WO2024229596A1 - 包覆型正极材料及其制备方法和应用 - Google Patents

包覆型正极材料及其制备方法和应用 Download PDF

Info

Publication number
WO2024229596A1
WO2024229596A1 PCT/CN2023/092282 CN2023092282W WO2024229596A1 WO 2024229596 A1 WO2024229596 A1 WO 2024229596A1 CN 2023092282 W CN2023092282 W CN 2023092282W WO 2024229596 A1 WO2024229596 A1 WO 2024229596A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
electrode material
preparation
reaction
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2023/092282
Other languages
English (en)
French (fr)
Inventor
余海军
李爱霞
谢英豪
李长东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Original Assignee
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to CN202380009468.4A priority Critical patent/CN116848662B/zh
Priority to PCT/CN2023/092282 priority patent/WO2024229596A1/zh
Publication of WO2024229596A1 publication Critical patent/WO2024229596A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention belongs to the technical field of lithium ion battery positive electrode materials, and specifically relates to a coated positive electrode material and a preparation method and application thereof.
  • Lithium-ion batteries have become a research hotspot in the new energy industry due to their high energy density, long cycle life, and environmental friendliness.
  • the positive electrode material is the core of lithium-ion batteries and plays a decisive role in the energy density of lithium-ion batteries.
  • Nickel cobalt manganese oxide ternary positive electrode material has the advantages of high specific capacity, high energy density, low price and environmental friendliness.
  • the discharge capacity of high nickel ternary material can reach more than 200mAh/g.
  • nickel ions are easily reduced and enter the lithium layer, serious ion mixing phenomenon will occur, lithium is easy to precipitate, and the extra lithium salt added during sintering will also remain on the surface of the material in the form of oxide.
  • Residual lithium is very sensitive to moisture and easily absorbs water and carbon dioxide in the air to generate lithium hydroxide and lithium carbonate, causing the surface of the material to deteriorate. If the residual lithium content of the material is too high, the slurry will easily form a jelly-like state during the slurrying and coating process of battery production, resulting in uneven coating, which can easily cause problems such as difficulty in electrode production and capacity attenuation. In addition, the residual lithium has poor conductivity, which will hinder the deintercalation of lithium ions and cause polarization of the electrode. Residual alkali easily reacts with the electrolyte at high temperature to generate gas, causing battery bloating and posing serious safety hazards. Therefore, high-nickel ternary positive electrode materials have more stringent requirements on storage conditions and subsequent processing conditions.
  • high-nickel materials are generally treated by water washing or surface coating to reduce the generation of residual alkali.
  • water washing consumes a lot of water resources and reacts with high-nickel ternary positive electrode materials, resulting in lithium loss, damage to the material structure, and ultimately a decrease in material capacity.
  • Solid-phase coating has poor surface uniformity and cannot completely block the contact between the material and H2O and CO2 in the air.
  • Chinese patent CN108807969A discloses a method for reducing residual alkali on the surface of layered positive electrode materials for lithium-ion batteries.
  • the invention reduces the residual alkali on the surface by washing with water, then quickly removes the residual surface moisture by washing with alcohol, and then adds sodium
  • the invention effectively reduces the residual alkali on the surface of the positive electrode material.
  • the material structure is destroyed after washing.
  • the surface structure is stabilized by adding nano zirconium oxide, the amount of lithium loss during the washing process is still high.
