WO2023179613A1 - 一种复合正极材料及其制备方法和应用 - Google Patents

一种复合正极材料及其制备方法和应用 Download PDF

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WO2023179613A1
WO2023179613A1 PCT/CN2023/082812 CN2023082812W WO2023179613A1 WO 2023179613 A1 WO2023179613 A1 WO 2023179613A1 CN 2023082812 W CN2023082812 W CN 2023082812W WO 2023179613 A1 WO2023179613 A1 WO 2023179613A1
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lithium
manganese
cathode material
optionally
source
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French (fr)
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温圣耀
张�林
刘范芬
吴婷婷
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Eve Power Co Ltd
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Eve Power Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • 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
    • H01M4/36—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
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

  • This application belongs to the field of batteries and relates to a composite cathode material and its preparation method and application.
  • LFP lithium iron phosphate
  • NCM ternary materials
  • Lithium iron manganese phosphate is a cathode material obtained by adding manganese element to LFP.
  • the doping of manganese can make LMFP have a higher voltage platform (4.1Vvs3.4V), and the energy density of the battery can be increased by 15 It is a cathode material with great application prospects.
  • LMFP cathode materials are still in the early stages of industrialization. The main reason is that LMFP has dual platforms and poor cycle performance, which seriously affects its commercial implementation. Therefore, eliminating its double discharge platform and improving the electrical cycle stability of LMFP materials are the current technical keys.
  • CN111129463A discloses a method for preparing a MOF-coated single crystal ternary cathode material and its precursor.
  • the core of the method adopts a high-nickel and low-manganese precursor synthesized by a co-precipitation method, and the outer shell is synthesized by coordination of Mn and organic carboxylates.
  • Mn-MOF the uniformity of the Mn shell at the atomic level.
  • CN114620708A discloses a method for preparing a modified Al-based MOF derivative coated lithium-ion battery cathode material.
  • the Al-based MOF material is first immersed in a solution containing Z elements to obtain a modified Al-based MOF material, and then mixed with lithium.
  • the cathode material of the ion battery is dry-coated, and finally a multi-element (Al, Z) coated and modified lithium-ion battery cathode material is obtained.
  • the cathode materials described in the above scheme have problems such as harsh production conditions, high cost, and poor cycle performance and safety performance of high-nickel ternary materials, which hinders large-scale application in the battery field.
  • This application uses MOF-coated LMFP and NCM composite cathode materials as lithium-ion battery cathode materials to make batteries that exhibit good high-rate performance and high temperature performance. Storage and high temperature cycling performance.
  • inventions of the present application provide a method for preparing a composite cathode material.
  • the preparation method includes the following steps:
  • the hydroxide is mixed with the second lithium source, and the lithium nickel cobalt manganate cathode material is obtained by sintering;
  • step (3) Calcining the mixed powder obtained in step (2) to obtain the composite cathode material.
  • the composite cathode material described in the embodiment of the present application is made by composite coating MOF material with lithium iron manganese phosphate powder and ternary nickel cobalt manganese cathode material. After the lithium iron manganese phosphate is mixed with the ternary cathode material, when the lithium manganese iron phosphate material is When the ternary cathode material dominates, the dual-platform problem can be improved; when the ternary cathode material dominates, both safety and cost can be taken into consideration.
  • MOF serves as a protective coating covering the surface of the cathode material, reducing side reactions between the active material and the electrolyte, enhancing the structural stability of the material, and thereby improving the cycle performance of the electrode material.
  • the MOF material coating layer prepared by the method described in the embodiments of the present application has good uniformity, consistency and conductivity.
  • the preparation process of this method is simple and controllable, and is easy for large-scale industrial production.
  • the first lithium source in step (1) includes lithium carbonate and/or lithium dihydrogen phosphate.
  • the manganese source includes any one or a combination of at least two of manganese sulfate, manganese carbonate, manganese nitrate, manganese acetate or manganese oxalate.
  • the iron source includes iron phosphate and/or iron powder.
  • the phosphorus source includes phosphoric acid and/or ammonium dihydrogen phosphate.
  • the solvent includes water.
