CN114014377B - Lithium ion battery positive ternary material, preparation method thereof, positive electrode plate and lithium ion battery - Google Patents

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

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CN114014377B
CN114014377B CN202111203964.2A CN202111203964A CN114014377B CN 114014377 B CN114014377 B CN 114014377B CN 202111203964 A CN202111203964 A CN 202111203964A CN 114014377 B CN114014377 B CN 114014377B
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lithium ion
ion battery
ternary material
nickel
cobalt
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CN114014377A (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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    • 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 positive ternary material, a preparation method thereof, a positive pole piece and a lithium ion battery. The preparation method of the lithium ion battery anode ternary material comprises the following steps: coating a metal oxide layer on at least part of the surface of a nickel-cobalt-manganese precursor by a metal compound through a mode of reducing and oxidizing to obtain a lithium ion battery positive 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 semi-finished product of the lithium ion battery positive ternary material with a lithium source, and then sintering to obtain the lithium ion battery positive 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 retaining 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 multiplying power performance of the battery.

Description

Lithium ion battery positive ternary material, preparation method thereof, positive electrode 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 positive ternary material, a preparation method thereof, a positive pole piece and a lithium ion battery.
Background
In recent years, along with the popularization of electric passenger cars, car owners find that the endurance mileage of the electric car using the lithium iron phosphate battery is seriously reduced in winter in the north, and compared with the standard mileage, the reduction 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 choose to use the primary 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 a positive electrode, a negative electrode, electrolyte and a diaphragm. The low-temperature performance of the lithium battery is improved mainly by positive and negative electrode active materials and electrolyte, and the method comprises the following steps: firstly, the positive and negative electrode active materials reduce the particle size of the positive and negative electrode materials, increase the interface 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; thirdly, adjusting the components of electrolyte additives and changing the components and thickness of the negative electrode SEI film.
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 positive electrode material adopted by the ternary lithium ion battery is nickel cobalt manganese oxide, has better low-temperature performance than lithium iron phosphate, but still has 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 positive electrode ternary material, a preparation method thereof, a positive electrode plate and a lithium ion battery, wherein the core of the lithium ion battery positive electrode ternary material is a secondary particle sphere, and a layer of foam porous LiNi is wrapped outside the secondary particle sphere X Co Y Mn (1-X-Y) O 2 The contact area of the electrolyte and the positive electrode material is increased, and lithium ions can enter and exit the positive electrode 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 lithium ion battery anode ternary material comprises the following steps:
coating a metal oxide layer on at least part of the surface of a nickel-cobalt-manganese precursor by a metal compound through a mode of reducing and oxidizing to obtain a lithium ion battery positive 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 semi-finished product of the lithium ion battery positive ternary material with a lithium source, and then sintering to obtain the lithium ion battery positive ternary material.
In a preferred embodiment of the present invention, triethanolamine is used as the reducing agent in the reduction reaction;
further preferably, the molar ratio of the metal element to triethanolamine in the metal compound is 1 (1-3).
In a preferred embodiment of the present invention, the reduction-before-oxidation mode specifically includes:
(1) Complexing a metal compound with triethanolamine, adding a nickel-cobalt-manganese precursor, drying, and then carrying out sintering heat treatment on the dried product in an inert atmosphere or a reducing atmosphere to form a metal simple substance 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, and wrapping a metal oxide layer on at least part of the surface of the nickel cobalt manganese precursor, thereby obtaining a semi-finished product of the lithium ion battery anode ternary material;
further preferably, the sintering heat treatment in the step (1) is performed at a temperature of 500-700 ℃ for 10-20min; the temperature of the oxidation heat treatment in the step (2) is 300-400 ℃ and the time is 20-40min.
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 0 < a < 1,0 < b < 0.5, a+b < 1;
and/or the nickel source compound is selected from one or more than two 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 than two 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;
further preferably, the chemical formula of the nickel cobalt manganese precursor is Ni x Co y Mn 1-x-y (OH) 2 Wherein 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 in the range of 2-4 mu m.
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 mixing the lithium ion battery anode ternary material semi-finished product with a lithium source, and sintering at the temperature of 450-800 ℃ for 2-4 hours.
The invention also provides a lithium ion battery anode ternary material which is prepared by the preparation method, and preferably, the D50 particle size of the lithium ion battery anode ternary material is in the range of 4-7 mu m.