  • the present disclosure aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present disclosure proposes a coated positive electrode material and a preparation method and application thereof.
  • a method for preparing a coated positive electrode material comprising the following steps:
  • the positive electrode material is placed in a reaction device, silicon tetrafluoride gas is introduced first to heat the reaction, and then ammonia gas is introduced to heat the reaction. After the reaction is completed, the reaction is cooled to obtain the coated positive electrode material.
  • the present invention utilizes silicon tetrafluoride gas to react with residual alkali components (Li 2 CO 3 and LiOH) on the surface of the positive electrode material to form a Li 2 SiO 3 /LiF composite coating layer on the surface of the positive electrode material, and then introduces ammonia gas to react with the residual silicon tetrafluoride gas in the reaction device to generate silicon nitride, which is deposited on the surface of the positive electrode material after cooling.
  • residual alkali components Li 2 CO 3 and LiOH
  • the positive electrode material is a high-nickel ternary positive electrode material or a lithium iron phosphate material.
  • the average particle size D50 of the positive electrode material is 2-15 ⁇ m.
  • the temperature of the silicon tetrafluoride gas for heating the reaction is 500-600°C.
  • the flow rate of the silicon tetrafluoride gas is 0.05-0.15 L/min.
  • the silicon tetrafluoride gas is introduced for a heating reaction time of 2-4 hours.
  • the reaction device is a tubular furnace; the filling volume ratio of the positive electrode material in the reaction device is 5%-15%.
  • a protective gas is first introduced.
  • the oxygen is discharged, the temperature is raised to the reaction temperature at a rate of 2-10°C/min, and then the silicon tetrafluoride gas is introduced to carry out the reaction.
  • the temperature of the ammonia gas introduced for heating reaction is 500-600°C.
  • the flow rate of the ammonia gas is 0.01-0.1 L/min.
  • the heating reaction time of the ammonia gas is 0.5-2 hours.
  • the amount of the Si 3 N 4 coating layer can be controlled by controlling the flow rate of the ammonia gas and the reaction time.
  • the present disclosure also provides a coated positive electrode material, which is prepared by the preparation method.
  • the coated positive electrode material is sequentially coated with a Li 2 SiO 3 /LiF composite coating layer and a Si 3 N 4 coating layer from the inside to the outside.
  • the coating amount of the Si 3 N 4 coating layer is 0.2%-1% of the mass of the positive electrode material.
  • the present disclosure also provides application of the coated positive electrode material in a lithium ion battery.
  • the present disclosure adopts a gas phase coating method to fully contact SiF 4 with the surface of the positive electrode material.
  • SiF 4 will not damage the ternary material structure, and reacts with the residual alkali components (Li 2 CO 3 and LiOH), which can reduce the amount of residual alkali on the surface of the material without causing lithium loss, forming a conductive Li 2 SiO 3 /LiF composite coating layer.
  • NH 3 is introduced to react with the residual SiF 4 , and the generated Si 3 N 4 is deposited on the surface of the positive electrode material, making the coating layer more uniform and complete, thereby improving the cycle life, cycle stability and safety of the positive electrode material.
  • the Li 2 SiO 3 /LiF composite coating layer is selectively generated at the residual alkali, and Si 3 N4 can increase the uniformity of the coating layer and enhance the protective effect of the coating layer; the Si 3 N 4 coating layer is non-conductive, and the Li 2 SiO 3 /LiF composite coating layer has lithium ion conductivity.
  • the synergistic effect of the two can enhance the strength of the material without reducing the lithium ion conductivity of the material.
