CN113903900A - Modified lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery positive electrode plate - Google Patents

Modified lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery positive electrode plate Download PDF

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CN113903900A
CN113903900A CN202111319421.7A CN202111319421A CN113903900A CN 113903900 A CN113903900 A CN 113903900A CN 202111319421 A CN202111319421 A CN 202111319421A CN 113903900 A CN113903900 A CN 113903900A
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lithium nickel
nickel manganese
manganese oxide
positive electrode
electrode material
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莫方杰
孙化雨
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

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Abstract

The invention provides a modified lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery positive electrode plate. The modified lithium nickel manganese oxide positive electrode material comprises a doped or coated metal oxide MOxThe lithium nickel manganese oxide of (1), wherein the metal oxide MOxThe mass ratio of the lithium nickel manganese oxide to the lithium nickel manganese oxide is (0.01-1) to (99.99-99); the metal oxide MOxThe bond energy between the metal-oxygen bonds in (2.8 eV or more). The modified lithium nickel manganese oxide positive electrode material provided by the invention comprises stable metal oxide with higher metal-oxygen bond energy, inhibits the oxidation of the lithium nickel manganese oxide to electrolyte under high potential, stabilizes the interface between the positive electrode material and the electrolyte,the generation of side reaction is inhibited, so that the gas production in the storage process of the battery is reduced, and the cycling stability of the battery is improved.

Description

Modified lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery positive electrode plate
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to a modified lithium nickel manganese oxide positive electrode material, and particularly relates to a modified lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery positive electrode plate.
Background
The spinel lithium nickel manganese oxide is applied to a power battery system with high energy density due to the fact that the spinel lithium nickel manganese oxide has high reaction potential (higher than 4.6V) and high theoretical specific capacity (higher than 140 mAh/g). However, the reaction potential is too high (> 4.6V), so that the compatibility of the existing system is poor, especially the oxidation of the electrolyte is strong, the interface stability of the anode and the electrolyte is poor, a large amount of anode interface side reactions exist, and the cycle stability of the battery system is reduced.
How to improve the problems that spinel lithium nickel manganese oxide is strong in oxidation of electrolyte and interface stability of a positive electrode and the electrolyte is poor, side reactions existing in a positive electrode interface are reduced, and circulation stability of a battery system is reduced, and the method is a technical problem to be solved urgently for a positive electrode material of a lithium ion battery.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a modified lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery positive electrode plate, wherein stable metal oxide MO is usedxAnd the side reaction of the electrolyte is inhibited, and the stability of the electrode and the electrolyte interface is improved, so that the stability of the battery is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a modified lithium nickel manganese oxide positive electrode material, which comprises a doped or coated metal oxide MOxOf lithium nickel manganese oxide, wherein
The metal oxide MOxThe mass ratio of the lithium nickel manganese oxide to the lithium nickel manganese oxide is (0.01-1) to (99.99-99);
the metal oxide MOxThe bond energy between the metal-oxygen bonds in (2.8 eV or more).
The metal oxide MOxThe mass ratio of the lithium nickel manganese oxide to the lithium nickel manganese oxide is (0.01-1): (99.99-99), and may be, for example, 0.01:99.99, 0.1:99.9, 0.2:99.8, 0.5:99.5 or 1:99, but is not limited to the values listed, and other values not listed in the numerical range may be similarly applied.
The modified lithium nickel manganese oxide positive electrode material provided by the invention comprises metal oxidationObject MOxThe bond energy between the metal-oxygen bond is 2.8eV or more, and the metal-oxygen bond is stable and is not easily subjected to oxidation-reduction reaction. When the voltage is above 4.6V, the metal oxide in the modified lithium nickel manganese oxide positive electrode material can effectively inhibit the oxidation of lithium nickel manganese oxide on electrolyte, and reduces the generation of side reactions, thereby improving the stability of the battery in the storage and circulation processes.
