CN111430700B - Quaternary cathode material for lithium ion battery, preparation method of quaternary cathode material and lithium ion battery - Google Patents

Quaternary cathode material for lithium ion battery, preparation method of quaternary cathode material and lithium ion battery Download PDF

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CN111430700B
CN111430700B CN201910959426.2A CN201910959426A CN111430700B CN 111430700 B CN111430700 B CN 111430700B CN 201910959426 A CN201910959426 A CN 201910959426A CN 111430700 B CN111430700 B CN 111430700B
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positive electrode
quaternary
electrode material
equal
lithium
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CN111430700A (en
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白艳
张树涛
潘海龙
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Svolt 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 quaternary anode material for a lithium ion battery, a preparation method of the quaternary anode material and the lithium ion battery. The quaternary positive electrode material comprises an inner core and a coating layer, wherein the coating layer is formed on at least part of the surface of the inner core, the quaternary positive electrode material has a composition shown in a formula (I), and LixNiaCobMncAldMyO2(I) In the formula (I), x is more than or equal to 1.00 and less than or equal to 1.05, y is more than or equal to 0.00 and less than or equal to 0.05, a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03, c is more than or equal to 0.01 and less than or equal to 0.03, a + b + c + d is 1, and M is at least one element selected from a second main group element, a third main group element, a fourth main group element, a fifth main group element, a fourth subgroup element and a fifth subgroup element. According to the quaternary positive electrode material, the doping elements are introduced into the core to form the coating layer, so that the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.

Description

Quaternary cathode material for lithium ion battery, preparation method of quaternary cathode material and lithium ion battery
Technical Field
The invention relates to the field of electrochemistry, in particular to a quaternary anode material for a lithium ion battery, a preparation method of the quaternary anode material and the lithium ion battery.
Background
Lithium ion batteries are widely used in electric vehicles, hybrid vehicles and energy storage systems due to their high capacity and high energy density, and the positive electrode material, as one of the core components of lithium ion batteries, has a significant impact on the performance of lithium ion batteries.
Researchers have found that high-nickel cathode materials have the advantages of high capacity and low cost, and are gradually replacing LiCoO2The cycle performance of the cathode material is poor. In order to improve the performance of the battery, the residual alkali content on the surface of the cathode material needs to be reduced, otherwise, the cathode material is gelatinized in the homogenizing process, and the industrial application of the cathode material is hindered. In addition, the anode material in the battery is in contact with the electrolyte, and the anode material is easy to chemically react with the electrolyte, so that the transition metal in the anode material is dissolved in the electrolyte, thereby increasing the interface impedance of the anode material and reducing the capacity and cycle performance of the battery. Therefore, the existing lithium ion battery cathode material still needs to be improved.
Disclosure of Invention
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Therefore, the invention aims to provide a quaternary cathode material for a lithium ion battery, a preparation method thereof and the lithium ion battery. According to the quaternary positive electrode material, the doping elements are introduced into the core to form the coating layer, so that the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
In one aspect of the invention, a quaternary positive electrode material for a lithium ion battery is presented. According to the embodiment of the invention, the quaternary positive electrode material comprises an inner core and a coating layer, the coating layer is formed on at least part of the surface of the inner core, the quaternary positive electrode material has the composition shown in the formula (I),
LixNiaCobMncAldMyO2(I)
in the formula (I), x is more than or equal to 1.00 and less than or equal to 1.05, y is more than or equal to 0.00 and less than or equal to 0.05, a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03, c is more than or equal to 0.01 and less than or equal to 0.03, a + b + c + d is 1, and M is at least one selected from the group consisting of second main group elements, third main group elements, fourth main group elements, fifth main group elements, fourth subgroup elements and fifth subgroup elements.
The quaternary positive electrode material for the lithium ion battery provided by the embodiment of the invention has a core-shell structure comprising a core and a coating layer, wherein the core can be obtained by doping an M element with a nickel-cobalt-manganese-aluminum quaternary material (NCMA material), and is also provided with the coating layer, and the whole quaternary positive electrode material has a composition shown in a formula (I). According to the quaternary positive electrode material, the doping elements are introduced into the core to form the coating layer, so that the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
In addition, the quaternary positive electrode material according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, M is at least one selected from Mg, Ba, B, Al, Si, P, Ti, Zr, Nb.
In some embodiments of the invention, M is Al, Zr, B.
In some embodiments of the invention, M is Al, Ti, Nb.
In some embodiments of the invention, M is Al, Mg, Ti.
