CN114014377A - Lithium ion battery anode ternary material and preparation method thereof, anode plate and lithium ion battery - Google Patents

Lithium ion battery anode ternary material and preparation method thereof, anode plate and lithium ion battery Download PDF

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CN114014377A
CN114014377A CN202111203964.2A CN202111203964A CN114014377A CN 114014377 A CN114014377 A CN 114014377A CN 202111203964 A CN202111203964 A CN 202111203964A CN 114014377 A CN114014377 A CN 114014377A
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lithium ion
ion battery
cobalt
nickel
ternary material
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CN114014377B (en
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王元杰
薄晋科
田秀君
曹仕良
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Dalian CBAK Power Battery Co Ltd
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Dalian CBAK Power Battery Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention provides a lithium ion battery anode ternary material and a preparation method thereof, an anode plate and a lithium ion battery. The preparation method of the ternary material for the anode of the lithium ion battery comprises the following steps: coating a metal oxide layer on at least part of the surface of a nickel-cobalt-manganese precursor by reducing and oxidizing a metal compound to obtain a lithium ion battery anode ternary material semi-finished product; wherein the metal compound comprises a cobalt source compound, a nickel source compound, and a manganese source compound; and mixing the lithium ion battery anode ternary material semi-finished product with a lithium source and then sintering to obtain the lithium ion battery anode ternary material. The ternary material for the positive electrode of the lithium ion battery provided by the invention effectively improves the wettability of the positive electrode plate and electrolyte, improves the liquid retention capacity of the positive electrode plate, reduces the charge-discharge migration distance of lithium ions, reduces the interface reaction impedance of the lithium ions, and optimizes the low-temperature performance and the rate performance of the battery.

Description

Lithium ion battery anode ternary material and preparation method thereof, anode plate and lithium ion battery
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a lithium ion battery anode ternary material and a preparation method thereof, an anode plate and a lithium ion battery.
Background
In recent years, with the popularization of electric passenger cars, car owners find that the endurance mileage of electric cars using lithium iron phosphate batteries is seriously shrunk in winter in the north, and compared with the standard mileage, the shrinkage is 30-50%; the ternary lithium battery electric vehicle can shrink, and compared with the standard mileage, the shrinkage is 20-30%; therefore, consumers in the north increasingly select the element lithium battery electric vehicle, but the problems of slow charging and the like still exist under the low-temperature condition.
The lithium battery consists of four parts of a positive electrode, a negative electrode, electrolyte and a diaphragm. The main components for improving the low-temperature performance of the lithium battery are anode and cathode active materials and electrolyte, and the specific components are as follows: the positive and negative electrode active materials reduce the particle size of the positive and negative electrode materials, increase the interfaces of lithium ions entering and exiting the positive and negative electrode materials and are beneficial to improving the low-temperature performance; secondly, the migration rate of lithium ions in the electrolyte is increased by reducing the viscosity of the electrolyte at low temperature; and thirdly, adjusting the components of the electrolyte additive and changing the components and the thickness of the SEI film of the negative electrode.
Experimental results prove that the discharge capacity ratio of the lithium battery can be improved by optimizing the granularity of the positive and negative active materials, and the discharge voltage platform of the lithium battery can be improved by optimizing the electrolyte.
The cathode material adopted by the ternary lithium ion battery is an oxide of nickel, cobalt and manganese, has better low-temperature performance than lithium iron phosphate, but still shows the problems of shortened endurance mileage, slow low-temperature charging and the like at low temperature.
Disclosure of Invention
The invention aims to provide a lithium ion battery anode ternary material and a preparation method thereof, an anode pole piece and a lithium ion batteryXCoYMn(1-X-Y)O2The contact area between the electrolyte and the anode material is increased, and lithium ions can enter and exit from the anode material, so that the low-temperature performance of the battery is improved.
Specifically, the invention provides the following technical scheme: .