  • the temperature of the heat treatment is 600-950°C, for example: 600°C, 700°C, 800°C, 900°C or 950°C, etc.
  • the heat treatment time is 5-24h, for example: 5h, 10h, 15h, 20h or 24h, etc.
  • the second lithium source in step (1) includes lithium hydroxide and/or lithium carbonate.
  • the temperature of the sintering treatment is 450-1000°C, for example: 450°C, 500°C, 600°C, 700°C, 800°C or 1000°C, etc.
  • the sintering treatment time is 5-12 hours, for example: 5 hours, 8 hours, 10 hours, 11 hours or 12 hours, etc.
  • the chemical formula of lithium iron manganese phosphate in step (2) is LiMn x Fe 1-x PO 4 , 0 ⁇ x ⁇ 1.
  • the mass ratio of the lithium iron manganese phosphate powder and the nickel cobalt manganese cathode material in step (2) is 1: (0.1-10), for example: 1:0.1, 1:0.2, 1:0.5, 1:1, 1:5 or 1:10 etc.
  • the MOF material includes any one or a combination of at least two of IRMOFs, MILs, MOF-5, MOF-74 or ZIF-8.
  • Metal organic framework (MOF) material is a porous material with a periodic network formed by self-assembly through coordination bonds with metal ions as nodes and organic ligands as connecting bridges.
  • MOF materials have huge application potential in fields such as catalysis, batteries, and energy storage due to their high specific surface area, component designability, and topological diversity.
  • the metal sites of MOF can be oxidized into amorphous oxides and are highly ordered at the nanometer level, which can keep the coating layer at the nanometer level.
  • the stirring speed in step (2) is 300-800rpm, for example: 300rpm, 400rpm, 500rpm, 600rpm or 800rpm, etc.
  • the stirring time is 0.5-5h, for example: 0.5h, 1h, 2h, 3h, 4h or 5h, etc.
  • the temperature of the calcination treatment in step (3) is 200-600°C, for example: 200°C, 300°C, 400°C, 500°C or 600°C, etc.
  • the calcination treatment time is 2-12h, such as: 2h, 5h, 8h, 10h or 12h, etc.
  • embodiments of the present application provide a composite cathode material, which is prepared by the method described in the first aspect.
  • the battery made of MOF-coated LMFP and NCM composite cathode material as the cathode material of the lithium-ion battery shows good high-rate performance, high-temperature storage and high-temperature cycle performance.
  • the composite cathode material includes a core and a coating layer disposed on the surface of the core.
  • the core includes nickel-cobalt-manganese ternary cathode material and lithium iron manganese phosphate cathode material.
  • the cladding layer includes MOF material.
  • the mass fraction of the coating layer is 0.1-1.0%, for example: 0.1%, 0.2%, 0.3%, 0.5% or 1.0%, etc. .
  • embodiments of the present application provide a cathode electrode sheet, which contains the composite cathode material as described in the second aspect.
  • embodiments of the present application provide a lithium-ion battery, which includes the positive electrode sheet as described in the third aspect.
  • This application combines lithium iron manganese phosphate powder with ternary nickel cobalt manganese cathode material, and coats its surface
  • the MOF coating layer can improve the rate performance and cycle performance of the material while taking into account material safety, cost and energy density.
  • This application provides a method for preparing a MOF-coated LMFP and NCM composite cathode material.
  • ferromanganese is mixed with ternary elements, when the ferromanganese material dominates, the dual platform problem can be improved; when the ternary material is Dominant, taking into account both safety and cost.
  • the organic components in the MOF form a carbon matrix after the MOF is carbonized in an inert atmosphere, which is evenly coated on the surface of the composite cathode material, playing a bridging role, forming an electron transfer channel, and improving the performance of the LMFP electrode material.
  • MOF serves as a protective coating covering the surface of the cathode material, reducing side reactions between the active material and the electrolyte, enhancing the structural stability of the material, and thereby improving the cycle performance of the electrode material.
  • Batteries made of MOF-coated LMFP and NCM composite cathode materials as lithium-ion battery cathode materials show good high-rate performance, high-temperature storage and high-temperature cycle performance.
  • This embodiment provides a composite cathode material.
