WO2024026984A1 - Preparation method for and use of positive electrode material - Google Patents

Preparation method for and use of positive electrode material Download PDF

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WO2024026984A1
WO2024026984A1 PCT/CN2022/118781 CN2022118781W WO2024026984A1 WO 2024026984 A1 WO2024026984 A1 WO 2024026984A1 CN 2022118781 W CN2022118781 W CN 2022118781W WO 2024026984 A1 WO2024026984 A1 WO 2024026984A1
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dopant
cathode material
preparation
preparing
material according
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French (fr)
Chinese (zh)
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彭卓
李长东
阮丁山
杜锐
孙金鸣
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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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    • 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
    • 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
    • H01M4/58—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
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of new energy materials, and specifically relates to a preparation method of a positive electrode material and its application.
  • Lithium-ion batteries are widely used in new energy vehicles, mobile equipment, energy storage power stations and other fields because of their high operating voltage and excellent cycle performance. With the continuous development of technology, people have also put forward higher requirements for lithium-ion batteries. The design and development of electrode materials with higher capacity, high power, high energy density and good cycle stability have become one of the research hotspots in the field of new energy. .
  • Lithium iron phosphate (LFP) with olivine structure is mainly used in lithium-ion batteries, batteries for electric/hybrid vehicles or energy storage power stations.
  • the low charge/discharge voltage platform (3.4V) results in low energy density, which limits Its development in the field of energy storage.
  • Lithium iron manganese phosphate (LMFP) cathode material has a higher discharge voltage than LFP (two platforms of 3.4V and 4.1V), and its energy density is 20% higher than LFP.
  • the crystal structure of LMFP is very similar to that of LFP, both of which are olivine structures, with a theoretical specific capacity of 170mAh g -1 .
  • the electrochemical performance of LMFP is limited by electron transmission and ion diffusion.
  • the strong PO covalent bond in PO 4 3- stabilizes the oxygen atoms and ensures that Li + can be inserted/extracted in a stable crystal structure.
  • the olivine-type LMFP structure exhibits Outstanding safety and cycle stability.
  • strong The PO covalent bond also prevents Li + from passing through the PO 4 3- tetrahedron.
  • the transport of Li+ can only be one-dimensional diffusion along the b axis, which reduces the diffusion rate of Li+ and leads to poor conductivity.
  • the present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a method for preparing a cathode material, which can prepare a cathode material that improves the Li + diffusion rate and electronic conductivity of lithium iron manganese phosphate.
  • the invention also provides an application of the cathode material prepared by the above-mentioned cathode material preparation method in the preparation of secondary batteries.
  • step S2 The powder obtained after drying in step S1 is subjected to heat treatment, and the heat treatment is carried out in a microwave plasma environment;
  • step S2 The powder obtained in step S2 is carbon coated and then pulverized; the carbon coating method is microwave plasma chemical vapor deposition.
  • step S3 not only protects the carbon-coated positive electrode piece from electrolyte corrosion, but also improves the corrosion resistance of the positive electrode material due to its high degree of graphitization. Electronic conductivity ultimately improves the electrochemical performance of the resulting cathode material.
  • MPCVD microwave plasma chemical vapor deposition method
  • the carbon-coated lithium iron manganese phosphate synthesized by the MPCVD method has controllable particle size. Compared with conventional nitrogen atmosphere sintering, it overcomes the growth and agglomeration of particles under high-temperature calcination of the material, and improves the specific capacity and cycle stability of the material. .
  • Coating a layer of carbon on the surface of lithium iron manganese phosphate material is an effective means to improve the electrochemical performance of electrode materials.
  • the carbon layer exists between particles, which can enhance the conductivity of the material and weaken the polarization; on the other hand, the carbon layer can also provide more fast tunnels for electron transmission, and carbon coating can inhibit grain growth. , which is conducive to shortening the movement distance of lithium ions, thereby improving the rate performance of lithium iron manganese phosphate active materials.
  • the manganese source includes at least one of manganese oxalate, manganese monoxide, manganese tetroxide, manganese trioxide, manganous phosphate and manganese hydrogen phosphate.
  • the iron source is at least one of iron phosphate, iron oxide, ferrous oxalate and iron powder.
  • the phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, lithium phosphate and phosphoric acid.
  • the lithium source is at least one of lithium phosphate, lithium dihydrogen phosphate, lithium carbonate and lithium hydroxide.
  • the dispersion further includes adding a dopant
  • the dopants include Zn dopant, Mg dopant, Ti dopant, Al dopant, Cr dopant, Zr dopant, Ni dopant and Co at least one of the dopants.
  • MO 6 Mo
  • the Li-O bonds in the facets will become longer, making the lithium ion diffusion channel wider and easier to migrate, which is beneficial to the improvement of electrochemical performance. Therefore, the lattice distortion caused by the doping of the above-mentioned metal elements can reduce the surface energy of the crystal of the cathode material, inhibit the growth of the crystal, and synthesize nanoscale lithium iron manganese phosphate.
  • the doping of metal elements can improve the lithium ion diffusion rate of lithium iron manganese phosphate materials, making the lithium ion diffusion channel wider and easier to migrate, thereby improving the electrochemical performance of the material.
  • Different metal elements do not have charge compensation defects in the same valence (such as Mg 2+ and Ni 2+ at the M 2+ position). Due to the charge compensation mechanism, equivalent doping can generate vacancies and the energy of equivalent substitution is the lowest.
  • the greater the charge difference between the dopant and host ions the higher the incorporation energy of the dopant, which makes heterovalent doping difficult.
  • step S1 the D50 of the particle size of the crushed material is 0.3-1.0 ⁇ m.
  • the lithium iron manganese phosphate material can accommodate a large amount of Li + and reversibly deintercalate without causing its own structural change. Under the above particle size, it is avoided that the material's particle size is too large, which will increase the diffusion path of Li + , reduce the migration rate of Li + , and make the rate performance of the material worse; at the same time, it avoids the increase in surface energy caused by the material's particle size being too small. , prone to agglomeration.
  • the crushing includes grinding.
  • the grinding time is 1 to 10 hours.
  • step S1 the drying includes spray drying.
  • the temperature of the air inlet of the drying process is 180-250°C.
  • the temperature of the air outlet during the drying process is 90-140°C.
  • step S1 the spray drying includes constant speed spray drying and reduced speed spray drying.
  • the feed rate of the spray drying is 5 to 10 L/min.
  • the temperature of the droplets remains unchanged, the water on the surface continues to evaporate, the water inside the droplets migrates to the surface, the dry air continuously transfers heat to the droplets, and the temperature of the carrier gas decreases; in the slow-speed drying stage, the moisture in the droplets
  • the surface of the drop has begun to solidify, the temperature gradually decreases from the outside to the inside, and the water content of the particles gradually decreases.
  • the inlet/outlet air temperature is low, below 180/90°C, it takes a long time for the surface of the droplets to solidify, and the particles are more likely to agglomerate during the continuous collision process.
  • the temperature is too high, higher than 250/140°C, which changes the chemical properties of the precursor. Fe and Mn in the material are easily oxidized to high valence states, which increases energy consumption and costs.
  • the present invention can realize rapid transfer of heat and mass, so that the material can be quickly dried and formed into regular nanoparticles with good uniformity.
  • the MPCVD method can then be used to better coat a uniform carbon layer on the surface of the particles.
  • the temperature of the heat treatment is 600-800°C.
  • the heat treatment time is 10 to 60 minutes.
  • Microwave plasma chemical vapor deposition can synthesize nanoparticles in a very short time, which can avoid grain growth caused by traditional long-term high-temperature heat treatment.
  • the small particle size is conducive to shortening the migration path of lithium ions during the deintercalation process and effectively improving the electrochemical performance of lithium iron manganese phosphate.
  • the plasma used in the microwave plasma includes hydrogen plasma.
  • the flow rate of the hydrogen plasma is 10-100 sccm.
  • the above temperature, time, and methane flow rate are used as parameters to adjust the speed of methane cracking, affecting the effect of carbon coating, ensuring that the carbon atoms obtained by the decomposition of methane in unit time are avoided, while avoiding the excessive speed of methane cracking. , forming a large number of carbon-accumulated carbon particles.