A preparation method of a ternary material of a positive electrode of a lithium ion battery comprises the following steps:
coating a metal oxide layer on at least part of the surface of a nickel-cobalt-manganese precursor by reducing and oxidizing a metal compound to obtain a lithium ion battery anode ternary material semi-finished product; wherein the metal compound comprises a cobalt source compound, a nickel source compound, and a manganese source compound;
and mixing the lithium ion battery anode ternary material semi-finished product with a lithium source and then sintering to obtain the lithium ion battery anode ternary material.
In a preferred embodiment of the present invention, triethanolamine is used as a reducing agent in the reduction reaction;
further preferably, the molar ratio of the metal element to the triethanolamine in the metal compound is 1 (1-3).
In a preferred embodiment of the present invention, the reduction-before-oxidation specifically includes:
(1) performing complexation treatment on a metal compound and triethanolamine, adding a nickel-cobalt-manganese precursor, drying, and performing sintering heat treatment on a dried product in an inert atmosphere or a reducing atmosphere to form a metal single layer on the surface of the nickel-cobalt-manganese precursor;
(2) exposing the metal simple substance layer to an oxidizing atmosphere for oxidation heat treatment, so as to oxidize at least part of metal simple substances in the metal simple substance layer, so as to wrap a metal oxide layer on at least part of the surface of the nickel-cobalt-manganese precursor, and thus obtaining a semi-finished product of the lithium ion battery anode ternary material;
further preferably, the temperature of the sintering heat treatment in the step (1) is 500-700 ℃, and the time is 10-20 min; the temperature of the oxidation heat treatment in the step (2) is 300-400 ℃, and the time is 20-40 min.
In a preferred embodiment of the present invention, the molar ratio of the metal element to the nickel-cobalt-manganese precursor in the metal compound is (1-5): (5-9).
In a preferred embodiment of the present invention, the molar ratio of the nickel element in the nickel source compound, the cobalt element in the cobalt source compound, and the manganese element in the manganese source compound is a: b: (1-a-b), wherein a is more than 0 and less than 1, b is more than 0 and less than 0.5, and a + b is less than 1;
and/or the nickel source compound is selected from one or more of nickel (II) nitrate, nickel (II) carbonate, nickel (II) hydroxide or nickel (II) oxide;
and/or the cobalt source compound is selected from one or more of cobalt (II) nitrate, cobalt (II) carbonate, cobalt (II) hydroxide or cobalt (II) oxide;
and/or the manganese source compound is selected from one or more than two of manganese (II) nitrate, manganese (II) carbonate, manganese (II) hydroxide or manganese (II) oxide.
In a preferred embodiment of the present invention, the nickel-cobalt-manganese precursor is one or a mixture of several of nickel-cobalt-manganese hydroxide, nickel-cobalt-manganese carboxyl oxide, and nickel-cobalt-manganese oxide;
more preferably, the chemical formula of the nickel-cobalt-manganese precursor is NixCoyMn1-x-y(OH)2Wherein x is more than 0 and less than 1, y is more than 0 and less than 0.5, and x + y is less than 1;
and/or the D50 particle size of the nickel-cobalt-manganese precursor is within the range of 2-4 μm.
In a preferred embodiment of the present invention, the lithium ion battery positive electrode ternary material semi-finished product and the lithium source are mixed according to a molar ratio (Ni + Co + Mn): li-1: (1-1.2) mixing;
and/or the temperature for sintering the lithium ion battery anode ternary material semi-finished product after being mixed with a lithium source is 450-800 ℃, and the time is 2-4 h.
The invention also provides a ternary material for the positive electrode of the lithium ion battery, which is prepared by the preparation method, and preferably, the D50 particle size of the ternary material for the positive electrode of the lithium ion battery is within the range of 4-7 mu m.
