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WO2023035781A1 - 一种缓解释氧的包覆型正极材料、其制备方法和应用 - Google Patents

一种缓解释氧的包覆型正极材料、其制备方法和应用 Download PDF

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Publication number
WO2023035781A1
WO2023035781A1 PCT/CN2022/106715 CN2022106715W WO2023035781A1 WO 2023035781 A1 WO2023035781 A1 WO 2023035781A1 CN 2022106715 W CN2022106715 W CN 2022106715W WO 2023035781 A1 WO2023035781 A1 WO 2023035781A1
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Prior art keywords
positive electrode
coated
electrode material
oxygen
active material
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English (en)
French (fr)
Inventor
郑晓醒
江卫军
李子郯
陈思贤
许鑫培
杨红新
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
    • 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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 present disclosure relates to the field of new energy technology, for example, relates to a coated cathode material for slow decomposing oxygen, its preparation method and application.
  • Lithium battery is the key to promote the next generation of sustainable energy technology, among which high energy density lithium ion battery has been paid more and more attention by researchers.
  • Oxygen-containing cathodes are the main components of high-voltage, high-energy-density lithium-ion batteries. Since graphite is used as the anode in most commercial Li-ion batteries, the electrochemical performance of the battery (such as energy density and operating voltage) is determined by the choice of cathode material.
  • the current main technical route is to use high-nickel, high-voltage positive electrode materials, and the main problem brought about by the increase in the high gram capacity of positive electrode materials is the decline in thermal stability, which leads to Security Question.
  • the positive electrode material decomposes, and a large amount of oxygen is released, which leads to a serious decline in the performance of the positive electrode, and rapidly releases a large amount of heat and energy, endangering the safety of the battery and triggering thermal runaway, that is, the battery catches fire.
  • the present disclosure provides a coated positive electrode material that slows and decomposes oxygen.
  • the coated positive electrode material includes a positive electrode active material and a metal layer coated on the surface of the positive electrode active material.
  • the metal layer consists of The metal element is melted to form a metal element, and the metal element includes at least one of zinc or tin.
  • the metal layer is formed on the surface of the positive electrode active material after melting the metal element to solve the problem of oxygen release from the positive electrode material.
  • the technical principle is as follows: 1
  • the metal element has certain reducibility. When out of control, the positive electrode active material decomposes to release oxygen, and the metal element coated on the surface of the positive electrode active material can reduce oxygen to form metal oxides, achieving the effect of slowing down the release of oxygen and avoiding the release of oxygen in the case of accumulated heat. Flammable electrolyte, reducing the risk of battery runaway.
  • this coating state is conducive to better play the effect of the metal layer on improving the conductivity of the positive electrode, reducing the internal resistance of the battery, and improving cycle performance; on the other hand, this coating state improves the metal element and oxygen
  • the contact area can absorb oxygen more efficiently.
  • the dense and complete metal layer can well block the escape of oxygen, and better solve the safety problem caused by the oxygen release from the positive electrode.
  • the elemental metal includes at least one of zinc and tin, and the elemental metal has suitable reducibility and melting point, which can avoid high temperature due to the high melting point of the metal (for example, the melting point of iron is 1533°C). The problem that the performance of the positive electrode active material decreases during the melting process.
  • the positive electrode material of the present disclosure should be used to prepare a lithium-ion battery, which not only exhibits an excellent effect of slowing and decomposing oxygen, improves the safety performance of the battery, but also ensures good electrochemical performance, such as higher discharge capacity and cycle capacity retention.
  • the release of oxygen from the positive electrode is relieved by introducing a metal layer, which belongs to the chemical oxygen absorption method, compared to other physical oxygen absorption methods (such as aluminosilicate, zeolite, activated carbon, etc. or molecular sieves, etc.), which is convenient for accurate quantitative control of the coating amount and oxygen absorption amount through calculation.
  • a metal layer which belongs to the chemical oxygen absorption method, compared to other physical oxygen absorption methods (such as aluminosilicate, zeolite, activated carbon, etc. or molecular sieves, etc.), which is convenient for accurate quantitative control of the coating amount and oxygen absorption amount through calculation.
  • the metal mobility of the metal element cannot be too strong. If the metal mobility of the metal element is too strong, it may lead to the reduction of the positive electrode active material during the coating process, which not only causes the effect of slowing down and decomposing oxygen to deteriorate. , It also destroys the structure of the positive electrode active material and affects the electrochemical performance of the positive electrode material.
  • a magnesium metal layer is formed on the surface of the magnesium powder by annealing after mixing with the positive active material. Due to the strong metal mobility of the magnesium powder, the positive active material may be reduced during the annealing process to form a structure. The problem of destruction reduces the electrochemical performance of the cathode material.