In another aspect of the present invention, the present invention provides a method of preparing the quaternary positive electrode material of the above embodiment. According to an embodiment of the invention, the method comprises: (1) mixing a quaternary positive electrode material precursor, a lithium source and a doping agent to obtain a first mixed material; (2) performing first sintering treatment on the first mixed material to obtain a quaternary positive electrode material core; (3) mixing the quaternary positive electrode material kernel with a first coating agent to obtain a second mixed material; (4) performing second sintering treatment on the second mixed material to obtain a primary coated product; (5) mixing the primary coated product with a second coating agent to obtain a third mixed material; and (6) calcining the third mixed material to obtain the quaternary positive electrode material. The method is simple and convenient to operate and easy to implement industrially, and the prepared quaternary anode material can improve the thermal stability and the cycle performance of the material while keeping the high nickel capacity of the material.
In addition, the method for preparing the quaternary positive electrode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the quaternary positive electrode material precursor has a composition as shown in formula (II), NiaCobMncAld(OH)2(II). In the formula (II), a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03 and less than or equal to 0.06, c is more than or equal to 0.01 and less than or equal to 0.03, d is more than or equal to 0.01 and less than or equal to 0.03, and a + b + c + d is 1;
in some embodiments of the invention, the lithium source comprises at least one selected from the group consisting of lithium nitrate, lithium carbonate, lithium hydroxide monohydrate.
In some embodiments of the present invention, the dopant comprises at least one selected from the group consisting of zirconium hydroxide, zirconium oxide, titanium oxide, magnesium hydroxide, magnesium oxide, magnesium carbonate, magnesium nitrate, barium hydroxide, aluminum oxide, aluminum hydroxide, aluminum oxyhydroxide, zinc oxide, niobium pentoxide, and the like;
in some embodiments of the present invention, the first coating agent comprises at least one selected from the group consisting of alumina, aluminum hydroxide, aluminum nitrate, aluminum oxyhydroxide, and the like;
in some embodiments of the present invention, the second coating agent comprises at least one selected from boric acid, boron oxide, lithium phosphate, lithium niobate, and the like.
In some embodiments of the invention, in the step (1), the molar ratio of the quaternary positive electrode material precursor to lithium element in the lithium source is 1 (1.00-1.05); the mass ratio of the quaternary positive electrode material precursor to the doping elements in the dopant is 1 (0.001-0.003).
In some embodiments of the present invention, in the step (3), the mass ratio of the quaternary positive electrode material core to the coating element in the first coating agent is 1 (0.0005-0.001).
In some embodiments of the invention, in the step (5), the mass ratio of the primary coating product to the coating element in the second coating agent is 1 (0.001-0.01).
In some embodiments of the present invention, the first sintering treatment is performed at 700 to 820 ℃ for 8 to 20 hours.
In some embodiments of the present invention, the second sintering treatment is performed at 600-700 ℃ for 6-15 h.
In some embodiments of the present invention, the calcination treatment is performed at 300-600 ℃ for 8-18 h.
In some embodiments of the present invention, step (5) is preceded by: and carrying out water washing treatment and drying treatment on the primary coated product.
In some embodiments of the invention, the mass ratio of the primary coating product to the water in the water washing treatment is (1-2): 1, and the water washing treatment is carried out at a stirring speed of 500-800 rpm for 30-600 s.
In some embodiments of the invention, the drying treatment is performed at 100-180 ℃ for 3-20 hours.
In yet another aspect of the present invention, a lithium ion battery is presented. According to an embodiment of the present invention, the lithium ion battery includes: a positive electrode, a negative electrode, a separator and an electrolyte; wherein the positive electrode includes: a positive current collector and a positive electrode material supported on the positive current collector, the positive electrode material comprising: a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; the positive electrode active material is the quaternary positive electrode material described in the above embodiment. The negative electrode includes: a negative electrode current collector and a negative electrode material supported on the negative electrode current collector, the negative electrode material including: a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
The lithium ion battery according to the embodiment of the invention has all the features and advantages described above for the quaternary positive electrode material by using the quaternary positive electrode material of the above embodiment as the positive electrode active material, and thus, the description thereof is omitted. In general, the lithium ion battery has higher capacity and better cycle stability.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow diagram of a method of making a quaternary positive electrode material according to one embodiment of the invention;
fig. 2 is a graph showing the first charge and discharge curves of a battery fabricated using the quaternary positive electrode material prepared in example 1 according to the present invention;
fig. 3 is a graph showing the first charge and discharge curves of a battery fabricated using the quaternary positive electrode material prepared in comparative example 1 according to the present invention;
fig. 4 is a graph showing the first charge and discharge curves of a battery fabricated using the quaternary positive electrode material prepared in comparative example 2 according to the present invention;
fig. 5 is a graph showing the first charge and discharge curves of a battery fabricated using the quaternary positive electrode material prepared in comparative example 3 according to the present invention.