The invention also provides a positive electrode plate, 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 positive ternary material of the lithium ion battery or the positive ternary material of the lithium ion battery prepared by the preparation method; preferably, the method comprises the steps of,
the current collector is aluminum foil with the thickness of 12-20 mu m;
and/or the coating material has an areal density of 34-42mg/cm 2 ；
And/or the coating material comprises 2-5wt% of conductive agent, 2-5wt% of binder and the balance of ternary material of the positive electrode of the lithium ion battery;
and/or the conductive agent is selected from one or more than two of carbon black, acetylene black, conductive graphite, carbon nanotubes, conductive carbon fibers and graphene.
The invention also provides a lithium ion battery which comprises the positive electrode plate, the diaphragm, the electrolyte and the negative electrode plate, wherein the excessive negative electrode is 1.06-1.20.
The invention has the beneficial effects that:
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 retaining 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; the interface reaction impedance of lithium ions is reduced, so that the low-temperature performance and the multiplying power performance of the battery are correspondingly optimized, and particularly in the aspect of low-temperature charging, the constant current charging ratio of the battery is higher than 90% at-30 ℃ and is far higher than that of a common ternary material.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications.
In the following examples, the equipment and the like used were conventional products available for purchase by a regular channel manufacturer, without specifying the manufacturer. The methods are conventional methods unless otherwise specified, and the starting materials are commercially available from the public sources unless otherwise specified.
Example 1
1. Example 1 provides a lithium ion battery positive ternary material, which is prepared by the following steps:
(1) Selecting a precursor Ni with the granularity D50 of 3.5 mu m 1/3 Co 1/3 Mn 1/3 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the The molar amount is 100mol;
(2) Will be composed of Co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Mn(NO 3 ) 2 ·4H 2 The metal compound consisting of O is dissolved in a certain amount of CH 3 In OH, the molar quantity ratio is 1/3:1/3:1/3; the molar amount of Co+Ni+Mn in step (2) and Ni in step (1) 1/3 Co 1/3 Mn 1/3 (OH) 2 The molar quantity ratio is 3:7, preparing a base material;
(3) Adding a certain amount of TEA (triethanolamine) solution into the solution in the step (2) to form a complex solution with Co, ni and Mn, and then adding the Ni in the step (1) 1/3 Co 1/3 Mn 1/3 (OH) 2 Vacuum drying under stirring at 80deg.C for 2 hr; the dried product was placed in an alumina crucible at 650 c with N 2 Calcining for 20min in 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 ·6H 2 0、Ni(NO 3 ) 2 ·6H 2 0、Mn(NO 3 ) 2 ·4H 2 O and TEA generate oxidation-reduction reaction, a large amount of gas is generated during the oxidation-reduction reaction, and foam porous high-activity metal simple substances Co, ni and Mn are formed to be coated on Ni 1/3 Co 1/3 Mn 1/3 (OH) 2 Applying;
N(CH 2 CH 2 OH) 3 +Co(N0 3 ) 2 →Co+NOx↑+COy↑+H 2 0↑
N(CH 2 CH 2 OH) 3 +Ni(N0 3 ) 2 →Ni+NOx↑+COy↑+H 2 0↑
N(CH 2 CH 2 OH) 3 +Mn(N0 3 ) 2 →Mn+NOx↑+COy↑+H 2 0↑
(4) Subsequently, the simple substance of the high-activity Co, ni and Mn metal wraps the Ni 1/3 Co 1/3 Mn 1/3 (OH) 2 At O 2 Reacting for 30min at 350 ℃ in atmosphere to generate CoO, niO, mnO-coated Ni 1/3 Co 1/3 Mn 1/3 (OH) 2 Obtaining a semi-finished product of the lithium ion battery anode ternary material;
(5) Semi-finished product of lithium ion battery anode ternary material and Li 2 CO 3 According to (ni+co+mn): li=1: calcining at 500 ℃ for 2 hours in a molar ratio of 1 to obtain the foam porous structure ternary material LiNi with the D50 granularity of 5.6 mu m 1/3 Co 1/3 Mn 1/3 O 2 。
2. The embodiment also provides a positive electrodeThe pole piece 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 and the balance of the prepared foam porous structure ternary material LiNi 1/3 Co 1/3 Mn 1/3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The surface density of the coating material is 42mg/cm 2 ；
The current collector of the positive electrode plate is aluminum foil with the thickness of 15 mu m.