  • step S2 the heat treatment is performed in a microwave plasma chemical vapor deposition (MPCVD) reaction tank.
  • MPCVD microwave plasma chemical vapor deposition
  • step S2 the lithium iron manganese phosphate powder material is obtained after the plasma treatment.
  • the carbon-coated carbon source includes methane.
  • the flow rate of the methane is 10 to 100 sccm.
  • the crushing method includes jet mill crushing.
  • the classification frequency of the airflow mill is 150 to 260 Hz.
  • the air pressure of the air flow mill for grinding is 0.3 to 0.6 MPa.
  • Lithium iron manganese phosphate is not a simple physical mixture of lithium manganese phosphate and lithium iron phosphate. Since the ion radii of iron and manganese in the material are similar, they easily form a solid solution, so atomic level mixing can be achieved.
  • the Mn content is too high, the elongation of the Mn-O bond caused by the Jahn-Teller distortion of Mn 3+ during charge and discharge processes (shared with the edges of the PO 4 3- tetrahedron, is responsible for increasing the activation of carrier migration (can), which brings about the sluggishness of the intrinsic dynamics of LMFP with high Mn content. Therefore, the best performance can be achieved when Mn:Fe is approximately 6:4.
  • the application of the cathode material prepared by the above preparation method in secondary batteries is proposed.
  • Figure 1 is an XRD pattern in Example 3 of the present invention.
  • Figure 2 is an SEM image of Example 3 of the present invention.
  • Figure 3 is an electrochemical performance diagram of Example 3.
  • Figure 4 is an electrochemical performance diagram of Comparative Example 1
  • Figure 5 is an AC impedance diagram of Example 3 and Comparative Example 1.
  • This embodiment discloses a preparation method of cathode material.
  • This embodiment discloses a preparation method of cathode material.
  • This embodiment discloses a preparation method of cathode material.
  • the XRD pattern of the product prepared in Example 3 is shown in Figure 1.
  • the results show that the diffraction peaks of the sample belong to the orthorhombic olivine crystal structure, and the diffraction peaks can all be consistent with the LiMnPO 4 (PFD#77-0178) standard card.
  • the diffraction peaks match, and the X-ray diffraction peaks are shifted at high angles because Mn 2+ radius ratio
  • the larger the Fe 2+ the lattice spacing of the cathode material is reduced; the obtained peak intensities are equivalent and the crystallinity is good. It can be seen that pure lithium iron manganese phosphate is synthesized, and the carbon exists in an amorphous form and cannot be detected by XRD , so the presence of carbon does not affect the crystal structure of the material.
  • the SEM image of the product prepared in Example 3 is shown in Figure 2.
  • the results show that carbon-coated lithium iron manganese phosphate has a uniform particle size distribution, which indicates that MPCVD is a very effective way to control particle size. This is because MPCVD can synthesize nanoparticles in a very short time, which can avoid due to Grain growth caused by traditional long-term high-temperature heat treatment.
  • the prepared small particle size is conducive to shortening the migration path of lithium ions during the deintercalation process, and can effectively improve the electrochemical performance of lithium iron manganese phosphate.
  • This embodiment discloses a preparation method of cathode material.
  • S2 Spray dry the sand-ground slurry.
  • the drying conditions are the inlet temperature is 210°C, the outlet temperature is 110°C, and the feed rate is 6L/min to obtain the dry powder of the precursor;
  • This embodiment discloses a method for preparing a cathode material.
  • This embodiment discloses a method for preparing a cathode material.
  • the difference from Example 3 is that the precursor powder obtained by spray drying is placed on the substrate in the MPCVD reaction tank, and hydrogen plasma is introduced for treatment.
  • the reaction temperature is 700°C.
  • the treatment time is 20 minutes, and the hydrogen flow rate is 80 sccm.
  • This embodiment discloses a method for preparing a cathode material.
  • the difference from Embodiment 3 is that the added dopant containing doping elements is Ni, and the other conditions are the same.
  • This embodiment discloses a method for preparing a cathode material.
  • the difference from Example 3 is that in step S1, a sand mill is used for sand grinding until the slurry D 50 is 0.8 ⁇ m.
  • This embodiment discloses a method for preparing a cathode material.
  • the difference from Example 3 is that in step S3, the reaction temperature is 750°C.
  • This embodiment discloses a method for preparing a cathode material.
  • the difference from Example 3 is that in step S3, the processing time is 25 minutes.
  • This embodiment discloses a method for preparing a cathode material.
  • the difference from Example 3 is that in step S3, the hydrogen gas flow rate is 100 sccm.
  • This embodiment discloses a method for preparing a cathode material.
  • the difference from Example 3 is that in step S4, the reaction temperature is 600°C.
  • This embodiment discloses a method for preparing a cathode material.
  • the difference from Example 3 is that in step S3, the processing time is 25 minutes.
  • This embodiment discloses a method for preparing a cathode material.
  • the difference from Example 3 is that in step S3, the methane flow rate is 100 sccm.
  • This comparative example discloses a preparation method of a cathode material.
  • the difference from Example 3 is that a soluble organic carbon source (glucose) is used as the carbon source, mixed in the slurry, sanded, spray-dried, and then dried in a tube furnace.
  • LiMn 0.6 Fe 0.37 M 0.03 PO 4 /C nanoparticles were synthesized under nitrogen atmosphere.
  • FIG. 3 is the charge and discharge curve of the sample prepared in Example 3 at 0.1C, and the 0.1C discharge specific capacity is 155mAh/g;
  • Figure 4 is the charge and discharge curve of the sample prepared in Comparative Example 1 at 0.1C, and the 0.1C discharge ratio The capacity is 142mAh/g; the results show that the carbon-coated lithium iron manganese phosphate material through the MPCVD method has better performance.
  • FIG. 4 is the AC impedance spectrum of Example 3 and Comparative Example 1.
  • the impedance spectrum consists of a high-frequency area and a low-frequency area.
  • the diameter of the semicircle in the high-frequency area represents the electrochemical transfer impedance Rct
  • the straight line in the low-frequency area represents the diffusion rate of Li +
  • Comparative Example 1 has the largest Rct value, indicating that the sample is greatly hindered and has low electronic conductivity, resulting in large polarization and low specific capacity during the charge and discharge process.
  • This test example tested the charge and discharge detection results of the cathode materials of Examples 1 to 14 and Comparative Example 1.
  • the test results are shown in Table 1, in which Examples 1 to 14 and Comparative Example 1 used equal volumes of LiPF 6 and carbonic acid. Diethyl ester (DEC) electrolyte, the concentration of LiPF 6 is 1M, and the metal lithium sheet is used as the negative electrode to prepare a button half cell.
  • DEC Diethyl ester
  • the battery rate performance is tested using a LAND battery program control tester (LAND CT2001A).
  • the carbon layer deposited by microwave plasma chemical vapor deposition (MPCVD) in Examples 1 to 14 not only protects the carbon-coated positive electrode plate from electrolyte corrosion, but also has high graphitization due to the positive electrode material. degree, it also improves the electronic/ion conductivity and electrochemical performance.
  • MPCVD microwave plasma chemical vapor deposition

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Abstract

Disclosed in the present invention are a preparation method for and the use of a positive electrode material. The preparation method comprises the following steps: S1, dispersing a manganese source, an iron source, a lithium source and a phosphorus source, and then crushing and drying same; S2, subjecting the powder obtained by the drying in step S1 to a microwave plasma chemical vapor deposition treatment, wherein a lithium manganese iron phosphate material is obtained after the heat treatment; and S3, subjecting the powder obtained by the plasma treatment in step S2 to carbon coating, and then crushing same. In the present invention, a positive electrode material capable of improving the Li+ diffusion rate and the electronic conductivity of lithium manganese iron phosphate can be prepared.

Description

一种正极材料的制备方法及其应用Preparation method of cathode material and its application 技术领域Technical field
本发明属于新能源材料技术领域，具体涉及一种正极材料的制备方法及其应用。The invention belongs to the technical field of new energy materials, and specifically relates to a preparation method of a positive electrode material and its application.
