WO2024082539A1 - Matériau d'électrode positive au phosphate de lithium-fer-manganèse et sa méthode de préparation et son utilisation - Google Patents

Matériau d'électrode positive au phosphate de lithium-fer-manganèse et sa méthode de préparation et son utilisation Download PDF

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Publication number
WO2024082539A1
WO2024082539A1 PCT/CN2023/082867 CN2023082867W WO2024082539A1 WO 2024082539 A1 WO2024082539 A1 WO 2024082539A1 CN 2023082867 W CN2023082867 W CN 2023082867W WO 2024082539 A1 WO2024082539 A1 WO 2024082539A1
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WIPO (PCT)
Prior art keywords
manganese
iron
acetylacetonate
lithium
positive electrode
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PCT/CN2023/082867
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English (en)
Chinese (zh)
Inventor
余海军
王涛
谢英豪
李爱霞
张学梅
李长东
Original Assignee
广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2024082539A1 publication Critical patent/WO2024082539A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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 invention belongs to the technical field of lithium battery positive electrode materials, and in particular relates to a lithium manganese iron phosphate positive electrode material and a preparation method and application thereof.
  • lithium iron phosphate batteries Compared with ternary batteries, lithium iron phosphate batteries have higher safety and lower cost advantages. They have the advantages of good thermal stability, long cycle life, environmental friendliness, and abundant raw material sources. They are currently the most promising positive electrode material for power lithium-ion batteries. They are gaining favor from more automobile manufacturers and their market share is constantly increasing. Especially in the energy storage market, lithium iron phosphate has broad application prospects.
  • LiFePO 4 material has a low lithium insertion and extraction potential platform (about 3.4V), which reduces the overall energy density of the battery and limits its development in electric vehicles.
  • the working voltage of LiMnPO 4 to Li is 4.1V. If LiMnPO 4 can obtain a specific capacity equivalent to that of LiFePO 4 , it means that the energy density will be 35% higher than that of LiFePO 4. At the same time, low raw material cost and environmental friendliness are also the advantages of LiMnPO 4.
  • LiMnPO 4 the electrical conductivity of LiMnPO 4 is very low, almost an insulator, only one thousandth of LiFePO 4 ; at the same time, there will be a Jahn-Teller effect during the redox reaction, resulting in poor material rate performance and low discharge specific capacity.
  • LiMn x Fe (1-x) PO 4 positive electrode material has a high energy density, which can compensate for the shortcomings of LiFePO 4 positive electrode material in this regard, while improving the problem of low rate and discharge specific capacity of LiMnPO 4 positive electrode material, and increasing the possibility of phosphoric acid-based positive electrode material becoming a power lithium-ion battery material.
  • the co-precipitation reaction of phosphate and ferrous salt, manganese salt and oxidant has the following problems: since the pH of iron phosphate precipitation is low, while the pH of manganese phosphate precipitation is high, at a higher pH, the reaction of ferrous salt and oxidant will produce iron hydroxide, resulting in high iron hydroxide content, low purity, and low phosphorus content.
  • the phosphorus-manganese ratio in the formed divalent manganese phosphate is less than 1, and an additional phosphorus source needs to be supplemented.
  • the present invention aims to solve at least one of the technical problems existing in the prior art.
  • the present invention provides a lithium iron manganese phosphate positive electrode material and a preparation method and application thereof, which can prepare a lithium iron manganese phosphate positive electrode material with a uniform mixture of iron and manganese, and the positive electrode material has a high specific capacity and cycle performance.
  • a method for preparing a lithium iron manganese phosphate positive electrode material comprises the following steps: (1) mixing manganese acetylacetonate, iron acetylacetonate, a phosphorus source and an organic solvent to obtain an organic solution, wherein the manganese in the manganese acetylacetonate is trivalent manganese and the iron in the iron acetylacetonate is trivalent iron; (2) heating the organic solution obtained in step (1) and then evaporating it to obtain a solid gel; (3) mixing a lithium source, a carbon source and water with the solid gel obtained in step (2), drying, calcining under an inert gas, and cooling to obtain the lithium iron manganese phosphate positive electrode material.
  • the CAS number of the manganese acetylacetonate is 14284-89-0.
  • the CAS number of the ferric acetylacetonate is 14024-18-1.
  • the phosphorus source is phosphoric acid.
  • the mass concentration of the phosphoric acid is 80%-95%.
  • the mass concentration of the phosphoric acid is 85%-95%.
  • the organic solvent is at least one of toluene, methanol, n-butanol, glacial acetic acid and ethylene glycol.
  • the manganese acetylacetonate, the iron acetylacetonate and the phosphorus source are mixed in a molar ratio of (Fe+Mn) to P of 1:(1-1.1).
  • step (1) the manganese acetylacetonate, the iron acetylacetonate and the phosphorus source are mixed in a molar ratio of (Fe+Mn) to P of 1:1.
  • the mixing method is to first mix manganese acetylacetonate and iron acetylacetonate to obtain a mixture, then dissolve the mixture in the organic solvent, and then add phosphoric acid dropwise to mix.
  • step (1) manganese acetylacetonate and iron acetylacetonate are mixed in a molar ratio of iron to manganese of (0.1-5):1 to obtain a mixture.
  • step (1) manganese acetylacetonate and acetyl acetonate are mixed in a molar ratio of iron to manganese of (0.25-4):1. and ferric acetone to obtain a mixture.
  • step (1) the mixture is dissolved in the organic solvent at a ratio of (3-15) g/100 g.
  • step (1) the mixture is dissolved in the organic solvent at a ratio of (5-10) g/100 g.
  • the temperature after heating is 100-150°C.
