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WO2025007998A1 - Procédé de purification de graphite lamellaire naturel, graphite purifié et batterie au lithium-ion - Google Patents

Procédé de purification de graphite lamellaire naturel, graphite purifié et batterie au lithium-ion Download PDF

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Publication number
WO2025007998A1
WO2025007998A1 PCT/CN2024/112659 CN2024112659W WO2025007998A1 WO 2025007998 A1 WO2025007998 A1 WO 2025007998A1 CN 2024112659 W CN2024112659 W CN 2024112659W WO 2025007998 A1 WO2025007998 A1 WO 2025007998A1
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WO
WIPO (PCT)
Prior art keywords
graphite
purification method
natural flake
flake graphite
heating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/112659
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English (en)
Chinese (zh)
Inventor
王斌
刘倩
利凯文
朱家乐
吴伟
张祖豪
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Eve Energy Co Ltd
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Eve Energy Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eve Energy Co Ltd filed Critical Eve Energy Co Ltd
Publication of WO2025007998A1 publication Critical patent/WO2025007998A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
    • 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
    • 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

Definitions

  • the present application relates to the field of battery technology, and in particular to a method for purifying natural flake graphite, purified graphite and a lithium-ion battery.
  • Natural flake graphite Due to the rapid development of lithium-ion batteries, natural flake graphite is used in large quantities as a low-cost raw material, but the large amount of impurities and defects in natural flake graphite limit its application in the negative electrode of lithium-ion batteries.
  • Natural flake graphite usually contains metal impurity elements, such as Fe, Cr, Ni and Zn, and the above-mentioned metal impurity elements are magnetic material components, which makes natural flake graphite magnetic and not conducive to use.
  • the content of metal impurity elements and magnetic substances in graphite needs to be controlled at the ppb level. Therefore, natural flake graphite needs to be purified.
  • the existing methods for purifying natural flake graphite mainly include: 1 flotation purification method; 2 pickling and high temperature treatment.
  • 1 flotation purification method 2 pickling and high temperature treatment.
  • large-scale graphite factories usually use a combination of pickling and high temperature treatment to purify graphite, but this method consumes a lot of energy and produces a lot of pollution, which increases the production cost of graphite.
  • the present application provides a method for purifying natural flake graphite, purified graphite and a lithium-ion battery.
  • the present application purifies natural flake graphite by heating it in an atmosphere of reaction gas, and under the synergistic effect of at least two gases among nitrogen, chlorine, CO2 , CO and helium, the content of impurity elements and magnetic substances in the natural flake graphite can be reduced to ensure the purity of the graphite; and the purification method of the present application has simple procedures, low energy consumption and cost, and less pollution.
  • the present application provides a method for purifying natural flake graphite, the purification method comprising:
  • the natural flake graphite is heated in an atmosphere of a reaction gas
  • the reaction gas includes a combination of at least two of nitrogen (N 2 ), chlorine (Cl 2 ), CO 2 , CO or helium.
  • the present application provides a purified graphite, wherein the purified graphite is prepared by the purification method described in the first aspect.
  • the present application provides a lithium-ion battery, wherein the negative electrode of the lithium-ion battery includes the purified graphite described in the second aspect.
  • the present application provides a method for purifying natural flake graphite, wherein the natural flake graphite is purified by heating it in an atmosphere of a reaction gas, wherein the reaction gas includes a combination of at least two of nitrogen, chlorine, CO 2 , CO or helium. Under the heating condition, nitrogen, chlorine, CO 2 , CO and helium can react with metal impurity elements in the natural flake graphite to reduce the boiling point of the impurity compound, so that the impurity compound can be separated from the graphite under high temperature heating, and the content of metal impurities and magnetic substances can be reduced.
  • the content of impurity elements and magnetic substances in the natural flake graphite can be reduced to ensure the purity of the graphite; at the same time, the heating step can also improve the graphitization degree of the material, increase the crystallinity of the graphite and reduce the defects of the graphite crystals.
  • the purification method of the present application has a simple process, low energy consumption and cost, and less pollution, which greatly optimizes the purification process and timeliness.
  • FIG1 is a schematic flow chart of a method for purifying natural flake graphite provided in an embodiment of the present application.
  • FIG. 2 is a schematic flow diagram of a conventional method for purifying natural flake graphite.
  • the present application provides a method for purifying natural flake graphite, the purification method comprising:
  • the natural flake graphite is heated in an atmosphere of a reaction gas
  • the reaction gas includes a combination of at least two of nitrogen (N 2 ), chlorine (Cl 2 ), CO 2 , CO or helium.
  • the present application provides a method for purifying natural flake graphite, wherein the natural flake graphite is purified by heating it in an atmosphere of a reaction gas, wherein the reaction gas includes a combination of at least two of nitrogen, chlorine, CO 2 , CO or helium. Under the heating condition, nitrogen, chlorine, CO 2 , CO and helium can react with metal impurity elements in the natural flake graphite to reduce the boiling point of the impurity compound, so that the impurity compound can be separated from the graphite under high temperature heating, and the content of metal impurities and magnetic substances can be reduced.
  • the content of impurity elements and magnetic substances in the natural flake graphite can be reduced to ensure the purity of the graphite; at the same time, the heating step can also improve the graphitization degree of the material, increase the crystallinity of the graphite and reduce the defects of the graphite crystals.