The invention also provides a positive pole piece, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises a conductive agent, a binder and the lithium ion battery positive ternary material or the lithium ion battery positive ternary material prepared by the preparation method; preferably, the first and second liquid crystal materials are,
the current collector is an aluminum foil with the thickness of 12-20 microns;
and/or the areal density of the coating material is 34-42mg/cm2；
And/or in the coating material, the using amount of a conductive agent is 2-5 wt%, the using amount of a binder is 2-5 wt%, and the balance is the lithium ion battery anode ternary material;
and/or the conductive agent is selected from one or more of carbon black, acetylene black, conductive graphite, carbon nano tubes, conductive carbon fibers and graphene.
The invention also provides a lithium ion battery which comprises the positive pole piece, the diaphragm, the electrolyte and the negative pole piece, wherein the negative pole excess is 1.06-1.20.
The beneficial effects obtained by the invention are as follows:
the ternary material for the positive electrode of the lithium ion battery provided by the invention effectively improves the wettability of the positive electrode plate and electrolyte, improves the liquid retention capacity of the positive electrode plate, reduces the charge-discharge migration distance of lithium ions, and reduces the interface reaction impedance of the lithium ions; because the interface reaction impedance of lithium ions is reduced, the low-temperature performance and the rate performance of the battery are correspondingly optimized, and particularly in the aspect of low-temperature charging, the constant current rush-in ratio of the battery is higher than 90% at minus 30 ℃, and is far larger than that of a common ternary material.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
In the following examples, the equipment and the like used are not shown to manufacturers, and are all conventional products available from regular vendors. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature.
Example 1
1. Embodiment 1 provides a lithium ion battery anode ternary material, which is prepared by the following steps:
(1) selecting precursor Ni with the particle size D50 of 3.5 mu m1/3Co1/3Mn1/3(OH)2(ii) a The molar quantity is 100 mol;
(2) will consist of Co (NO)3)2·6H2O、Ni(NO3)2·6H2O、Mn(NO3)2·4H2A metal compound consisting of O is dissolved in a certain amount of CH3In OH, the molar quantity ratio is 1/3: 1/3: 1/3, respectively; the molar quantity of Co + Ni + Mn in the step (2) and the molar quantity of Ni in the step (1)1/3Co1/3Mn1/3(OH)2The molar quantity ratio is 3: 7;
(3) adding a certain amount of TEA (triethanolamine) solution into the solution obtained in the step (2) to form a complex solution with Co, Ni and Mn, and then adding the Ni obtained in the step (1)1/3Co1/3Mn1/3(OH)2Vacuum drying under stirring at 80 deg.C for 2 h; the dried product was placed in an alumina crucible at 650 ℃ N2Calcining for 20min under a protective atmosphere; wherein the ratio of the molar quantity of Co + Ni + Mn to the molar quantity of TEA in the metal compound is 1: 1; co (NO)3)2·6H20、Ni(NO3)2·6H20、Mn(NO3)2·4H2O and TEA are subjected to redox reaction, a large amount of gas is generated in the redox reaction, and foam-like porous high-activity metal simple substances Co, Ni and Mn are coated on Ni1/3Co1/3Mn1/3(OH)2The above step (1);
N(CH2CH2OH)3+Co(N03)2→Co+NOx↑+COy↑+H20↑
N(CH2CH2OH)3+Ni(N03)2→Ni+NOx↑+COy↑+H20↑
N(CH2CH2OH)3+Mn(N03)2→Mn+NOx↑+COy↑+H20↑
(4) then, high-activity Co, Ni and Mn metal simple substances wrap Ni1/3Co1/3Mn1/3(OH)2At O2Reacting for 30min at 350 ℃ in the atmosphere to generate CoO, NiO and MnO wrapped Ni1/3Co1/3Mn1/3(OH)2Obtaining a lithium ion battery anode ternary material semi-finished product;
(5) preparing lithium ion battery anode ternary material semi-finished product and Li2CO3According to (Ni + Co + Mn): li-1: calcining at 500 ℃ for 2h in a molar ratio of 1 to obtain the foam porous structure ternary material LiNi with the D50 particle size of 5.6 mu m1/3Co1/3Mn1/3O2。
2. The embodiment also provides a positive pole piece, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 3% of acetylene black, 3% of binder PVDF (polyvinylidene fluoride), and the balance of the foam-shaped porous ternary material LiNi prepared by the method1/3Co1/3Mn1/3O2(ii) a The areal density of the coating material was 42mg/cm2；
The current collector of the positive pole piece is an aluminum foil with the thickness of 15 mu m.