Preferably, the metal oxide MOxIncluding Al2O3、Y2O3、La2O3、CeO2、ZrO2Or Sm2O3Any one or a combination of at least two of them, typical but not limiting combinations include Al2O3And Y2O3Combination of (A) and (B), Y2O3And La2O3A combination of (A) and (B), La2O3With CeO2Combination of (A) CeO2And ZrO2Combination of (A) and (B), ZrO2And Sm2O3Combination of (A) and (B), Y2O3、La2O3With CeO2A combination of (A) and (B), La2O3、CeO2And ZrO2Combination of (A) CeO2、ZrO2And Sm2O3Combination of (A) and (B), Y2O3、La2O3、CeO2And ZrO2Combination of (A) and (B), Al2O3、Y2O3、La2O3、CeO2And ZrO2A combination of (2), or Al2O3、Y2O3、La2O3、CeO2、ZrO2And Sm2O3Combinations of (a) and (b).
Preferably, the metal oxide MOxComprising La2O3And/or Y2O3。
La2O3The bond energy between La and O in the alloy is as high as 3.326eV, Y2O3The bond energy between the Y and the O is as high as 3.317eV, and the release of oxygen atoms can be effectively inhibited.
Preferably, the chemical formula of the lithium nickel manganese oxide is LiNiyMn2-yO4Where 0.2. ltoreq. y.ltoreq.0.8, for example 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8, but is not limited to the values listed, and other values not listed in the numerical range are likewise suitable.
Preferably, the modified lithium nickel manganese oxide cathode material comprises a secondary sphere form and/or a single crystal form.
Preferably, when the modified lithium nickel manganese oxide cathode material is in a secondary sphere form, the particle size D is50Is 18 μm to 35 μm, and may be, for example, 18 μm, 20 μm, 25 μm, 30 μm or 35 μm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, when the modified lithium nickel manganese oxide cathode material is in a single crystal form, the particle size D is50From 5 μm to 16 μm, and may be, for example, 5 μm, 8 μm, 10 μm, 15 μm or 16 μm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
In a second aspect, the invention provides a preparation method of the modified lithium nickel manganese oxide positive electrode material according to the first aspect, and the preparation method comprises the following steps:
mixing a lithium source, a nickel source, a manganese source and a metal oxide precursor to obtain a doping material; and
and sintering the obtained doped material to obtain the modified lithium nickel manganese oxide positive electrode material.
According to the preparation method of the modified lithium nickel manganese oxide cathode material, the doped cathode material can be prepared by mixing and sintering the metal oxide precursor with the lithium source, the nickel source and the manganese source.
Preferably, the lithium source comprises any one or a combination of at least two of lithium oxide, hydroxide, nitrate, acetate or phosphate, typical but non-limiting combinations include lithium oxide and hydroxide combinations, lithium nitrate and acetate combinations, lithium acetate and phosphate combinations, lithium hydroxide and nitrate combinations, lithium nitrate and acetate combinations, lithium oxide, hydroxide and nitrate combinations, lithium oxide, acetate and phosphate combinations, lithium nitrate, acetate and phosphate combinations, lithium oxide, hydroxide, nitrate, acetate and acetate combinations, lithium hydroxide, nitrate, acetate and phosphate combinations, or lithium oxide, hydroxide, nitrate, acetate and phosphate combinations.
Preferably, the nickel source comprises any one of, or a combination of at least two of, nickel oxides, hydroxides, nitrates, acetates or phosphates, typical but non-limiting combinations include nickel oxides and hydroxides, nickel nitrates and acetates, nickel acetates and phosphates, nickel hydroxides and nitrates, nickel nitrates and acetates, nickel oxides, hydroxides and nitrates, nickel oxides, acetates and phosphates, nickel nitrates, acetates and phosphates, nickel oxides, hydroxides, nitrates, acetates and acetates, nickel hydroxides, nitrates, acetates and phosphates, or nickel oxides, hydroxides, nitrates, acetates and phosphates.