背景技术Background technique
锂离子电池因其具有较高的工作电压和出色的循环性能，在新能源汽车、移动设备、储能电站等领域受到广泛应用。随着技术的不断发展，人们对锂离子电池也提出更高的要求，设计研发具有更高容量、高功率、高能量密度、循环稳定性好的电极材料已经成为新能源领域的研究热点之一。Lithium-ion batteries are widely used in new energy vehicles, mobile equipment, energy storage power stations and other fields because of their high operating voltage and excellent cycle performance. With the continuous development of technology, people have also put forward higher requirements for lithium-ion batteries. The design and development of electrode materials with higher capacity, high power, high energy density and good cycle stability have become one of the research hotspots in the field of new energy. .
橄榄石型结构的磷酸铁锂(LFP)主要用于锂离子电池、电动/混合动力汽车的电池或储能电站，然而，低充电/放电电压平台(3.4V)导致低能量密度，这限制了其在储能领域的发展。磷酸铁锰锂(LMFP)正极材料与LFP相比有高的放电电压(3.4V和4.1V两个平台)，其能量密度比LFP高20％。LMFP的晶体结构与LFP非常相似都是橄榄石型结构，理论比容量为170mAh g -1。LMFP的电化学性能受到电子传输和离子扩散的限制，PO 4 3-中强大的P-O共价键稳定了氧原子，确保Li +可以在稳定的晶体结构中嵌入/脱出，橄榄石型LMFP结构表现出良好的安全性和循环稳定性。然而，LMFP是一种具有极低电子传导性的半导体化合物，原因在于M-O(M＝Fe，Mn)八面体被P-O四面体隔离，在其晶体结构中没有形成连续的M-O网络，此外，强的P-O共价键也阻止了Li +通过PO 4 3-四面体，Li+的传输只能是沿b轴的一维扩散，这就降低了Li+的扩散速率，导致导电性差。 Lithium iron phosphate (LFP) with olivine structure is mainly used in lithium-ion batteries, batteries for electric/hybrid vehicles or energy storage power stations. However, the low charge/discharge voltage platform (3.4V) results in low energy density, which limits Its development in the field of energy storage. Lithium iron manganese phosphate (LMFP) cathode material has a higher discharge voltage than LFP (two platforms of 3.4V and 4.1V), and its energy density is 20% higher than LFP. The crystal structure of LMFP is very similar to that of LFP, both of which are olivine structures, with a theoretical specific capacity of 170mAh g -1 . The electrochemical performance of LMFP is limited by electron transmission and ion diffusion. The strong PO covalent bond in PO 4 3- stabilizes the oxygen atoms and ensures that Li + can be inserted/extracted in a stable crystal structure. The olivine-type LMFP structure exhibits Outstanding safety and cycle stability. However, LMFP is a semiconductor compound with extremely low electronic conductivity. The reason is that the MO (M=Fe, Mn) octahedron is isolated by PO tetrahedron, and no continuous MO network is formed in its crystal structure. In addition, strong The PO covalent bond also prevents Li + from passing through the PO 4 3- tetrahedron. The transport of Li+ can only be one-dimensional diffusion along the b axis, which reduces the diffusion rate of Li+ and leads to poor conductivity.
因此，如何进一步提高磷酸铁锰锂中Li+的扩散速率和电子导电率是目前的当务之急。Therefore, how to further improve the diffusion rate and electronic conductivity of Li+ in lithium iron manganese phosphate is a top priority.
发明内容Contents of the invention
本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明提出一种正极材料的制备方法，能够制备得到提高磷酸铁锰锂的Li +的扩散速率和电子导电率的正极材料。 The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a method for preparing a cathode material, which can prepare a cathode material that improves the Li + diffusion rate and electronic conductivity of lithium iron manganese phosphate.
本发明还提供一种上述正极材料的制备方法制备的正极材料在制备二次电池中的应用。The invention also provides an application of the cathode material prepared by the above-mentioned cathode material preparation method in the preparation of secondary batteries.
根据本发明的第一方面实施例的一种正极材料的制备方法，包括以下步骤：A method for preparing a cathode material according to the first embodiment of the present invention includes the following steps:
S1.将锰源、铁源、锂源和磷源混合分散后，破碎，干燥；S1. Mix and disperse the manganese source, iron source, lithium source and phosphorus source, crush and dry;
S2.将步骤S1干燥后所得粉末进行热处理，所述热处理在微波等离子体的环境中进行；S2. The powder obtained after drying in step S1 is subjected to heat treatment, and the heat treatment is carried out in a microwave plasma environment;
所述气相沉积处理后得到磷酸铁锰锂材料；After the vapor deposition treatment, a lithium iron manganese phosphate material is obtained;
S3.将步骤S2所得粉末进行碳包覆后粉碎；所述碳包覆的方法为微波等离子体化学气相沉积法。S3. The powder obtained in step S2 is carbon coated and then pulverized; the carbon coating method is microwave plasma chemical vapor deposition.
根据本发明实施例的一种正极材料的制备方法，至少具有以下有益效果：A method for preparing a cathode material according to an embodiment of the present invention has at least the following beneficial effects:
1、通过步骤S3微波等离子体化学气相沉积方法(MPCVD)沉积的碳层不仅保护碳包覆后的正极极片免受电解液腐蚀，而且由于正极材料具有较高的石墨化程度，还提升了电子导电性，最终提升了所得正极材料的电化学性能。1. The carbon layer deposited by the microwave plasma chemical vapor deposition method (MPCVD) in step S3 not only protects the carbon-coated positive electrode piece from electrolyte corrosion, but also improves the corrosion resistance of the positive electrode material due to its high degree of graphitization. Electronic conductivity ultimately improves the electrochemical performance of the resulting cathode material.
2、MPCVD方法合成的碳包覆磷酸铁锰锂，颗粒大小可控，与常规的氮气气氛烧结相比，克服了材料在高温煅烧下颗粒的生长以及团聚，提高材料的比容量和循环稳定性。2. The carbon-coated lithium iron manganese phosphate synthesized by the MPCVD method has controllable particle size. Compared with conventional nitrogen atmosphere sintering, it overcomes the growth and agglomeration of particles under high-temperature calcination of the material, and improves the specific capacity and cycle stability of the material. .
3、在磷酸铁锰锂材料表面包覆一层碳，是提高电极材料的电化学性能的有效手段。一方面，碳层存在于颗粒之间，可以增强的材料的导电性，使得极化作用减弱；另一方面碳层还能为电子传输提供更多快速的隧道，碳包覆可以抑制晶粒增长，利于缩短锂离子运动距离，从而提高磷酸铁锰锂活性材料的倍率性能。3. Coating a layer of carbon on the surface of lithium iron manganese phosphate material is an effective means to improve the electrochemical performance of electrode materials. On the one hand, the carbon layer exists between particles, which can enhance the conductivity of the material and weaken the polarization; on the other hand, the carbon layer can also provide more fast tunnels for electron transmission, and carbon coating can inhibit grain growth. , which is conducive to shortening the movement distance of lithium ions, thereby improving the rate performance of lithium iron manganese phosphate active materials.
根据本发明的一些实施例，所述锰源包括草酸锰、一氧化锰、四氧化三锰、三氧化二锰、磷酸亚锰和磷酸氢锰中的至少一种。According to some embodiments of the present invention, the manganese source includes at least one of manganese oxalate, manganese monoxide, manganese tetroxide, manganese trioxide, manganous phosphate and manganese hydrogen phosphate.
根据本发明的一些实施例，所述铁源为磷酸铁、氧化铁、草酸亚铁和铁粉中的至少一种。According to some embodiments of the present invention, the iron source is at least one of iron phosphate, iron oxide, ferrous oxalate and iron powder.
根据本发明的一些实施例，所述磷源为磷酸二氢铵、磷酸氢二铵、磷酸二氢锂、磷酸锂和磷酸中的至少一种。According to some embodiments of the present invention, the phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, lithium phosphate and phosphoric acid.