3. The embodiment provides a lithium ion secondary battery, which consists of the positive pole piece, the negative pole piece, a diaphragm and electrolyte;
the negative pole piece comprises a copper foil current collector with the thickness of 8 mu m and a coating material arranged on the surface of the current collector, wherein the coating material comprises 1% of acetylene black, 1.5% of binder SBR 2%, 1.5% of binder CMC and 95.5% of artificial graphite. The density of the coated surface is 17.74mg/cm2；
The diaphragm is made of polypropylene;
the lithium salt of the electrolyte is LiPF618 wt% of organic solvent is carbon40 wt% of dimethyl carbonate, 20 wt% of ethylene carbonate and 20 wt% of ethyl methyl carbonate, wherein the additive consists of 1 wt% of ethylene sulfate and 1 wt% of vinylene carbonate;
wherein the negative pole piece is in excess of 1.08;
the lithium ion secondary battery has an outer diameter of 32mm and a height of 140 mm.
Example 2
1. Embodiment 2 provides a lithium ion battery anode ternary material, which is prepared by the following steps:
(1) selecting precursor Ni with the particle size D50 of 4.1 mu m0.5Co0.2Mn0.3(OH)2(ii) a The molar quantity is 100 mol;
(2) will be composed of Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·4H2A metal compound consisting of O is dissolved in a certain amount of CH3In OH, the molar quantity ratio is 0.5: 0.2: 0.3; the molar quantity of Co + Ni + Mn in the step (2) and the molar quantity of Ni in the step (1)0.5Co0.2Mn0.3(OH)2The molar quantity ratio is 5: 5;
(3) adding a certain amount of TEA (triethanolamine) solution into the solution to form a complex solution with Co, Ni and Mn, and then adding Ni0.5Co0.2Mn0.3(OH)2Vacuum drying under stirring at 80 deg.C for 2 h; the dried product was placed in an alumina crucible at 650 ℃ N2Calcining for 15min under a protective atmosphere; wherein the ratio of the molar quantity of Co + Ni + Mn to the molar quantity of TEA in the metal compound is 1: 2; co (NO)3)2·6H2O、Ni(NO3)2·6H2O、Mn(NO3)2·4H2O and TEA are subjected to redox reaction, a large amount of gas is generated in the redox reaction, and foam-like porous high-activity metal simple substances Co, Ni and Mn are coated on Ni0.5Co0.2Mn0.3(OH)2The above step (1);
N(CH2CH2OH)3+Co(NO3)2→Co+NOx↑+COy↑+H20↑
N(CH2CH2OH)3+Ni(NO3)2→Ni+NOx↑+COy↑+H20↑
N(CH2CH2OH)3+Mn(NO3)2→Mn+NOx↑+COy↑+H20↑
(4) then, high-activity Co, Ni and Mn metal simple substances wrap Ni0.5Co0.2Mn0.3(OH)2At O2Reacting for 30min at 380 ℃ in the atmosphere to generate CoO, NiO and MnO wrapped Ni0.5Co0.2Mn0.3(OH)2Obtaining a lithium ion battery anode ternary material semi-finished product;
(5) preparing lithium ion battery anode ternary material semi-finished product and Li2CO3According to (Ni + Co + Mn): li-1: calcining at 600 ℃ for 3h according to the molar ratio of 1 to obtain the foam porous structure ternary material LiNi with the D50 particle size of 6.3 mu m0.5Co0.2Mn0.3O2。
2. The embodiment also provides a positive pole piece, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 3% of acetylene black, 3% of binder PVDF (polyvinylidene fluoride), and the balance of the foam-shaped porous ternary material LiNi prepared by the method0.5Co0.2Mn0.3O2(ii) a The areal density of the coating material was 42mg/cm2；
The current collector of the positive pole piece is an aluminum foil with the thickness of 15 mu m.