Preferably, the manganese source comprises any one or a combination of at least two of manganese oxides, hydroxides, nitrates, acetates or phosphates, typical but non-limiting combinations include combinations of manganese oxides and hydroxides, manganese nitrates and acetates, manganese acetates and phosphates, manganese hydroxides and nitrates, manganese nitrates and acetates, manganese oxides, hydroxides and nitrates, manganese oxides, acetates and phosphates, manganese nitrates, acetates and phosphates, manganese oxides, hydroxides, nitrates, acetates and acetates, manganese hydroxides, acetates, phosphates, or manganese oxides, hydroxides, nitrates, acetates and phosphates, or combinations of manganese oxides, hydroxides, nitrates, acetates and phosphates.
Preferably, the metal oxide precursor comprises any one of, or a combination of at least two of, a metal hydroxide, a metal oxide, or a metal acetate, and typical but non-limiting combinations include a combination of a metal hydroxide and a metal oxide, a combination of a metal oxide and a metal acetate, a combination of a metal hydroxide and a metal acetate, or a combination of a metal hydroxide, a metal oxide, and a metal acetate.
Preferably, the sintering is performed in a nitrogen and/or inert gas atmosphere.
Preferably, the aeration flow rate of the sintering is 1Nm3H to 7Nm3H, for example, may be 1Nm3/h、2Nm3/h、3Nm3/h、5Nm3H or 7Nm3The values/h are not limited to the values listed, but other values within the range of values not listed are equally applicable.
Preferably, the sintering temperature is 600 ℃ to 750 ℃, for example 600 ℃, 650 ℃, 700 ℃, 725 ℃ or 750 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the co-sintering time is 18h to 35h, for example 18h, 20h, 25h, 30h or 35h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
In a third aspect, the invention provides a preparation method of the modified lithium nickel manganese oxide positive electrode material, which comprises the following steps:
mixing lithium nickel manganese oxide with a metal oxide precursor to obtain a coating material; and
and sintering the obtained coating material to obtain the modified lithium nickel manganese oxide cathode material.
Wherein the metal oxide precursor comprises any one or a combination of at least two of metal hydroxide, metal oxide or metal acetate, and typical but non-limiting combinations comprise a combination of metal hydroxide and metal oxide, a combination of metal oxide and metal acetate, a combination of metal hydroxide and metal acetate, or a combination of metal hydroxide, metal oxide and metal acetate.
According to the preparation method of the modified lithium nickel manganese oxide positive electrode material, the coated positive electrode material can be prepared by mixing and sintering the metal oxide precursor and the lithium nickel manganese oxide material.
Preferably, the sintering is performed in a nitrogen and/or inert gas atmosphere.
Preferably, the ventilation flow rate of the sintering is 3Nm3H to 5Nm3H, for example, may be 3Nm3/h、3.5Nm3/h、4Nm3/h、4.5Nm3H or 5Nm3The values/h are not limited to the values listed, but other values within the range of values not listed are equally applicable.
Preferably, the sintering temperature is 250 ℃ to 600 ℃, for example 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or 600 ℃, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the sintering time is 6h to 18h, for example 6h, 10h, 12h, 15h or 18h, but not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
In a fourth aspect, the invention provides a lithium ion battery positive plate, which contains the modified lithium nickel manganese oxide positive electrode material in the first aspect.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the modified lithium nickel manganese oxide positive electrode material provided by the invention comprises the stable metal oxide with higher metal-oxygen bond energy, the stable metal oxide inhibits the oxidation of the lithium nickel manganese oxide on the electrolyte under high potential, the interface between the positive electrode material and the electrolyte is stabilized, and the generation of side reaction is inhibited, so that the gas yield in the storage process of the battery is reduced, and the cycling stability of the battery is improved.
(2) The invention provides two preparation methods of modified lithium nickel manganese oxide cathode materials, which effectively realize doping or coating of metal oxide with metal-oxygen bond energy of more than 2.8eV, improve the stability of the materials, show excellent electrochemical performance, and have simple preparation process and high production efficiency.
Detailed Description
The conventional method for modifying the lithium nickel manganese oxide cathode material provided by the prior art comprises the steps of coating the material by adopting a non-metal oxide, reducing the influence of an electrolyte in the charging and discharging process, or doping other materials such as Mg, Al, F, Cr or Fe in the material to enable the material to form a more stable structure. When the nickel lithium manganate anode material prepared by the method has more charge-discharge times, a large number of side reactions still exist between the battery and the electrolyte, the stability of the system is influenced, and the electrochemical performance of the material is reduced.
