CN107369815B - Lithium ion secondary battery composite positive electrode material and preparation method thereof - Google Patents

Lithium ion secondary battery composite positive electrode material and preparation method thereof Download PDF

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CN107369815B
CN107369815B CN201710384214.7A CN201710384214A CN107369815B CN 107369815 B CN107369815 B CN 107369815B CN 201710384214 A CN201710384214 A CN 201710384214A CN 107369815 B CN107369815 B CN 107369815B
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lithium
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ion secondary
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CN107369815A (en
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申兰耀
王汝娜
张振宇
沈伟
周恒辉
杨新河
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Qinghai Taifeng pulead lithium Technology Co. Ltd.
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Qinghai Taifeng Xianxing Lithium Energy Technology 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
    • H01M4/362—Composites
    • 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
    • H01M4/485—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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 discloses a lithium ion secondary battery composite anode material and a preparation method thereof, the material comprises a high nickel anode material and lithium cobaltate in a lithium-poor state, residual lithium on the surface layer of the high nickel material can be effectively removed by taking the lithium cobaltate in the lithium-poor state as a means, and the surface layer structure of the high nickel material is not damaged, so that the stability and the storage performance of the surface layer structure of the material are improved, and the exertion of the cycle performance is facilitated.

Description

Lithium ion secondary battery composite positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a lithium ion secondary battery composite positive electrode material and a preparation method thereof.
Background
Lithium ion batteries, as a rechargeable secondary battery, have been widely used in digital electronic products such as notebooks and mobile phones due to their advantages of high energy density, small self-discharge, and long cycle life. Particularly, with the continuous rise of oil prices and the increasing severity of environmental pollution in the recent years, the development of pure electric vehicles is more and more concerned by governments and enterprises.
At present, a key factor limiting the development of electric automobiles is that the endurance mileage of the electric automobiles cannot meet the living demands of people. Therefore, the development of high energy density and long cycle life lithium ion battery cathode materials is becoming more and more urgent. Among them, the high nickel system positive electrode material, particularly NCA and NCM811, has attracted much attention and research.
Although nickel materials such as nickel cobalt lithium aluminate and the like have higher charge-discharge specific capacity, the problem of electrochemical performance attenuation caused by the surface activity of the materials and the content of surface residual alkali such as lithium hydroxide and lithium carbonate is more and more serious along with the increase of the content of nickel in a material system. The existing improvement method is generally to coat the surface of the anode material with metal oxide, fluoride or phosphate. However, residual lithium on the surface layer cannot be effectively removed by the coating method, and the increase of the coating amount causes the reduction of the discharge capacity of the material.
Or the storage and cycle performance of the material is improved by a method of washing the nickel material with water and washing out residual alkali on the surface layer. However, the water washing method usually destroys the surface layer structure of the material, thereby causing the reduction of coulomb efficiency, charge and discharge capacity and the like of the material, and the electrical property requirement cannot be met.
In addition, the disadvantages of the nickel material are expected to be offset or weakened to some extent by other electrode materials by mixing or compounding the nickel material with other commercial electrode materials. As described in the invention patent of application No. 201410461935.X, "a high-capacity lithium ion battery positive electrode material and a preparation method thereof", two active materials, namely, lithium nickel cobalt aluminate and lithium cobaltate, are uniformly mixed according to a certain proportion, added into a trivalent aluminum source solution, stirred to form a solid-liquid mixture, so that the aluminum source solution uniformly coats the surfaces of active material particles, and then dried and calcined to obtain the lithium ion battery positive electrode material. However, the above-mentioned composite coating method still cannot effectively remove the surface layer material of the high nickel system or still has the above-mentioned disadvantages, and cannot effectively improve the problems of the high nickel material itself.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a composite positive electrode material of a lithium ion secondary battery, which comprises a high nickel positive electrode material and lithium cobaltate in a poor lithium state, so that residual lithium on the surface layer of the high nickel system material is obviously reduced, and the specific capacity, the coulombic efficiency, the cycle life and the like of the material are effectively improved.