3. The embodiment provides a lithium ion secondary battery, which consists of the positive electrode plate, the negative electrode plate, a diaphragm and electrolyte;
the negative electrode plate comprises an 8-mu m thick copper foil current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 1% of acetylene black, 2% of binder SBR, 1.5% of binder CMC and 95.5% of artificial graphite. Coating area Density 17.74mg/cm 2 ；
The diaphragm is made of polypropylene;
the lithium salt of the electrolyte is LiPF 6 18wt% of organic solvent, namely 40wt% of dimethyl carbonate, 20wt% of ethylene carbonate and 20wt% of methyl ethyl carbonate, wherein the additive consists of 1wt% of ethylene sulfate and 1wt% of vinylene carbonate;
wherein the negative electrode piece is excessive by 1.08;
the outer diameter of the lithium ion secondary battery is 32mm, and the height of the lithium ion secondary battery is 140mm.
Example 2
1. Example 2 provides a lithium ion battery positive ternary material, which is prepared by the following steps:
(1) Selecting a precursor Ni with the granularity D50 of 4.1 mu m 0.5 Co 0.2 Mn 0.3 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the The molar amount is 100mol;
(2) Will be made of Ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Mn(NO 3 ) 2 ·4H 2 The metal compound consisting of O is dissolved in a certain amount of CH 3 In OH, the molar quantity ratio is 0.5:0.2:0.3; the molar amount of Co+Ni+Mn in step (2) and Ni in step (1) 0.5 Co 0.2 Mn 0.3 (OH) 2 The molar quantity ratio is 5:5, a step of;
(3) Adding a certain amount of TEA (triethanolamine) solution to form a complex solution with Co, ni and Mn, and then adding Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 Vacuum drying under stirring at 80deg.C for 2 hr; the dried product was placed in an alumina crucible at 650 c with N 2 Calcining for 15min in a protective atmosphere; wherein the molar quantity ratio of Co+Ni+Mn to TEA in the metal compound is 1:2; co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Mn(NO 3 ) 2 ·4H 2 O and TEA generate oxidation-reduction reaction, a large amount of gas is generated during the oxidation-reduction reaction, and foam porous high-activity metal simple substances Co, ni and Mn are formed to be coated on Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 Applying;
N(CH 2 CH 2 OH) 3 +Co(NO 3 ) 2 →Co+NOx↑+COy↑+H 2 0↑
N(CH 2 CH 2 OH) 3 +Ni(NO 3 ) 2 →Ni+NOx↑+COy↑+H 2 0↑
N(CH 2 CH 2 OH) 3 +Mn(NO 3 ) 2 →Mn+NOx↑+COy↑+H 2 0↑
(4) Subsequently, the simple substance of the high-activity Co, ni and Mn metal wraps the Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 At O 2 Reacting at 380 ℃ for 30min in atmosphere to generate CoO, niO, mnO-coated Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 Obtaining a semi-finished product of the lithium ion battery anode ternary material;
(5) Semi-finished product of lithium ion battery anode ternary material and Li 2 CO 3 According to (ni+co+mn): li=1: calcining at 600 ℃ for 3 hours in a molar ratio of 1 to obtain the foam porous structure ternary material LiNi with the D50 granularity of 6.3 mu m 0.5 Co 0.2 Mn 0.3 O 2 。
2. The embodiment also provides a positive electrode plate, which comprises a current collector and a positive electrode plate arranged on the surface of the current collectorThe surface coating material comprises 3% of acetylene black, 3% of binder PVDF and the balance of the prepared foam porous structure ternary material LiNi 0.5 Co 0.2 Mn 0.3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The surface density of the coating material is 42mg/cm 2 ；
The current collector of the positive electrode plate is aluminum foil with the thickness of 15 mu m.
3. The embodiment provides a lithium ion secondary battery, which consists of the positive electrode plate, the negative electrode plate, a diaphragm and electrolyte;
the negative electrode plate comprises an 8-mu m thick copper foil current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 1% of acetylene black, 2% of binder SBR, 1.5% of binder CMC and 95.5% of artificial graphite. The density of the coating surface is 19.39mg/cm 2 ；
The diaphragm is made of polypropylene;
the lithium salt of the electrolyte is LiPF 6 18wt% of organic solvent, namely 40wt% of dimethyl carbonate, 20wt% of ethylene carbonate and 20wt% of methyl ethyl carbonate, wherein the additive consists of 1wt% of ethylene sulfate and 1wt% of vinylene carbonate;
wherein the negative electrode piece is excessive by 1.08;
the outer diameter of the lithium ion secondary battery is 32mm, and the height of the lithium ion secondary battery is 140mm.