  • step (2) the temperature after heating is 110-140°C.
  • the mass of the added water accounts for 10%-45% of the total mass.
  • step (3) the mass of the added water accounts for 20%-35% of the total mass.
  • the lithium source is at least one of lithium acetate, lithium hydroxide, lithium carbonate and lithium oxalate.
  • the carbon source is at least one of glucose, sucrose and fructose.
  • the drying method is spray drying.
  • the calcination temperature is 500-1000° C. and the calcination time is 5-25 h.
  • the calcination temperature is 600-850° C.
  • the calcination time is 6-20 h.
  • a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
  • an acetylacetone complex of trivalent manganese and trivalent iron is used in an organic phase to be co-heated with phosphoric acid, and the organic solvent is evaporated to prepare a solid gel.
  • phosphorus, iron and manganese are uniformly mixed, which is beneficial to the subsequent preparation of lithium iron manganese phosphate and improves the specific capacity and cycle performance of the material.
  • manganese is stably present in a divalent state, resulting in a phosphorus-manganese ratio in the prepared manganese phosphate of less than 1, and the precipitation conditions of iron and manganese in the aqueous phase are different, making it difficult to achieve uniform mixing of iron and manganese.
  • the iron and manganese in the generated solid gel are both in a trivalent state combined with phosphate.
  • the lithium iron manganese phosphate is subsequently sintered with a lithium source and a carbon source to prepare the lithium iron manganese phosphate, the generation of metal oxides or metal elements is avoided, thereby further improving the specific capacity and cycle performance of the material.
  • FIG. 1 is a SEM image of the lithium manganese iron phosphate positive electrode material prepared in Example 1 of the present invention.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
  • step (4) The product obtained in step (4) is calcined at 800° C. for 15 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
  • a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above, and its SEM image is shown in FIG1 .
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
  • step (4) The product obtained in step (4) is calcined at 850° C. for 10 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
  • a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
  • step (4) The product obtained in step (4) is calcined at 600° C. for 20 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
  • a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
  • Comparative Example 1 (The difference from Example 1 is that it is prepared by aqueous phase coprecipitation)
  • a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
  • a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
  • Comparative Example 2 (The difference from Example 2 is that it is prepared by aqueous phase coprecipitation)
  • a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
  • a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
  • Comparative Example 3 (The difference from Example 3 is that it is prepared by aqueous phase coprecipitation)
  • a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
  • a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
  • Comparative Example 4 (The only difference from Example 1 is that the manganese in manganese acetylacetonate is divalent manganese)
  • a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
  • step (4) The product obtained in step (4) is calcined at 800° C. for 15 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
  • a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
  • Comparative Example 5 (The only difference from Example 2 is that the manganese in manganese acetylacetonate is divalent manganese)
  • a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
  • step (4) The product obtained in step (4) is calcined at 850° C. for 10 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
  • a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
  • Comparative Example 6 (The only difference from Example 3 is that the manganese in manganese acetylacetonate is divalent manganese)
  • a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
  • step (4) The product obtained in step (4) is calcined at 600° C. for 20 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
  • a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
  • the manganese acetylacetonate (CAS No.: 14284-89-0) used in Examples 1-3 is trivalent manganese
  • the manganese acetylacetonate (CAS No.: 14024-58-9) used in Comparative Examples 4-6 is divalent manganese
  • Comparative Examples 1-3 adopt aqueous phase co-precipitation.
  • the amount of precipitate first increases-remains unchanged-and then increases-remains unchanged, that is, due to the different pH values of iron and manganese precipitation, iron phosphate is precipitated first, and then manganese phosphate.
  • the lithium iron manganese phosphate positive electrode material obtained in the embodiment and the comparative example, acetylene black as a conductive agent, PVDF as a binder, are mixed at a mass ratio of 8:1:1, and a certain amount of organic solvent NMP is added, and after stirring, it is coated on an aluminum foil to make a positive electrode sheet, and a metal lithium sheet is used for the negative electrode;
  • the diaphragm is a Celgard2400 polypropylene porous membrane;
  • the solvent in the electrolyte is EC, DMC and EMC at a mass ratio of The solution is composed of 1:1:1, the solute is LiPF 6 , and the concentration of LiPF 6 is 1.0 mol/L; 2023 button cells are assembled in the glove box.
  • the battery is tested for charge and discharge cycle performance, and the 0.2C and 1C discharge specific capacities are tested within the cut-off voltage range of 2.0-4.3V; the test electrochemical performance results are shown in Table 2:
  • the 0.2C discharge capacity of the lithium manganese iron phosphate positive electrode material prepared by the preparation method of the present application can reach more than 149.3 mAh/g
  • the 1C discharge capacity can reach more than 142.4 mAh/g
  • the capacity retention rate after 500 cycles at 1C can reach more than 94.06%.