3. The embodiment provides a lithium ion secondary battery, which consists of the positive pole piece, the negative pole piece, a diaphragm and electrolyte;
the negative pole piece comprises a copper foil current collector with the thickness of 8 mu m and a coating material arranged on the surface of the current collector, wherein the coating material comprises 1% of acetylene black, 1.5% of binder SBR 2%, 1.5% of binder CMC and 95.5% of artificial graphite. The density of the coated surface is 19.39mg/cm2；
The diaphragm is made of polypropylene;
the lithium salt of the electrolyte is LiPF618 wt% of organic solvent, 40 wt% of dimethyl carbonate, 20 wt% of ethylene carbonate and methyl carbonate20 wt% of ethyl ester, and the additive consists of 1 wt% of ethylene sulfate and 1 wt% of vinylene carbonate;
wherein the negative pole piece is in excess of 1.08;
the lithium ion secondary battery has an outer diameter of 32mm and a height of 140 mm.
Example 3
1. Embodiment 3 provides a lithium ion battery anode ternary material, which is prepared by the following steps:
(1) selecting precursor Ni with the particle size D50 of 4.2 mu m0.8Co0.1Mn0.1(OH)2(ii) a The molar quantity is 100 mol;
(2) will be composed of Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·4H2A metal compound consisting of O is dissolved in a certain amount of CH3In OH, the molar quantity ratio is 0.8: 0.1: 0.1; the molar quantity of Co + Ni + Mn in the step (2) and the molar quantity of Ni in the step (1)0.8Co0.1Mn0.1(OH)2The molar quantity ratio is 2: 8;
(3) adding a certain amount of TEA (triethanolamine) solution into the solution to form a complex solution with Co, Ni and Mn, and then adding Ni0.8Co0.1Mn0.1(OH)2Vacuum drying under stirring at 80 deg.C for 2 h; the dried product was placed in an alumina crucible at 650 ℃ N2Calcining for 15min under a protective atmosphere; wherein the ratio of the molar quantity of Co + Ni + Mn to the molar quantity of TEA in the metal compound is 1: 3; co (NO)3)2·6H2O、Ni(NO3)2·6H2O、Mn(NO3)2·4H2O and TEA are subjected to redox reaction, a large amount of gas is generated in the redox reaction, and foam-like porous high-activity metal simple substances Co, Ni and Mn are coated on Ni0.8Co0.1Mn0.1(OH)2The above step (1);
N(CH2CH2OH)3+Co(N03)2→Co+NOx↑+COy↑+H20↑
N(CH2CH2OH)3+Ni(N03)2→Ni+NOx↑+COy↑+H20↑
N(CH2CH2OH)3+Mn(N03)2→Mn+NOx↑+COy↑+H20↑
(4) then, high-activity Co, Ni and Mn metal simple substances wrap Ni0.5Co0.2Mn0.3(OH)2At O2Reacting for 30min at 380 ℃ in the atmosphere to generate CoO, NiO and MnO wrapped Ni0.8Co0.1Mn0.1(OH)2Obtaining a lithium ion battery anode ternary material semi-finished product;
(5) preparing lithium ion battery anode ternary material semi-finished product and Li2CO3According to (Ni + Co + Mn): li-1: calcining at 700 ℃ for 3h in a molar ratio of 1 to obtain the foam porous structure ternary material LiNi with the D50 particle size of 6.5 mu m0.8Co0.1Mn0.1O2。
2. The embodiment also provides a positive pole piece, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 3% of acetylene black, 3% of binder PVDF (polyvinylidene fluoride), and the balance of the foam-shaped porous ternary material LiNi prepared by the method0.8Co0.1Mn0.1O2(ii) a The areal density of the coating material was 38mg/cm2；
The current collector of the positive pole piece is an aluminum foil with the thickness of 15 mu m.
