superior to that of the material which is subjected to primary calcination, and the method is particularly suitable for single crystal materials.
The embodiment of the invention also provides a lithium ion battery ternary cathode material prepared by the preparation method, wherein the chemical formula of the ternary cathode material is LiNixCoyMn1-x-yO2Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1.
In one embodiment, the chemical formula of the ternary cathode material is LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2Or LiNi0.4Co0.2Mn0.4O2。
The particle size of the ternary cathode material particles can reach 1-2 microns. The particle size distribution can meet the requirement that D95-D5 is less than or equal to 1 mu m, namely, the particle size distribution is narrower.
The embodiment of the invention also provides a positive electrode containing the ternary positive electrode material of the lithium ion battery.
The positive electrode also comprises a positive electrode current collector, a positive electrode binder and a positive electrode conductive agent. The positive electrode binder, the positive electrode conductive agent and the lithium ion battery ternary positive electrode material are formed on the surface of the positive electrode current collector. The positive electrode current collector may be an aluminum foil. The positive electrode binder can be high molecular compounds such as starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone, tetrafluoroethylene, styrene-butadiene rubber, polyethylene, polypropylene and the like. The positive electrode conductive agent can be conductive carbon black, superconducting carbon black, conductive graphite, acetylene black, oily carbon nanotubes and the like.
The embodiment of the present invention further provides a lithium ion battery, including:
as in the case of the positive electrode described above,
a negative electrode;
a separator spaced between the positive electrode and the negative electrode;
an electrolyte; and
and a battery outer package enclosing the positive electrode, the negative electrode and the separator and containing the electrolyte.
The negative pole piece comprises a negative pole current collector and a negative pole active layer formed on the surface of the negative pole current collector. The negative electrode current collector may be a copper foil. The negative electrode active layer may include a negative electrode active material, a negative electrode binder, and a negative electrode conductive agent. As the negative electrode active material, those used in general lithium ion batteries, such as graphite, non-graphitizable carbon, amorphous carbon, a polymer compound sintered body (for example, a sintered body obtained by sintering and carbonizing a phenol resin, a furan resin, or the like), cokes (for example, pitch coke, needle coke, petroleum coke, or the like), carbon fibers, and other suitable carbon materials can be used. The negative electrode binder and the negative electrode conductive agent may use those known to those skilled in the art. The negative binder can be styrene butadiene rubber, polyacrylonitrile, sodium carboxymethylcellulose, polyvinyl acrylic acid, polyacrylic acid, polyvinyl alcohol, carboxymethyl chitosan and the like. The negative conductive agent can be conductive carbon black, superconducting carbon black, conductive graphite, acetylene black, oily carbon nanotubes and the like.
The separator is a separator used in a general lithium ion battery, and examples thereof include a microporous membrane made of polyethylene or polypropylene; a multi-layer film of a porous polyethylene film and polypropylene; nonwoven fabrics formed of polyester fibers, aramid fibers, glass fibers, and the like; and a base film formed by adhering ceramic fine particles such as silica, alumina, and titania to the surfaces thereof.
The electrolyte may include an electrolyte and a non-aqueous organic solvent. The electrolyte may use an electrolytic solution known in lithium ion batteries. Preferred examples thereof include: LiPF6、LiBF4、LiSbF6、LiAsF6Lithium salt electrolyte of inorganic acid, LiN (FSO)2)2、LiN(CF3SO2)2、LiN(C2F5SO2)2Etc. of a fluorine atom-containing sulfonyl imide electrolyte, LiC (CF)3SO2)3And the like, a sulfonyl methide-based electrolyte having a fluorine atom. The nonaqueous organic solvent may be a nonaqueous solvent used in a usual electrolytic solution, and examples thereof include lactone compounds, cyclic or chain carbonates, chain carboxylates, cyclic or chain ethers, phosphate esters, nitrile compounds, amide compounds, sulfones, sulfolane, and the like, and mixtures thereof. Preferred examples of the organic solvent for the carbonate-based wastewater include propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl n-propyl carbonate, ethyl n-propyl carbonate, and di-n-propyl carbonate.
The following are specific examples:
EXAMPLE 1 ternary cathode Material LiNi0.5Co0.2Mn0.3O2Preparation of
(1) 4.9768gNi (CH)3COO)2·4H2O(20mmol)、1.9926g Co(CH3COO)2·4H2O(8mmol)、2.9411gMn(CH3COO)2·4H2Adding O (12mmol) into a mortar, mixing and grinding for 30min, then adding 6.3035g of oxalic acid, mixing and grinding for 30min, wherein the raw material is changed into slurry from solid state in the grinding process, and then is changed into paste, and finally a powdery ternary precursor is obtained, and the ternary precursor has strong pungent smell during grinding and is acetic acid volatilization.