  • the mass content of the metal layer is 500ppm-50000ppm, such as 500ppm, 600ppm, 800ppm, 1000ppm, 1750ppm, 2000ppm, 2500ppm, 3000ppm, 4000ppm ⁇ 4500ppm ⁇ 5000ppm ⁇ 6000ppm ⁇ 7000ppm ⁇ 7500ppm ⁇ 8000ppm ⁇ 8500ppm ⁇ 9000ppm ⁇ 10000ppm ⁇ 11000ppm ⁇ 13000ppm ⁇ 15000ppm ⁇ 17500ppm ⁇ 18500ppm ⁇ 20000ppm ⁇ 21500ppm ⁇ 25000ppm ⁇ 26000ppm ⁇ 28000ppm ⁇ 30000ppm ⁇ 35000ppm ⁇ 40000ppm ⁇ 45000ppm ⁇ 50000ppm ⁇ , in some embodiments, the mass content of the metal layer is 5000ppm ⁇ 30000ppm.
  • the metal layer should be controlled within an appropriate content. If the content of the metal layer is too low, there will be no oxygen absorption effect; if the content of the metal layer is too high, the coated metal layer will be too thick, which will not It is beneficial to achieve a better effect of slowing and decomposing oxygen under the condition of thermal runaway and affects the electrochemical performance of the positive electrode material.
  • the metal elements in the metal layer enter into the lattice of the positive electrode active material. This improves the coating effect, stabilizes the structure of the positive electrode material, and is conducive to obtaining good electrochemical performance.
  • the positive active material includes at least one of a doped positive active material or an undoped positive active material.
  • the positive active material includes Li 1+x1 Ni y Co z Mn t M' s O 2- ⁇ , LiM” x2 Mn 2-x2 O 4 , LiFe 1-x3 M”’ x3 PO 4 , Li At least one of 2 Fe 1-x4 N x4 SiO 4 , LiFe 1-x5 N' x5 SO 4 F, where 0 ⁇ x1 ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ t ⁇ 1, 0 ⁇ s ⁇ 1, 0 ⁇ 0.2, 0 ⁇ x2 ⁇ 0.5, 0 ⁇ x3 ⁇ 1, 0 ⁇ x4 ⁇ 1, 0 ⁇ x5 ⁇ 1; for example, x1 is 0, 0.01, 0.05, 0.1, 0.2, 0.3, 0.5, 0.8 or 1 etc., y is 0, 0.1, 0.2, 0.3, 0.4, 0.6, 0.7, 0.8 or 1 etc., z is 0, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.6, 0.7, 0.8 or
  • the positive electrode active material includes nickel-cobalt-manganese ternary material, nickel-cobalt-aluminum ternary material, cobalt-free binary material, lithium manganate material, lithium iron phosphate material, lithium iron silicate material, lithium iron fluoride sulfate wait.
  • the positive active material includes or does not include doping elements, and the doping elements include cations or anions.
  • the positive electrode active material doping element is a cation, including Li 1+x1 Ni y Co z Mn t M' s O 2- ⁇ , LiM” x2 Mn 2-x2 O 4 , LiFe 1-x3 M”
  • the types of doping elements are selected independently, and the types of doping elements are the same or different.
  • the present disclosure provides a method for preparing a coated positive electrode material, the method comprising the following steps:
  • annealing is performed after mixing the metal element and the positive electrode active material to obtain the coated positive electrode material; wherein, the temperature of the annealing treatment is higher than the melting point of the metal element.
  • the annealing treatment is carried out after mixing the metal element and the positive electrode active material, and the temperature of the annealing treatment is controlled to be higher than the melting point of the metal element, so that the metal element is melted and coated on the surface of the positive electrode active material, and formed after cooling.
  • the metal layer is conducive to obtaining a dense and complete metal layer that is more tightly bound to the positive active material.
  • the elements in the metal layer can also enter the lattice of the positive active material during the annealing process, improving the coating effect and stabilizing The structure of the cathode material, thereby improving the performance of the cathode material.
  • the metal element includes at least one of micron-scale metal element particles or nanometer-scale metal element particles.
  • the preparation process of the coated positive electrode material is carried out under the protection of a protective gas, so as to avoid oxidation of the metal element, thereby avoiding affecting the effect of the metal layer on absorbing oxygen and alleviating the release of oxygen from the positive electrode material.
  • the protective gas includes at least one of nitrogen, helium, neon, argon, krypton and xenon.
  • the mixing method includes dry mixing or wet mixing, for example, mixing by using a fluidized bed or mixing by spray drying.
  • the mixing method adopts dry mixing, and the positive electrode active material is added to the mixing equipment for dry mixing, and the mixing time is 5min to 30min, such as 5min, 8min, 10min, 15min, 20min, 25min or 30min, etc.
  • the rotating speed during mixing is 500rpm ⁇ 4000rpm, such as 500rpm, 600rpm, 800rpm, 1000rpm, 1250rpm, 1500rpm, 2000rpm, 2500rpm, 3000rpm, 3500rpm or 4000rpm, etc.
  • a dry mixing method is used to obtain a uniform mixing effect and to achieve a certain coating effect. Moreover, the method is simple and easy, has low cost and is suitable for industrial production.