  • the preparation method of the composite cathode material is as follows:
  • lithium iron manganese phosphate LiMn 0.6 Fe 0.4 PO 4
  • step (1) Put the lithium iron manganese phosphate powder and the ternary nickel cobalt manganese cathode material obtained in step (1) according to the mass. Mix the IRMOFs material with a ratio of 7:3 and stir at 500 rpm for 2 hours to obtain a mixed powder;
  • step (3) Calculate the mixed powder obtained in step (2) at 400°C for 6 hours, and cool to room temperature in a nitrogen atmosphere to obtain the composite cathode material;
  • the mass proportion of the MOF coating layer is 0.3%.
  • This embodiment provides a composite cathode material.
  • the preparation method of the composite cathode material is as follows:
  • step (3) Calculate the mixed powder obtained in step (2) at 500°C for 5 hours, and cool to room temperature in a nitrogen atmosphere to obtain the composite cathode material;
  • the mass proportion of the MOF coating layer is 0.5%.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that in the composite material, the mass proportion of the MOF coating layer is 0.1%, and other conditions and parameters are exactly the same as those in Embodiment 1.
  • Example 1 The only difference between this comparative example and Example 1 is that no lithium iron manganese phosphate cathode material is added, and other conditions and parameters are exactly the same as Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that the ternary nickel-cobalt-manganese cathode material is not added, and other conditions and parameters are exactly the same as Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that no MOF material is added, and other conditions and parameters are exactly the same as Example 1.
  • the cathode materials obtained in Examples 1-4 and Comparative Examples 1-3 were used, graphite was used as the anode material, and PE/PP polymer materials were used as separators. They were assembled into a roll core by winding or lamination, and were packaged in an aluminum shell or into the aluminum plastic film, and inject 1MLiPF 6 /EC+EMC lithium-ion electrolyte to assemble it into a soft-pack lithium-ion battery. The performance test of the obtained lithium-ion battery was performed, and the test results are shown in Table 1:
  • Example 1 From the comparison between Example 1 and Examples 3-4, it can be seen that in the composite cathode material described in this application, the mass proportion of the MOF coating layer will affect its performance.
  • the mass proportion of the MOF coating layer is controlled at 0.1-1.0 %, the performance of the composite cathode material produced is better. If the mass proportion of the MOF coating layer is too low, the coating effect will not be obvious and cannot play a good role. If the mass proportion of the MOF coating layer is too high, The reduction in the proportion of active materials leads to a reduction in gram capacity.
  • the core of the composite cathode material described in this application is composed of lithium iron manganese phosphate powder and ternary nickel cobalt manganese cathode material.
  • the core of the composite cathode material described in this application is composed of lithium iron manganese phosphate powder and ternary nickel cobalt manganese cathode material.
  • the iron manganese material dominates, the performance can be improved. Its dual platform problem; when ternary materials are dominant, both safety and cost can be taken into consideration.
  • Example 1 From the comparison between Example 1 and Comparative Example 3, it can be seen that after the MOF is carbonized in an inert atmosphere, the organic components in the MOF form a carbon matrix, which is evenly coated on the surface of the composite cathode material, plays a bridging role, forms an electron transfer channel, and improves The conductivity of the LMFP electrode material; on the other hand, MOF serves as a protective coating covering the surface of the cathode material, reducing side reactions between the active material and the electrolyte, enhancing the structural stability of the material, and thereby improving the cycle performance of the electrode material.