  • This embodiment prepares a coated ternary positive electrode material, and the specific process is as follows:
  • step (3) maintaining the temperature of step (2), introducing ammonia gas into the tube furnace at a gas flow rate of 0.1 L/min and a reaction time of 0.5 h;
  • Si 3 N 4 is deposited on the surface of the positive electrode material to form a uniform coating layer.
  • the mass of the Si 3 N 4 coating layer is 1% of the mass of the high-nickel ternary positive electrode material.
  • This embodiment prepares a coated ternary positive electrode material, and the specific process is as follows:
  • step (3) maintaining the temperature of step (2), introducing ammonia gas into the tube furnace at a gas flow rate of 0.05 L/min and a reaction time of 0.5 h;
  • Si 3 N 4 is deposited on the surface of the positive electrode material to form a uniform coating layer.
  • the mass of the Si 3 N 4 coating layer is 0.5% of the mass of the high-nickel ternary positive electrode material.
  • This embodiment prepares a coated ternary positive electrode material, and the specific process is as follows:
  • step (3) maintaining the temperature of step (2), introducing ammonia gas into the tube furnace at a gas flow rate of 0.01 L/min and a reaction time of 2 h;
  • Si 3 N 4 is deposited on the surface of the positive electrode material to form a uniform coating layer.
  • the mass of the Si 3 N 4 coating layer is 0.2% of the mass of the high-nickel ternary positive electrode material.
  • This comparative example prepares a low residual alkali ternary positive electrode material.
  • the difference from Example 1 is that the residual alkali on the surface of the high nickel ternary material LiNi 0.8 Co 0.1 Mn 0.1 O 2 is directly removed by water washing.
  • the specific process is:
  • the ternary material is separated from the water by filtration and dried in vacuum at 100° C. for 4 h to obtain the washed low residual alkali ternary positive electrode material.
  • This embodiment prepares a coated ternary positive electrode material, and the specific process is as follows:
  • This embodiment prepares a coated ternary cathode material.
  • the difference from the embodiment 1 is that ammonia gas is not introduced into the reaction.
  • the specific process is as follows:
  • a protective gas is introduced into the tube furnace to completely expel oxygen, the temperature is raised to 600°C at a rate of 10°C/min, and silicon tetrafluoride gas is introduced at a flow rate of 0.15 L/min.
  • the reaction time is 2 h;
  • LiNi 0.8 Co 0.1 Mn 0.1 O 2 containing a Li 2 SiO 3 /LiF composite coating layer was obtained.
  • the materials prepared in the embodiments and comparative examples were made into positive electrode sheets: high-nickel ternary materials, binder PVDF, and conductive agent SP were dissolved in NMP at a mass ratio of 8:1:1, stirred to form a slurry, coated the slurry on aluminum foil, dried, assembled into button batteries, and subjected to charge, discharge and cycle tests.
  • the results are shown in Table 1.
  • Comparative Example 1 As can be seen from Table 1, the residual lithium in Comparative Example 1 is similar to that in Example 1, but the discharge capacity and cycle performance are lower than those in Example 1. This is because Comparative Example 1 uses a water washing method to remove residual lithium, and the material structure is damaged to a certain extent after water washing, resulting in a decrease in material capacity and cycle performance. The discharge capacity and cycle performance of Comparative Example 2 are also lower than those in Example 1. This is because Comparative Example 2 uses solid phase coating, and the surface uniformity of the coating layer is poor, which cannot completely block the contact between the material and H2O and CO2 in the air. Comparative Example 3 introduces silicon tetrafluoride gas to react with residual alkali, achieving a good effect of reducing residual alkali, but due to When not coated with silicon nitride, the electrochemical performance is still inferior to that of Example 1.