  • the mass ratio of the metal element to the positive active material is (0.05-5):(95-99.95), for example, 0.05:99.95, 0.1:99.9, 0.2:99.8, 0.3:99.7, 0.4:99.6 , 0.5:99.5, 0.7:99.3, 0.8:99.2, 1:99, 1.2:98.8, 1.5:98.5, 2:98, 2.5:97.5, 3:97, 3.5:96.5, 4:96, 4.5:95.5 or 5 :95, in some embodiments, the mass ratio of metal element and positive electrode active material is (0.5 ⁇ 3):(97 ⁇ 99.5).
  • the temperature of the annealing treatment is 200°C to 700°C, such as 200°C, 240°C, 280°C, 320°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C or 700°C, etc.; the time for the annealing treatment is 3h to 8h, for example, 3h, 4h, 4.5h, 5h, 6h, 6.5h, 7h or 8h.
  • the temperature of the annealing treatment will affect the coating effect, and may also affect the electrochemical performance of the positive electrode active material itself.
  • the coating state includes, for example, the bonding between the metal layer and the positive electrode active material, etc. . In the temperature range of 200° C. to 700° C., it is beneficial to obtain a more complete and dense metal layer with good binding properties with the positive electrode active material while ensuring good electrochemical performance of the positive electrode active material.
  • the metal element is pretreated before use, and the pretreatment includes grinding and dispersing the element.
  • the agglomerates are opened through a pretreatment step, so as to obtain nanoscale metal particles with good dispersibility, for example, evenly dispersed.
  • the grinding and dispersing includes dry grinding or wet grinding followed by drying, for example, the solvent in the wet grinding includes at least one of ethanol, methanol or acetone.
  • the mesh size of the sieve selected for sieving includes 300 mesh to 400 mesh, such as 300 mesh, 325 mesh, 350 mesh or 400 mesh.
  • An embodiment of the present disclosure provides an application of the coated positive electrode material described in one embodiment in alleviating oxygen release from the positive electrode.
  • the metal layer is formed by melting a metal element.
  • the coated positive electrode material includes a positive electrode active material and a metal layer coated on the surface of the positive electrode active material, and the metal element in the metal layer has stronger metal mobility than hydrogen.
  • the metal element when the annealing temperature is higher than or equal to the melting point, the metal element forms a continuous metal layer on the surface of the positive electrode active material, and when the annealing temperature is lower than the melting point, the metal particles and the positive electrode active material exist in point contact.
  • the lithium battery includes a positive electrode, a negative electrode and a separator, and the positive electrode adopts the coated positive electrode material described in an embodiment.
  • the lithium battery includes a lithium ion battery, a lithium metal battery, a lithium air battery, or a lithium sulfur battery.
  • a coated positive electrode material for slowing and decomposing oxygen comprising a high-nickel positive electrode material and a zinc layer coated on the surface of the high-nickel positive electrode material; taking the coated positive electrode material as a whole, the mass content of the zinc layer is 10000ppm.
  • This embodiment also provides a method for preparing the above-mentioned coated positive electrode material, including the following steps:
  • This embodiment provides a coated positive electrode material for slowing and decomposing oxygen, including a high-nickel positive electrode material and a tin layer coated on the surface of the high-nickel positive electrode material; taking the coated positive electrode material as a whole, the mass of the tin layer The content is 20000ppm.
  • This embodiment also provides a method for preparing the above-mentioned coated positive electrode material, including the following steps:
  • This embodiment provides a coated positive electrode material for slowing and decomposing oxygen, including a high-nickel positive electrode material and a zinc layer coated on the surface of the high-nickel positive electrode material; taking the coated positive electrode material as a whole, the mass of the zinc layer The content is 500ppm.
  • This embodiment also provides a method for preparing the above-mentioned coated positive electrode material, including the following steps:
  • This embodiment provides a coated positive electrode material for slowing and decomposing oxygen, including a high-nickel positive electrode material and a zinc layer coated on the surface of the high-nickel positive electrode material; taking the coated positive electrode material as a whole, the mass of the zinc layer The content is 10000ppm.
  • This embodiment also provides a method for preparing the above-mentioned coated positive electrode material, including the following steps:
  • This comparative example is a high-nickel positive electrode material without any coating treatment.
  • This comparative example provides a kind of coated positive electrode material that slows down and decomposes oxygen, comprises high-nickel positive electrode material and the magnesium layer that is coated on the surface of described high-nickel positive electrode material; The content is 10000ppm.
  • This comparative example also provides the preparation method of above-mentioned coated positive electrode material, comprises the following steps:
  • This comparative example provides a kind of coated positive electrode material that slows down and decomposes oxygen, comprises high-nickel positive electrode material and the zinc layer that is coated on the surface of described high-nickel positive electrode material; The content is 10000ppm.
  • This comparative example also provides the preparation method of above-mentioned coated positive electrode material, comprises the following steps:
  • This comparative example provides a coated positive electrode material, including a high-nickel positive electrode material and CoS 2 coated on the surface of the high-nickel positive electrode material; taking the coated positive electrode material as a whole, the mass content of CoS 2 is 10000ppm.