Detailed Description
The following describes in detail embodiments of the present invention. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a quaternary positive electrode material for a lithium ion battery is presented. According to the embodiment of the invention, the quaternary positive electrode material comprises an inner core and a coating layer, the coating layer is formed on at least part of the surface of the inner core, the quaternary positive electrode material has the composition shown in the formula (I),
LixNiaCobMncAldMyO2(I)
in the formula (I), x is more than or equal to 1.00 and less than or equal to 1.05, y is more than or equal to 0.00 and less than or equal to 0.05, a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03, c is more than or equal to 0.01 and less than or equal to 0.03, a + b + c + d is 1, and M is at least one selected from the group consisting of second main group elements, third main group elements, fourth main group elements, fifth main group elements, fourth subgroup elements and fifth subgroup elements.
The quaternary positive electrode material for the lithium ion battery according to the embodiment of the invention has a core-shell structure comprising an inner core and a coating layer, wherein the inner core can be obtained by doping an M element with a nickel-cobalt-manganese-aluminum quaternary material (NCMA material), and simultaneously has the coating layer, and the whole quaternary positive electrode material has the composition shown in the formula (I). According to the quaternary positive electrode material, the doping elements are introduced into the core to form the coating layer, so that the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
Specifically, in formula (I), x may be 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, etc., y may be 0, 0.01, 0.02, 0.03, 0.04, 0.05, etc., a may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.92, etc., b may be 0.03, 0.04, 0.05, 0.06, etc., c may be 0.01, 0.02, 0.03, etc., d may be 0.01, 0.02, 0.03, etc., and a, b, c, d satisfy a + b + c + d ═ 1.
Specifically, M is a doping element and/or a coating element of the NCMA material, and may be present in the core of the quaternary positive electrode material, the coating layer of the quaternary positive electrode material, or both. Therefore, the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
According to an embodiment of the present invention, M may be at least one selected from Mg, Ba, B, Al, Si, P, Ti, Zr, Nb. By doping and/or coating the NCMA material by adopting the elements, the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
According to a preferred embodiment of the invention, M is Zr, Al, B. The Zr is used as a doping element of the NCMA material core, so that the material can be kept to have higher capacity, and the Al and the B are used as coating elements of the NCMA material core, so that the NCMA material core surface active sites can be shielded, the occurrence of side reactions between the anode material and the electrolyte can be effectively reduced, and the cycle performance and the thermal stability of the material can be further improved.
According to a preferred embodiment of the invention, M is Al, Ti, Nb. The Ti is used as a doping element of the NCMA material core, so that the material can be kept to have higher capacity, and the Al and the Nb are used as coating elements of the NCMA material core, so that the NCMA material core surface active sites can be shielded, the occurrence of side reactions between the anode material and the electrolyte can be effectively reduced, and the improvement of the cycle performance and the thermal stability of the material is further facilitated.
According to a preferred embodiment of the invention, M is Al, Mg, Ti. The Mg and the Ti are used as doping elements of the NCMA material core, so that the material can be kept to have higher capacity, and the Al is used as a coating element of the NCMA material core, so that the NCMA material core surface active sites can be shielded, the occurrence of side reactions between the anode material and the electrolyte can be effectively reduced, and the cycle performance and the thermal stability of the material can be further improved.
The inventor finds in research that doping of Al, Mg, Zr, Ti and other elements can stabilize the structure of the material, improve the electronic conductivity and the ionic conductivity, improve the capacity of the material, and improve the cycling stability and the thermal stability of the material. And can resist the corrosion of the electrolyte to the anode material through the coating effect, prevent the dissolution of metal ions in the anode material, reduce the surface impedance and improve the cycle stability and the thermal stability.
In another aspect of the present invention, the present invention provides a method of preparing the quaternary positive electrode material of the above embodiment. According to an embodiment of the invention, the method comprises: (1) mixing a quaternary positive electrode material precursor, a lithium source and a doping agent to obtain a first mixed material; (2) performing first sintering treatment on the first mixed material to obtain a quaternary positive electrode material core; (3) mixing the quaternary positive electrode material kernel with a first coating agent to obtain a second mixed material; (4) performing second sintering treatment on the second mixed material to obtain a primary coated product; (5) mixing the primary coating product with a second coating agent to obtain a third mixed material; and (6) calcining the third mixed material to obtain the secondary coated quaternary anode material. The method is simple and convenient to operate and easy to implement industrially, and the prepared quaternary anode material can improve the thermal stability and the cycle performance of the material while keeping the high nickel capacity of the material.
