CN111129482B - Method for improving characteristics of lithium battery positive electrode material - Google Patents

Method for improving characteristics of lithium battery positive electrode material Download PDF

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Publication number
CN111129482B
CN111129482B CN201910749284.7A CN201910749284A CN111129482B CN 111129482 B CN111129482 B CN 111129482B CN 201910749284 A CN201910749284 A CN 201910749284A CN 111129482 B CN111129482 B CN 111129482B
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argon
heating furnace
positive electrode
ncm
electrode material
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CN111129482A (en
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梁运康
姜李芳
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Jiangsu Foxlink New Energy Technology Co ltd
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Jiangsu Foxlink New 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
    • H01M4/50—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a method for improving the characteristics of a lithium battery anode material, which is characterized by comprising the following steps: s1: respectively placing an NCM positive electrode material and a metal compound in a tubular heating furnace; s2: pumping out the air of the tubular heating furnace to be below 30 mtorr, and then introducing high-concentration argon until the pressure is recovered to normal pressure; s3: repeating the step S2 for a plurality of times to increase the argon concentration in the tubular heating furnace; s4: extracting the air of the tubular heating furnace to be below 30 mtorr, continuously introducing argon, controlling the flow of the argon to be more than 8 sccm, and controlling the pressure in the tube to be 90 mtorr; s5: heating the tube type heating furnace to 100-200 ℃ to gasify the metal compound; s6: the metal steam is sent to the NCM anode material through argon to react, so that the metal ion vacancy in the NCM anode material is filled; s7: and (3) cooling after reacting for a period of time, introducing high-purity argon when the temperature is lower than 25 ℃, returning the pressure in the heating pipe to normal pressure, and taking out the NCM cathode material.

Description

Method for improving characteristics of lithium battery positive electrode material
Technical Field
The invention discloses a method for improving the characteristics of a lithium battery anode material.
Background
In recent years, with the rapid development of electric vehicles, the demand for lithium batteries is greatly increased due to the wide application of excellent electric storage performance. However, the characteristics of lithium batteries for vehicles are rather demanding, and lithium batteries are particularly required to have a rather high capacity.
The capacity of the lithium battery is mainly dominated by the positive electrode material, and the capacity of the lithium battery needs to be improved, namely, the positive electrode material with higher capacity needs to be used. Nowadays, the positive electrode material widely used in the lithium battery for vehicles is NCM111, however, the material cannot meet the requirement of high capacity of the lithium battery for vehicles, and therefore, in order to increase the capacity of the lithium battery, the positive electrode of the lithium battery uses NCM622 or NCM811 material with higher nickel content.
However, when the nickel content of the positive electrode of the lithium battery is increased, the positive electrode material becomes very unstable, the lithium battery is prone to outgassing, metal ions dissolving out, and a large amount of insulating film is formed on the surface of the negative electrode, which affects the working efficiency of the battery.
Therefore, the stable high nickel content lithium battery positive electrode material becomes the focus of research of many scholars and manufacturers.
Further, it has been found that, in a lithium battery using NCM622 or NCM811 as a positive electrode material, a phenomenon such as outgassing, elution of metal ions, formation of a large amount of insulating film, and the like occurs, mainly because the positive electrode material has a manganese vacancy, i.e., a position originally occupied by manganese is vacant. Because manganese has a high vapor pressure and a small electronegativity, manganese is easily lost from a manganese-containing material during synthesis, which is a phenomenon that often occurs. The existence of manganese vacancy greatly improves the probability of metal ion diffusion and dissolution and loses the structural stability. This is the root cause of failure of the positive electrode material such as NCM622 or NCM 811.
Disclosure of Invention
The invention aims to provide a method for improving the characteristics of a lithium battery anode material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for improving the characteristics of a positive electrode material of a lithium battery comprises the following steps:
s1: respectively placing an NCM positive electrode material and a metal compound in a tubular heating furnace;
s2: pumping out the air of the tubular heating furnace to be below 30 mtorr, and then introducing high-concentration argon until the pressure is recovered to normal pressure;
s3: repeating the step S2 for a plurality of times to increase the argon concentration in the tubular heating furnace;
s4: pumping out the air of the tubular heating furnace to be below 30 mtorr, continuously introducing argon, controlling the flow of the argon to be more than 8 sccm and controlling the pressure in the tube to be 90 mtorr;
s5: heating the tube type heating furnace to 100-200 ℃ to gasify the metal compound;
s6: sending metal steam to the NCM anode material through argon to react, and filling the metal ion vacancy in the NCM anode material;
s7: and (3) cooling after reacting for a period of time, introducing high-purity argon when the temperature is lower than 25 ℃, returning the pressure in the heating pipe to normal pressure, and taking out the NCM positive electrode material.
Preferably, the metal compound in step S1 is a metal compound of Al, cr, mn, ni, zr, or the like. Two considerations are mainly taken into consideration in filling up the vacant metal ions. First, the metal ions filling the gaps should effectively improve the structural stability, and at this time, metal ions such as Al and Cr can be selected, which have strong bonding force with oxygen atoms, and the octahedron of (AlO 6) -9 and (CrO 6) -9 formed in the NCM structure also has better stability. Secondly, the metal ions filling the vacancy are expected to increase the capacitance of the NCM positive electrode material, and in this case, atoms such as Mn and Ni may be selected.
Preferably, the metal compound is characterized by a vaporization temperature of less than 200 ℃.
Preferably, the NCM positive electrode material in step S1 is a LiNixCoyMnzO2 positive electrode material or another positive electrode material containing manganese.
In order to improve the stability of the high-nickel anode of the lithium battery, manganese vacancies in the structure must be effectively reduced, and metal ion steam is adopted for heat treatment, so that metal ions can diffuse into the material to fill the material vacancies.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description.
Detailed Description
The following embodiments of the present invention will be described in detail with reference to the accompanying examples, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented. It should be noted that, as long as there is no conflict, the embodiments and the features of the embodiments of the present invention may be combined with each other, and the technical solutions formed are within the scope of the present invention.
A method for improving the characteristics of a positive electrode material of a lithium battery comprises the following steps:
s1: respectively placing an NCM positive electrode material and a metal compound in a tubular heating furnace;
s2: pumping out the air of the tubular heating furnace to be below 30 mtorr, and then introducing high-concentration argon until the pressure is recovered to normal pressure;
s3: repeating the step S2 for a plurality of times to increase the argon concentration in the tubular heating furnace;
s4: pumping out the air of the tubular heating furnace to be below 30 mtorr, continuously introducing argon, controlling the flow of the argon to be more than 8 sccm and controlling the pressure in the tube to be 90 mtorr;
s5: heating the tube type heating furnace to 100-200 ℃ to gasify the metal compound;
s6: the metal steam is sent to the NCM anode material through argon to react, so that the metal ion vacancy in the NCM anode material is filled;
s7: and (3) cooling after reacting for a period of time, introducing high-purity argon when the temperature is lower than 25 ℃, returning the pressure in the heating pipe to normal pressure, and taking out the NCM positive electrode material. And (4) identifying the atomic coordination number in the structure and observing the atomic filling degree by utilizing an X-ray absorption spectrum for the final finished product.
Preferably, the metal compound in step S1 is a metal compound of Al, cr, mn, ni, zr, or the like. Two considerations are mainly taken into consideration in filling up the vacant metal ions. First, the metal ions filling the gaps should effectively improve the structural stability, and at this time, metal ions such as Al and Cr can be selected, which have strong bonding force with oxygen atoms, and the octahedron of (AlO 6) -9 and (CrO 6) -9 formed in the NCM structure also has better stability. Second, the metal ions filling the vacancy are expected to increase the capacitance of the NCM positive electrode material, and in this case, atoms such as Mn and Ni may be used.
Preferably, the metal compound is characterized by a vaporization temperature of less than 200 ℃.
Preferably, the NCM positive electrode material in step S1 is a LiNixCoyMnzO2 positive electrode material or another positive electrode material containing manganese.
In order to improve the stability of the high-nickel anode of the lithium battery, manganese vacancy in the structure must be effectively reduced, and metal ion steam is adopted for heat treatment, so that metal ions can diffuse into the material to fill the material vacancy.
The invention relates to a method for improving the characteristics of a lithium battery anode material, which selects a compound with low gasification temperature as a precursor and carries out reaction at the temperature lower than 200 ℃. The problems that the structural stability of the known high-nickel-content manganese oxide-containing positive electrode material is lost, the lithium battery generates air release, metal ions are dissolved out, an insulating film is proliferated and the like in the charging and discharging process, and the battery is invalid can be effectively solved. The NCM anode material with high nickel content and high electric capacity can be practically applied to lithium batteries. Effectively improving the stability and the electric capacity of the battery.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (2)