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

Abstract

La présente invention concerne un matériau d'électrode positive au phosphate de lithium-fer-manganèse et sa méthode de préparation et son utilisation. La méthode de préparation comprend les étapes suivantes, consistant à : (1) mélanger de l'acétylacétonate de manganèse, de l'acétylacétonate de fer, une source de phosphore et un solvant organique pour obtenir une solution organique, le manganèse dans l'acétylacétonate de manganèse étant du manganèse trivalent, et le fer dans l'acétylacétonate de fer étant du fer trivalent ; (2) chauffer la solution organique obtenue à l'étape (1) puis évaporer à sec pour obtenir un gel solide ; et (3) mélanger une source de lithium, une source de carbone, de l'eau et le gel solide obtenu à l'étape (2), sécher, calciner sous un gaz inerte, et refroidir pour obtenir le matériau d'électrode positive au phosphate de lithium-fer-manganèse. Selon la méthode, le matériau d'électrode positive au phosphate de lithium-fer-manganèse dans lequel le fer et le manganèse sont mélangés uniformément peut être préparé, et le matériau d'électrode positive a une capacité spécifique et une performance de cycle relativement élevées.
PCT/CN2023/082867 2022-10-21 2023-03-21 Matériau d'électrode positive au phosphate de lithium-fer-manganèse et sa méthode de préparation et son utilisation WO2024082539A1 (fr)

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CN202211293362.5 2022-10-21
CN202211293362.5A CN115893357A (zh) 2022-10-21 2022-10-21 一种磷酸锰铁锂正极材料及其制备方法和应用

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103702934A (zh) * 2011-06-27 2014-04-02 新加坡国立大学 制备有效中孔性纳米复合材料正极LiMn1-xFexPO4材料的方法
WO2015003568A1 (fr) * 2013-07-10 2015-01-15 江苏华东锂电技术研究院有限公司 Procédé de préparation de matière active d'électrode positive d'une batterie aux ions lithium
JP2015032345A (ja) * 2013-07-31 2015-02-16 太平洋セメント株式会社 リン酸マンガンリチウム正極活物質の製造方法
CN104752718A (zh) * 2013-12-27 2015-07-01 比亚迪股份有限公司 一种LiMnxFe1-xPO4正极活性材料及其制备方法
CN115072695A (zh) * 2022-07-07 2022-09-20 江苏协鑫锂电科技有限公司 一种高容量磷酸铁锰锂材料的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103702934A (zh) * 2011-06-27 2014-04-02 新加坡国立大学 制备有效中孔性纳米复合材料正极LiMn1-xFexPO4材料的方法
WO2015003568A1 (fr) * 2013-07-10 2015-01-15 江苏华东锂电技术研究院有限公司 Procédé de préparation de matière active d'électrode positive d'une batterie aux ions lithium
JP2015032345A (ja) * 2013-07-31 2015-02-16 太平洋セメント株式会社 リン酸マンガンリチウム正極活物質の製造方法
CN104752718A (zh) * 2013-12-27 2015-07-01 比亚迪股份有限公司 一种LiMnxFe1-xPO4正极活性材料及其制备方法
CN115072695A (zh) * 2022-07-07 2022-09-20 江苏协鑫锂电科技有限公司 一种高容量磷酸铁锰锂材料的制备方法

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