The method of preparing a quaternary positive electrode material according to an embodiment of the present invention is further described in detail below. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: obtaining a first mixed material
In the step, a quaternary positive electrode material precursor, a lithium source and a dopant are mixed to obtain a first mixed material.
According to an embodiment of the present invention, the specific type of the quaternary positive electrode material precursor is not particularly limited, and those skilled in the art can select the quaternary positive electrode material precursor according to actual needs, for example, nickel cobalt manganese aluminum hydroxide is used. According to the method provided by the invention, the conventional commercial quaternary anode material precursor is doped by using the dopant, and the prepared quaternary anode material has better thermal stability and cycle performance while keeping high nickel capacity through subsequent coating. In some embodiments of the invention, the quaternary positive electrode material precursor has a composition as shown in formula (II),
NiaCobMncAld(OH)2(II)。
in the formula (II), a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03 and less than or equal to 0.06, c is more than or equal to 0.01 and less than or equal to 0.03, d is more than or equal to 0.01 and less than or equal to 0.03, and a + b + c + d is equal to 1. In the formula (II), a may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.92, etc., b may be 0.03, 0.04, 0.05, 0.06, etc., c may be 0.01, 0.02, 0.03, etc., d may be 0.01, 0.02, 0.03, etc., and a, b, c, d satisfy a + b + c + d of 1.
According to an embodiment of the present invention, a specific kind of the above-described lithium source is not particularly limited, and a lithium source commonly used in the art for preparing a positive active material of a lithium battery may be used. According to a specific example of the present invention, the lithium source may include at least one selected from the group consisting of lithium nitrate, lithium carbonate, and lithium hydroxide monohydrate. The lithium source has wide sources, is cheap and easy to obtain, and has good compatibility with nickel, cobalt, manganese and aluminum elements and doping elements (namely M elements).
According to embodiments of the present invention, the doping element may be provided in the form of an oxide, hydroxide, chloride, etc. of M. That is, the dopant includes a dopant selected from the group consisting of zirconium hydroxide (Zr (OH)4) Zirconium oxide (ZrO)2) Titanium oxide (TiO)2) Magnesium hydroxide (Mg (OH))2) Magnesium oxide (MgO), magnesium carbonate (MgCO)3) Magnesium nitrate (Mg (NO)3)2) Barium hydroxide (Ba (OH)2) Aluminum oxide (Al)2O3) Aluminum hydroxide (Al (OH)3) Aluminum oxyhydroxide (AlOOH), zinc oxide (ZnO), niobium pentoxide (Nb)2O5) In or forOne less. By adopting the doping agent, the required doping elements can be introduced into the quaternary positive electrode material core, so that the thermal stability and the cycle performance of the material are improved while the high nickel capacity of the material is kept.
According to an embodiment of the present invention, a quaternary positive electrode material precursor, a lithium source, and a doping element may be mixed in the following ratio: the molar ratio of the quaternary positive electrode material precursor to the lithium element in the lithium source is 1 (1.00-1.05), such as 1:1.00, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, and the like; the mass ratio of the quaternary positive electrode material precursor to the doping element (i.e., M element) in the dopant is 1 (0.001-0.003), for example, 1:0.001, 1:0.002, 1:0.003, and the like. Therefore, the capacity, the thermal stability and the cycle performance of the prepared quaternary anode material can be further improved.
S200: first sintering process
In the step, the first mixed material is subjected to first sintering treatment to obtain a quaternary positive electrode material core. Specifically, the first sintering process may be performed in an oxygen atmosphere to introduce a doping element into the NCMA material and form a quaternary positive electrode material core.
According to the embodiment of the invention, the first sintering treatment can be completed at 700-820 ℃ for 8-20 h. Specifically, the sintering temperature can be 700 ℃, 720 ℃, 750 ℃, 790 ℃, 820 ℃ and the like, and the sintering time can be 8h, 12h, 15h, 18h, 20h and the like. By performing the first sintering treatment under the above conditions, the quality of the sintered quaternary positive electrode material core can be further improved.
According to the embodiment of the invention, after the first sintering treatment is completed, the quaternary positive electrode material core can be cooled, crushed and sieved to obtain a material with the average particle size of 5-20 μm, and the specific particle size can be determined according to the particle size of the quaternary positive electrode material precursor.
S300: obtaining a second mixed material
In the step, the quaternary positive electrode material core is mixed with a first coating agent, so that the first coating agent is uniformly coated on the surface of the quaternary positive electrode material core, and a second mixed material is obtained.