3. The embodiment provides a lithium ion secondary battery, which consists of the positive pole piece, the negative pole piece, a diaphragm and electrolyte;
the negative pole piece comprises a copper foil current collector with the thickness of 8 mu m and a coating material arranged on the surface of the current collector, wherein the coating material comprises 1% of acetylene black, 1.5% of binder SBR 2%, 1.5% of binder CMC and 95.5% of artificial graphite. Coating surface density is 41.37mg/cm2；
The diaphragm is made of polypropylene;
the lithium salt of the electrolyte is LiPF618 wt%, organic solvent of 40 wt% dimethyl carbonate, 20 wt% ethylene carbonate and 20 wt% ethyl methyl carbonate, and additive of 1 wt% ethylene sulfate and 20 wt% carbon1 wt% of vinylene acid ester;
wherein the negative pole piece is in excess of 1.08;
the lithium ion secondary battery has an outer diameter of 32mm and a height of 140 mm.
Comparative example 1
This comparative example provides a lithium ion secondary battery made of LiNi of a commercially available New Hunansequoia Material Co., Ltd1/ 3Co1/3Mn1/3O2The positive electrode plate prepared from the ternary material (the preparation of the positive electrode plate is the same as that in example 1), the negative electrode plate, the diaphragm and the electrolyte;
the material of the negative electrode plate is the same as that of example 1;
the material of the separator was the same as in example 1
The composition of the electrolyte was the same as in example 1;
wherein the negative pole piece is in excess of 1.08.
Test examples Low temperature Performance test
(1) The lithium batteries prepared in the examples 1-3 and the comparative example 1 are charged at 0.5C rate under the condition of-30 ℃, and the constant current charging ratio data during charging are recorded;
(2) the lithium batteries prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to 0.5C rate discharge at-30 ℃, and the percentage of their discharge capacity was calculated, with the results shown in table 1 below;
the percentage of discharge capacity is-30 ℃ battery discharge capacity/25 ℃ discharge capacity.
TABLE 1
Figure BDA0003306151550000091
As is clear from table 1, it was confirmed that the lithium batteries of examples 1 to 3 had a constant current rush-in ratio of more than 93% and excellent low-temperature double-charge performance in a low-temperature environment of-30 ℃. Meanwhile, the percentage of the discharge capacity of the lithium batteries of examples 1 to 3 is still more than 93% at a low temperature of-30 ℃, and the low-temperature discharge performance is excellent.
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a ternary material for a positive electrode of a lithium ion battery is characterized by comprising the following steps:
coating a metal oxide layer on at least part of the surface of a nickel-cobalt-manganese precursor by reducing and oxidizing a metal compound to obtain a lithium ion battery anode ternary material semi-finished product; wherein the metal compound comprises a cobalt source compound, a nickel source compound, and a manganese source compound;
and mixing the lithium ion battery anode ternary material semi-finished product with a lithium source and then sintering to obtain the lithium ion battery anode ternary material.
2. The method for preparing the ternary material for the positive electrode of the lithium ion battery according to claim 1, wherein in the reduction reaction, the reducing agent is triethanolamine;
preferably, the molar ratio of the metal element to the triethanolamine in the metal compound is 1 (1-3).