The invention also aims to provide a preparation method of the composite cathode material of the lithium ion secondary battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the composite positive electrode material of the lithium ion secondary battery comprises a high nickel positive electrode material of the lithium ion secondary battery and lithium cobaltate in a lithium-poor state, wherein the high nickel positive electrode material of the lithium ion secondary battery is represented by a general formula Li1+xNi1-y-zCoyMzO2M is at least one element selected from the group consisting of Al and Mn, 0<x is less than or equal to 0.2, y is less than or equal to 0 and less than or equal to 0.4, z is less than or equal to 0 and less than or equal to 0.4, and y + z is less than or equal to 0 and less than or equal to 0.6, wherein the lithium cobaltate in the lithium-poor state is represented by the general formula LiaCoO2The lithium-containing composite oxide is represented by 0 < a < 1.
Further, the weight percentage of the lithium cobaltate in the lithium-poor state in the composite positive electrode material of the lithium ion secondary battery is 0.1-40%, and preferably 0.1-33%.
Furthermore, the median particle diameter of the high-nickel positive electrode material of the lithium ion secondary battery is 2-20 μm, and preferably 7-12 μm.
Further, the lithium cobaltate in the lithium-poor state has a median particle diameter of 0.1 to 15 μm, preferably 0.6 to 2 μm.
Further, the crystal structure of the lithium cobaltate in the lithium-deficient state may be a layered, spinel or rock-salt structure.
The preparation method of the composite cathode material of the lithium ion secondary battery comprises the following steps:
1) mixing Ni1-y-zCoyMz(OH)2Mixing with lithium source according to the mol ratio of 1-1.2, sintering, cooling to room temperature to obtain Li1+xNi1-y-zCoyMzO2A lithium-containing oxide;
2) mixing a cobalt source with Li obtained in step 1)1+xNi1-y-zCoyMzO2Lithium-containing oxideAnd mixing the materials according to the molar ratio of 0.001-0.5, and sintering to obtain the lithium ion secondary battery composite positive electrode material containing the lithium ion secondary battery high nickel positive electrode material and lithium cobaltate in a lithium-poor state.
Further, in step 1), the lithium source is one or more selected from lithium hydroxide, lithium carbonate, lithium acetate or lithium nitrate.
Further, the temperature range for sintering in step 1) is 650-.
Further, in step 2), the cobalt source is selected from cobalt hydroxide, cobalt oxide, cobalt nitrate, cobalt acetate or LiaCoO2(0 < a < 1).
Further, the step 2) also comprises the step of mixing a cobalt source and the Li obtained in the step 1)1+xNi1-y-zCoyMzO2When the lithium-containing oxide is mixed, part of the lithium source is added simultaneously, wherein the molar ratio of the added lithium source to the cobalt source is 0.001-1.
Further, the temperature range for sintering in step 2) is 650-1100 ℃, preferably 650-950 ℃.
In addition, under the central idea of the present invention, the coating or doping of the composite positive electrode material of the lithium ion secondary battery of the high nickel material and the lithium cobaltate in the lithium-poor state can be realized by known means. The coating material can be one or more of alumina, titanium oxide, zirconium oxide, magnesium oxide, zinc oxide and lithium-containing phosphate. The doping element can be one or more of magnesium, aluminum, titanium, zirconium, manganese, nickel, niobium and the like.
The composite cathode material of the lithium ion secondary battery has the following advantages:
(1) by taking lithium cobaltate in a poor lithium state as a means, the method can effectively remove residual lithium such as lithium carbonate and lithium hydroxide on the surface layer of the high-nickel material, and does not damage the surface layer structure of the high-nickel material, thereby increasing the stability and storage performance of the surface layer structure of the material and being beneficial to the exertion of the cycle performance.
(2) The method effectively eliminates residual lithium on the surface layer of the high-nickel material, and simultaneously generates lithium cobaltate in a lithium poor state which has high electronic conductivity and ionic conductivity compared with lithium cobaltate with a standard stoichiometric ratio and has completed the conversion from a semiconductor to a conductor, thereby effectively increasing the rate capability and the coulombic efficiency of the material.
(3) According to the invention, residual lithium on the surface layer of the high-nickel material is effectively eliminated, and meanwhile, lithium cobaltate in a poor lithium state with electrochemical activity is generated, so that the charge-discharge specific capacity of the material is further improved.
Drawings
Fig. 1 is an SEM image of the sample after modification in example 1.
Fig. 2 is an SEM image of the sample before modification in example 1.
FIG. 3 is a first cycle charge and discharge curve of the sample before and after the improvement in example 1.