  • This comparative example also provides the preparation method of above-mentioned coated positive electrode material, comprises the following steps:
  • the coating agent CoS 2 was ground and dispersed in ethanol, and dried in vacuum at 80°C.
  • test method is TG-MS test, the test conditions are: room temperature - 300°C, heating rate: 10°C/min, argon atmosphere, the test results are shown in Table 2.
  • Positive sheet preparation get solid content and be 6.25% PVDF/NMP solution 0.1904g, NMP solution 0.8g, conductive carbon 0.068g, get the positive electrode material 1.574g of each embodiment and comparative example respectively, carry out homogenization, coating (scraper Gap 22 ⁇ m), drying. Rolling to the same thickness, punching 12mm discs to obtain positive electrode sheets.
  • the negative electrode is lithium metal
  • the diaphragm is PE diaphragm
  • the lithium salt in the electrolyte is LiPF 6
  • the concentration of lithium salt is 1M
  • the solvent is ethylene carbonate (EC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC) according to A mixture with a volume ratio of 1:1:1 is assembled into a button-type half-cell by using the above-mentioned positive electrode sheet, negative electrode, separator and electrolyte.
  • the disclosure solves the problem of oxygen release from the positive electrode material by melting the metal elemental substance and coating the surface of the positive electrode active material to form a metal layer, improves the safety performance of the battery, and ensures good battery life. chemical properties.
  • Example 1 From the comparison between Example 1 and Example 4, it can be seen that the temperature of the annealing treatment will affect the oxygen release performance of the prepared coated positive electrode material, and the high annealing temperature will lead to deviations in the effect of slowing down the release of oxygen.
  • Example 1 From the comparison of Example 1 and Comparative Example 2, it can be seen that the metal elemental magnesium is used for coating, and the magnesium powder particles are coated in the form of point contact, and the effect of slowing down and releasing oxygen is limited. In the process of reducing the positive electrode active material, the effect of slowing down and decomposing oxygen becomes worse.