In order to solve the technical problems, the invention provides a modified lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery positive electrode plate, wherein stable metal oxide MO is used for preparing the modified lithium nickel manganese oxide positive electrode materialxAnd the side reaction of the electrolyte is inhibited, and the stability of the electrode and the electrolyte interface is improved, so that the stability of the battery is improved.
The present invention will be described in further detail with reference to the following embodiments. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
The embodiment provides a modified lithium nickel manganese oxide positive electrode material, which comprises a doped La2O3Lithium nickel manganese oxide of La2O3And lithium nickel manganese LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the lithium nickel manganese LiNi0.5Mn1.5O4In the form of a secondary sphere, D50The particle size was 25 μm.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixing of Ni (NO)3)2、Mn(NO3)4、LiNO3And La (CH)3COO)3Obtaining a doping material; at 2.5Nm3Introducing nitrogen at the flow rate of/h, and sintering the obtained doped material at the temperature of 700 ℃ for 24h to obtain the modified lithium nickel manganese oxide cathode material.
Example 2
The embodiment provides a modified lithium nickel manganese oxide positive electrode material, which comprises a doped Y2O3Of lithium nickel manganese oxide, Y2O3And lithium nickel manganese LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the lithium nickel manganese LiNi0.5Mn1.5O4In the form of a secondary sphere, D50The particle size was 25 μm.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixed NiO, MnO and Li2O and Y (OH)3Obtaining a doping material; at 2.5Nm3Introducing nitrogen at the flow rate of/h, and sintering the obtained doped material at the temperature of 700 ℃ for 24h to obtain the modified lithium nickel manganese oxide cathode material.
Example 3
The embodiment provides a modified lithium nickel manganese oxide positive electrode material, which comprises lithium nickel manganese oxide doped with a metal oxide, wherein the metal oxide is Al in a mass ratio of 1:12O3And CeO2The metal oxide and the lithium nickel manganese LiNi0.5Mn1.5O4In a mass ratio of 1: 99; the lithium nickel manganese LiNi0.5Mn1.5O4In the form of a single crystal, D50The particle size was 5 μm.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixed Ni (OH)2、Mn(OH)4、LiOH、Al2O3And CeO2Obtaining a doping material; at 3.0Nm3Introducing argon at the flow rate of/h, and sintering the obtained doped material at the temperature of 600 ℃ for 35h to obtain the modified lithium nickel manganese oxide cathode material.
Example 4
The embodiment provides a modified lithium nickel manganese oxide cathode material, wherein the modified nickel manganese oxide cathode materialThe lithium ion anode material comprises nickel lithium manganate doped with metal oxide, wherein the metal oxide is Al with the mass ratio of 1:12O3And CeO2The metal oxide and the lithium nickel manganese LiNi0.5Mn1.5O4In a mass ratio of 0.1: 99.9; the lithium nickel manganese LiNi0.5Mn1.5O4In the form of a secondary sphere, D50The particle size was 18 μm.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixed Ni (OH)2、Mn(OH)4、LiOH、Al2O3And CeO2Obtaining a doping material; at 3.5Nm3Introducing argon at the flow rate of/h, and sintering the obtained doped material at the temperature of 750 ℃ for 18h to obtain the modified lithium nickel manganese oxide cathode material.
Example 5
The embodiment provides a modified lithium nickel manganese oxide positive electrode material, which comprises lithium nickel manganese oxide coated with a metal oxide, wherein the metal oxide is ZrO at a mass ratio of 1:12And Sm2O3The metal oxide and the lithium nickel manganese LiNi0.5Mn1.5O4In a mass ratio of 0.01: 99.99; the lithium nickel manganese LiNi0.5Mn1.5O4In the form of a single crystal, D50The particle size was 16 μm.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixed LiNi0.5Mn1.5O4、ZrO2And Sm2O3Obtaining a coating material; at 4.0Nm3Introducing argon at the flow rate of/h, and sintering the obtained coating material for 18h at the temperature of 250 ℃ to obtain the modified lithium nickel manganese oxide cathode material.