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

Abstract

本公开属于锂离子电池正极材料技术领域，公开了一种包覆型正极材料及其制备方法和应用，本公开利用四氟化硅气体与正极材料表面残碱成分发生反应，在正极材料表面形成Li2SiO3/LiF复合包覆层，再通入氨气使反应装置内残余的四氟化硅气体与氨气发生反应生成氮化硅，经冷却后沉积到正极材料表面形成Si3N4包覆层。

Description

包覆型正极材料及其制备方法和应用 技术领域
本公开属于锂离子电池正极材料技术领域，具体涉及一种包覆型正极材料及其制备方法和应用。
背景技术
随着对节能环保的追求，新能源汽车迅速成为汽车市场热点，锂离子电池因其高的能量密度、较长的循环寿命、环境友好等优点而成为新能源行业的研究热点。正极材料是锂离子电池的核心，对锂离子电池的能量密度起决定性作用。
镍钴锰酸锂三元正极材料具有比容量高、能量密度高、价格低、环境友好等优点，高镍三元材料放电容量可达到200mAh/g以上，但由于镍离子较易被还原而进入锂层，会产生严重的离子混排现象，锂容易析出，且在烧结时多加入的锂盐也会以氧化物的形式残留在材料表面。
残锂对水分非常敏感，易于吸收空气中的水和二氧化碳，生成氢氧化锂和碳酸锂，使材料表面劣化。材料过高的残锂在电池制作的匀浆、涂布过程中料浆极易形成果冻状，导致涂布不均匀，容易造成电极生产难度大、容量衰减等问题。而且残锂导电性很差，会阻碍锂离子的脱嵌，造成电极的极化。残碱在高温下易与电解液发生反应生成气体，导致电池胀气，带来严重的安全隐患。因此，高镍三元正极材料对储存条件和后续加工条件要求更为严格。
为解决上述问题，一般采用水洗或表面包覆的方法对高镍材料进行处理，减少残碱的产生。但水洗需要消耗大量的水资源，与高镍三元正极材料发生反应，会导致锂的损失，破坏材料结构，最终导致材料容量下降。而固相包覆表面均匀性差，无法完全阻隔材料与空气中H2O和CO2的接触。
中国专利CN108807969A公开了一种降低锂离子电池层状正极材料表面残碱的方法，该发明通过水洗降低表面残碱，再通过醇洗快速去除残留表面的水分，然后通过添加纳 米氧化锆烧结稳定表面结构。该发明有效的减少了正极材料的表面残碱。但是，水洗之后材料结构被破坏，尽管通过添加纳米氧化锆稳定表面结构，但水洗过程中锂流失量仍然很多。
发明内容
本公开旨在至少解决上述现有技术中存在的技术问题之一。为此，本公开提出一种包覆型正极材料及其制备方法和应用。
根据本公开的一个方面，提出了一种包覆型正极材料的制备方法，包括以下步骤：
将正极材料置于反应装置内，先通入四氟化硅气体加热反应，再通入氨气加热反应，反应结束后冷却，即得所述包覆型正极材料。
本公开利用四氟化硅气体与正极材料表面残碱成分(Li2CO3和LiOH)发生反应，在正极材料表面形成Li2SiO3/LiF复合包覆层，再通入氨气使反应装置内残余的四氟化硅气体与氨气发生反应生成氮化硅，经冷却后沉积到正极材料表面，反应式如下：
SiF4+6LiOH＝＝Li2SiO3+4LiF+3H2O；
SiF4+2Li2CO3+2H2O＝＝H4SiO4+4LiF+2CO2；
3SiF4+4NH3＝＝Si3N4+12HF。
在本公开的一些实施方式中，所述正极材料为高镍三元正极材料或磷酸铁锂材料。
在本公开的一些实施方式中，所述高镍三元正极材料的化学式为LiNixCoyMnzO2，0.7≤x≤0.9，0.05≤y≤0.15，0.05≤z≤0.15，且x+y+z＝1。
在本公开的一些实施方式中，所述正极材料的平均粒径D50为2-15μm。