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Abstract

本申请提供了一种复合正极材料及其制备方法和应用，所述制备方法包括以下步骤：(1)将第一锂源、锰源、铁源和磷源与溶剂混合，得到磷酸铁锰锂前驱体，将所述磷酸锰铁锂经热处理得到磷酸锰铁锂粉料，将镍钴锰氢氧化物和第二锂源混合，经烧结处理得到镍钴锰酸锂正极材料；(2)将步骤(1)得到的磷酸锰铁锂粉料、镍钴锰酸锂正极材料与MOF材料混合进行搅拌得到混合粉料；(3)对步骤(2)得到的混合粉料进行煅烧处理得到所述复合正极材料，本申请以MOF包覆LMFP和NCM复合正极材料作为锂离子电池正极材料制成的电池，表现出良好的高倍率性能、高温存储和高温循环性能。

Description

一种复合正极材料及其制备方法和应用
本申请要求在2022年12月14日提交中国专利局、申请号为202211610254.6的中国专利申请的优先权，以上申请的全部内容通过引用结合在本申请中。
技术领域
本申请属于电池领域，涉及一种复合正极材料及其制备方法和应用。
背景技术
近年来“碳中和”已经受到全世界各国重点关注，新能源汽车蓬勃发展，带动了锂离子动力电池需求的迅速增长。目前，锂离子动力电池的正极材料主要磷酸铁锂(LFP)和三元材料(NCM)。其中，LFP凭借高性价比、高安全性以及资源瓶颈小等优势，逐渐成为储能和动力电池企业的优先选择，然而其存在能量密度低的问题；三元材料因高能量密度，然后其在安全性上饱受诟病。
磷酸锰铁锂(LMFP)是在LFP的基础上添加锰元素后获得的一种正极材料，锰的掺杂可使LMFP具有更高的电压平台(4.1Vvs3.4V)，电池的能量密度提升15％左右，是一种具有极大应用前景的正极材料。当前LMFP正极材料还处于产业化初期，其主要原因是LMFP具有双平台，循环性能差，这严重影响其商业落地。因此，消除其双放电平台，提高LMFP材料的电循环稳定性是当前的技术关键。
CN111129463A公开了一种MOF包覆的单晶三元正极材料及其前驱体的制备方法，该方法内核采用共沉淀法合成的高镍低锰前驱体，外壳采用Mn与有机物羧酸盐配位合成Mn-MOF，外壳的Mn在原子级别的均匀性。
CN114620708A公开了一种改性Al基MOF衍生物包覆锂离子电池正极材料的制备方法，先将Al基MOF材料浸渍在含Z元素的溶液中，以获得改性Al基MOF材料，再和锂离子电池正极材料干法包覆，最终得到多元素(Al、Z)包覆改性的锂离子电池正极材料。
上述方案所述正极材料存在有生产条件苛刻，成本高，且高镍三元材料的循环性能、安全性能较差的问题，阻碍了在电池领域的大规模应用。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请的目的在于提供一种复合正极材料及其制备方法和应用，本申请以MOF包覆LMFP和NCM复合正极材料作为锂离子电池正极材料制成的电池，表现出良好的高倍率性能、高温存储和高温循环性能。
为达到此申请目的，本申请采用以下技术方案：
第一方面，本申请实施例提供了一种复合正极材料的制备方法，所述制备方法包括以下步骤：
(1)将第一锂源、锰源、铁源和磷源与溶剂混合，得到磷酸铁锰锂前驱体，将所述磷酸锰铁锂经热处理得到磷酸锰铁锂粉料，将镍钴锰氢氧化物和第二锂源混合，经烧结处理得到镍钴锰酸锂正极材料；
(2)将步骤(1)得到的磷酸锰铁锂粉料、镍钴锰酸锂正极材料与MOF材料混合进行搅拌得到混合粉料；
(3)对步骤(2)得到的混合粉料进行煅烧处理得到所述复合正极材料。
本申请实施例所述复合正极材料通过磷酸锰铁锂粉料和三元镍钴锰正极材料复合包覆MOF材料制得，磷酸锰铁锂掺混三元正极材料后，当磷酸锰铁锂材料占主导时，可改善其双平台问题；当三元正极材料材料为主导，可兼顾安全与成本。在其表面包覆MOF后，MOF在惰性气氛下碳化后MOF中的有机成分形成碳基质，均匀地包覆在复合正极材料表面，起到桥联作用，形成电子传递通道，提高LMFP电极材料的导电性；另一方面MOF作为保护涂层覆盖在正极材料表面，减少活性物质和电解液之间的副反应，增强材料的结构稳定性，进而提高电极材料的循环性能。
