WO2020259436A1 - Procédé pour améliorer la stabilité et l'aptitude au traitement d'un matériau d'électrode positive ternaire - Google Patents

Procédé pour améliorer la stabilité et l'aptitude au traitement d'un matériau d'électrode positive ternaire Download PDF

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WO2020259436A1
WO2020259436A1 PCT/CN2020/097428 CN2020097428W WO2020259436A1 WO 2020259436 A1 WO2020259436 A1 WO 2020259436A1 CN 2020097428 W CN2020097428 W CN 2020097428W WO 2020259436 A1 WO2020259436 A1 WO 2020259436A1
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WIPO (PCT)
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positive electrode
electrode material
ternary positive
processability
ternary
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PCT/CN2020/097428
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English (en)
Chinese (zh)
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夏阳
王坤
陈安琪
张文魁
吴海军
钱志挺
毛秦钟
黄辉
甘永平
张俊
梁初
Original Assignee
浙江工业大学
浙江美都海创锂电科技有限公司
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Publication of WO2020259436A1 publication Critical patent/WO2020259436A1/fr

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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
    • 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
    • H01M4/362—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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 invention relates to a modification method for improving the storage stability and processability of a ternary positive electrode material, and belongs to the technical field of lithium ion battery positive electrode materials.
  • ternary cathode materials have higher requirements for storage and processing environments, and ternary cathode materials are prone to a series of side reactions with the electrolyte during charge and discharge, such as electrolysis at high voltage at the end of charging.
  • the decomposition of the liquid, the acidic substance after the decomposition of the electrolyte corrodes the electrode, the dissolution of the electrode active material, etc.
  • researchers usually use surface coating to solve the above problems in order to improve the cycle stability of the material.
  • Stable lithium salt substances such as Li 3 PO 4 , LiFePO 4 , LiAlO 2, etc.
  • Materials that do not contain lithium ions such as SiO 2 , Al 2 O 3 , ZrO 2 etc.
  • solid-phase coating and liquid-phase coating sintering The coating layer obtained by the two coating methods is weakly bonded to the substrate, and the thickness is not uniform.
  • the present invention provides a supercritical carbon dioxide surface modification treatment method.
  • the method Compared with the traditional coating method, the method has the advantages of simple and convenient operation, fast and efficient, low cost, no "three wastes", etc., and has great potential for large-scale production.
  • the present invention provides a fast, high-efficiency, low-cost, no "three wastes" and other advantages to improve the storage stability and processability of lithium ion battery ternary cathode materials.
  • a modification method for improving the storage stability and processability of a ternary cathode material of a lithium ion battery comprising the following steps:
  • the reaction kettle is heated and reacted for a period of time and exhausted to obtain the modified ternary cathode material.
  • the chemical formula of the ternary cathode material is LiNi (1-xy) Co x M y O 2 , x+y ⁇ 0.7, and M is Mn or Al.
  • the chemical formula of the ternary cathode material is LiNi 0.83 Co 0.085 Mn 0.085 O 2 , LiNi 0.80 Co 0.15 Al 0.05 O 2 , LiNi 0.80 Co 0.10 Mn 0.10 O 2 or Li Ni 0.6 Co 0.2 Al 0.2 O 2 .
  • the pressure range of the carbon dioxide gas introduced in step S1 is 7.1 MPa-10 MPa.
  • the temperature of the heat preservation reaction in step S2 is 35-80° C., and the time is 0.1-48 h.
  • the temperature of the heat preservation reaction in step S2 is 35-45° C., and the time is 8-15 h.
  • the invention also discloses a lithium ion battery, which comprises the modified ternary positive electrode material prepared by the method of the invention.
  • the present invention uses supercritical carbon dioxide surface modification treatment to construct a dense metal carbonate coating layer on the surface of the ternary positive electrode material, and the coating layer is tightly combined with the ternary positive electrode material matrix; this surface coating treatment method
  • the ternary cathode material can be isolated from the humid environment to prevent it from reacting with water vapor to generate lithium hydroxide or metal hydroxide, destroying its surface and interface structure, improving its storage performance and subsequent processing performance, thereby greatly improving its cycle performance and increasing use Life:
  • the method is simple in process, easy to operate, fast and efficient, no "three wastes" are generated, carbon dioxide and recycled use, and economic benefits are significant.
  • Figure 1 is a SEM image of the modified ternary cathode material prepared in Example 1 of the present invention.
  • Example 2 is a graph of the first three charge and discharge curves of the battery prepared in Example 1 of the present invention at a current density of 20 mA g -1 ;
  • Fig. 3 is a charge-discharge cycle curve diagram of the battery prepared in Example 1 of the present invention activated for three cycles at a current density of 20 mA g -1 and then cycled 110 times at a current density of 100 mA g -1 .
  • Step 1 Preparation of surface-modified ternary cathode material
  • the reactor containing the ternary cathode material of the lithium ion battery and carbon dioxide is kept at 35° C. for reaction for 10 hours and exhausted to obtain the modified ternary cathode material.
  • step S3 Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
  • conductive agent acetylene black
  • binder polyvinylidene fluoride
  • step S4 The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
  • the third step battery performance test
  • Figure 1 is an SEM chart of the LiNi 0.83 Co 0.085 Mn 0.085 O 2 ternary cathode material of this embodiment after treatment. The chart shows that the surface of the material is uniform after carbon dioxide supercritical treatment, and the morphology is unchanged;
  • Figure 2 is a graph of the first three charge and discharge curves of the battery prepared in this embodiment at a current density of 20 mA g -1 and a voltage range of 3 to 4.2V, and the first discharge capacity is 190 mA h g -1 ;
  • Figure 3 is a graph showing the cycle performance of the battery prepared in this example at a current density of 20 mA g -1 for 3 times, and then at a current density of 100 mA g -1 . After 110 cycles, the discharge capacity is still 157 mA. hg -1 , the capacity retention rate is 93.2% (relative to the fourth charge and discharge).
  • Step 1 Preparation of surface-modified ternary cathode material
  • the reactor containing the ternary cathode material of the lithium ion battery and carbon dioxide is kept at 38° C. for reaction for 12 hours and then exhausted to obtain the modified ternary cathode material.
  • step S3 Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
  • conductive agent acetylene black
  • binder polyvinylidene fluoride
  • step S4 The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
  • the third step battery performance test
  • the button battery assembled with this material is charged and discharged 3 times at a current density of 20mA g -1 within the voltage range of 3 to 4.2V, and the first discharge capacity is 207mA h g -1 , and then at a current density of 100mA g -1 After 110 cycles, the discharge capacity is still 163 mA hg -1 , and the capacity retention rate is 96% (relative to the fourth charge and discharge).
  • Step 1 Preparation of surface-modified ternary cathode material
  • the ternary positive electrode material containing the lithium ion battery and the carbon dioxide reactor are kept at 43° C. for 6 hours and then exhausted to obtain the modified ternary positive electrode material.
  • step S3 Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
  • conductive agent acetylene black
  • binder polyvinylidene fluoride
  • step S4 The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
  • the third step battery performance test
  • the button battery assembled with this material is charged and discharged 3 times at a current density of 20mA g -1 within the voltage range of 3 to 4.2V, and the first discharge capacity is 208mA h g -1 , and then at a current density of 100mA g -1 After 110 cycles, the discharge capacity is still 166 mA hg -1 , and the capacity retention rate is 95% (relative to the fourth charge and discharge).
  • Step 1 Preparation of surface-modified ternary cathode material
  • the ternary cathode material containing the lithium ion battery and the carbon dioxide reactor are kept at 40° C. for 8 hours and then exhausted to obtain the modified ternary cathode material.
  • step S3 Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
  • conductive agent acetylene black
  • binder polyvinylidene fluoride
  • step S4 The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
  • the third step battery performance test
  • the button cell assembled with this material is charged and discharged 3 times at a current density of 20mA g -1 within the voltage range of 3 to 4.2V, and the first discharge capacity is 197mA h g -1 , and then at a current density of 100mA g -1 After 110 cycles, the discharge capacity is still 156mA hg -1 , and the capacity retention rate is 93% (relative to the fourth charge and discharge).
  • the modified ternary cathode material obtained by the method of the present application is used in lithium ion batteries, which can significantly improve the cycle stability of lithium ion batteries, and the modification method is simple, easy to operate, fast and efficient, and has no "three wastes". The economic benefits are significant.