在本公开的一些实施方式中，通入所述四氟化硅气体加热反应的温度为500-600℃。
在本公开的一些实施方式中，所述四氟化硅气体通入的流量为0.05-0.15L/min。
在本公开的一些实施方式中，通入所述四氟化硅气体加热反应的时间为2-4h。
在本公开的一些实施方式中，所述反应装置为管式炉；所述正极材料在所述反应装置中的装填体积比为5％-15％。
在本公开的一些实施方式中，将所述正极材料置于反应装置后，先通入保护性气体 将氧气排出，以2-10℃/min的速率升温至反应温度，再通入所述四氟化硅气体进行反应。
在本公开的一些实施方式中，通入所述氨气加热反应的温度为500-600℃。
在本公开的一些实施方式中，所述氨气通入的流量为0.01-0.1L/min。
在本公开的一些实施方式中，通入所述氨气加热反应的时间为0.5-2h。通过控制氨气通入的流量及反应时间控制Si3N4包覆层的量。
本公开还提供一种包覆型正极材料，由所述的制备方法制得，所述包覆型正极材料由内至外依次包覆有Li2SiO3/LiF复合包覆层和Si3N4包覆层。
在本公开的一些实施方式中，所述Si3N4包覆层的包覆量为所述正极材料质量的0.2％-1％。
本公开还提供所述的包覆型正极材料在锂离子电池中的应用。
本公开至少具有以下有益效果：
1、本公开采用气相包覆的方式，将SiF4与正极材料的表面充分接触，SiF4不会对三元材料结构造成损坏，与残碱成分(Li2CO3和LiOH)发生反应，既能够降低材料表面的残碱量，又不会造成锂的损失，形成导电的Li2SiO3/LiF复合包覆层。残碱完全反应后，通入NH3与残余的SiF4发生反应，生成的Si3N4沉积到正极材料表面，使包覆层更均匀、完整，进而提高正极材料的循环寿命、循环稳定性和安全性。
2、通过气固反应，避免了液体浸泡对正极材料结构造成的破坏及锂的流失，也可有效避免固相研磨不均匀问题，气固接触使该方法残碱去除得更完全，得到的包覆层均匀度高，可避免正极材料与电解液的直接接触，Si3N4具有硬度大、耐磨损、耐腐蚀、热稳定性高等特征，作为包覆层能够有效增强正极材料的强度，稳定材料结构。
3、Li2SiO3/LiF复合包覆层是在残碱处选择性生成，Si3N4能增加包覆层的均匀性，并且加强包覆层的保护作用；Si3N4包覆层不导电，Li2SiO3/LiF复合包覆层具有锂离子导电性，两者协同作用能够在增强材料强度的同时不降低材料的锂离子导电性。
具体实施方式
以下将结合实施例对本公开的构思及产生的技术效果进行清楚、完整地描述，以充 分地理解本公开的目的、特征和效果。
实施例1
本实施例制备了一种包覆型三元正极材料，具体过程为：
(1)将1kg平均粒径D50为10μm的高镍三元正极材料LiNi0.8Co0.1Mn0.1O2粉末置于管式炉中；
(2)往管式炉内通入保护性气体以使氧气完全排出，以10℃/min的速率升温至600℃，再通入四氟化硅气体，通入气体的流量为0.15L/min，反应时间为2h，残碱转化为Li2SiO3/LiF复合包覆层；
(3)维持步骤(2)的温度，往管式炉内通入氨气，气体的流量为0.1L/min，反应时间为0.5h；
(4)自然冷却至室温后，Si3N4沉积到正极材料表面，形成均匀的包覆层，Si3N4包覆层的质量为高镍三元正极材料质量的1％。
实施例2
本实施例制备了一种包覆型三元正极材料，具体过程为：
(1)将1kg平均粒径D50为2.7μm的高镍三元正极材料LiNi0.7Co0.1Mn0.2O2粉末置于管式炉中；