根据本发明的一些实施例，所述锂源为磷酸锂、磷酸二氢锂、碳酸锂和氢氧化锂中的至少一种。According to some embodiments of the present invention, the lithium source is at least one of lithium phosphate, lithium dihydrogen phosphate, lithium carbonate and lithium hydroxide.
根据本发明的一些实施例，步骤S1中，所述分散前还包括加入掺杂剂；According to some embodiments of the present invention, in step S1, the dispersion further includes adding a dopant;
根据本发明的一些实施例，所述掺杂剂包括Zn掺杂剂、Mg掺杂剂、Ti掺杂剂、Al掺杂剂、Cr掺杂剂、Zr掺杂剂、Ni掺杂剂和Co掺杂剂中的至少一种。According to some embodiments of the present invention, the dopants include Zn dopant, Mg dopant, Ti dopant, Al dopant, Cr dopant, Zr dopant, Ni dopant and Co at least one of the dopants.
锂离子传输路径是沿[010]晶面方向；上述掺杂元素的金属离子的掺入缩短了橄榄石结构MO 6(M＝Mn、Fe、Mg)八面体中的键长，而LiO 6八面体中的Li-O键会变长，使锂离子扩散通道更宽容易迁移，有利于电化学性能的提高。因此，上述金属元素的掺杂产生的晶格畸变可以降低正极材料的晶体的表面能，也可以抑制晶体的生长，合成纳米级的磷酸铁锰锂。 The lithium ion transmission path is along the [010] crystal plane direction; the incorporation of metal ions of the above-mentioned doping elements shortens the bond length in the olivine structure MO 6 (M=Mn, Fe, Mg) octahedron, while LiO 6 octahedron The Li-O bonds in the facets will become longer, making the lithium ion diffusion channel wider and easier to migrate, which is beneficial to the improvement of electrochemical performance. Therefore, the lattice distortion caused by the doping of the above-mentioned metal elements can reduce the surface energy of the crystal of the cathode material, inhibit the growth of the crystal, and synthesize nanoscale lithium iron manganese phosphate.
金属元素的掺杂可以改善磷酸铁锰锂材料的锂离子扩散速率，使锂离子扩散通道更宽容易迁移，来提高材料的电化学性能。不同金属元素，在同价中不存在电荷补偿缺陷(例如M 2+位上的Mg 2+、Ni 2+)，由于电荷补偿机制，等价掺杂可以产生空位并且同价取代的能量最低。此外，掺杂剂与主体离子的电荷差越大，掺杂剂的掺入能越高，这使得异价掺杂变得困难。 The doping of metal elements can improve the lithium ion diffusion rate of lithium iron manganese phosphate materials, making the lithium ion diffusion channel wider and easier to migrate, thereby improving the electrochemical performance of the material. Different metal elements do not have charge compensation defects in the same valence (such as Mg 2+ and Ni 2+ at the M 2+ position). Due to the charge compensation mechanism, equivalent doping can generate vacancies and the energy of equivalent substitution is the lowest. In addition, the greater the charge difference between the dopant and host ions, the higher the incorporation energy of the dopant, which makes heterovalent doping difficult.
根据本发明的一些实施例，步骤S1中，所述破碎后材料的粒径的D 50为0.3～1.0μm。 According to some embodiments of the present invention, in step S1, the D50 of the particle size of the crushed material is 0.3-1.0 μm.
磷酸铁锰锂材料在上述粒径下，能容纳大量Li +可逆脱嵌而不引起自身结构变化。在上述粒径下避免了材料因粒径过大会增大Li +的扩散路径，降低Li +的迁移速率，使得材料倍率性 能变差；同时避免因材料粒径过小会导致的表面能升高，易于发生团聚的现象。 At the above particle size, the lithium iron manganese phosphate material can accommodate a large amount of Li + and reversibly deintercalate without causing its own structural change. Under the above particle size, it is avoided that the material's particle size is too large, which will increase the diffusion path of Li + , reduce the migration rate of Li + , and make the rate performance of the material worse; at the same time, it avoids the increase in surface energy caused by the material's particle size being too small. , prone to agglomeration.
根据本发明的一些实施例，所述破碎包括研磨。According to some embodiments of the invention, the crushing includes grinding.
根据本发明的一些实施例，所述研磨的时间为1～10h。According to some embodiments of the present invention, the grinding time is 1 to 10 hours.
根据本发明的一些实施例，步骤S1中，所述干燥包括喷雾干燥。According to some embodiments of the present invention, in step S1, the drying includes spray drying.
根据本发明的一些实施例，所述干燥过程的进风口的温度为180～250℃。According to some embodiments of the present invention, the temperature of the air inlet of the drying process is 180-250°C.
根据本发明的一些实施例，所述干燥过程的出风口的温度为90～140℃。According to some embodiments of the present invention, the temperature of the air outlet during the drying process is 90-140°C.
根据本发明的一些实施例，步骤S1中，所述喷雾干燥包括等速喷雾干燥和降速喷雾干燥。According to some embodiments of the present invention, in step S1, the spray drying includes constant speed spray drying and reduced speed spray drying.
根据本发明的一些实施例，所述喷雾干燥的进料速度为5～10L/min。According to some embodiments of the present invention, the feed rate of the spray drying is 5 to 10 L/min.
等速干燥阶段，雾滴的温度保持不变，表面的水分不断蒸发，液滴内部的水分向表面迁移，干燥空气不断地把热量传递给雾滴，载气温度降低；降速干燥阶段，雾滴的表面已开始固化，温度从外到内逐渐降低，颗粒的含水量逐渐减小。进/出风温度较低，低于180/90℃时，雾滴表面固化所需的时间较长，颗粒在不断的碰撞过程中较容易发生团聚。但温度过高，高于250/140℃，使得前驱体的化学性质改变，材料中Fe、Mn易被氧化成高价态，且增加能耗，成本增加。In the constant-speed drying stage, the temperature of the droplets remains unchanged, the water on the surface continues to evaporate, the water inside the droplets migrates to the surface, the dry air continuously transfers heat to the droplets, and the temperature of the carrier gas decreases; in the slow-speed drying stage, the moisture in the droplets The surface of the drop has begun to solidify, the temperature gradually decreases from the outside to the inside, and the water content of the particles gradually decreases. When the inlet/outlet air temperature is low, below 180/90°C, it takes a long time for the surface of the droplets to solidify, and the particles are more likely to agglomerate during the continuous collision process. However, the temperature is too high, higher than 250/140°C, which changes the chemical properties of the precursor. Fe and Mn in the material are easily oxidized to high valence states, which increases energy consumption and costs.
本发明通过结合喷雾干燥技术可以实现热量和质量的快速转移，使物料迅速干燥并形成规则的纳米颗粒，均匀性好，再使用MPCVD方法能在颗粒表面更好的包覆均匀的碳层。By combining spray drying technology, the present invention can realize rapid transfer of heat and mass, so that the material can be quickly dried and formed into regular nanoparticles with good uniformity. The MPCVD method can then be used to better coat a uniform carbon layer on the surface of the particles.
根据本发明的一些实施例，步骤S2中，所述热处理的温度为600～800℃。According to some embodiments of the present invention, in step S2, the temperature of the heat treatment is 600-800°C.
根据本发明的一些实施例，步骤S2中，所述热处理的时间为10～60min。According to some embodiments of the present invention, in step S2, the heat treatment time is 10 to 60 minutes.
微波等离子体化学气相沉积处理(MPCVD)以在极短时间内合成纳米颗粒，可以避免由于传统长时间高温热处理所引起的晶粒长大。小颗粒尺寸有利于缩短锂离子在脱嵌过程中的迁移路径，有效提高磷酸锰铁锂电化学性能。Microwave plasma chemical vapor deposition (MPCVD) can synthesize nanoparticles in a very short time, which can avoid grain growth caused by traditional long-term high-temperature heat treatment. The small particle size is conducive to shortening the migration path of lithium ions during the deintercalation process and effectively improving the electrochemical performance of lithium iron manganese phosphate.