According to an embodiment of the present invention, the first coating element may be provided in the form of an oxide, a hydroxide, or the like of the M element, that is, the above-mentioned first coating agent may include a material selected from alumina (Al)2O3) Aluminum hydroxide (Al (OH)3) At least one of [ sic ]. cndot.. cndot. The coating layer containing the M element is introduced to the surface of the quaternary positive electrode material kernel by using the first coating agent, so that active sites on the surface of the NCMA material can be effectively shielded, the side reaction of the quaternary positive electrode material kernel and electrolyte is reduced, and the thermal stability and the cycle performance of the material are improved.
According to an embodiment of the present invention, a quaternary positive electrode material may be mixed with a first coating agent in the following ratio: the mass ratio of the quaternary positive electrode material core to the coating element (i.e., M element) in the first coating agent is 1 (0.0005 to 0.001), for example, 1:0.0005, 1:0.0006, 1:0.0007, 1:0.0008, 1:0.001, and the like. Therefore, the capacity, the thermal stability and the cycle performance of the prepared quaternary cathode material can be further improved.
S400: second sintering treatment
In the step, the second mixed material is subjected to second sintering treatment to obtain a primary coated product. Specifically, the second sintering treatment may be performed in an oxygen atmosphere to form a stable coating layer on the surface of the quaternary positive electrode material core.
According to the embodiment of the invention, the second sintering treatment can be completed at 600-700 ℃ for 6-15 h. Specifically, the sintering temperature can be 600 ℃, 620 ℃, 680 ℃, 700 ℃ and the like, and the sintering time can be 6h, 8h, 10h, 12h, 15h and the like. By performing the second sintering treatment under the above conditions, the quality of the primary-coated quaternary positive electrode material obtained by sintering can be further improved.
According to the embodiment of the invention, after the second sintering treatment is completed, the quaternary positive electrode material core can be cooled, crushed and sieved to obtain a material with the average particle size of 5-20 μm, and the specific particle size can be determined according to the particle size of the precursor of the quaternary positive electrode material.
S500: obtaining a third mixed material
In the step, the primary coated product is mixed with a second coating agent, so that the second coating agent is uniformly coated on the surface of the primary coated quaternary anode material, and a third mixed material is obtained.
According to an embodiment of the present invention, the second coating element may be provided in the form of an oxide, a hydroxide, or the like of the M element, that is, the above-mentioned second coating agent may include a compound selected from boric acid (H)3BO3) Boron oxide (B)2O3) At least one of. By introducing the second coating element to the surface of the primary coated quaternary anode material by using the second coating agent, the active sites on the surface of the NCMA material can be further effectively shielded, the occurrence of side reactions between the quaternary anode material core and the electrolyte can be further reduced, and the thermal stability and the cycle performance of the material can be further improved.
According to an embodiment of the present invention, the primary-coated quaternary positive electrode material may be mixed with the second coating agent in the following ratio: the mass ratio of the primary coating product to the coating element (i.e., M element) in the second coating agent is 1 (0.001-0.01), for example, 1:0.001, 1:0.003, 1:0.005, 1:0.008, 1:0.01, etc. Therefore, the capacity, the thermal stability and the cycle performance of the prepared quaternary cathode material can be further improved.
S600: calcination treatment
In the step, the third mixed material is calcined to obtain a secondary coated quaternary anode material. Specifically, the calcination treatment may be performed in an oxygen atmosphere in order to stably introduce the second coating element into the primary coated quaternary positive electrode material.
According to the embodiment of the invention, the calcination treatment can be completed at 300-600 ℃ for 8-18 h. Specifically, the calcination temperature can be 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 600 ℃ and the like, and the sintering time can be 8h, 12h, 14h, 16h, 18h and the like. By performing the calcination treatment under the above conditions, the quality of the secondarily coated quaternary positive electrode material obtained by sintering can be further improved.
According to the embodiment of the invention, after the calcination treatment is completed, the quaternary positive electrode material can be cooled, crushed and sieved to obtain a product with the average particle size of 5-20 μm, and the specific particle size can be determined according to the particle size of the precursor of the quaternary positive electrode material.
In order to further improve the quality of the quaternary cathode material prepared, according to an embodiment of the present invention, the primary coated product may be subjected to a water washing process and a drying process before S500. Thus, impurities contained in the primary coated product can be effectively removed. The inventor finds in research that the primary coating product contains part of residual alkali Li2CO3、LiOH、Li2O and the like. If the impurities are not removed, the viscosity of the battery slurry is increased and even the battery slurry is in a gel or jelly shape in the battery manufacturing process, and the material cannot enter the next process.