Example 3
1. Example 3 provides a lithium ion battery positive ternary material, which is prepared by the following steps:
(1) Selecting a precursor Ni with granularity D50 of 4.2 mu m 0.8 Co 0.1 Mn 0.1 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the The molar amount is 100mol;
(2) Will be made of Ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Mn(NO 3 ) 2 ·4H 2 The metal compound consisting of O is dissolved in a certain amount of CH 3 In OH, the molar quantity ratio is 0.8:0.1:0.1; the molar amount of Co+Ni+Mn in step (2) and Ni in step (1) 0.8 Co 0.1 Mn 0.1 (OH) 2 The molar quantity ratio is 2:8, 8;
(3) Adding a certain amount of TEA (triethanolamine) solution to form a complex solution with Co, ni and Mn, and then adding Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Vacuum drying under stirring at 80deg.C for 2 hr; the dried product was placed in an alumina crucible at 650 c with N 2 Calcining for 15min in a protective atmosphere; wherein the molar quantity ratio of Co+Ni+Mn to TEA in the metal compound is 1:3; co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Mn(NO 3 ) 2 ·4H 2 O and TEA generate oxidation-reduction reaction, a large amount of gas is generated during the oxidation-reduction reaction, and foam porous high-activity metal simple substances Co, ni and Mn are formed to be coated on Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Applying;
N(CH 2 CH 2 OH) 3 +Co(N0 3 ) 2 →Co+NOx↑+COy↑+H 2 0↑
N(CH 2 CH 2 OH) 3 +Ni(N0 3 ) 2 →Ni+NOx↑+COy↑+H 2 0↑
N(CH 2 CH 2 OH) 3 +Mn(N0 3 ) 2 →Mn+NOx↑+COy↑+H 2 0↑
(4) Subsequently, the simple substance of the high-activity Co, ni and Mn metal wraps the Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 At O 2 Reacting at 380 ℃ for 30min in atmosphere to generate CoO, niO, mnO-coated Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Obtaining a semi-finished product of the lithium ion battery anode ternary material;
(5) Semi-finished product of lithium ion battery anode ternary material and Li 2 CO 3 According to (ni+co+mn): li=1: calcining at 700 ℃ for 3 hours in a molar ratio of 1 to obtain the foam porous structure ternary material LiNi with the D50 granularity of 6.5 mu m 0.8 Co 0.1 Mn 0.1 O 2 。
2. The embodiment also provides a positive electrode plate, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises acetylene black3% of binder PVDF 3%, and the balance of the foam porous structure ternary material LiNi prepared by the method 0.8 Co 0.1 Mn 0.1 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The surface density of the coating material is 38mg/cm 2 ；
The current collector of the positive electrode plate is aluminum foil with the thickness of 15 mu m.
3. The embodiment provides a lithium ion secondary battery, which consists of the positive electrode plate, the negative electrode plate, a diaphragm and electrolyte;
the negative electrode plate comprises an 8-mu m thick copper foil current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 1% of acetylene black, 2% of binder SBR, 1.5% of binder CMC and 95.5% of artificial graphite. Coating area Density 41.37mg/cm 2 ；
The diaphragm is made of polypropylene;
the lithium salt of the electrolyte is LiPF 6 18wt% of organic solvent, namely 40wt% of dimethyl carbonate, 20wt% of ethylene carbonate and 20wt% of methyl ethyl carbonate, wherein the additive consists of 1wt% of ethylene sulfate and 1wt% of vinylene carbonate;
wherein the negative electrode piece is excessive by 1.08;
the outer diameter of the lithium ion secondary battery is 32mm, and the height of the lithium ion secondary battery is 140mm.
Comparative example 1
This comparative example provides a lithium ion secondary battery, liNi from New materials Co., ltd. Of Hunan China fir, which is commercially available 1/ 3 Co 1/3 Mn 1/3 O 2 The positive electrode plate (the positive electrode plate is manufactured in the same way as in the embodiment 1), the negative electrode plate, the diaphragm and the electrolyte are prepared from ternary materials;
the material of the negative electrode plate is the same as that of the embodiment 1;
the separator was the same as in example 1
The composition of the electrolyte was the same as in example 1;
wherein the negative electrode plate is excessive by 1.08.
Test example Low temperature Performance test
(1) The lithium batteries prepared in examples 1-3 and comparative example 1 were subjected to 0.5C rate charging at-30℃and constant current charging ratio data at the time of charging was 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 discharge capacity percentages thereof were calculated, and the results are shown in Table 1 below;
the discharge capacity percentage= -30 ℃ battery discharge capacity/25 ℃ discharge capacity.