  • the purification method of the present application has a simple process, low energy consumption and cost, and less pollution, which greatly optimizes the purification process and timeliness.
  • typical non-limiting combinations of the reaction gases include: a combination of nitrogen and chlorine, a combination of CO 2 and CO, a combination of CO 2 and chlorine, and a combination of CO 2 and helium, etc.
  • a screening and demagnetization step is performed.
  • the reaction gas is a combination of CO 2 and nitrogen or a combination of CO 2 and chlorine.
  • reaction gas a combination of CO2 and nitrogen or a combination of CO2 and chlorine is used as the reaction gas, and the gas has the highest reaction efficiency with the metal impurities and the production cost is also low.
  • the flow rate of the reaction gas is 1-20 L/min, for example, it can be 1 L/min, 2 L/min, 3 L/min, 4 L/min, 5 L/min, 6 L/min, 7 L/min, 8 L/min, 9 L/min, 10 L/min, 11 L/min, 12 L/min, 13 L/min, 14 L/min, 15 L/min, 16 L/min, 17 L/min, 18 L/min, 19 L/min or 20 L/min, but is not limited to the listed values, other unlisted values within the numerical range are also applicable, which can be selected as 3-18 L/min.
  • the flow rates of CO2 and nitrogen are independently 5-8 L/min, for example, 5 L/min, 6 L/min, 7 L/min or 8 L/min, etc., but are not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the particle size D50 of the natural flake graphite is 7-20 ⁇ m, for example, 7 ⁇ m, 8 ⁇ m, 10 ⁇ m, 12 ⁇ m, 14 ⁇ m, 16 ⁇ m, 18 ⁇ m or 20 ⁇ m, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the heating temperature is 800-3200°C, for example, it can be 800°C, 900°C, 1000°C, 1100°C, 1200°C, 1500°C, 1800°C, 2000°C, 2100°C, 2200°C, 2300°C, 2500°C, 2600°C, 2800°C, 2900°C, 2950°C, 3000°C, 3050°C, 3100°C, 3150°C or 3200°C, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the heating time is 5-56h, for example, it can be 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 48h, 50h, 52h, 55h or 56h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the heating includes one-stage heating and two-stage heating performed sequentially.
  • a first stage of heating is performed to allow the natural flake graphite to fully contact and mix with the reaction gas in advance; and a second stage of heating is performed to allow the metal impurity elements to fully react with the reaction gas to generate compounds and separate from the graphite.
  • the temperature of the heating stage is 800-1200°C, for example, it can be 800°C, 900°C, 1000°C, 1100°C or 1200°C, etc.; the time of the heating stage is 2-8h, for example, it can be 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the temperature of the second stage heating is 2800-3100°C, for example, it can be 2800°C, 2900°C, 2950°C, 3000°C, 3050°C or 3100°C;
  • the time of the second stage heating is 5-48h, for example, it can be 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the purification method specifically includes:
  • the natural flake graphite with a particle size D50 of 7-20 ⁇ m is shaped, the shaped natural flake graphite is placed in a container, and a reaction gas is introduced into the container, and then heated at a temperature of 800-1200° C. for 2-8 hours, and then heated at a temperature of 2800-3100° C. for 5-48 hours, and then sieved and demagnetized to complete the purification;
  • the reaction gas includes a combination of at least two of nitrogen, chlorine, CO 2 , CO or helium.
  • the present application provides a purified graphite, wherein the purified graphite is prepared by the purification method described in the first aspect.
  • the present application provides a lithium-ion battery, wherein the negative electrode of the lithium-ion battery includes the purified graphite described in the second aspect.
  • the present application provides a method for purifying natural flake graphite, the process of which is shown in FIG1 , comprising the following steps:
  • the natural flake graphite is shaped, then heated in an atmosphere of reaction gas, and then sieved and demagnetized to complete the purification.
  • the process is shown in Figure 2
  • Figure 2 which includes the following steps: shaping the natural flake graphite, then acid washing the shaped natural flake graphite, and then high-temperature treatment and screening for demagnetization; the method for purifying natural flake graphite provided in the present application can not only achieve purification, but also has a simple process, low energy consumption and cost, and less pollution.
  • This embodiment provides a method for purifying natural flake graphite, comprising the following steps:
  • Natural flake graphite with a particle size D50 of 10 ⁇ m was shaped and placed in a container. Reaction gas was introduced into the container. The reaction gas was a combination of CO 2 and N 2. The flow rate of CO 2 was 5 L/min and the flow rate of N 2 was 5 L/min. Then, it was heated at 800°C for 5 h for the first stage and then heated at 2800°C for 48 h for the second stage. After cooling, the graphite sample was sieved and demagnetized to obtain the graphite sample.
  • Examples 2-25 and Comparative Examples 1-2 are based on Example 1 with parameter changes. The specific changed parameters are detailed in Table 1.
  • the graphite samples provided in the above embodiments and comparative examples were subjected to ICP testing to detect the content of metal impurity elements and magnetic substances therein.
  • Example 10 It can be seen from the data results of Example 10 and Examples 21-22 that if the temperature of the second stage heating is too low, the content of impurity elements and magnetic substances in the sample will be higher; if the temperature of the second stage heating is too high, although the purification effect is better, it will lead to increased energy consumption and increased costs.
  • Example 10 It can be seen from the data results of Example 10 and Example 23 that if only one-stage heating is used, the gas will not react fully with the metal elements in the graphite, and the content of metal impurities and magnetic substances in the product will be high.
  • Example 10 It can be seen from the data results of Example 10 and Comparative Examples 1-2 that if only one gas is used as the reaction gas, the content of metal impurities and magnetic substances will increase slightly. It is possible that some metal elements have higher reaction activity with specific gases, and the impurity removal effect of mixing multiple gases is better.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