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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)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un procédé de modification de surface de matériau d'électrode positive ternaire permettant d'améliorer la stabilité au stockage et l'aptitude au traitement d'un matériau d'électrode positive ternaire d'une batterie au lithium-ion en vue de résoudre les problèmes de l'état de la technique selon lesquels les exigences de stockage du matériau d'électrode positive ternaire de la batterie au lithium-ion sont élevées, l'aptitude au traitement et la stabilité de cyclage de la batterie sont médiocres, et analogues. Du dioxyde de carbone supercritique réagit avec de l'hydroxyde métallique sur la surface du matériau d'électrode positive ternaire, et une couche de revêtement de carbonate métallique uniforme et dense est formée sur la surface du matériau d'électrode positive ternaire in situ. La couche de revêtement est étroitement combinée à la matrice de matériau d'électrode positive ternaire, et peut également inhiber efficacement la réaction entre le matériau d'électrode positive ternaire et l'air humide, de telle sorte que les exigences d'environnements de stockage et d'utilisation sont réduites, et les performances de traitement d'électrode subséquentes sont améliorées ; de plus, la couche de revêtement de construction in situ peut isoler le matériau d'électrode positive ternaire d'un électrolyte, de telle sorte que l'apparition de réactions secondaires sur la surface de l'électrode est réduite, la stabilité de structure du matériau d'électrode est améliorée, et la performance de cyclage de la batterie est améliorée. En outre, le procédé de modification de surface est simple à mettre en œuvre et peu coûteux.
PCT/CN2020/097428 2019-06-25 2020-06-22 Procédé pour améliorer la stabilité et l'aptitude au traitement d'un matériau d'électrode positive ternaire WO2020259436A1 (fr)

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