  • Example 1 From the comparison of Example 1 and Comparative Example 3, it can be seen that the annealing temperature is too low, the zinc powder particles are coated in the form of electrical contact, and the effect of slowing down oxygen release is limited.

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Abstract

本公开提供了一种缓解释氧的包覆型正极材料、其制备方法和应用。所述包覆型正极材料包括正极活性物质和包覆于所述正极活性物质表面的金属层，所述金属层由金属单质熔融后形成，所述金属单质的金属活动性强于氢且弱于镁。本发明正极材料制备的锂离子电池，不仅能够缓解释氧，提升安全性能，还具有良好的电化学性能。

Description

一种缓解释氧的包覆型正极材料、其制备方法和应用 技术领域
本公开涉及新能源技术领域，例如涉及一种缓解释氧的包覆型正极材料、其制备方法和应用。
背景技术
锂电池是推动下一代可持续能源技术的关键，其中高能量密度锂离子电池受到越来越多研究学者的重视。含氧正极是高电压、高能量密度锂离子电池的主要组成部分。由于石墨在大多数商业化的锂离子电池中用作负极，电池的电化学性能(如能量密度和工作电压)则是由正极材料的选择决定的。
为了获得高能量密度的锂离子电池，目前主要的技术路线是使用高镍、高电压的正极材料，而正极材料高克容量提升的同时带来的最主要问题就是热稳定性下降，由此引发安全问题。高温高压下正极材料分解，大量的氧气释放导致正极性能严重下降，并且迅速释放大量的热量和能量，危及电池的安全，触发热失控，即电池着火。
公开内容
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本公开提供一种无钴无镍正极材料、其制备方法以及电池。
本公开在一实施例中提供一种缓解释氧的包覆型正极材料，所述包覆型正极材料包括正极活性物质和包覆于所述正极活性物质表面的金属层，所述金属层由金属单质熔融后形成金属单质，所述金属单质包括锌或锡中的至少一种。
在一实施例中，通过将金属单质熔融后在正极活性物质的表面包覆形成金属层，解决正极材料释氧的问题，其技术原理如下：①金属单质具有一定的还原性，当电池出现热失控时，正极活性物质分解发生释氧，包覆于正极活性物 质表面的金属单质能够将氧气还原，形成金属氧化物，达到缓解释氧的效果，避免了释放的氧气在积累热量的情况下点燃可燃电解液，降低电池失控的风险。②由于金属层是金属单质熔融后形成的，金属熔融后的流动性使其更容易实现完全或接近完全的包覆效果，且包覆的金属层更致密、结合性更强，这样的好处主要有：一方面，这种包覆状态有利于更好地发挥金属层对于正极导电性的提升效果，降低电池内阻，提高循环性能；另一方面，这种包覆状态提高了金属单质与氧气的接触面积，更高效地吸收氧气，同时，致密且完全的金属层能够很好地阻挡氧气的逸出，更好地解决因正极释氧导致的安全问题。
在一实施例中，所述金属单质包括锌和锡中的至少一种，上述金属单质具有合适的还原性和熔点，能够避免因为金属熔点过高(例如铁的熔点为1533℃)而导致高温熔融过程中导致正极活性物质性能下降的问题。
在一实施例中，采用本公开的正极材料应制备锂离子电池，不仅表现出优异的缓解释氧的效果，提升了电池的安全性能，还保证了良好的电化学性能，例如较高的放电容量和循环容量保持率。
在一实施例中，通过引入金属层的方式来缓解正极的释氧，属于化学吸氧方式，相比于其他的物理吸氧方式(采用的吸氧剂例如是硅铝酸盐、沸石、活性炭或分子筛等)，便于通过计算对包覆量及吸氧量进行精准的定量控制。
在一实施例中，金属单质的金属活动性不能过强，若金属单质的金属活动性过强，有可能导致在包覆的过程中将正极活性物质还原，不仅造成缓解释氧的效果变差，还破坏正极活性物质的结构，影响正极材料电化学性能的发挥。例如，通过将镁粉与正极活性物质混合后退火处理的方式在其表面形成镁金属层，由于镁粉的金属活动性很强，在退火处理过程中有可能导致正极活性物质 被还原而产生结构破坏的问题，降低正极材料的电化学性能。
本公开提供的一实施例中，以所述包覆型正极材料为总体计，所述金属层的质量含量为500ppm～50000ppm，例如500ppm、600ppm、800ppm、1000ppm、1750ppm、2000ppm、2500ppm、3000ppm、4000ppm、4500ppm、5000ppm、6000ppm、7000ppm、7500ppm、8000ppm、8500ppm、9000ppm、10000ppm、11000ppm、13000ppm、15000ppm、17500ppm、18500ppm、20000ppm、21500ppm、25000ppm、26000ppm、28000ppm、30000ppm、35000ppm、40000ppm、45000ppm或50000ppm等，在一些实施方式中，金属层的质量含量为5000ppm～30000ppm。
在一实施例中，所述金属层应控制在合适的含量内，若金属层的含量过低，没有吸氧效果；若金属层的含量过高，会导致包覆的金属层过厚，不利于在热失控条件下达到更佳的缓解释氧的效果且影响正极材料的电化学性能。