La présente demande concerne un procédé de purification de graphite lamellaire naturel, du graphite purifié et une batterie au lithium-ion. Le procédé de purification consiste à : chauffer du graphite lamellaire naturel dans une atmosphère de gaz de réaction, les gaz de réaction comprenant une combinaison d'au moins deux gaz parmi de l'azote, du chlore, du CO2, du CO ou de l'hélium. Dans la présente demande, en chauffant du graphite lamellaire naturel dans une atmosphère des gaz de réaction pour obtenir une purification, sous l'effet synergique d'au moins deux gaz parmi de l'azote, du chlore, du CO2, du CO et de l'hélium, la teneur en éléments d'impureté et en substances magnétiques dans du graphite lamellaire naturel peut être réduite, ce qui permet d'assurer la pureté du graphite ; de plus, le procédé de purification de la présente invention présente des étapes simples, une consommation d'énergie et un coût relativement faibles, et une pollution relativement faible.
PCT/CN2024/112659 2023-12-13 2024-08-16 Procédé de purification de graphite lamellaire naturel, graphite purifié et batterie au lithium-ion Pending WO2025007998A1 (fr)

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Application Number Priority Date Filing Date Title
CN202311719894.5 2023-12-13
CN202311719894.5A CN117699794A (zh) 2023-12-13 2023-12-13 一种天然鳞片石墨的提纯方法、提纯后石墨和锂离子电池

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WO2025007998A1 true WO2025007998A1 (fr) 2025-01-09

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Families Citing this family (1)

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CN117699794A (zh) * 2023-12-13 2024-03-15 惠州亿纬锂能股份有限公司 一种天然鳞片石墨的提纯方法、提纯后石墨和锂离子电池

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