1. A method for improving the characteristics of a positive electrode material of a lithium battery is characterized by comprising the following steps:
s1: respectively placing an NCM positive electrode material and a metal compound in a tubular heating furnace;
s2: pumping out the air of the tubular heating furnace to be below 30 mtorr, and then introducing high-concentration argon until the pressure is recovered to normal pressure;
s3: repeating the step S2 for a plurality of times to increase the argon concentration in the tubular heating furnace;
s4: pumping out the air of the tubular heating furnace to be below 30 mtorr, continuously introducing argon, controlling the flow of the argon to be more than 8 sccm and controlling the pressure in the tube to be 90 mtorr;
s5: heating the tube type heating furnace to 100-200 ℃ to gasify the metal compound;
s6: sending metal steam to the NCM anode material through argon to react, and filling the metal ion vacancy in the NCM anode material;
s7: cooling after reacting for a period of time, introducing high-purity argon when the temperature is lower than 25 ℃, returning the pressure in the heating pipe to normal pressure, and taking out the NCM positive electrode material;
wherein, the metal compound in the step S1 is a metal compound of Al, cr, mn and Zr.
2. The method as claimed in claim 1, wherein the metal compound is vaporized at a temperature lower than 200 ℃.
CN201910749284.7A 2019-08-14 2019-08-14 Method for improving characteristics of lithium battery positive electrode material Active CN111129482B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108493429A (en) * 2018-05-03 2018-09-04 中南大学 The preparation method of anode composite material of lithium ion battery
CN108615863A (en) * 2018-04-17 2018-10-02 成都新柯力化工科技有限公司 A kind of atomic level method for coating of ternary anode material of lithium battery

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100404891B1 (en) * 2001-03-13 2003-11-10 주식회사 엘지화학 Positive active material for lithium secondary battery and method for preparing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108615863A (en) * 2018-04-17 2018-10-02 成都新柯力化工科技有限公司 A kind of atomic level method for coating of ternary anode material of lithium battery
CN108493429A (en) * 2018-05-03 2018-09-04 中南大学 The preparation method of anode composite material of lithium ion battery

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