(2)往管式炉内通入保护性气体以使氧气完全排出，以5℃/min的速率升温至550℃，再通入四氟化硅气体，通入气体的流量为0.1L/min，反应时间为2.5h，残碱转化为Li2SiO3/LiF复合包覆层；
(3)维持步骤(2)的温度，往管式炉内通入氨气，气体的流量为0.05L/min，反应时间为0.5h；
(4)自然冷却至室温后，Si3N4沉积到正极材料表面，形成均匀的包覆层，Si3N4包覆层的质量为高镍三元正极材料质量的0.5％。
实施例3
本实施例制备了一种包覆型三元正极材料，具体过程为：
(1)将1kg平均粒径D50为14.3μm的高镍三元正极材料LiNi0.9Co0.05Mn0.05O2粉末置于管式炉中；
(2)往管式炉内通入保护性气体以使氧气完全排出，以2℃/min的速率升温至500℃，再通入四氟化硅气体，通入气体的流量为0.05L/min，反应时间为4h，残碱转化为Li2SiO3/LiF复合包覆层；
(3)维持步骤(2)的温度，往管式炉内通入氨气，气体的流量为0.01L/min，反应时间为2h；
(4)自然冷却至室温后，Si3N4沉积到正极材料表面，形成均匀的包覆层，Si3N4包覆层的质量为高镍三元正极材料质量的0.2％。
对比例1
本对比例制备了一种低残碱三元正极材料，与实施例1的区别在于，直接采用水洗的方式去除高镍三元材料LiNi0.8Co0.1Mn0.1O2表面的残碱。具体过程为：
(1)将1kg平均粒径D50为10μm的高镍三元正极材料LiNi0.8Co0.1Mn0.1O2粉末分散至2kg清水中，搅拌清洗10min，搅拌速度为1000r/min，洗涤温度为35℃；
(2)洗涤完成后，将三元材料与水过滤分离，100℃真空干燥4h得到水洗后的低残碱三元正极材料。
对比例2
本实施例制备了一种包覆型三元正极材料，具体过程为：
(1)将1kg平均粒径D50为10μm的高镍三元正极材料LiNi0.8Co0.1Mn0.1O2与10g Al2O3混合研磨；
(2)放入管式炉中煅烧，煅烧温度为600℃，时间为5h；
(3)冷却至室温，研磨得到Al2O3包覆的LiNi0.8Co0.1Mn0.1O2。
对比例3
本实施例制备了一种包覆型三元正极材料，与实施例1的区别在于，不通入氨气反应，具体过程为：
(1)将1kg平均粒径D50为10μm的高镍三元正极材料LiNi0.8Co0.1Mn0.1O2粉末置于管式炉中；
(2)往管式炉内通入保护性气体以使氧气完全排出，以10℃/min的速率升温至600℃，再通入四氟化硅气体，通入气体的流量为0.15L/min，反应时间为2h；
(3)自然冷却至室温后，得到含Li2SiO3/LiF复合包覆层的LiNi0.8Co0.1Mn0.1O2。
试验例
1、对实施例和对比例所得高镍三元正极材料的残锂进行检测，结果如表1所示。
2、为检测高镍三元正极材料的电化学性能，将实施例和对比例制得的材料制成正极片：将高镍三元材料、粘结剂PVDF、导电剂SP按8:1:1的质量比溶于NMP中，搅拌形成浆料，将浆料涂布在铝箔上，烘干，组装成扣式电池，进行充放电和循环测试，结果如表1所示。
表1实施例和对比例的残锂和电化学性能测试
由表1可见，对比例1的残锂与实施例1差不多，但放电容量和循环性能低于实施例1，这是由于对比例1采用水洗法除残锂，水洗之后材料结构遭到一定破坏，导致材料容量和循环性能下降。对比例2的放电容量和循环性能较实施例1也有一定降低，这是由于对比例2采用固相包覆，包覆层表面均匀性差，无法完全阻隔材料与空气中H2O和CO2的接触。对比例3通入四氟化硅气体与残碱反应，达到很好的降残碱效果，但由 于未包覆氮化硅，其电化学性能仍然不如实施例1。