在一实施例中，所述金属层中的金属元素进入正极活性物质的晶格中。如此提高包覆效果，稳定正极材料结构，有利于获得良好的电化学性能。
在一实施例中，所述正极活性物质包括掺杂的正极活性物质或未掺杂的正极活性物质中的至少一种。
在一实施例中，正极活性物质包括Li 1+x1Ni yCo zMn tM' sO 2-δ、LiM” x2Mn 2-x2O 4、LiFe 1-x3M”' x3PO 4、Li 2Fe 1-x4N x4SiO 4、LiFe 1-x5N' x5SO 4F中的至少一种，其中，0≤x1≤1，0≤y≤1，0≤z≤1，0≤t≤1，0≤s≤1，0≤δ≤0.2，0≤x2≤0.5，0≤x3≤1，0≤x4≤1，0≤x5≤1；例如，x1是0、0.01、0.05、0.1、0.2、0.3、0.5、0.8或1等，y是0、0.1、0.2、0.3、0.4、0.6、0.7、0.8或1等，z是0、0.01、0.05、0.1、0.2、0.3、0.4、0.6、0.7、0.8或1等，t是0、0.1、0.2、0.3、0.4、0.6、0.7、0.8或1等，s是0、0.01、0.02、0.03、0.05、0.08、0.1、0.15、0.2、0.25、0.3、0.4、0.5、0.6、0.7、0.8或 1等，δ是0、0.01、0.02、0.04、0.06、0.1、0.15或0.2等，x2是0、0.02、0.05、0.1、0.2、0.3、0.4或0.5等，x3是0、0.05、0.1、0.3、0.5、0.6、0.8或1等，x4是0、0.05、0.1、0.2、0.3、0.5、0.6、0.7、0.8或1等，x5是0、0.05、0.1、0.2、0.3、0.5、0.6、0.7、0.8或1等；M'、M”、M”'、N和N'各自独立地选自Li、Na、K、Mg、Ca、Sr、Ba、Al、Ga、In、Si、Ge、Sn、Pb、Sc、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、La、Ce、Pr、Nd、Sm、Eu、Gd、Er、Tm、Yb、Lu、W、Pt和Au中的至少一种。
在一实施例中，正极活性物质包括镍钴锰三元材料、镍钴铝三元材料、无钴二元材料、锰酸锂材料、磷酸铁锂材料、硅酸铁锂材料、硫酸氟铁锂等。
在一实施例中，正极活性物质包括掺杂元素或不包括掺杂元素，所述掺杂元素包括阳离子或阴离子。
在一实施例中，正极活性物质掺杂元素为阳离子，包括Li 1+x1Ni yCo zMn tM' sO 2-δ、LiM” x2Mn 2-x2O 4、LiFe 1-x3M”' x3PO 4、Li 2Fe 1-x4N x4SiO 4和LiFe 1-x5N' x5SO 4F，掺杂元素种类的选择各自独立，掺杂元素的种类相同或者不同。
本公开在一实施例中提供了一种包覆型正极材料的制备方法，所述方法包括以下步骤：
在保护性气体的保护下，将金属单质和正极活性物质混合后进行退火处理，得到所述的包覆型正极材料；其中，所述退火处理的温度高于所述金属单质的熔点。
在一实施例中，通过将金属单质和正极活性物质混合后进行退火处理，并控制退火处理的温度高于金属单质的熔点，使金属单质熔融后包覆于正极活性物质的表面，冷却后形成金属层，有利于获得致密完全且与正极活性物质结合 性更紧密的金属层，而且，在退火过程中金属层中的元素还能够进入到正极活性物质的晶格中，提高包覆效果，稳定正极材料结构，进而提升正极材料的性能。
在一实施例中，所述金属单质包括微米级的金属单质颗粒或者纳米级的金属单质颗粒中的至少一种。
在一实施例中，所述包覆型正极材料的制备过程在保护性气体的保护下进行，避免金属单质被氧化，进而避免影响金属层发挥吸收氧气、缓解正极材料释氧的效果，
在一实施例中，所述保护性气体包括氮气、氦气、氖气、氩气、氪气和氙气中的至少一种。
在一实施例中，所述混合方法包括干法混合或湿法混合，例如，采用流化床进行混合或喷雾干燥进行混合。
在一实施例中，混合方法采用干法混合，将正极活性物质和一起加入到混合设备中进行干法混合，混合时间5min～30min，例如5min、8min、10min、15min、20min、25min或30min等，混合时的转速为500rpm～4000rpm，例如500rpm、600rpm、800rpm、1000rpm、1250rpm、1500rpm、2000rpm、2500rpm、3000rpm、3500rpm或4000rpm等。
在一实施例中，采用干法混合的方式获得均匀的混料效果，并能够达到一定的包覆效果。而且，该方法简单易行，成本低，适合工业化生产。
在一实施例中，所述金属单质和正极活性物质的质量比为(0.05～5):(95～99.95)，例如0.05:99.95、0.1:99.9、0.2:99.8、0.3:99.7、0.4:99.6、0.5:99.5、0.7:99.3、0.8:99.2、1:99、1.2:98.8、1.5:98.5、2:98、2.5:97.5、3:97、 3.5:96.5、4:96、4.5:95.5或5:95，在一些实施方式中，金属单质和正极活性物质的质量比为(0.5～3):(97～99.5)。
在一实施例中，所述退火处理的温度为200℃～700℃，例如200℃、240℃、280℃、320℃、350℃、400℃、450℃、500℃、550℃、600℃、650℃或700℃等；所述退火处理的时间为3h～8h，例如3h、4h、4.5h、5h、6h、6.5h、7h或8h等。