TABLE 1
Figure BDA0003306151550000091
As is clear from Table 1, the constant current charging ratio of the lithium batteries of examples 1 to 3 was more than 93% in a low temperature environment of-30℃and the low temperature double charging performance was excellent. Meanwhile, the discharge capacity percentage of the lithium batteries of examples 1-3 is still more than 93% under the low-temperature environment 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, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

1. The preparation method of the lithium ion battery anode ternary material is characterized by comprising the following steps of:
coating a metal oxide layer on at least part of the surface of a nickel-cobalt-manganese precursor by a metal compound through a mode of reducing and oxidizing to obtain a lithium ion battery positive ternary material semi-finished product; wherein the metal compound comprises a cobalt source compound, a nickel source compound, and a manganese source compound;
mixing the semi-finished product of the lithium ion battery positive ternary material with a lithium source, and then sintering to obtain the lithium ion battery positive ternary material;
the reduction-before-oxidation mode specifically comprises the following steps:
(1) Complexing a metal compound with triethanolamine, adding a nickel-cobalt-manganese precursor, drying, and then carrying out sintering heat treatment on the dried product in an inert atmosphere or a reducing atmosphere to form a metal simple substance layer on the surface of the nickel-cobalt-manganese precursor;
(2) And 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, and wrapping a metal oxide layer on at least part of the surface of the nickel cobalt manganese precursor, thereby obtaining the lithium ion battery anode ternary material semi-finished product.
2. The method for preparing a lithium ion battery positive ternary material according to claim 1, wherein in the reduction reaction, the reducing agent is triethanolamine;
the molar ratio of the metal element to the triethanolamine in the metal compound is 1 (1-3).
3. The method for preparing the lithium ion battery positive electrode ternary material according to claim 2, wherein the sintering heat treatment in the step (1) is carried out at a temperature of 500-700 ℃ for 10-20min; the temperature of the oxidation heat treatment in the step (2) is 300-400 ℃ and the time is 20-40min.
4. A 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 (1-5): (5-9).
5. A method according to any one of claims 1 to 3, 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 0 < a < 1,0 < b < 0.5, a+b < 1;
and/or the nickel source compound is selected from one or more than two 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 than two 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. A method according to any one of claims 1 to 3, wherein 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.
7. The method of claim 6, wherein the nickel cobalt manganese precursor has a chemical formula of Ni x Co y Mn 1-x-y (OH) 2 Wherein 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 in the range of 2-4 mu m.
8. A method according to any one of claims 1 to 3, wherein the lithium ion battery positive electrode ternary material semi-finished product and the lithium source are mixed in a molar ratio (ni+co+mn): li=1: (1-1.2) mixing;
and/or mixing the lithium ion battery anode ternary material semi-finished product with a lithium source, and sintering at the temperature of 450-800 ℃ for 2-4 hours.
9. The lithium ion battery anode ternary material is characterized in that the ternary material is prepared by the preparation method according to any one of claims 1-8, and the D50 particle size of the lithium ion battery anode ternary material is in the range of 4-7 mu m.
10. A positive electrode sheet, 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 binder and the lithium ion battery positive electrode ternary material according to claim 9 or the lithium ion battery positive electrode ternary material prepared by the preparation method according to any one of claims 1-8;
the current collector is aluminum foil with the thickness of 12-20 mu m;
and/or the coating material has an areal density of 34-42mg/cm 2 ；
And/or the coating material comprises 2-5wt% of conductive agent, 2-5wt% of binder and the balance of the lithium ion battery anode ternary material;
and/or the conductive agent is selected from one or more than two of carbon black, acetylene black, conductive graphite, carbon nanotubes, conductive carbon fibers and graphene.
11. The lithium ion battery is characterized by comprising the positive electrode plate, the diaphragm, the electrolyte and the negative electrode plate according to claim 10, wherein the negative electrode excess is 1.06-1.20.
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CN107204423A (en) * 2017-05-18 2017-09-26 山东玉皇新能源科技有限公司 A kind of preparation method and applications of high magnification tertiary cathode material
CN109638232A (en) * 2018-10-25 2019-04-16 宁夏汉尧石墨烯储能材料科技有限公司 A kind of preparation method of cladded type ternary cobalt nickel oxide manganses lithium anode material

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