(2) And (2) drying the ternary precursor prepared in the step (1) for 12 hours in vacuum at the temperature of 150 ℃.
(3) 2.9556g of lithium carbonate and the ternary precursor dried in the step (2) are placed in a mortar to be mixed, ethanol and water are added into the mixture, the mixture is fully ground and dried, then the mixture is placed in a muffle furnace to be calcined for 4 hours at 750 ℃ in the air atmosphere, the mixture is cooled to room temperature, 100ml of ethanol is added to be ground, centrifugal washing is carried out after ultrasonic dispersion, the mixture is placed in the muffle furnace to be calcined for 6 hours at 900 ℃ in the air atmosphere after vacuum drying, the temperature rising rate is 5 ℃/min, the mixture is cooled to room temperature, grinding and crushing are carried out, and LiNi is obtained0.5Co0.2Mn0.3O2。
Referring to FIGS. 2 and 3, FIG. 2 is a micrograph of a ternary precursor, and FIG. 3 is a graph of LiNi prepared0.5Co0.2Mn0.3O2As can be seen from the microscopic morphology of the powder, the ternary precursor is a secondary particle composed of a plurality of primary particles with the particle size of nanometer level, and the particle size of the particle is less than 2 μm. LiNi0.5Co0.2Mn0.3O2The particle size is about 2 mu m, the particle surface is smooth and has no impurities, the particle size distribution is uniform, and the monodispersion effect is good.
Comparative example 1
(1) 1.6784g of LiOH & H2O (40mmol) and 6.3035g oxalic acid (50mmol) were added to the mortar and mixed for 30min to mix thoroughly, where no sticky material was formed.
(2) 4.9768gNi (CH)3COO)2·4H2O(20mmol)、1.9926g Co(CH3COO)2·4H2O(8mmol)、2.9411gMn(CH3COO)2·4H2O (12mmol) was added to the mixture in step (1) and the trituration was continuedGrinding to obtain a pasty precursor.
(3) And (3) taking out the pasty precursor in the step (2), and drying for 12 hours in vacuum at 150 ℃.
(4) And (3) calcining the dried precursor in a muffle furnace at 750 ℃ in air atmosphere for 4 hours, cooling to room temperature, adding 100ml of ethanol for grinding, performing centrifugal washing after ultrasonic dispersion, performing vacuum drying, calcining in the muffle furnace at 900 ℃ in air atmosphere for 6 hours at the heating rate of 5 ℃/min, cooling to room temperature, grinding and crushing to obtain LiNi0.5Co0.2Mn0.3O2。
Referring to FIG. 4, FIG. 4 shows LiNi prepared in comparative example 10.5Co0.2Mn0.3O2The microscopic morphology of the powder shows that LiNi0.5Co0.2Mn0.3O2The dispersibility of the particles is poor, the particles are adhered together, the agglomeration phenomenon is serious, the surfaces of the particles are rough, small-sized crystal particles are attached, and the cycle performance of the material is poor directly in the charging and discharging process of the battery.
Comparative example 2
(1) 1.6784g of LiOH & H2O(40mmol)、4.9768gNi(CH3COO)2·4H2O(20mmol)、1.9926g Co(CH3COO)2·4H2O(8mmol)、2.9411gMn(CH3COO)2·4H2O (12mmol) and 6.3035g oxalic acid (50mmol) were added to a mortar and mixed and ground for 30min to react well to a viscous mixture.
(2) Adding the mixture into the viscous mixture obtained in the step (1), and drying the mixture at 150 ℃ for 12 hours in vacuum.
(3) And (3) calcining the precursor dried in the step (2) in a muffle furnace at 750 ℃ in air atmosphere for 4 hours, cooling to room temperature, adding 100ml of ethanol for grinding, performing ultrasonic dispersion, performing centrifugal washing, performing vacuum drying, calcining in the muffle furnace at 900 ℃ in air atmosphere for 6 hours at the heating rate of 5 ℃/min, cooling to room temperature, and grinding and crushing to obtain LiNi0.5Co0.2Mn0.3O2。
Referring to FIG. 5, FIG. 5 shows a preparation of comparative example 2Prepared LiNi0.5Co0.2Mn0.3O2Microscopic morphology of powder, albeit LiNi0.5Co0.2Mn0.3O2Is single crystal grain with smooth surface and no impurity. However, the particles are formed into LiNi due to the severe agglomeration of the precursor0.5Co0.2Mn0.3O2The particle size distribution is wide, the larger particle size is about 3-4 mu m, and the smaller particle size is about 0.3-0.4 mu m.