根据本发明的一些实施例，步骤S2中，所述微波等离子体中所用等离子体包括氢等离子。根据本发明的一些实施例，所述氢等离子体的流速为10～100sccm。According to some embodiments of the present invention, in step S2, the plasma used in the microwave plasma includes hydrogen plasma. According to some embodiments of the present invention, the flow rate of the hydrogen plasma is 10-100 sccm.
在MPCVD中，上述温度、时间、甲烷流速作为调节甲烷裂解的速度的参数，影响碳包覆的效果，保证了甲烷在单位时间内分解得到的碳原子，同时避免了因甲烷的裂解速度过快，形成大量的碳堆积的碳颗粒。In MPCVD, the above temperature, time, and methane flow rate are used as parameters to adjust the speed of methane cracking, affecting the effect of carbon coating, ensuring that the carbon atoms obtained by the decomposition of methane in unit time are avoided, while avoiding the excessive speed of methane cracking. , forming a large number of carbon-accumulated carbon particles.
根据本发明的一些优选地实施例，步骤S2中，所述热处理在微波等离子体化学气相沉积(MPCVD)反应罐内进行。According to some preferred embodiments of the present invention, in step S2, the heat treatment is performed in a microwave plasma chemical vapor deposition (MPCVD) reaction tank.
根据本发明的一些实施例，步骤S2中，所述等离子处理后得到磷酸铁锰锂粉末材料。According to some embodiments of the present invention, in step S2, the lithium iron manganese phosphate powder material is obtained after the plasma treatment.
根据本发明的一些实施例，步骤S3中，所述碳包覆的碳源包括甲烷。According to some embodiments of the present invention, in step S3, the carbon-coated carbon source includes methane.
根据本发明的一些实施例，所述甲烷的流速为10～100sccm。According to some embodiments of the present invention, the flow rate of the methane is 10 to 100 sccm.
根据本发明的一些实施例，所述粉碎的方法包括气流磨粉碎。According to some embodiments of the present invention, the crushing method includes jet mill crushing.
根据本发明的一些实施例，所述气流磨粉碎的分级频率为150～260Hz。According to some embodiments of the present invention, the classification frequency of the airflow mill is 150 to 260 Hz.
根据本发明的一些实施例，所述气流磨粉碎的气压为0.3～0.6MPa。According to some embodiments of the present invention, the air pressure of the air flow mill for grinding is 0.3 to 0.6 MPa.
根据本发明的一些实施例，所述正极材料为LiMn xFe yM zPO 4/C，0.59≤x≤0.61，0.36≤y≤0.38，0.02≤z≤0.04，x+y+z＝1，M为Zn、Mg、V、Ti、Al、Cr、Zr、Ni和Co中的至少一种。 According to some embodiments of the present invention, the cathode material is LiMn x Fe y M z PO 4 /C, 0.59≤x≤0.61, 0.36≤y≤0.38, 0.02≤z≤0.04, x+y+z=1, M is at least one of Zn, Mg, V, Ti, Al, Cr, Zr, Ni and Co.
磷酸铁锰锂并非磷酸锰锂和磷酸铁锂的简单物理混合，由于材料中铁和锰离子半径相近，易形成固溶体，因此能够实现原子级别的混合。当Mn含量过高时，由Mn 3+的在充放电过程中Jahn-Teller畸变引起的Mn-O键的伸长(与PO 4 3-四面体的边缘共享，负责增加载流子迁移的活化能)，这带来了高Mn含量的LMFP内在动力学的迟缓。因此在Mn：Fe约为6：4时能够发挥最好的性能。 Lithium iron manganese phosphate is not a simple physical mixture of lithium manganese phosphate and lithium iron phosphate. Since the ion radii of iron and manganese in the material are similar, they easily form a solid solution, so atomic level mixing can be achieved. When the Mn content is too high, the elongation of the Mn-O bond caused by the Jahn-Teller distortion of Mn 3+ during charge and discharge processes (shared with the edges of the PO 4 3- tetrahedron, is responsible for increasing the activation of carrier migration (can), which brings about the sluggishness of the intrinsic dynamics of LMFP with high Mn content. Therefore, the best performance can be achieved when Mn:Fe is approximately 6:4.
根据本发明的第二方面实施例，提出了上述制备方法制备的正极材料在二次电池中的应用。According to an embodiment of the second aspect of the present invention, the application of the cathode material prepared by the above preparation method in secondary batteries is proposed.
本发明的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本发明而了解。Additional features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention.
附图说明Description of the drawings
本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：The above and/or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:
图1是本发明实施例3中的XRD图；Figure 1 is an XRD pattern in Example 3 of the present invention;
图2是本发明实施例3的SEM图；Figure 2 is an SEM image of Example 3 of the present invention;
图3是实施例3的电化学性能图；Figure 3 is an electrochemical performance diagram of Example 3;
图4是对比例1的电化学性能图；Figure 4 is an electrochemical performance diagram of Comparative Example 1;
图5是实施例3和对比例1的交流阻抗图。Figure 5 is an AC impedance diagram of Example 3 and Comparative Example 1.
具体实施方式Detailed ways
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the drawings are exemplary and are only used to explain the present invention and cannot be understood as limiting the present invention.
实施例1Example 1
本实施例公开了一种正极材料的制备方法，按照x：y：z＝0.8：0.18：0.02的比例合成LiMn 0.8Fe 0.18M 0.02PO 4/C，M为Zn，制备方法如下： This embodiment discloses a preparation method of cathode material. LiMn 0.8 Fe 0.18 M 0.02 PO 4 /C is synthesized according to the ratio of x:y:z=0.8:0.18:0.02, M is Zn, and the preparation method is as follows:
S1：称取1790g草酸锰，405g草酸亚铁，1303g磷酸二氢锂，21g氧化锌混合在10L去 离子水中，充分搅拌均匀后使用砂磨机进行砂磨，浆料D 50为0.35μm； S1: Weigh 1790g manganese oxalate, 405g ferrous oxalate, 1303g lithium dihydrogen phosphate, and 21g zinc oxide and mix them in 10L deionized water. Stir them thoroughly and use a sand mill to grind them. The slurry D 50 is 0.35 μm;
S2：将砂磨好的浆料进行离心喷雾干燥，干燥条件为进口温度210℃，出口温度为110℃，进料速度5L/min，得到前驱体干燥粉末；S2: Carry out centrifugal spray drying of the sand-ground slurry. The drying conditions are as follows: the inlet temperature is 210°C, the outlet temperature is 110°C, and the feed rate is 5L/min, to obtain dry precursor powder;
S3：将喷雾干燥得到的前驱体粉末放置在MPCVD反应罐内的基底上，通入氢等离子处理，反应温度600℃，处理时间15min，氢气流速为10sccm，得到LiMn 0.8Fe 0.18Mg 0.02PO 4纳米颗粒； S3: Place the precursor powder obtained by spray drying on the substrate in the MPCVD reaction tank, and pass in hydrogen plasma for treatment. The reaction temperature is 600°C, the treatment time is 15 minutes, and the hydrogen flow rate is 10 sccm to obtain LiMn 0.8 Fe 0.18 Mg 0.02 PO 4 nanometers. particles; particles
S4：通入甲烷气体在LiMn 0.8Fe 0.18Mg 0.02PO 4纳米颗粒表面实现碳包覆，反应温度700℃，处理时间10min，氢气流速为100sccm，甲烷流速为10sccm，得到LiMn 0.8Fe 0.18Mg 0.02PO 4/C； S4: Inject methane gas to achieve carbon coating on the surface of LiMn 0.8 Fe 0.18 Mg 0.02 PO 4 nanoparticles. The reaction temperature is 700°C, the treatment time is 10 minutes, the hydrogen flow rate is 100 sccm, and the methane flow rate is 10 sccm. LiMn 0.8 Fe 0.18 Mg 0.02 PO is obtained. 4 /C;
S5：采用气流磨将LiMn 0.8Fe 0.18Mg 0.02PO 4/C进行粉碎，其中分级频率为220Hz，气压为0.5MPa，得到最终成品。 S5: Use an airflow mill to pulverize LiMn 0.8 Fe 0.18 Mg 0.02 PO 4 /C, where the classification frequency is 220Hz and the air pressure is 0.5MPa to obtain the final product.