Example 6
The embodiment provides a modified lithium nickel manganese oxide positive electrode material, which comprises lithium nickel manganese oxide coated with a metal oxide, wherein the metal oxide is ZrO at a mass ratio of 1:12And Sm2O3The metal oxide and the lithium nickel manganese LiNi0.5Mn1.5O4The mass ratio of (A) to (B) is 0.8: 99.2; the lithium nickel manganese LiNi0.5Mn1.5O4In the form of a secondary sphere, D50The particle size was 35 μm.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixed LiNi0.5Mn1.5O4、ZrO2And Sm2O3Obtaining a coating material; at 4.5Nm3Introducing argon at the flow rate of/h, and sintering the obtained coating material for 6h at the temperature of 600 ℃ to obtain the modified lithium nickel manganese oxide cathode material.
Example 7
The embodiment provides a modified lithium nickel manganese oxide cathode material, and the component content of the material is the same as that of the material in embodiment 1.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixed LiNi0.5Mn1.5O4And La (CH)3COO)3Obtaining a coating material; at 2.0Nm3Introducing nitrogen at the flow rate of/h, and sintering the obtained coating material for 12h at the temperature of 400 ℃ to obtain the modified lithium nickel manganese oxide cathode material.
Example 8
The embodiment provides a modified lithium nickel manganese oxide cathode material, and the component content of the material is the same as that of the material in embodiment 2.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixed LiNi0.5Mn1.5O4And Y (OH)3Obtaining a coating material; at 2.5Nm3Introducing nitrogen at the flow rate of/h, and sintering the obtained coating material for 12h at the temperature of 400 ℃ to obtain the modified lithium nickel manganese oxide cathode material.
Example 9
This embodiment provides a modified lithium nickel manganese oxide cathode material, except that the chemical formula of lithium nickel manganese oxide is LiNi0.2Mn1.8O4Except that, the remaining components and the preparation method were the same as in example 1.
Example 10
The embodiment provides a modified lithium nickel manganese oxide cathode material, except thatThe chemical formula of the lithium nickel manganese oxide is LiNi0.8Mn1.2O4Except that, the remaining components and the preparation method were the same as in example 1.
Example 11
This example provides a modified lithium nickel manganese oxide cathode material, except that the lithium nickel manganese oxide LiNi0.5Mn1.5O4In the form of a single crystal, D50The other components and preparation method were the same as in example 1 except that the particle size was 12 μm.
Example 12
This example provides a modified lithium nickel manganese oxide cathode material, except that the lithium nickel manganese oxide LiNi0.5Mn1.5O4In the form of a single crystal, D50The other components and preparation method were the same as in example 2 except that the particle size was 12 μm.
Example 13
The embodiment provides a modified lithium nickel manganese oxide positive electrode material, which comprises a doped La2O3Lithium nickel manganese oxide of La2O3And lithium nickel manganese LiNi0.5Mn1.5O4In a mass ratio of 0.1: 99.9; the lithium nickel manganese LiNi0.5Mn1.5O4In the form of a secondary sphere, D50The particle size was 35 μm.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixing of Ni (NO)3)2、Mn(NO3)4、LiNO3And La (CH)3COO)3Obtaining a doping material; at 3.5Nm3Introducing nitrogen at the flow rate of/h, and sintering the obtained doped material at the temperature of 600 ℃ for 18h to obtain the modified lithium nickel manganese oxide cathode material.
Example 14
The embodiment provides a modified lithium nickel manganese oxide positive electrode material, which comprises a coated La2O3Lithium nickel manganese oxide of La2O3And lithium nickel manganese LiNi0.5Mn1.5O4In a mass ratio of 1: 99; the lithium nickel manganese LiNi0.5Mn1.5O4In the form of a single crystal, D50The particle size was 16 μm.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixed LiNi0.5Mn1.5O4And La2O3Obtaining a coating material; at 4.0Nm3Introducing nitrogen at the flow rate of/h, and sintering the obtained coating material for 10h at the temperature of 400 ℃ to obtain the modified lithium nickel manganese oxide cathode material.