在一实施例中，所述退火处理的温度会影响包覆效果，还有可能影响正极活性物质本身的电化学性能，所述包覆状态例如包括金属层与正极活性物质之间的结合性等。在温度范围200℃～700℃范围内，有利于在保证正极活性物质良好的电化学性能的同时，获得更加完全、致密且与正极活性物质结合性好的金属层。
在一实施例中，所述金属单质在使用前进行预处理，所述预处理包括对单质进行研磨分散。
在一实施例中，通过预处理步骤将团聚体打开，进而获得具有良好分散性的，例如获得分散均匀的纳米级金属颗粒。
在一实施例中，所述研磨分散包括干法研磨或湿法研磨后干燥，例如，湿法研磨中的溶剂包括乙醇、甲醇或丙酮中的至少一种。
在一实施例中，所述包覆后进行筛分的步骤，筛分选用的筛网目数包括300目～400目，例如300目、325目、350目或400目。
本公开一实施例中提供了一种一实施例所述的包覆型正极材料在缓解正极释氧中的应用。
在一实施例中，金属层由金属单质熔融后形成。
在一实施例中，所述包覆型正极材料包括正极活性物质和包覆于所述正极活性物质表面的金属层，所述金属层中的金属单质的金属活动性强于氢。
在一实施例中，退火温度高于或等于熔点时，金属单质在正极活性物质表面形成连续的金属层，退火温度低于熔点时，金属颗粒与正极活性物质以点接触的方式存在。
本公开在一实施例中提供一种锂电池，所述锂电池包括正极、负极和隔膜，所述正极采用一实施例所述的包覆型正极材料。
在一实施例中，锂电池包括锂离子电池、锂金属电池、锂空气电池或锂硫电池。
具体实施例
下面通过具体实施例来进一步说明本公开的技术方案。
实施例1
一种缓解释氧的包覆型正极材料，包括高镍正极材料和包覆于所述高镍正极材料表面的锌层；以包覆型正极材料为总体计，锌层的质量含量为10000ppm。
本实施例还提供了上述的包覆型正极材料的制备方法，包括以下步骤：
将包覆剂锌粉在乙醇中研磨分散，80℃真空烘干。
将1g锌粉与99g高镍正极材料一起加入到混合设备进行混合，混合时间：15min，转速：2000rpm。将包覆完的物料在450℃，氩气氛围下，处理8h，冷却，锌粉熔化并冷却后在高镍正极材料表面形成连续的包覆层，400目筛分得到锌包覆的高镍正极材料，即包覆型正极材料。
实施例2
本实施例提供一种缓解释氧的包覆型正极材料，包括高镍正极材料和包覆于所述高镍正极材料表面的锡层；以包覆型正极材料为总体计，锡层的质量含量为20000ppm。
本实施例还提供了上述的包覆型正极材料的制备方法，包括以下步骤：
将包覆剂锡粉在乙醇中研磨分散，80℃真空烘干。
将2g锡粉与98g高镍正极材料一起加入到混合设备进行混合，混合时间：20min，转速：1500rpm。将包覆完的物料在270℃，氮气氛围下，处理6h，冷却，锡粉熔化并冷却后在高镍正极材料表面形成连续的包覆层，325目筛分得到锡包覆的高镍正极材料，即包覆型正极材料。
实施例3
本实施例提供一种缓解释氧的包覆型正极材料，包括高镍正极材料和包覆于所述高镍正极材料表面的锌层；以包覆型正极材料为总体计，锌层的质量含量为500ppm。
本实施例还提供了上述的包覆型正极材料的制备方法，包括以下步骤：
将包覆剂锌粉在乙醇中研磨分散，80℃真空烘干。
将0.05g锌粉与99.95g高镍正极材料一起加入到混合设备进行混合，混合时间：15min，转速：2000rpm。将包覆完的物料在450℃，氩气氛围下，处理8h，冷却，锌粉熔化并冷却后在高镍正极材料表面形成连续的包覆层，400目筛分得到锌包覆的高镍正极材料，即包覆型正极材料。
实施例4
本实施例提供一种缓解释氧的包覆型正极材料，包括高镍正极材料和包覆于所述高镍正极材料表面的锌层；以包覆型正极材料为总体计，锌层的质量含量为10000ppm。
本实施例还提供了上述的包覆型正极材料的制备方法，包括以下步骤：
将包覆剂锌粉在乙醇中研磨分散，80℃真空烘干。
将1g锌粉与99g高镍正极材料一起加入到混合设备进行混合，混合时间：15min，转速：2000rpm。将包覆完的物料在800℃，氩气氛围下，处理8h，冷却，锌粉熔化并冷却后在高镍正极材料表面形成连续的包覆层，400目筛分得到锌包覆的高镍正极材料，即包覆型正极材料。
对比例1
本对比例为未进行任何包覆处理的高镍正极材料。
对比例2
本对比例提供一种缓解释氧的包覆型正极材料，包括高镍正极材料和包覆于所述高镍正极材料表面的镁层；以包覆型正极材料为总体计，镁层的质量含量为10000ppm。
本对比例还提供了上述的包覆型正极材料的制备方法，包括以下步骤：
将镁粉在乙醇中研磨分散，80℃真空烘干。
将1g镁粉与99g高镍正极材料一起加入到混合设备进行混合，混合时间：15min，转速：2000rpm。将包覆完的物料在450℃，氩气氛围下，处理8h，冷却后400目筛分得到镁包覆的高镍正极材料，即包覆型正极材料。
对比例3
本对比例提供一种缓解释氧的包覆型正极材料，包括高镍正极材料和包覆于所述高镍正极材料表面的锌层；以包覆型正极材料为总体计，锌层的质量含量为10000ppm。
本对比例还提供了上述的包覆型正极材料的制备方法，包括以下步骤：
将锌粉在乙醇中研磨分散，80℃真空烘干。
将1g锌粉与99g高镍正极材料一起加入到混合设备进行混合，混合时间：15min，转速：2000rpm。将包覆完的物料在150℃，氩气氛围下，处理8h，冷却，锌粉熔化并冷却后在高镍正极材料表面形成连续的包覆层，400目筛分得到锌包覆的高镍正极材料，即包覆型正极材料。
对比例4
本对比例提供一种包覆型正极材料，包括高镍正极材料和包覆于所述高镍正极材料表面的CoS 2；以包覆型正极材料为总体计，CoS 2的质量含量为10000ppm。