本申请实施例所述方法制备的MOF材料包覆层具有良好的均匀性、一致性与导电性，该方法制备过程简单可控，易于大规模工业化生产。
在一个实施例中，步骤(1)所述第一锂源包括碳酸锂和/或磷酸二氢锂。
在一个实施例中，所述锰源包括硫酸锰、碳酸锰、硝酸锰、醋酸锰或草酸锰中的任意一种或至少两种的组合。
在一个实施例中，所述铁源包括磷酸铁和/或铁粉。
在一个实施例中，所述磷源包括磷酸和/或磷酸二氢铵。
在一个实施例中，所述溶剂包括水。
在一个实施例中，所述热处理的温度为600-950℃，例如：600℃、700℃、800℃、900℃或950℃等。
在一个实施例中，所述热处理的时间为5-24h，例如：5h、10h、15h、20h或24h等。
在一个实施例中，步骤(1)所述第二锂源包括氢氧化锂和/或碳酸锂。
在一个实施例中，所述烧结处理的温度为450-1000℃，例如：450℃、500℃、600℃、700℃、800℃或1000℃等。
在一个实施例中，所述烧结处理的时间为5-12h，例如：5h、8h、10h、11h或12h等。
在一个实施例中，步骤(2)所述磷酸锰铁锂的化学式为LiMnxFe1-xPO4，0＜x＜1。
在一个实施例中，所述镍钴锰酸锂的化学式为LiNiaCobMn(1-a-b)O2，a＝0.5-0.8，b＝0.1-0.2。
在一个实施例中，步骤(2)所述磷酸锰铁锂粉料和镍钴锰正极材料的质量比为1:(0.1-10)，例如：1:0.1、1:0.2、1:0.5、1:1、1:5或1:10等。
在一个实施例中，所述MOF材料包括IRMOFs、MILs、MOF-5、MOF-74或ZIF-8中的任意一种或至少两种的组合。
金属有机框架(MOF)材料是一种以金属离子为结点，有机配位体为联接桥，通过配位键自组装形成的具有周期性网络的多孔材料。MOF材料由于高比表面积、组分可设计性、拓扑结构多样性等优势，在催化、电池、能源存储等领域具有巨大的应用潜力。MOF的金属位点可氧化成为无定型氧化物，并且在纳米级别上高度有序，可使包覆层保持在纳米级别。
在一个实施例中，步骤(2)所述搅拌的速度为300-800rpm，例如：300rpm、400rpm、500rpm、600rpm或800rpm等。
在一个实施例中，所述搅拌的时间为0.5-5h，例如：0.5h、1h、2h、3h、4h或5h等。
在一个实施例中，步骤(3)所述煅烧处理的温度为200-600℃，例如：200℃、300℃、400℃、500℃或600℃等。
在一个实施例中，所述煅烧处理的时间为2-12h，例如：2h、5h、8h、10h或12h等。
第二方面，本申请实施例提供了一种复合正极材料，所述复合正极材料通过如第一方面所述方法制得。
本申请实施例以MOF包覆LMFP和NCM复合正极材料作为锂离子电池正极材料制成的电池，表现出良好的高倍率性能、高温存储和高温循环性能。
在一个实施例中，所述复合正极材料包括内核和设置于所述内核表面的包覆层。
在一个实施例中，所述内核包括镍钴锰三元正极材料和磷酸锰铁锂正极材料。
在一个实施例中，所述包覆层包括MOF材料。
在一个实施例中，以所述复合正极材料的质量为100％计，所述包覆层的质量分数为0.1-1.0％，例如：0.1％、0.2％、0.3％、0.5％或1.0％等。
第三方面，本申请实施例提供了一种正极极片，所述正极极片包含如第二方面所述的复合正极材料。
第四方面，本申请实施例提供了一种锂离子电池，所述锂离子电池包含如第三方面所述的正极极片。
相对于相关技术，本申请具有以下有益效果：
(1)本申请将磷酸锰铁锂粉料和三元镍钴锰正极材料复合，在其表面包覆 MOF包覆层，可以兼顾材料安全、成本以及能量密度的同时，提高材料的倍率性能和循环性能。