According to the embodiment of the invention, in the water washing treatment, the mass ratio of the primary coating product to the water can be (1-2): 1, and the water washing treatment can be completed at a stirring speed of 500-800 rpm for 30-600 s.
According to the embodiment of the invention, the drying treatment is carried out at 100-180 ℃ for 3-20 h. Specifically, the drying temperature may be 100 ℃, 120 ℃, 140 ℃, 180 ℃ and the like, and the drying time may be 3 hours, 5 hours, 12 hours, 15 hours, 18 hours, 20 hours and the like. Therefore, the moisture in the material can be effectively removed, and the problems of deterioration and the like of the material due to overhigh drying temperature or drying time process can be guaranteed.
In another aspect of the present invention, a lithium ion battery is provided. According to an embodiment of the present invention, the lithium ion battery includes: a positive electrode, a negative electrode, a separator and an electrolyte; wherein, positive pole includes: the positive pole current collector and the positive pole material of load on the positive pole current collector, positive pole material includes: a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; the positive electrode active material is the quaternary positive electrode material of the above embodiment. The negative electrode includes: a negative electrode current collector and a negative electrode material supported on the negative electrode current collector, the negative electrode material including: a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
The lithium ion battery according to the embodiment of the invention has all the features and advantages described above for the quaternary positive electrode material by using the quaternary positive electrode material of the above embodiment as the positive electrode active material, and thus, the description thereof is omitted. In general, the lithium ion battery has higher capacity and better cycle stability.
According to some embodiments of the present invention, a positive electrode material includes a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder; the mass ratio of the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is not particularly limited, and may be selected according to actual needs. The positive electrode active material was the quaternary positive electrode material of the above-described embodiment. The specific types of the positive electrode conductive agent and the positive electrode binder are not particularly limited, and for example, the positive electrode conductive agent may be at least one of common positive electrode binders such as conductive carbon black SP or ECP, carbon nanotubes (CNT or WCNT), graphene, and the like; the positive electrode binder may be at least one of common positive electrode binders such as polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), and the like. The positive electrode material may further include a common solvent (e.g., NMP) for mixing the positive electrode material, and the ratio of the solvent to the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is not particularly limited, and may be selected by those skilled in the art according to actual needs.
According to some embodiments of the present invention, the negative electrode material includes a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder; the mass ratio of the negative electrode active material, the negative electrode conductive agent, the negative electrode binder, and the thickening stabilizer is not particularly limited, and may be selected according to actual needs. The specific types of the negative electrode active material, the negative electrode conductive agent and the negative electrode binder are not particularly limited, and the negative electrode active material can be at least one of common negative electrode active materials selected from natural graphite, artificial graphite, mesophase microspheres, soft carbon, hard carbon and the like; the negative electrode conductive agent can be at least one of common negative electrode conductive agents such as conductive carbon black SP or ECP, carbon nano tubes (CNT or WCNT), graphene and the like; the negative electrode binder may be at least one of common negative electrode binders such as polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), and the like. In addition, the negative electrode material may further include a common solvent (e.g., NMP, deionized water, etc.) for mixing the negative electrode material, and the solvent is not particularly limited and may be selected by those skilled in the art according to actual needs.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1) Making quaternary precursor Ni of positive electrode materialaCobMncAld(OH)2(a-0.88, b-0.06, c-0.03, d-0.03), a lithium source and a dopant in the following proportions: wherein Li elements in the quaternary precursor (nickel cobalt manganese aluminum hydroxide) and the lithium source (LiOH) of the anode material are mixed according to the mol ratio of 1:1.035, and the doping agent (Zr (OH)4) The mass ratio of the Zr element to the quaternary precursor is 0.003: 1. And (3) sintering the dry-mixed material for 10h at 740 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the primary-sintered quaternary anode material (first product).
(2) Mixing the first product with a first coating agent (Al)2O3) And (3) uniformly mixing the first product and Al element by a dry method according to the mass ratio of 1:0.0005 to ensure that the first coating agent is uniformly coated on the surface of the first product, sintering the material subjected to dry mixing for 6 hours at 600 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain a primary coated quaternary anode material (second product).
(3) And mixing the second product with deionized water according to the mass ratio of 2:1, stirring at the room temperature of 600rpm for 60s, filtering, and performing vacuum drying at 150 ℃ for 8h to obtain the primary coated quaternary anode material (third product) which is subjected to washing and drying.
(4) Mixing the third product with a second coating agent (B)2O3) And uniformly mixing the third product and the element B by a dry method according to the mass ratio of 0.001:1 to ensure that the second coating agent is uniformly coated on the surface of the third product, calcining the material obtained after the dry mixing at a certain temperature of 400 ℃ in an oxygen atmosphere for 10 hours, cooling, crushing and sieving to obtain the secondary coated quaternary anode material.