FIG. 4 is a 100-cycle performance curve for the samples before and after the improvement in example 1.
Detailed Description
The invention is further illustrated by the following examples. These examples are only illustrative and are not intended to limit the scope of the invention.
Example 1
One) preparation of Li1.1Ni0.8Co0.1Mn0.1O2Lithium-containing oxide
Mixing lithium hydroxide monohydrate and 20g of Ni0.8Co0.1Mn0.1(OH)2The mixing was carried out at a molar ratio of 1.1. Heating the mixed raw materials from room temperature to 850 ℃ in an oxygen atmosphere at a heating rate of 5 ℃/min, calcining for 10h, and naturally cooling to room temperature to obtain Li1.1Ni0.6Co0.2Mn0.2O2The product, which contains lithium oxide, is a sample before modification, as shown in fig. 2, in which spherical particles are the morphology, and the median particle size is about 10 μm.
II) preparation of Li0.7CoO2Lithium-containing oxide
Lithium carbonate and 10g of Co3O4Mixing was carried out in a lithium/cobalt molar ratio of 0.7. Calcining the mixed powder in air at 950 ℃ for 5h to obtain Li0.7CoO2Lithium-containing oxideThe median particle size is about 2 μm.
III) preparation of Li1.1Ni0.8Co0.1Mn0.1O2And Li0.7CoO2Composite positive electrode material of
1mol of Li1.1Ni0.8Co0.1Mn0.1O2Lithium-containing oxide and 0.5mol of Li0.7CoO2And mixing the lithium-containing oxides. Calcining the mixed powder in oxygen at 800 ℃ for 3h to obtain Li1.1Ni0.8Co0.1Mn0.1O2And Li0.7CoO2The composite positive electrode material of (1), wherein the mass fraction of the lithium-deficient lithium cobaltate in the composite material is about 33%. As shown in fig. 1, the spherical particles in the graph are the morphology of the improved lithium nickel cobalt manganese oxide, and the small particles on the surface are the morphology of lithium-poor lithium cobalt oxide existing in the material.
And (2) taking N-methyl pyrrolidone as a solvent, uniformly stirring the powder obtained after sintering, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 90:5:5, coating the mixture on the surface of a clean aluminum foil, and blade-coating the mixture to form a film. After air blast drying, the electrode sheet was punched into a circular sheet with a diameter of 8mm, and further dried in a vacuum oven at 120 ℃ for 6 hours to remove moisture. The prepared electrode plate is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/L LiPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, and the charge and discharge current density is 0.1C. The first-cycle charge-discharge curve of the sample is shown in fig. 3, and it can be seen that the charge-discharge polarization of the sample is reduced after improvement, the discharge capacity is improved, and the first-time coulombic efficiency is improved. The cycle performance is shown in fig. 4, and it can be seen that the cycle performance of the improved sample is also significantly improved.
Table 1 example 1 residual lithium on the surface of the sample before and after modification
LiOH％ Li2CO3
Before improvement 1.146 0.086
After improvement 0.057 0.052
As can be seen from the above table, the residual lithium content, especially lithium hydroxide content, of the surface layer of the sample after the improvement is obviously reduced.
Example 2
One) preparation of Li1.1Ni0.8Co0.1Mn0.1O2Lithium-containing oxide
Mixing lithium hydroxide monohydrate and 20g of Ni0.8Co0.1Mn0.1(OH)2The mixing was carried out at a molar ratio of 1.1. Heating the mixed raw materials from room temperature to 900 ℃ in oxygen at a heating rate of 5 ℃/min, calcining for 10h, and naturally cooling to room temperature to obtain Li1.1Ni0.6Co0.2Mn0.2O2A lithium-containing oxide having a median particle diameter of about 12 μm.
II) preparation of Li1.1Ni0.8Co0.1Mn0.1O2And Li0.83CoO2Composite positive electrode material of
1mol of Li1.1Ni0.8Co0.1Mn0.1O2Dissolving lithium-containing oxide and 0.12mol of cobalt acetate in ethanol, stirring and evaporating to dryness, and drying in a 120 ℃ oven. Calcining the dried powder in oxygen at 800 ℃ for 3h to obtain Li1.1Ni0.8Co0.1Mn0.1O2And Li0.83CoO2Compounding the positive electrode material to obtain a composite material with a median particle diameter of about 11 μm, wherein the mass fraction of lithium cobaltate in a lithium-deficient state in the composite material is about 11%.