(2)本申请提供了一种MOF包覆LMFP和NCM复合正极材料的制备方法，锰铁掺混三元后，当锰铁材料占主导时，可改善其双平台问题；当三元材料为主导，可兼顾安全与成本。在其表面包覆MOF后，MOF在惰性气氛下碳化后MOF中的有机成分形成碳基质，均匀地包覆在复合正极材料表面，起到桥联作用，形成电子传递通道，提高LMFP电极材料的导电性；另一方面MOF作为保护涂层覆盖在正极材料表面，减少活性物质和电解液之间的副反应，增强材料的结构稳定性，进而提高电极材料的循环性能。以MOF包覆LMFP和NCM复合正极材料作为锂离子电池正极材料制成的电池，表现出良好的高倍率性能、高温存储和高温循环性能。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
实施例1
本实施例提供了一种复合正极材料，所述复合正极材料的制备方法如下：
(1)按摩尔比Li:Mn:Fe:P＝1.1:0.6:0.4:1称取碳酸锂、硫酸锰、铁粉、磷酸，加入到去离子水中分散搅拌球磨，得到前驱体，将所述前驱体放入箱式炉，在氮气保护下，以5℃/min的升温速率，升温至750℃，保温12h后，在氮气气氛下冷却至室温，得到磷酸锰铁锂(LiMn0.6Fe0.4PO4)粉料，取Ni0.5Co0.2Mn0.3(OH)2与氢氧化锂进行混合搅拌，在800℃煅烧8h，得到NCM523正极材料；
(2)将步骤(1)得到的磷酸锰铁锂粉料和三元镍钴锰正极材料按照质量 比为7:3与IRMOFs材料混合在500rpm下搅拌2h得到混合粉料；
(3)对步骤(2)得到的混合粉料在400℃下煅烧6h，在氮气气氛下冷却至室温，获得所述复合正极材料；
所述复合正极材料中，MOF包覆层的质量占比为0.3％。
实施例2
本实施例提供了一种复合正极材料，所述复合正极材料的制备方法如下：
(1)按摩尔比Li:Mn:Fe:P＝1.1:0.6:0.4:1称取碳酸锂、硫酸锰、铁粉、磷酸，加入到去离子水中分散搅拌球磨，得到前驱体，将所述前驱体放入箱式炉，在氮气保护下，以5℃/min的升温速率，升温至800℃，保温11h后，在氮气气氛下冷却至室温，得到磷酸锰铁锂粉料，取Ni0.8Co0.1Mn0.1(OH)2与氢氧化锂进行混合搅拌，在750℃煅烧8h，得到NCM811正极材料；
(2)将步骤(1)得到的磷酸锰铁锂粉料和三元镍钴锰正极材料按照质量比为3:7与MOF-5材料混合在600rpm下搅拌2h得到混合粉料；
(3)对步骤(2)得到的混合粉料在500℃下煅烧5h，在氮气气氛下冷却至室温，获得所述复合正极材料；
所述复合正极材料中，MOF包覆层的质量占比为0.5％。
实施例3
本实施例与实施例1区别就在于，所述复合材料中，MOF包覆层的质量占比为0.1％，其他条件与参数与实施例1完全相同。
实施例4
本实施例与实施例1区别就在于，所述复合材料中，MOF包覆层的质量占比 为1.0％，其他条件与参数与实施例1完全相同。
对比例1
本对比例与实施例1区别仅在于，不加入磷酸锰铁锂正极材料，其他条件与参数与实施例1完全相同。
对比例2
本对比例与实施例1区别仅在于，不加入三元镍钴锰正极材料，其他条件与参数与实施例1完全相同。
对比例3
本对比例与实施例1区别仅在于，不加入MOF材料，其他条件与参数与实施例1完全相同。
性能测试：
使用实施例1-4和对比例1-3得到的正极材料，以石墨作为负极材料，搭配PE/PP高分子材料作为隔膜，采用卷绕或者叠片方式组装成卷芯，封装在铝壳或者铝塑膜中，并注入1MLiPF6/EC+EMC锂离子电解液，组装成软包锂离子电池。对得到的锂离子电池进行性能测试，测试结果如表1所示：
表1

由表1可以看出，由实施例1-2可得，LMFP和NCM的比例不同，材料的性能侧重不同，LMFP占比多，有利于循环、DCR和电压降；NCM占比多，有利于存储和倍率性能。