Example 15
The embodiment provides a modified lithium nickel manganese oxide positive electrode material, which comprises a doped Y2O3Of lithium nickel manganese oxide, Y2O3And lithium nickel manganese LiNi0.5Mn1.5O4In a mass ratio of 0.1: 99.9; the lithium nickel manganese LiNi0.5Mn1.5O4In the form of a secondary sphere, D50The particle size was 35 μm.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixing of Ni (NO)3)2、Mn(NO3)4、LiNO3And Y (CH)3COO)3Obtaining a doping material; at 2.8Nm3Introducing nitrogen at the flow rate of/h, and sintering the obtained doped material at the temperature of 600 ℃ for 18h to obtain the modified lithium nickel manganese oxide cathode material.
Example 16
The embodiment provides a modified lithium nickel manganese oxide positive electrode material, which comprises a Y-coated positive electrode material2O3Of lithium nickel manganese oxide, Y2O3And lithium nickel manganese LiNi0.5Mn1.5O4In a mass ratio of 1: 99; the lithium nickel manganese LiNi0.5Mn1.5O4In the form of a single crystal, D50The particle size was 16 μm.
The preparation method of the modified lithium nickel manganese oxide positive electrode material comprises the following steps: mixed LiNi0.5Mn1.5O4And Y2O3Obtaining a coating material; at 3.2Nm3Introducing nitrogen at the flow rate of/h, and sintering the obtained coating material for 10h at the temperature of 400 ℃ to obtain the modified nickel manganese acidA lithium positive electrode material.
Comparative example 1
The comparative example provides a modified lithium nickel manganese oxide positive electrode material, which is not doped or coated with metal oxide, and the rest components are the same as the preparation method and the example 1.
Comparative example 2
The comparative example provides a modified lithium nickel manganese oxide cathode material, except doped metal oxide Co2O3Except that, the other components were the same as in example 1.
Comparative example 3
The comparative example provides a modified lithium nickel manganese oxide cathode material except La2O3And lithium nickel manganese LiNi0.5Mn1.5O4The preparation method and the example 1 are the same except that the mass ratio of the components is 1.5: 98.5.
The positive electrode materials obtained in examples 1 to 16 and comparative examples 1 to 3 are respectively mixed with conductive carbon black, conductive carbon tubes, a nitrogen methyl pyrrolidone solvent and polyvinylidene fluoride according to the mass ratio of 99:1:0.5:40:1 to prepare a positive electrode sheet, and the obtained positive electrode sheet is assembled into a 1Ah flexible package battery. After formation and aging, the material is charged and discharged at the rate of 1C at the temperature of 25 ℃, and the charging and discharging voltage window is 3-4.85V. After the circulation for 200 weeks, the ratio of the discharge capacity to the first week is the capacity retention rate of 200 weeks; the initial volume V of the cell was recorded at 25 ℃ and charged to 4.8V at 0.33C using the drainage method0. The cells were then stored in a 60 ℃ constant temperature oven, removed from the oven every 7 days, allowed to stand to room temperature, the volume of the cells tested, and the cells were recharged at 0.33C to 4.8V. The volume change of the battery after 28 days was recorded, corresponding to the gas generation ratio of the cell, and the above results are shown in table 1.
TABLE 1
Figure BDA0003344998430000121
Figure BDA0003344998430000131
From the data in table 1, it can be derived:
(1) from embodiments 1 to 6, the modified lithium nickel manganese oxide positive electrode material provided by the invention includes a stable metal oxide with a higher metal-oxygen bond energy, so that oxidation of lithium nickel manganese oxide to an electrolyte under a high potential is inhibited, an interface between the positive electrode material and the electrolyte is stabilized, and generation of side reactions is inhibited, thereby reducing gas production in a battery storage process and improving a cycle capacity retention rate of the battery.