实施例2Example 2
本实施例公开了一种正极材料的制备方法，按照x：y：z＝0.7：0.29：0.01的比例合成LiMn 0.7Fe 0.29M 0.01PO 4/C，M为Ni，制备方法如下： This embodiment discloses a preparation method of cathode material. LiMn 0.7 Fe 0.29 M 0.01 PO 4 /C is synthesized according to the ratio of x:y:z=0.7:0.29:0.01, M is Ni, and the preparation method is as follows:
S1：称取994.5g磷酸氢锰，895g草酸锰，626.5g磷酸铁，523.5g碳酸锂，11g氧化镍混合在8L去离子水中，充分搅拌均匀后使用砂磨机进行砂磨至浆料D 50为0.4μm； S1: Weigh 994.5g manganese hydrogen phosphate, 895g manganese oxalate, 626.5g iron phosphate, 523.5g lithium carbonate, and 11g nickel oxide and mix them in 8L deionized water. Stir thoroughly and use a sand mill to grind until the slurry is D 50 . is 0.4μm;
S2：将砂磨好的浆料进行离心喷雾干燥，干燥条件为进口温度220℃，出口温度为100℃，进料速度10L/min，得到前驱体干燥粉末；S2: Carry out centrifugal spray drying of the sand-ground slurry. The drying conditions are as follows: the inlet temperature is 220°C, the outlet temperature is 100°C, and the feed rate is 10L/min, to obtain dry powder of the precursor;
S3：将喷雾干燥得到的前驱体粉末放置在MPCVD反应罐内的基底上，通入氢等离子处理，反应温度700℃，处理时间10min，氢气流速为20sccm，得到LiMn 0.7Fe 0.29Ni 0.01PO 4纳米颗粒； S3: Place the precursor powder obtained by spray drying on the substrate in the MPCVD reaction tank, and pass in hydrogen plasma for treatment. The reaction temperature is 700°C, the treatment time is 10 minutes, and the hydrogen flow rate is 20 sccm to obtain LiMn 0.7 Fe 0.29 Ni 0.01 PO 4 nanometers. particles; particles
S4：通入甲烷气体在LiMn 0.7Fe 0.29Ni 0.01PO 4纳米颗粒表面实现碳包覆，反应温度650℃，处理时间20min，氢气流速为90sccm，甲烷流速为20sccm，得到LiMn 0.7Fe 0.29Ni 0.01PO 4/C。 S4: Inject methane gas to achieve carbon coating on the surface of LiMn 0.7 Fe 0.29 Ni 0.01 PO 4 nanoparticles. The reaction temperature is 650°C, the treatment time is 20 minutes, the hydrogen flow rate is 90 sccm, and the methane flow rate is 20 sccm. LiMn 0.7 Fe 0.29 Ni 0.01 PO is obtained. 4 /C.
S5：采用气流磨将LiMn 0.7Fe 0.29Ni 0.01PO 4/C进行粉碎，其中分级频率为200Hz，气压为0.55MPa，得到最终成品。 S5: Use airflow mill to crush LiMn 0.7 Fe 0.29 Ni 0.01 PO 4 /C, where the classification frequency is 200Hz and the air pressure is 0.55MPa to obtain the final product.
实施例3Example 3
本实施例公开了一种正极材料的制备方法，按照x：y：z＝0.6：0.37：0.03的比例合成LiMn 0.6Fe 0.37M 0.03PO 4/C，M为Mg，制备方法如下： This embodiment discloses a preparation method of cathode material. LiMn 0.6 Fe 0.37 M 0.03 PO 4 /C is synthesized according to the ratio of x:y:z=0.6:0.37:0.03, M is Mg, and the preparation method is as follows:
S1：称取1580g三氧化二锰，936g磷酸铁，1092g磷酸二氢锂，230g碳酸锂，20g氧化镁混合在10L去离子水中，充分搅拌均匀后使用砂磨机进行砂磨至浆料D 50为0.55μm； S1: Weigh 1580g manganese trioxide, 936g iron phosphate, 1092g lithium dihydrogen phosphate, 230g lithium carbonate, and 20g magnesium oxide and mix them in 10L deionized water. Stir thoroughly and use a sand mill to grind to a slurry of D 50 . is 0.55μm;
S2：将砂磨好的浆料进行离心喷雾干燥，干燥条件为进口温度200℃，出口温度为120℃，进料速度8L/min，得到前驱体干燥粉末；S2: Carry out centrifugal spray drying of the sand-ground slurry. The drying conditions are as follows: the inlet temperature is 200°C, the outlet temperature is 120°C, and the feed rate is 8L/min, to obtain the dry powder of the precursor;
S3：将喷雾干燥得到的前驱体粉末放置在MPCVD反应罐内的基底上，通入氢等离子处理，反应温度650℃，处理时间10min，氢气流速为50sccm，得到LiMn 0.6Fe 0.37Mg 0.03PO 4纳米颗粒； S3: Place the precursor powder obtained by spray drying on the substrate in the MPCVD reaction tank, pass in hydrogen plasma for treatment, the reaction temperature is 650°C, the treatment time is 10 minutes, the hydrogen flow rate is 50 sccm, and LiMn 0.6 Fe 0.37 Mg 0.03 PO 4 nanometers is obtained. particles; particles
S4：通入甲烷气体在LiMn 0.6Fe 0.37Mg 0.03PO 4纳米颗粒表面实现碳包覆，反应温度800℃，处理时间5min，氢气流速为50sccm，甲烷流速为50sccm，得到LiMn 0.6Fe 0.37Mg 0.03PO 4/C； S4: Inject methane gas to achieve carbon coating on the surface of LiMn 0.6 Fe 0.37 Mg 0.03 PO 4 nanoparticles. The reaction temperature is 800°C, the treatment time is 5 minutes, the hydrogen flow rate is 50 sccm, and the methane flow rate is 50 sccm. LiMn 0.6 Fe 0.37 Mg 0.03 PO is obtained. 4 /C;
S5：采用气流磨将LiMn 0.6Fe 0.37Mg 0.03PO 4/C进行粉碎，其中分级频率为180Hz，气压为0.6MPa，得到最终成品。 S5: Use an airflow mill to pulverize LiMn 0.6 Fe 0.37 Mg 0.03 PO 4 /C, where the classification frequency is 180Hz and the air pressure is 0.6MPa to obtain the final product.
实施例3制备得到的产品的XRD图如图1所示，结果表明，样品衍射峰属于正交晶系橄榄石型晶态结构，衍射峰都能与LiMnPO 4(PFD#77-0178)标准卡衍射峰相匹配，X射线衍射峰高角度偏移，这是因为
Figure PCTCN2022118781-appb-000001
的Mn 2+半径比
Figure PCTCN2022118781-appb-000002
的Fe 2+的大，正极材料晶格间距的减小；所得峰强度相当且结晶度均较好，可见合成了纯的磷酸锰铁锂，碳是以无定型的形式存在，XRD无法检测出来，所以碳的存在并不影响材料的晶体结构。 The XRD pattern of the product prepared in Example 3 is shown in Figure 1. The results show that the diffraction peaks of the sample belong to the orthorhombic olivine crystal structure, and the diffraction peaks can all be consistent with the LiMnPO 4 (PFD#77-0178) standard card. The diffraction peaks match, and the X-ray diffraction peaks are shifted at high angles because
Figure PCTCN2022118781-appb-000001
Mn 2+ radius ratio
Figure PCTCN2022118781-appb-000002
The larger the Fe 2+ , the lattice spacing of the cathode material is reduced; the obtained peak intensities are equivalent and the crystallinity is good. It can be seen that pure lithium iron manganese phosphate is synthesized, and the carbon exists in an amorphous form and cannot be detected by XRD , so the presence of carbon does not affect the crystal structure of the material.