由实施例1和实施例3-4对比可得，本申请所述复合正极材料中，MOF包覆层的质量占比会影响其性能，将MOF包覆层的质量占比控制在0.1-1.0％，制得复合正极材料的性能较好，若MOF包覆层的质量占比过低，包覆效果不明显，无法很好的起到作用，若MOF包覆层的质量占比过高，活性物质占比降低进而导致克容量降低。
由实施例1和对比例1-2对比可得，本申请所述复合正极材料的内核由磷酸锰铁锂粉料和三元镍钴锰正极材料复合，当锰铁材料占主导时，可改善其双平台问题；当三元材料为主导，可兼顾安全与成本。
由实施例1和对比例3对比可得，MOF在惰性气氛下碳化后MOF中的有机成分形成碳基质，均匀地包覆在复合正极材料表面，起到桥联作用，形成电子传递通道，提高LMFP电极材料的导电性；另一方面MOF作为保护涂层覆盖在正极材料表面，减少活性物质和电解液之间的副反应，增强材料的结构稳定性，进而提高电极材料的循环性能。

Claims (9)

  1. 一种复合正极材料的制备方法，所述制备方法包括以下步骤：
    (1)将第一锂源、锰源、铁源和磷源与溶剂混合，得到磷酸铁锰锂前驱体，将所述磷酸锰铁锂经热处理得到磷酸锰铁锂粉料，将镍钴锰氢氧化物和第二锂源混合，经烧结处理得到镍钴锰酸锂正极材料；
    (2)将步骤(1)得到的磷酸锰铁锂(LiMnxFe1-xPO4)粉料、镍钴锰酸锂(LiNiaCobMn(1-a-b)O2)正极材料与MOF材料混合进行搅拌得到混合粉料；
    (3)对步骤(2)得到的混合粉料进行煅烧处理得到所述复合正极材料。
  2. 如权利要求1所述的制备方法，其中，步骤(1)所述第一锂源包括碳酸锂和/或磷酸二氢锂；
    可选地，所述锰源包括硫酸锰、碳酸锰、硝酸锰、醋酸锰或草酸锰中的任意一种或至少两种的组合；
    可选地，所述铁源包括磷酸铁和/或铁粉；
    可选地，所述磷源包括磷酸和/或磷酸二氢铵；
    可选地，所述溶剂包括水；
    可选地，所述热处理的温度为600-950℃；
    可选地，所述热处理的时间为5-24h。
  3. 如权利要求1或2所述的制备方法，其中，步骤(1)所述第二锂源包括氢氧化锂和/或碳酸锂；
    可选地，所述烧结处理的温度为450-1000℃；
    可选地，所述烧结处理的时间为5-12h。
  4. 如权利要求1-3任一项所述的制备方法，其中，步骤(2)所述磷酸锰铁锂的化学式为LiMnxFe1-xPO4，0＜x＜1；
    可选地，所述镍钴锰酸锂的化学式为LiNiaCobMn(1-a-b)O2，a＝0.5-0.8，b＝0.1-0.2；
    所述磷酸锰铁锂粉料和镍钴锰正极材料的质量比为1:(0.1-10)；
    可选地，所述MOF材料包括IRMOFs、MILs、MOF-5、MOF-74或ZIF-8中的任意一种或至少两种的组合。
  5. 如权利要求1-4任一项所述的制备方法，其中，步骤(2)所述搅拌的速度为300-800rpm；
    可选地，所述搅拌的时间为0.5-5h。
  6. 如权利要求1-5任一项所述的制备方法，其中，步骤(3)所述煅烧处理的温度为200-600℃；
    可选地，所述煅烧处理的时间为2-12h。
  7. 一种复合正极材料，所述复合正极材料通过如权利要求1-6任一项所述方法制得。
  8. 如权利要求7所述的复合正极材料，其中，所述复合正极材料包括内核和设置于所述内核表面的包覆层；
    可选地，所述内核包括镍钴锰三元正极材料和磷酸锰铁锂正极材料；
    可选地，所述包覆层包括MOF材料；
    可选地，以所述复合正极材料的质量为100％计，所述包覆层的质量分数为0.1-1.0％。
  9. 一种正极极片，所述正极极片包含如权利要求7或8所述的复合正极材料。
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