(2) As can be seen from the comparison between the embodiment 1 and the embodiment 7, the modified lithium nickel manganese oxide cathode material with low gas production rate and high capacity retention rate can be prepared by both of the preparation methods provided by the invention, and is preferably co-sintered at one time.
(3) As can be seen from the comparison between the embodiment 2 and the embodiment 8, the modified lithium nickel manganese oxide cathode material with low gas production rate and high capacity retention rate can be prepared by both of the preparation methods provided by the invention, and preferably is co-sintered at one time.
(4) As can be seen from comparison between example 1 and examples 9 and 10, the lithium nickel manganese oxide LiNi provided by the inventionxMn2-xO4And x is more than or equal to 0.2 and less than or equal to 0.8, and the oxidation of the nickel lithium manganate to the electrolyte under high potential is inhibited by the stable metal oxide with higher metal-oxygen bond energy, the interface between the anode material and the electrolyte is stabilized, and the generation of side reactions is inhibited, so that the gas yield in the storage process of the battery is reduced, and the circulating capacity retention rate of the battery is improved.
(5) As can be seen from comparison between example 1 and example 11, when the lithium nickel manganese oxide provided by the present invention is in the form of single crystal or secondary sphere, the positive electrode material having high capacity retention rate and low gas generation rate can be prepared, the stability of the battery is improved, the cycle performance of the battery is improved, and the secondary sphere form is preferred.
(6) As can be seen from comparison between example 2 and example 12, when the lithium nickel manganese oxide provided by the present invention is in the form of single crystal or secondary sphere, the positive electrode material having high capacity retention rate and low gas generation rate can be prepared, the stability of the battery is improved, the cycle performance of the battery is improved, and the secondary sphere form is preferred.
(7) From examples 1, 13 and 14, the preferred metal oxide La provided by the present invention2O3The lithium nickel manganese oxide lithium battery cathode material has high metal-oxygen bond energy, effectively inhibits the oxidation of the lithium nickel manganese oxide to electrolyte under high potential, stabilizes the interface between the cathode material and the electrolyte, and inhibits the generation of side reaction, thereby reducing the gas production rate in the storage process of the battery and improving the circulating capacity retention rate of the battery.
(8) From examples 2, 15 and 16, it can be seen that the preferred metal oxide Y provided by the present invention2O3The lithium nickel manganese oxide lithium battery cathode material has high metal-oxygen bond energy, effectively inhibits the oxidation of the lithium nickel manganese oxide to electrolyte under high potential, stabilizes the interface between the cathode material and the electrolyte, and inhibits the generation of side reaction, thereby reducing the gas production rate in the storage process of the battery and improving the circulating capacity retention rate of the battery.
(9) As can be seen from example 1 and comparative example 1, when the metal oxide is not doped or coated, the prepared positive electrode material has low capacity retention rate and high gas production rate, which indicates that the doped or coated metal oxide provided by the invention is beneficial to preparing the positive electrode material with high capacity retention rate and low gas production rate, improves the stability of the battery, and improves the cycle performance of the battery.
(10) From the embodiment 1 and the comparative example 2, it can be seen that when the bond energy of the doped or coated metal oxide is less than 2.8eV, the prepared cathode material has low capacity retention rate and high gas production rate, which indicates that the bond energy of the metal oxide provided by the invention is beneficial to preparing the cathode material with high capacity retention rate and low gas production rate, the stability of the battery is improved, and the cycle performance of the battery is improved.
(11) From the example 1 and the comparative example 3, it can be seen that when the mass ratio of the doped or coated metal oxide to the lithium nickel manganese oxide is not in the range of (0.01-1): (99.99-99), the capacity retention rate of the prepared positive electrode material is low and the gas production rate is high, which indicates that the content of the metal oxide provided by the invention is beneficial to preparing the positive electrode material with high capacity retention rate and low gas production rate, the stability of the battery is improved, and the cycle performance of the battery is improved.