实施例3制备得到的产品的SEM图如图2所示。结果表明，碳包覆的磷酸锰铁锂具有均匀的颗粒尺寸分布，这表明MPCVD是一种非常有效的控制颗粒尺寸的途径，这是因为MPCVD可以在极短时间内合成纳米颗粒，可以避免由于传统长时间高温热处理所引起的晶粒长大。制备得到的小颗粒尺寸有利于缩短锂离子在脱嵌过程中的迁移路径，能有效提高磷酸锰铁锂电化学性能。The SEM image of the product prepared in Example 3 is shown in Figure 2. The results show that carbon-coated lithium iron manganese phosphate has a uniform particle size distribution, which indicates that MPCVD is a very effective way to control particle size. This is because MPCVD can synthesize nanoparticles in a very short time, which can avoid due to Grain growth caused by traditional long-term high-temperature heat treatment. The prepared small particle size is conducive to shortening the migration path of lithium ions during the deintercalation process, and can effectively improve the electrochemical performance of lithium iron manganese phosphate.
实施例4Example 4
本实施例公开了一种正极材料的制备方法，按照x：y：z＝0.5：0.48：0.02的比例合成LiMn 0.5Fe 0.48M 0.02PO 4/C，M为Ti，制备方法如下： This embodiment discloses a preparation method of cathode material. LiMn 0.5 Fe 0.48 M 0.02 PO 4 /C is synthesized according to the ratio of x:y:z=0.5:0.48:0.02, M is Ti, and the preparation method is as follows:
S1：称取790g三氧化二锰，768g氧化铁，1040g磷酸二氢锂，16g二氧化钛混合在8L去离子水中，充分搅拌均匀后使用砂磨机进行砂磨至浆料D 50为0.4μm； S1: Weigh 790g of manganese trioxide, 768g of iron oxide, 1040g of lithium dihydrogen phosphate, and 16g of titanium dioxide and mix them in 8L of deionized water. Stir thoroughly and use a sand mill to grind until the slurry D 50 is 0.4 μm;
S2：将砂磨好的浆料进行喷雾干燥，干燥条件为进口温度210℃，出口温度为110℃，进料速度6L/min，得到前驱体干燥粉末；S2: Spray dry the sand-ground slurry. The drying conditions are the inlet temperature is 210°C, the outlet temperature is 110°C, and the feed rate is 6L/min to obtain the dry powder of the precursor;
S3：将喷雾干燥得到的前驱体粉末放置在MPCVD反应罐内的基底上，通入氢等离子处理，反应温度700℃，处理时间10min，氢气流速为20sccm得到LiMn 0.5Fe 0.48M 0.02PO 4； S3: Place the precursor powder obtained by spray drying on the substrate in the MPCVD reaction tank, pass in hydrogen plasma for treatment, the reaction temperature is 700°C, the treatment time is 10 minutes, and the hydrogen flow rate is 20 sccm to obtain LiMn 0.5 Fe 0.48 M 0.02 PO 4 ;
S4：通入甲烷气体在LiMn 0.6Fe 0.37Mg 0.03PO 4纳米颗粒表面实现碳包覆，反应温度800℃，处理时间5min，氢气流速为50sccm，甲烷流速为50sccm，得到LiMn 0.6Fe 0.37Mg 0.03PO 4/C； S4: Inject methane gas to achieve carbon coating on the surface of LiMn 0.6 Fe 0.37 Mg 0.03 PO 4 nanoparticles. The reaction temperature is 800°C, the treatment time is 5 minutes, the hydrogen flow rate is 50 sccm, and the methane flow rate is 50 sccm. LiMn 0.6 Fe 0.37 Mg 0.03 PO is obtained. 4 /C;
S5：通入甲烷气体在LMFP纳米颗粒表面实现碳包覆，反应温度800℃，处理时间25min，氢气流速为100sccm，甲烷流速为10sccm，得到LiMn 0.5Fe 0.48M 0.02PO 4/C。 S5: Inject methane gas to achieve carbon coating on the surface of LMFP nanoparticles. The reaction temperature is 800°C, the treatment time is 25 minutes, the hydrogen flow rate is 100 sccm, and the methane flow rate is 10 sccm. LiMn 0.5 Fe 0.48 M 0.02 PO 4 /C is obtained.
实施例5Example 5
本实施例公开了一种正极材料的制备方法，和实施例3的区别在于不加入含掺杂元素的掺杂剂，按照x：y：z＝0.6：0.4：0的比例合成LiMn 0.6Fe 0.4PO 4/C纳米颗粒。其余条件相同。 This embodiment discloses a method for preparing a cathode material. The difference from Example 3 is that no dopant containing doping elements is added, and LiMn 0.6 Fe 0.4 is synthesized according to the ratio of x:y:z=0.6:0.4:0. PO 4 /C nanoparticles. The rest of the conditions are the same.
实施例6Example 6
本实施例公开了一种正极材料的制备方法，和实施例3的区别在于是将喷雾干燥得到的前驱体粉末放置在MPCVD反应罐内的基底上，通入氢等离子处理，反应温度700℃，处理时间20min，氢气流速为80sccm。This embodiment discloses a method for preparing a cathode material. The difference from Example 3 is that the precursor powder obtained by spray drying is placed on the substrate in the MPCVD reaction tank, and hydrogen plasma is introduced for treatment. The reaction temperature is 700°C. The treatment time is 20 minutes, and the hydrogen flow rate is 80 sccm.
实施例7Example 7
本实施例公开了一种正极材料的制备方法，和实施例3的区别在于加入的含掺杂元素的掺杂剂为Ni，其余条件相同。This embodiment discloses a method for preparing a cathode material. The difference from Embodiment 3 is that the added dopant containing doping elements is Ni, and the other conditions are the same.
实施例8Example 8
本实施例公开了一种正极材料的制备方法，和实施例3的区别在于步骤S1中，使用砂磨机进行砂磨至浆料D 50为0.8μm。 This embodiment discloses a method for preparing a cathode material. The difference from Example 3 is that in step S1, a sand mill is used for sand grinding until the slurry D 50 is 0.8 μm.
实施例9Example 9
本实施例公开了一种正极材料的制备方法，和实施例3的区别在于步骤S3中，反应温度750℃。This embodiment discloses a method for preparing a cathode material. The difference from Example 3 is that in step S3, the reaction temperature is 750°C.
实施例10Example 10
本实施例公开了一种正极材料的制备方法，和实施例3的区别在于步骤S3中，处理时间25min。This embodiment discloses a method for preparing a cathode material. The difference from Example 3 is that in step S3, the processing time is 25 minutes.
实施例11Example 11
本实施例公开了一种正极材料的制备方法，和实施例3的区别在于步骤S3中，氢气流速为100sccm。This embodiment discloses a method for preparing a cathode material. The difference from Example 3 is that in step S3, the hydrogen gas flow rate is 100 sccm.
实施例12Example 12
本实施例公开了一种正极材料的制备方法，和实施例3的区别在于步骤S4中，反应温度600℃。This embodiment discloses a method for preparing a cathode material. The difference from Example 3 is that in step S4, the reaction temperature is 600°C.
实施例13Example 13
本实施例公开了一种正极材料的制备方法，和实施例3的区别在于步骤S3中，处理时间25min。This embodiment discloses a method for preparing a cathode material. The difference from Example 3 is that in step S3, the processing time is 25 minutes.
实施例14Example 14
本实施例公开了一种正极材料的制备方法，和实施例3的区别在于步骤S3中，甲烷流速为100sccm。This embodiment discloses a method for preparing a cathode material. The difference from Example 3 is that in step S3, the methane flow rate is 100 sccm.
对比例1Comparative example 1
本对比例公开了一种正极材料的制备方法，和实施例3的区别在于使用可溶性有机碳源(葡萄糖)作为碳源，混合在浆料中进行砂磨、喷雾干燥，再在管式炉中氮气气氛下合成LiMn 0.6Fe 0.37M 0.03PO 4/C纳米颗粒。 This comparative example discloses a preparation method of a cathode material. The difference from Example 3 is that a soluble organic carbon source (glucose) is used as the carbon source, mixed in the slurry, sanded, spray-dried, and then dried in a tube furnace. LiMn 0.6 Fe 0.37 M 0.03 PO 4 /C nanoparticles were synthesized under nitrogen atmosphere.