LiNi prepared in example 1, comparative example 1 and comparative example 20.5Co0.2Mn0.3O2As the positive active material, a 2032 coin cell was assembled according to the following procedure, according to the conventional technical means of those skilled in the art.
(1) Preparation of Positive electrode sheet
The positive electrode active material LiNi prepared in example 1 or comparative example 2 was used0.5Co0.2Mn0.3O2Carbon black as a conductive additive and polyvinylidene fluoride (PVDF) as a binder are dispersed in N-methylpyrrolidone (NMP) according to the weight ratio of 80:10:10, and the mixture is uniformly mixed to prepare uniform positive electrode slurry. Uniformly coating the uniform anode slurry on an aluminum foil current collector with the thickness of 15 mu m, drying at 55 ℃ to form a pole piece with the thickness of 100 mu m, placing the pole piece under a roller press for rolling (the pressure is about 1MPa multiplied by 1.5cm2), cutting into a round piece with the diameter of 14mm, then placing the round piece in a vacuum oven for drying at 120 ℃ for 6 hours, naturally cooling, taking out and placing in a glove box for use as an anode pole piece.
(2) Assembling lithium ion secondary battery
In a glove box filled with inert atmosphere, metal lithium is taken as the negative electrode of the battery, a PP/PE/PP three-layer film with two sides coated with alumina is taken as a diaphragm and is placed between the positive electrode and the negative electrode, and 1M LiPF is dripped6And (3) dissolving the nonaqueous electrolyte in EC/DMC (volume ratio of 1: 1), and taking the positive pole piece prepared in the step (1) as a positive pole to assemble the button cell with the model number of CR 2032.
And (3) electrochemical performance testing:
testing the discharge of the electrode in the voltage range of 2.75V-4.3V and under the condition of 0.1C multiplying powerThe specific capacity was tested according to a conventional test method in the art, and the test result is shown in FIG. 6, using LiNi of example 10.5Co0.2Mn0.3O2The specific discharge capacity of the battery prepared as the positive electrode active material was 181.4mAh/g, based on LiNi of comparative example 10.5Co0.2Mn0.3O2The specific discharge capacity of the battery prepared as the positive active material was 141.1mAh/g, based on LiNi of comparative example 20.5Co0.2Mn0.3O2The specific discharge capacity of the battery prepared for the positive electrode active material was 164.9 mAh/g. From this, it can be seen that LiNi prepared in example 10.5Co0.2Mn0.3O2The electrochemical performance is more excellent.
Example 2 ternary cathode material LiNi0.6Co0.2Mn0.2O2Preparation of
(1) 4.9768g of Ni (CH)3COO)2·4H2O(20mmol)、1.6605g Co(CH3COO)2·4H2O(6.67mmol)、1.634gMn(CH3COO)2·4H2O (6.67mmol) is added into a mortar to be mixed and ground for 30min, then 5.5155g of oxalic acid (37.5mmol) is added to be mixed and ground for 30min, the raw material is changed into slurry from solid state and then into paste during grinding, and finally the powdery ternary precursor is obtained, and the powdery ternary precursor has strong pungent smell during grinding and is acetic acid volatile.
(2) And (2) drying the ternary precursor prepared in the step (1) for 12 hours in vacuum at the temperature of 150 ℃.
(3) Placing 1.232g of lithium carbonate and 5.5187g of the ternary precursor dried in the step (2) in a mortar for mixing, adding ethanol and water into the mixture, fully grinding and drying, placing in a muffle furnace for calcining at 750 ℃ in air atmosphere for 4 hours, cooling to room temperature, adding 100ml of ethanol for grinding, performing centrifugal washing after ultrasonic dispersion, vacuum drying, placing in the muffle furnace for calcining at 900 ℃ in air atmosphere for 6 hours at the heating rate of 5 ℃/min, cooling to room temperature, grinding and crushing to obtain LiNi0.6Co0.2Mn0.2O2。
LiNi prepared in this example0.6Co0.2Mn0.2O2The particle size is about 2 mu m, the particle surface is smooth and free of impurities, the particle size distribution is uniform, and the monodispersion effect is good.