In conclusion, the modified lithium nickel manganese oxide positive electrode material provided by the invention comprises the stable metal oxide with higher metal-oxygen bond energy, so that the oxidation of the lithium nickel manganese oxide on the electrolyte under high potential is inhibited, the interface between the positive electrode material and the electrolyte is stabilized, and the generation of side reactions is inhibited, so that the gas yield in the storage process of the battery is reduced, and the circulation capacity retention rate of the battery is improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The modified lithium nickel manganese oxide positive electrode material is characterized by comprising a doped or coated metal oxide MOxOf lithium nickel manganese oxide, wherein
The metal oxide MOxThe mass ratio of the lithium nickel manganese oxide to the lithium nickel manganese oxide is (0.01-1) to (99.99-99);
the metal oxide MOxThe bond energy between the metal-oxygen bonds in (2.8 eV or more).
2. The modified lithium nickel manganese oxide positive electrode material of claim 1, wherein the metal oxide MO is selected from the group consisting ofxIncluding Al2O3、Y2O3、La2O3、CeO2、ZrO2Or Sm2O3Any one or a combination of at least two of;
preferably, the metal oxide MOxComprising La2O3And/or Y2O3；
Preferably, the chemical formula of the lithium nickel manganese oxide is LiNiyMn2-yO4Wherein y is 0.2-0.8, preferably LiNi0.5Mn1.5O4；
Preferably, the modified lithium nickel manganese oxide cathode material comprises a secondary sphere form and/or a single crystal form.
3. The modified lithium nickel manganese oxide positive electrode material of claim 2, wherein the particle diameter D of the modified lithium nickel manganese oxide positive electrode material is in a secondary sphere form50Is 18 μm to 35 μm.
4. The modified lithium nickel manganese oxide positive electrode material of claim 2, wherein the particle diameter D of the modified lithium nickel manganese oxide positive electrode material is in a single crystal form50Is 5 μm to 16 μm.
5. A preparation method of the modified lithium nickel manganese oxide positive electrode material according to any one of claims 1 to 4, wherein the preparation method comprises the following steps:
mixing a lithium source, a nickel source, a manganese source and a metal oxide precursor to obtain a doping material; and
and sintering the obtained doped material to obtain the modified lithium nickel manganese oxide positive electrode material.
6. The method of claim 5, wherein the lithium source comprises any one of or a combination of at least two of an oxide, a hydroxide, a nitrate, an acetate, or a phosphate of lithium;
preferably, the nickel source comprises any one of or a combination of at least two of an oxide, hydroxide, nitrate, acetate or phosphate of nickel;
preferably, the manganese source comprises any one of or a combination of at least two of manganese oxide, hydroxide, nitrate, acetate or phosphate;
preferably, the metal oxide precursor comprises any one of a metal hydroxide, a metal oxide or a metal acetate, or a combination of at least two thereof.
7. The production method according to claim 5 or 6, characterized in that the sintering is performed in a nitrogen and/or inert gas atmosphere;
preferably, the aeration flow rate of the sintering is 1Nm3H to 7Nm3/h；
Preferably, the temperature of the sintering is 600 ℃ to 750 ℃;
preferably, the sintering time is 18h to 35 h.
8. A preparation method of the modified lithium nickel manganese oxide positive electrode material according to any one of claims 1 to 4, wherein the preparation method comprises the following steps:
mixing lithium nickel manganese oxide with a metal oxide precursor to obtain a coating material; and
sintering the obtained coating material to obtain the modified lithium nickel manganese oxide cathode material,
wherein the metal oxide precursor comprises any one of metal hydroxide, metal oxide or metal acetate or the combination of at least two of the metal hydroxide, the metal oxide and the metal acetate.
9. The production method according to claim 8, wherein the sintering is performed in a nitrogen or inert gas atmosphere;
preferably, the ventilation flow rate of the sintering is 3Nm3H to 5Nm3/h；
Preferably, the temperature of the sintering is 250 ℃ to 600 ℃;
preferably, the sintering time is 6h to 18 h.
10. A lithium ion battery positive plate, which is characterized by comprising the modified lithium nickel manganese oxide positive electrode material according to any one of claims 1 to 4.
CN202111319421.7A 2021-11-09 2021-11-09 Modified lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery positive electrode plate Pending CN113903900A (en)

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