And (2) taking N-methyl pyrrolidone as a solvent, uniformly stirring the powder obtained after sintering, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 90:5:5, coating the mixture on the surface of a clean aluminum foil, and blade-coating the mixture to form a film. After air blast drying, the electrode sheet was punched into a circular sheet with a diameter of 8mm, and further dried in a vacuum oven at 120 ℃ for 6 hours to remove moisture. The prepared electrode plate is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/L LiPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, and the charge and discharge current density is 0.1C.
Example 3
Example 2 was followed except that 0.05mol of aluminum nitrate was added simultaneously with the addition of cobalt acetate to achieve aluminum coating of the above-described cathode material. Wherein the lithium-deficient lithium cobaltate has a median particle size of about 0.8 μm and a mass fraction in the composite material of about 11%. The prepared electrode plate is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/L LiPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, and the charge and discharge current density is 0.1C.
Examples 4 to 6
Following example 2 except that the cobalt acetate was replaced with corresponding molar amounts of cobalt oxide, cobalt hydroxide and cobalt nitrate, the lithium-depleted lithium cobaltate had median particle diameters of about 4 μm, 2 μm and 0.6 μm, respectively, and the mass fraction of the lithium-depleted lithium cobaltate in the composite material was about 11%. The prepared electrode plate is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/L LiPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC to DMC 1:1) as electrolyte, assembled into battery in glove box and tested for charging and dischargingThe voltage range is 2.8-4.5V, and the charge-discharge current density is 0.1C.
Examples 7 to 10
Example 1 is followed except that Li1.1Ni0.8Co0.1Mn0.1O2In turn replaced by Li1.1Ni0.8Co0.1Al0.1O2、Li1.1Ni0.815Co0.15Al0.035O2、Li1.05Ni0.6Co0.2Mn0.2O2And Li1.2Ni0.6Co0.2Mn0.2O2The mass fraction of lithium cobaltate in the lithium deficient state in the composite material is about 33%. The prepared electrode plate is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/L LiPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, and the charge and discharge current density is 0.1C.
Examples 11 to 12
Following example 3 except that aluminum nitrate was replaced with aluminum isopropoxide and tetrabutyl titanate in this order, the electrode sheet thus produced was used as the working electrode of a half-cell, lithium metal was used as the counter electrode, and 1mol/L LiPF was used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, and the charge and discharge current density is 0.1C.
Example 13
Following example 2 except that 0.03mol of lithium hydroxide was added along with the addition of cobalt acetate, the lithium cobaltate in the lithium depleted state had a median particle size of about 1.1 μm. The prepared electrode plate is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/L LiPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, and the charge and discharge current density is 0.1C.
Example 14
Similar to example 1, except that the sintering temperature in the step one) is regulated to 850 ℃, the median particle size of the obtained high-nickel product is about 9 mu m, the prepared electrode slice is used as a working electrode of a half-cell, metal lithium is used as a counter electrode, and 1mol/LLIPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, and the charge and discharge current density is 0.1C.
Example 15
Following example 2 except that the sintering temperature in step two) was adjusted to 650 c, the lithium cobaltate in the lithium depleted state had a median particle size of about 1.2 μm. The prepared electrode plate is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/L LiPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, and the charge and discharge current density is 0.1C.
Examples 16 to 18
Example 1 is followed except that Li1.1Ni0.8Co0.1Mn0.1O2Sequentially replacing the following steps: li1.1Ni0.8Co0.2O2、Li1.1Ni0.8Mn0.2O2And Li1.1Ni0.7Mn0.2Al0.1O2The median particle size of the high nickel material is about 8 μm, 7.5 μm and 7 μm, respectively. The prepared electrode plate is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/L LiPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, and the charge and discharge current density is 0.1C.
Example 19
Following example 1 except that Ni was added0.8Co0.1Mn0.1(OH)2Replacement ofIs Ni (OH)2The median particle size of the high nickel material is about 8 μm. The prepared electrode slice is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/LLIPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, and the charge and discharge current density is 0.1C.