Example 3 ternary cathode material LiNi0.8Co0.1Mn0.1O2Preparation of
(1) 4.9768gNi (CH)3COO)2·4H2O(20mmol)、0.6227g Co(CH3COO)2·4H2O(2.5mmol)、0.6127gMn(CH3COO)2·4H2Adding O (2.5mmol) into a mortar, mixing and grinding for 30min, then adding 3.9396g of oxalic acid (31.25mmol), mixing and grinding for 30min, wherein the raw material is changed into slurry from solid state and then into paste during grinding, and finally obtaining powdery ternary precursor, wherein the ternary precursor has strong pungent smell during grinding and is acetic acid volatile.
(2) And (2) drying the ternary precursor prepared in the step (1) for 12 hours in vacuum at the temperature of 150 ℃.
(3) And (3) placing 1.045g of lithium hydroxide and 4.3043g of the ternary precursor dried in the step (2) into a mortar for mixing, adding ethanol and water into the mixture, fully grinding and drying, placing into a muffle furnace for calcining at 750 ℃ in pure oxygen atmosphere for 4 hours, cooling to room temperature, adding 100ml of ethanol for grinding, performing centrifugal washing after ultrasonic dispersion, placing into the muffle furnace for calcining at 900 ℃ in pure oxygen atmosphere for 6 hours after vacuum drying, raising the temperature at the rate of 5 ℃/min, cooling to room temperature, grinding and crushing. Obtaining LiNi0.8Co0.1Mn0.1O2。
LiNi prepared in this example0.8Co0.1Mn0.1O2The particle size is about 1-2 mu m, the surface of the particle is smooth and free of impurities, the particle size distribution is uniform, and the monodispersion effect is good.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (13)

1. A preparation method of a ternary cathode material of a lithium ion battery is characterized by comprising the following steps:
carrying out low-temperature solid phase reaction on + 2-valent solid nickel acetate, cobalt acetate, manganese acetate and solid organic acid to obtain a ternary precursor; and
and calcining the mixture obtained by mixing the ternary precursor and a lithium source at high temperature to obtain the cathode material.
2. The method for preparing the ternary cathode material for the lithium ion battery according to claim 1, wherein at least one of the solid nickel acetate, the cobalt acetate and the manganese acetate contains crystal water.
3. The method for preparing the ternary cathode material for the lithium ion battery according to claim 1, wherein the solid organic acid comprises one or more of oxalic acid, adipic acid, succinic acid, citric acid and tartaric acid.
4. The method of claim 1, wherein the lithium source is any one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium chloride, and lithium sulfate.
5. The method for preparing the ternary cathode material of the lithium ion battery according to claim 1, wherein the reaction temperature of the low-heat solid phase reaction is 20-100 ℃ and the reaction time is 20-40 min.
6. The method for preparing the ternary cathode material of the lithium ion battery according to claim 1, wherein the ratio of the total molar mass of the solid nickel acetate, the cobalt acetate and the manganese acetate to the molar mass of the solid organic acid is (0.8-1): 1.
7. the method of claim 1, further comprising a step of vacuum drying the ternary precursor before mixing it with the lithium source.
8. The preparation method of the ternary cathode material for the lithium ion battery according to claim 7, wherein the temperature of the vacuum drying step is 110-150 ℃, and the drying time is 12-24 h.
9. The method for preparing the ternary cathode material of the lithium ion battery according to claim 1, wherein the high-temperature calcination is performed at a temperature of 600 ℃ to 950 ℃ for 4 hours to 10 hours in an atmosphere containing oxygen.
10. The method for preparing the ternary cathode material for the lithium ion battery according to claim 1, wherein the high-temperature calcination step comprises:
a pre-sintering step, in which the mixture is calcined for 4 to 6 hours at the temperature of 600 to 750 ℃ in the atmosphere containing oxygen;
an impurity removing step, namely washing the product obtained in the pre-burning step to remove impurities, and drying in vacuum to obtain dry powder;
and a secondary sintering step, calcining the dry powder for 4 to 6 hours at the temperature of between 750 and 950 ℃ in an atmosphere containing oxygen.
11. The lithium ion battery ternary cathode material prepared by the preparation method of any one of claims 1 to 10, wherein the chemical formula of the ternary cathode material is LiNixCoyMn1-x-yO2Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1.
12. A positive electrode comprising the lithium ion battery ternary positive electrode material of claim 11.
13. A lithium ion battery comprising the positive electrode according to claim 12.
CN202011032176.7A 2020-09-27 2020-09-27 Ternary cathode material of lithium ion battery, preparation method of ternary cathode material, cathode and lithium ion battery Pending CN112349902A (en)

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Application publication date: 20210209