3. The preparation method of the ternary positive electrode material for the lithium ion battery according to claim 2, wherein the reduction and then oxidation mode specifically comprises the following steps:
(1) performing complexation treatment on a metal compound and triethanolamine, adding a nickel-cobalt-manganese precursor, drying, and performing sintering heat treatment on a dried product in an inert atmosphere or a reducing atmosphere to form a metal single layer on the surface of the nickel-cobalt-manganese precursor;
(2) exposing the metal simple substance layer to an oxidizing atmosphere for oxidation heat treatment, so as to oxidize at least part of metal simple substances in the metal simple substance layer, so as to wrap a metal oxide layer on at least part of the surface of the nickel-cobalt-manganese precursor, and thus obtaining a semi-finished product of the lithium ion battery anode ternary material;
preferably, the temperature of the sintering heat treatment in the step (1) is 500-700 ℃, and the time is 10-20 min; the temperature of the oxidation heat treatment in the step (2) is 300-400 ℃, and the time is 20-40 min.
4. The production method according to any one of claims 1 to 3, wherein the molar ratio of the metal element to the nickel-cobalt-manganese precursor in the metal compound is (1 to 5): (5-9).
5. The production method according to any one of claims 1 to 4, wherein the molar ratio of the nickel element in the nickel source compound, the cobalt element in the cobalt source compound, and the manganese element in the manganese source compound is a: b: (1-a-b), wherein a is more than 0 and less than 1, b is more than 0 and less than 0.5, and a + b is less than 1;
and/or the nickel source compound is selected from one or more of nickel (II) nitrate, nickel (II) carbonate, nickel (II) hydroxide or nickel (II) oxide;
and/or the cobalt source compound is selected from one or more of cobalt (II) nitrate, cobalt (II) carbonate, cobalt (II) hydroxide or cobalt (II) oxide;
and/or the manganese source compound is selected from one or more than two of manganese (II) nitrate, manganese (II) carbonate, manganese (II) hydroxide or manganese (II) oxide.
6. The preparation method of any one of claims 1 to 5, wherein the nickel-cobalt-manganese precursor is one or a mixture of nickel-cobalt-manganese hydroxide, nickel-cobalt-manganese carboxyl oxide and nickel-cobalt-manganese oxide;
preferably, the chemical formula of the nickel-cobalt-manganese precursor is NixCoyMn1-x-y(OH)2Wherein x is more than 0 and less than 1, y is more than 0 and less than 0.5, and x + y is less than 1;
and/or the D50 particle size of the nickel-cobalt-manganese precursor is within the range of 2-4 μm.
7. The preparation method according to any one of claims 1 to 6, characterized in that the lithium ion battery positive electrode ternary material semi-finished product and the lithium source are mixed according to a molar ratio (Ni + Co + Mn): li-1: (1-1.2) mixing;
and/or the temperature for sintering the lithium ion battery anode ternary material semi-finished product after being mixed with a lithium source is 450-800 ℃, and the time is 2-4 h.
8. The ternary material for the positive electrode of the lithium ion battery is prepared by the preparation method according to any one of claims 1 to 7, and preferably, the D50 particle size of the ternary material for the positive electrode of the lithium ion battery is in a range of 4-7 μm.
9. A positive pole piece is characterized by comprising a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises a conductive agent, a bonding agent and the lithium ion battery positive ternary material of claim 8 or the lithium ion battery positive ternary material prepared by the preparation method of any one of claims 1 to 7; preferably, the first and second liquid crystal materials are,
the current collector is an aluminum foil with the thickness of 12-20 microns;
and/or the areal density of the coating material is 34-42mg/cm2；
And/or in the coating material, the using amount of a conductive agent is 2-5 wt%, the using amount of a binder is 2-5 wt%, and the balance is the lithium ion battery anode ternary material;
and/or the conductive agent is selected from one or more of carbon black, acetylene black, conductive graphite, carbon nano tubes, conductive carbon fibers and graphene.
10. A lithium ion battery, characterized by comprising the positive electrode plate, the diaphragm, the electrolyte and the negative electrode plate of claim 9, wherein the negative electrode excess is 1.06-1.20.
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