Comparative example 1
(1) The quaternary precursor Ni of the anode materialaCobMncAld(OH)2(a-0.88, b-0.06, c-0.03, d-0.03), a lithium source and a dopant in the following proportions: wherein Li elements in the quaternary precursor (nickel cobalt manganese aluminum hydroxide) and the lithium source (LiOH) of the anode material are mixed according to the mol ratio of 1:1.035, and the doping agent (Zr (OH)4) The mass ratio of the Zr element to the quaternary precursor is 0.003: 1. And sintering the dry-mixed material for 10 hours at 735 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the quaternary anode material product.
Comparative example 2
(1) The quaternary precursor Ni of the anode materialaCobMncAld(OH)2(a-0.88, b-0.06, c-0.03, d-0.03), lithium source and dopant in the following proportions: wherein Li elements in the quaternary precursor (nickel cobalt manganese aluminum hydroxide) and the lithium source (LiOH) of the positive electrode material are mixed according to the mol ratio of 1:1.035, and a dopant (Zr (OH)4) The mass ratio of the Zr element to the quaternary precursor is 0.003: 1. And (3) sintering the dry-mixed material for 10 hours at 740 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the primary-sintered quaternary anode material (first product).
(2) Mixing the first product with a first coating agent (Al)2O3) And uniformly mixing the first product and the Al element in a mass ratio of 1:0.0005 by a dry method to ensure that the first coating agent is uniformly coated on the surface of the first product, sintering the material subjected to dry mixing for 6 hours at 600 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain a primary coated quaternary anode material product.
Comparative example 3
(1) Making quaternary precursor Ni of positive electrode materialaCobMncAld(OH)2(a-0.88, b-0.06, c-0.03, d-0.03), a lithium source and a dopant in the following proportions: wherein Li elements in the quaternary precursor (nickel cobalt manganese aluminum hydroxide) and the lithium source (LiOH) of the anode material are mixed according to the mol ratio of 1:1.035, and the doping agent(Zr(OH)4) The mass ratio of the Zr element to the quaternary precursor is 0.003: 1. And (3) sintering the dry-mixed material for 10h at 740 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the primary-sintered quaternary anode material (first product).
(2) Mixing the first product with a first coating agent (Al)2O3) And (3) uniformly mixing the first product and Al element by a dry method according to the mass ratio of 1:0.0005 to ensure that the first coating agent is uniformly coated on the surface of the first product, sintering the material subjected to dry mixing for 6 hours at 600 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain a primary coated quaternary anode material product (a second product).
(3) And mixing the second product with deionized water according to the mass ratio of 2:1, stirring at the room temperature and the rotating speed of 600rpm for 60s, filtering, and carrying out vacuum drying at 150 ℃ for 8h to obtain the primary coated quaternary anode material product after washing and drying.
Test example
(1) The quaternary positive electrode materials prepared in example 1 and comparative examples 1 to 3 were respectively used to prepare button cells for testing, the first charge-discharge curve of the button cells was obtained through testing, and the capacity retention rate after 50-week circulation of the button cells was tested at normal temperature, and the results are shown in fig. 2 to 5 and table 1.
(2) Differential Scanning Calorimetry (DSC) was performed on the quaternary positive electrode materials prepared in example 1 and comparative examples 1 to 3, and the results are shown in table 2.