实施例3和对比例1制备得到的产品的扣电性能图，如图3和4所示。图3为实施例3制备的样品在0.1C下的充放电曲线，0.1C放电比容量为155mAh/g；图4为对比例1制备的样品在0.1C下的充放电曲线，0.1C放电比容量为142mAh/g；结果表明，通过MPCVD方法进行碳包覆的磷酸铁锰锂材料具有更好的性能。The electricity-withholding performance diagrams of the products prepared in Example 3 and Comparative Example 1 are shown in Figures 3 and 4. Figure 3 is the charge and discharge curve of the sample prepared in Example 3 at 0.1C, and the 0.1C discharge specific capacity is 155mAh/g; Figure 4 is the charge and discharge curve of the sample prepared in Comparative Example 1 at 0.1C, and the 0.1C discharge ratio The capacity is 142mAh/g; the results show that the carbon-coated lithium iron manganese phosphate material through the MPCVD method has better performance.
实施例3和对比例1制备得到的产品的扣电性能图，如图4和5所示。图5为实施例3和对比例1的交流阻抗图谱，阻抗谱图由高频区和低频区组成，高频区的半圆直径表示电化学转移阻抗Rct，低频区的直线表示Li +的扩散速度，对比例1具有最大的Rct值，表明该样品受到的阻碍较大，电子导电率低，导致其在充放电过程中极化较大且比容量较低。 The electricity-withholding performance diagrams of the products prepared in Example 3 and Comparative Example 1 are shown in Figures 4 and 5. Figure 5 is the AC impedance spectrum of Example 3 and Comparative Example 1. The impedance spectrum consists of a high-frequency area and a low-frequency area. The diameter of the semicircle in the high-frequency area represents the electrochemical transfer impedance Rct, and the straight line in the low-frequency area represents the diffusion rate of Li + , Comparative Example 1 has the largest Rct value, indicating that the sample is greatly hindered and has low electronic conductivity, resulting in large polarization and low specific capacity during the charge and discharge process.
测试例1Test example 1
本测试例测试了实施例1～14和对比例1的正极材料的充放电检测结果，测试结果如表1所示，其中实施例1-14和对比例1采用为等体积的LiPF 6和碳酸二乙酯(DEC)电解质，LiPF 6的浓度为1M，以金属锂片为负极，制备得到扣式半电池，采用LAND电池程序控制测试仪(LAND CT2001A)检测电池倍率性能。 This test example tested the charge and discharge detection results of the cathode materials of Examples 1 to 14 and Comparative Example 1. The test results are shown in Table 1, in which Examples 1 to 14 and Comparative Example 1 used equal volumes of LiPF 6 and carbonic acid. Diethyl ester (DEC) electrolyte, the concentration of LiPF 6 is 1M, and the metal lithium sheet is used as the negative electrode to prepare a button half cell. The battery rate performance is tested using a LAND battery program control tester (LAND CT2001A).
表1 性能测试结果Table 1 Performance test results
Figure PCTCN2022118781-appb-000003
Figure PCTCN2022118781-appb-000003
Figure PCTCN2022118781-appb-000004
Figure PCTCN2022118781-appb-000004
本发明中，实施例1～14通过微波等离子体化学气相沉积方法(MPCVD)沉积的碳层不仅保护碳包覆后的正极极片免受电解液腐蚀，而且由于正极材料具有较高的石墨化程度，还提升了电子/离子导电性，电化学性能。In the present invention, the carbon layer deposited by microwave plasma chemical vapor deposition (MPCVD) in Examples 1 to 14 not only protects the carbon-coated positive electrode plate from electrolyte corrosion, but also has high graphitization due to the positive electrode material. degree, it also improves the electronic/ion conductivity and electrochemical performance.
上面结合附图对本发明实施例作了详细说明，但本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various modifications can be made without departing from the purpose of the present invention. Variety.

Claims (10)

  1. 一种正极材料的制备方法，其特征在于，包括以下步骤：A preparation method of cathode material, characterized in that it includes the following steps:
    S1.将锰源、铁源、锂源和磷源混合分散后，破碎，干燥；S1. Mix and disperse the manganese source, iron source, lithium source and phosphorus source, crush and dry;
    S2.将步骤S1干燥后所得粉末进行热处理，所述热处理在微波等离子体的环境中进行；S2. The powder obtained after drying in step S1 is subjected to heat treatment, and the heat treatment is carried out in a microwave plasma environment;
    所述热处理后得到磷酸铁锰锂材料；After the heat treatment, a lithium iron manganese phosphate material is obtained;
    S3.将步骤S2所得粉末进行碳包覆后粉碎；所述碳包覆的方法为微波等离子体化学气相沉积法。S3. The powder obtained in step S2 is carbon coated and then pulverized; the carbon coating method is microwave plasma chemical vapor deposition.
  2. 根据权利要求1所述的正极材料的制备方法，其特征在于，步骤S1中，所述分散前还包括加入掺杂剂；优选地，所述掺杂剂包括Zn掺杂剂、Mg掺杂剂、Ti掺杂剂、Al掺杂剂、Cr掺杂剂、Zr掺杂剂、Ni掺杂剂和Co掺杂剂中的至少一种。The preparation method of cathode material according to claim 1, characterized in that, in step S1, before the dispersion, a dopant is added; preferably, the dopant includes Zn dopant, Mg dopant , at least one of Ti dopant, Al dopant, Cr dopant, Zr dopant, Ni dopant and Co dopant.
  3. 根据权利要求1所述的正极材料的制备方法，其特征在于，步骤S1中，所述破碎后材料的D 50为0.3～1.0μm。 The method for preparing a cathode material according to claim 1, wherein in step S1, the D50 of the crushed material is 0.3-1.0 μm.
  4. 根据权利要求1所述的正极材料的制备方法，其特征在于，步骤S1中，所述干燥包括喷雾干燥；优选地，所述喷雾干燥过程的进风口的温度为180～250℃，优选地，所述喷雾干燥过程的出风口的温度为90～140℃。The preparation method of cathode material according to claim 1, characterized in that, in step S1, the drying includes spray drying; preferably, the temperature of the air inlet of the spray drying process is 180-250°C, preferably, The temperature of the air outlet during the spray drying process is 90-140°C.
  5. 根据权利要求1所述的正极材料的制备方法，其特征在于，步骤S2中，所述热处理的温度为600～800℃。The method for preparing a cathode material according to claim 1, wherein in step S2, the temperature of the heat treatment is 600-800°C.
  6. 根据权利要求1所述的正极材料的制备方法，其特征在于，步骤S2中，所述微波等离子体中所用等离子体包括氢等离子；优选地，所述氢等离子体的流速为10～100sccm。The method for preparing a cathode material according to claim 1, wherein in step S2, the plasma used in the microwave plasma includes hydrogen plasma; preferably, the flow rate of the hydrogen plasma is 10 to 100 sccm.
  7. 根据权利要求1所述的正极材料的制备方法，其特征在于，步骤S3中，所述碳包覆的碳源包括甲烷。The method for preparing a cathode material according to claim 1, wherein in step S3, the carbon-coated carbon source includes methane.
  8. 根据权利要求7所述的正极材料的制备方法，其特征在于，所述甲烷的流速为10～100sccm。The method for preparing a positive electrode material according to claim 7, wherein the flow rate of the methane is 10 to 100 sccm.
  9. 根据权利要求1所述的正极材料的制备方法，其特征在于，所述正极材料为LiMn xFe yM zPO 4/C，0<x≤1，0<y≤0.95，0≤z≤0.05，x+y+z＝1，M为Zn、Mg、V、Ti、Al、Cr、Zr、Ni和Co中的至少一种。 The method for preparing a positive electrode material according to claim 1, wherein the positive electrode material is LiMn x Fe y M z PO 4 /C, 0<x≤1, 0<y≤0.95, 0≤z≤0.05 , x+y+z=1, M is at least one of Zn, Mg, V, Ti, Al, Cr, Zr, Ni and Co.
  10. 一种如权利要求1～9任一项所述制备方法制备的正极材料在制备二次电池中的应用。An application of the cathode material prepared by the preparation method according to any one of claims 1 to 9 in the preparation of secondary batteries.
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