Example 20
Following example 1 except that 0.5mol of Li was added0.7CoO2Replacement of the lithium-containing oxide with 0.001mol of Li0.7CoO2A lithium-containing oxide, the high nickel material having a median particle size of about 8 μm, wherein the mass fraction of lithium cobaltate in a lithium-depleted state in the composite material is about 0.1%. The prepared electrode plate is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/L LiPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (weight ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, and the charge and discharge current density is 0.1C.
The electrochemical cycling results of the above examples are shown in table 2:
table 2 (specific charge/discharge capacity/quality of composite electrode material)
Figure BDA0001305912210000081
Figure BDA0001305912210000091
As can be seen from the above table, the material modified according to the technical scheme of the present invention can effectively remove lithium hydroxide and lithium carbonate with electronic insulation on the surface of the material, and simultaneously generate lithium cobaltate in a lithium-poor state with electrochemical activity, and further modify and improve the surface structure stability and the charge transfer characteristic of the material, so that the material has relatively good capacity exertion and cycling stability.

Claims (6)

1. The composite positive electrode material of the lithium ion secondary battery comprises a high nickel positive electrode material of the lithium ion secondary battery and lithium cobaltate in a lithium-poor state, wherein the high nickel positive electrode material of the lithium ion secondary battery is represented by a general formula Li1+xNi1-y-zCoyMzO2M is at least one element selected from the group consisting of Al and Mn, 0<x is less than or equal to 0.2, y is less than or equal to 0 and less than or equal to 0.4, z is less than or equal to 0 and less than or equal to 0.4, and y + z is less than or equal to 0 and less than or equal to 0.6, wherein the lithium cobaltate in the lithium-poor state is represented by the general formula LiaCoO2A is more than or equal to 0.7 and less than 1, and the crystal structure of the lithium cobaltate in the lithium-poor state is in a layer shape; the median particle size of the high-nickel anode material of the lithium ion secondary battery is 2-20 mu m, and the median particle size of the lithium cobaltate in a lithium-poor state is 0.1-4 mu m.
2. The composite positive electrode material for a lithium ion secondary battery according to claim 1, wherein the weight fraction of the lithium cobaltate in the lithium-poor state in the composite positive electrode material for a lithium ion secondary battery is 0.1-40%.
3. The method for preparing the composite positive electrode material for a lithium ion secondary battery as claimed in any one of claims 1 to 2, comprising the steps of:
1) mixing Ni1-y-zCoyMz(OH)2Mixing with lithium source according to the mol ratio of 1-1.2, sintering, cooling to room temperature to obtain Li1+xNi1-y-zCoyMzO2A lithium-containing oxide;
2) mixing a cobalt source with Li obtained in step 1)1+xNi1-y-zCoyMzO2And (3) simultaneously adding a part of lithium source into the lithium-containing oxide when the lithium-containing oxide is mixed according to a molar ratio of 0.001-0.5, and sintering to obtain the lithium-ion secondary battery composite positive electrode material comprising the lithium-ion secondary battery high-nickel positive electrode material and lithium cobaltate in a lithium-poor state, wherein the molar ratio of the lithium source to the cobalt source is 0.001-1.
4. The method of claim 3, wherein in step 1), the lithium source is selected from one or more of lithium hydroxide, lithium carbonate, lithium acetate, or lithium nitrate.
5. The method as claimed in claim 3, wherein the sintering temperature ranges in steps 1) and 2) are both 650-1100 ℃.
6. The method according to claim 3, wherein in the step 2), the cobalt source is one or more selected from cobalt hydroxide, cobalt oxide, cobalt nitrate and cobalt acetate.
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CN113381000B (en) * 2018-05-18 2023-03-24 宁德新能源科技有限公司 Cathode material and lithium ion battery
CN108695502A (en) * 2018-05-22 2018-10-23 青海泰丰先行锂能科技有限公司 A kind of lithium ion battery composite cathode material and preparation method thereof
EP3814280B1 (en) * 2018-06-28 2023-11-29 Basf Se Method for processing ni-rich electrode active materials
CN113471414A (en) * 2020-03-31 2021-10-01 北京卫蓝新能源科技有限公司 Lithium ion battery composite positive electrode material and preparation method and application thereof
CN114762151A (en) * 2020-06-08 2022-07-15 宁德新能源科技有限公司 Cathode material and electrochemical device comprising same
CN114784285B (en) * 2022-06-17 2022-10-25 宁德新能源科技有限公司 Positive electrode material, and electrochemical device and electronic device comprising same

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