TABLE 1 results of the cycle Performance test
Figure BDA0002228425490000121
TABLE 2DSC results
Example 1 Comparative example 1 Comparative example 2 Comparative example 3
DSC temperature 230℃ 199.32℃ 203.33℃ 209.44℃
The test result shows that the battery made of the secondary coated quaternary positive electrode material has higher capacity and cycle performance and better thermal stability compared with the battery made of a comparative example material. As can be seen from comparative example 1, the thermal stability of the uncoated NCMA quaternary positive electrode material was low, and the cycle performance of the fabricated battery was significantly reduced. As can be seen from comparative examples 2 and 3, the performance of the once-coated NCMA quaternary positive electrode material is improved compared with that of comparative example 1, but is still inferior to that of example 1. In addition, the material in comparative example 2 is not washed with water and dried before being applied to the manufacture of the battery, and the performance is inferior to that in comparative example 3, which shows that impurities generated in the primary coating process can cause adverse effects on the product performance if not removed.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (17)

1. A method for preparing a quaternary positive electrode material for a lithium ion battery, the quaternary positive electrode material comprising an inner core and a coating layer formed on at least a part of the surface of the inner core, the quaternary positive electrode material having a composition represented by formula (I), LixNiaCobMncAldMyO2(I) In the formula (I), x is not less than 1.00 and not more than 1.05, y is not less than 0.00 and not more than 0.05, a is not less than 0.3 and not more than 0.92, b is not less than 0.03 and not more than 0.06, c is not less than 0.01 and not more than 0.03, a + b + c + d is 1, and M is at least one element selected from the group consisting of a second main group element, a third main group element, a fourth main group element, a fifth main group element, a fourth subgroup element, and a fifth subgroup element, and the formula is characterized by comprising:
(1) mixing a quaternary positive electrode material precursor, a lithium source and a doping agent to obtain a first mixed material;
(2) carrying out first sintering treatment on the first mixed material to obtain a quaternary anode material core;
(3) mixing the quaternary positive electrode material kernel with a first coating agent to obtain a second mixed material;
(4) carrying out second sintering treatment on the second mixed material to obtain a primary coated product;
(5) mixing the primary coated product with a second coating agent to obtain a third mixed material;
(6) calcining the third mixed material to obtain the quaternary positive electrode material;
further comprising, before step (5): and carrying out water washing treatment and drying treatment on the primary coated product, wherein the drying treatment is carried out at 100-180 ℃.
2. The method of claim 1, wherein M is at least one selected from the group consisting of Mg, Ba, B, Al, Si, P, Ti, Zr, and Nb.
3. The method of claim 2, wherein M is Al, Zr, B, or M is Al, Ti, Nb, or M is Al, Mg, Ti.
4. The method of claim 1, wherein the quaternary positive electrode material precursor has a composition as shown in formula (II),
NiaCobMncAld(OH)2(II)
in the formula (II), a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03 and less than or equal to 0.06, c is more than or equal to 0.01 and less than or equal to 0.03, d is more than or equal to 0.01 and less than or equal to 0.03, and a + b + c + d is equal to 1.
5. The method of claim 1, wherein the lithium source comprises at least one selected from the group consisting of lithium nitrate, lithium carbonate, and lithium hydroxide monohydrate.
6. The method of claim 1, wherein the dopant comprises at least one selected from the group consisting of zirconium hydroxide, zirconium oxide, titanium oxide, magnesium hydroxide, magnesium oxide, magnesium carbonate, magnesium nitrate, barium hydroxide, aluminum oxide, aluminum hydroxide, aluminum oxyhydroxide, zinc oxide, and niobium pentoxide.
7. The method of claim 1, wherein the first coating agent comprises at least one selected from the group consisting of alumina, aluminum hydroxide, aluminum nitrate, and aluminum oxyhydroxide.
8. The method of claim 1, wherein the second coating agent comprises at least one selected from the group consisting of boric acid, boron oxide, lithium phosphate, and lithium niobate.
9. The method according to claim 1, wherein in the step (1), the molar ratio of the quaternary positive electrode material precursor to lithium in the lithium source is 1 (1.00-1.05); the mass ratio of the quaternary positive electrode material precursor to the doping elements in the dopant is 1 (0.001-0.003).
10. The method according to claim 1, wherein in the step (3), the mass ratio of the quaternary positive electrode material core to the coating element in the first coating agent is 1 (0.0005-0.001).
11. The method according to claim 1, wherein in the step (5), the mass ratio of the primary coating product to the coating element in the second coating agent is 1 (0.001-0.01).
12. The method according to claim 1, wherein the first sintering treatment is carried out at 700 to 820 ℃ for 8 to 20 hours.
13. The method of claim 1, wherein the second sintering treatment is performed at 600 to 700 ℃ for 6 to 15 hours.
14. The method according to claim 1, wherein the calcination treatment is performed at 300 to 600 ℃ for 8 to 18 hours.
15. The method according to claim 1, wherein the mass ratio of the primary coating product to water in the water washing treatment is (1-2): 1, and the water washing treatment is performed at a stirring speed of 500-800 rpm for 30-600 s.
16. The method according to claim 1, wherein the drying treatment is performed for 3 to 20 hours.
17. A lithium ion battery, comprising: a positive electrode, a negative electrode, a separator and an electrolyte; wherein the content of the first and second substances,
the positive electrode includes: a positive current collector and a positive electrode material supported on the positive current collector, the positive electrode material comprising: a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; wherein the positive electrode active material is a quaternary positive electrode material prepared by the method of any one of claims 1 to 16;
the negative electrode includes: a negative electrode current collector and a negative electrode material supported on the negative electrode current collector, the negative electrode material including: a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
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