本对比例还提供了上述的包覆型正极材料的制备方法，包括以下步骤：
将包覆剂CoS 2在乙醇中研磨分散，80℃真空烘干。
将1g CoS 2与99g高镍正极材料一起加入到混合设备进行混合，混合时间： 15min，转速：2000rpm。将包覆完的物料在450℃，氩气氛围下，处理8h，冷却后400目筛分得到CoS 2包覆的高镍正极材料，即包覆型正极材料，经检测，本对比例虽然能够起到一定的缓解释氧的作用，但是得到的包覆型正极材料的电化学性能较差，不利于实际应用。
实施例1～4以及对比例1-4的制备参数见表1。
对实施例1～4以及对比例1-4制备得到的材料进行测试。
一、释氧测试
测试方法为TG-MS测试，测试条件为：室温-300℃，升温速率：10℃/min，氩气氛围，测试结果参见表2。
二、电池制备和电化学性能测试
(1)电池制备：
正极片制备：取固含量为6.25％的PVDF/NMP溶液0.1904g，NMP溶液0.8g，导电炭0.068g，分别取各实施例和对比例的正极材料1.574g，进行匀浆，涂布(刮刀间隙22μm)，烘干。辊压至同一厚度，冲12mm圆片，得到正极片。
负极为锂金属，隔膜为PE隔膜，电解液中锂盐为LiPF 6，锂盐浓度为1M，溶剂为碳酸乙烯酯(EC)、碳酸二乙酯(DEC)和碳酸甲乙酯(EMC)按体积比1:1:1的混合物，采用上述的正极片、负极、隔膜和电解液组装成扣式半电池。
(2)电化学性能测试
在常温25℃条件下测试0.1C充放电容量、1C放电容量、以及循环50周容量保持率，电压范围3.0V～4.3V，测试结果参见表3。
表1
Figure PCTCN2022106715-appb-000001
Figure PCTCN2022106715-appb-000002
表2
编号 质量分数下降(％) 释氧温度(℃)
实施例1 4 208
实施例2 4.5 203
实施例3 5.8 193
实施例4 4.9 197
对比例1 6 191
对比例2 9 185
对比例3 5.2 195
表3
Figure PCTCN2022106715-appb-000003
结合表1～表3的数据可知，本公开通过将金属单质熔融后在正极活性物质的表面包覆形成金属层，解决正极材料释氧的问题，提升电池的安全性能，而且保证了良好的电化学性能。
分析表2可以看出，实施例1和实施例2的效果更好。
通过实施例1与实施例3和对比例1的对比可知，锌层的含量偏少，缓解 释氧效果不明显。
通过实施例1与实施例4的对比可知，退火处理的温度会影响制备得到的包覆型正极材料的释氧性能，退火温度偏高导致缓解释氧的效果偏差。
通过实施例1与对比例2的对比可知，采用金属单质镁进行包覆，镁粉颗粒以点接触的形式包覆，缓解释氧效果有限，且由于其还原性过强，有可能在包覆的过程中将正极活性物质还原，造成缓解释氧的效果变差。
通过实施例1与对比例3的对比可知，退火处理温度过低，锌粉颗粒以电接触的形式包覆，缓解释氧的效果有限。

Claims (9)

  1. 一种缓解释氧的包覆型正极材料，所述包覆型正极材料包括正极活性物质和包覆于所述正极活性物质表面的金属层，所述金属层由金属单质熔融后形成，所述金属单质包括锌或锡中的至少一种。
  2. 根据权利要求1所述的缓解释氧的包覆型正极材料，其中，以所述包覆型正极材料为总体计，所述金属层的质量含量为500ppm～50000ppm。
  3. 根据权利要求1或2所述的缓解释氧的包覆型正极材料，其中，所述金属层中的金属元素进入正极活性物质的晶格中。
  4. 根据权利要求1-3任一项所述的缓解释氧的包覆型正极材料，其中，所述正极活性物质包括Li 1+x1Ni yCo zMn tM' sO 2-δ、LiM” x2Mn 2-x2O 4、LiFe 1-x3M”' x3PO 4、Li 2Fe 1-x4N x4SiO 4和LiFe 1-x5N' x5SO 4F中的至少一种；
    其中，0≤x1≤1，0≤y≤1，0≤z≤1，0≤t≤1，0≤s≤1，0≤δ≤0.2，0≤x2≤0.5，0≤x3≤1，0≤x4≤1，0≤x5≤1；
    M'、M”、M”'、N和N'各自独立地选自Li、Na、K、Mg、Ca、Sr、Ba、Al、Ga、In、Si、Ge、Sn、Pb、Sc、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、La、Ce、Pr、Nd、Sm、Eu、Gd、Er、Tm、Yb、Lu、W、Pt和Au中的至少一种。
  5. 一种权利要求1-4任一项所述的缓解释氧的包覆型正极材料的制备方法，所述制备方法包括：
    在保护性气体的保护下，将金属单质和正极活性物质混合后进行退火处理，得到所述的包覆型正极材料；其中，所述退火处理的温度高于或等于所述金属单质的熔点。
  6. 根据权利要求5所述的制备方法，其中，所述金属单质和正极活性物质的质量比为(0.05～5):(95～99.95)。
  7. 根据权利要求5或6所述的制备方法，其中，所述退火处理的温度为200℃～700℃，所述退火处理的时间为3h～8h。
  8. 一种权利要求1-4任一项所述的缓解释氧的包覆型正极材料在缓解正极释氧中的应用。
  9. 一种锂电池，所述锂电池包括正极、负极和隔膜，所述正极采用权利要求1-4任一项所述的包覆型正极材料。
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