Claims (15)

  1. 一种包覆型正极材料的制备方法，其特征在于，包括以下步骤：
    将正极材料置于反应装置内，先通入四氟化硅气体加热反应，再通入氨气加热反应，反应结束后冷却，即得所述包覆型正极材料。
  2. 根据权利要求1所述的制备方法，其特征在于，所述正极材料为高镍三元正极材料或磷酸铁锂材料。
  3. 根据权利要求2所述的制备方法，其特征在于，所述高镍三元正极材料的化学式为LiNixCoyMnzO2，0.7≤x≤0.9，0.05≤y≤0.15，0.05≤z≤0.15，且x+y+z＝1。
  4. 根据权利要求1所述的制备方法，其特征在于，所述正极材料的平均粒径D50为2-15μm。
  5. 根据权利要求1所述的制备方法，其特征在于，通入所述四氟化硅气体加热反应的温度为500-600℃。
  6. 根据权利要求1所述的制备方法，其特征在于，所述四氟化硅气体通入的流量为0.05-0.15L/min。
  7. 根据权利要求1所述的制备方法，其特征在于，通入所述四氟化硅气体加热反应的时间为2-4h。
  8. 根据权利要求1所述的制备方法，其特征在于，所述反应装置为管式炉；所述正极材料在所述反应装置中的装填体积比为5％-15％。
  9. 根据权利要求1所述的制备方法，其特征在于，将所述正极材料置于反应装置后，先通入保护性气体将氧气排出，以2-10℃/min的速率升温至反应温度，再通入所述四氟化硅气体进行反应。
  10. 根据权利要求1所述的制备方法，其特征在于，通入所述氨气加热反应的温度为500-600℃。
  11. 根据权利要求1所述的制备方法，其特征在于，所述氨气通入的流量为0.01-0.1L/min。
  12. 根据权利要求1所述的制备方法，其特征在于，通入所述氨气加热反应的时间为0.5-2h。
  13. 一种包覆型正极材料，其特征在于，由权利要求1-12所述的制备方法制得，所述包覆型正极材料由内至外依次包覆有Li2SiO3/LiF复合包覆层和Si3N4包覆层。
  14. 根据权利要求13所述的包覆型正极材料，其特征在于，所述Si3N4包覆层的包覆量为所述正极材料质量的0.2％-1％。
  15. 如权利要求13所述的包覆型正极材料在锂离子电池中的应用。
PCT/CN2023/092282 2023-05-05 2023-05-05 包覆型正极材料及其制备方法和应用 Ceased WO2024229596A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202380009468.4A CN116848662B (zh) 2023-05-05 2023-05-05 包覆型正极材料及其制备方法和应用
PCT/CN2023/092282 WO2024229596A1 (zh) 2023-05-05 2023-05-05 包覆型正极材料及其制备方法和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2023/092282 WO2024229596A1 (zh) 2023-05-05 2023-05-05 包覆型正极材料及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2024229596A1 true WO2024229596A1 (zh) 2024-11-14

Family

ID=88169293

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/092282 Ceased WO2024229596A1 (zh) 2023-05-05 2023-05-05 包覆型正极材料及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN116848662B (zh)
WO (1) WO2024229596A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119400868B (zh) * 2024-10-29 2026-01-13 蜂巢能源科技股份有限公司 一种高镍正极活性材料的浆料及其制备方法与应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104505505A (zh) * 2014-12-04 2015-04-08 中国科学院大学 硅酸锂包覆锂离子电池三元层状正极材料的制备方法
KR20150069335A (ko) * 2013-12-13 2015-06-23 삼성정밀화학 주식회사 양극 활물질의 제조 방법, 이 방법에 따라 제조된 양극 활물질 및 이를 포함하는 리튬 이차 전지
CN107732199A (zh) * 2017-10-11 2018-02-23 中国科学院过程工程研究所 一种含氟锂离子电池正极材料及其制备方法
CN111063866A (zh) * 2018-10-16 2020-04-24 中国科学院宁波材料技术与工程研究所 一种复合材料及其制备方法
CN114023936A (zh) * 2021-10-29 2022-02-08 格林美股份有限公司 氮化物/石墨化碳纳米片包覆三元正极材料及其制备方法
CN114864886A (zh) * 2022-04-02 2022-08-05 万华化学集团股份有限公司 一种正极材料及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105336927B (zh) * 2015-09-28 2017-10-24 深圳市贝特瑞新能源材料股份有限公司 一种改性超疏水材料包覆的锂离子电池高镍正极材料及其制备方法
CN115692601B (zh) * 2022-11-14 2023-11-07 深圳市原速光电科技有限公司 一种锂离子电池及其具有多功能保护层的正极极片

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150069335A (ko) * 2013-12-13 2015-06-23 삼성정밀화학 주식회사 양극 활물질의 제조 방법, 이 방법에 따라 제조된 양극 활물질 및 이를 포함하는 리튬 이차 전지
CN104505505A (zh) * 2014-12-04 2015-04-08 中国科学院大学 硅酸锂包覆锂离子电池三元层状正极材料的制备方法
CN107732199A (zh) * 2017-10-11 2018-02-23 中国科学院过程工程研究所 一种含氟锂离子电池正极材料及其制备方法
CN111063866A (zh) * 2018-10-16 2020-04-24 中国科学院宁波材料技术与工程研究所 一种复合材料及其制备方法
CN114023936A (zh) * 2021-10-29 2022-02-08 格林美股份有限公司 氮化物/石墨化碳纳米片包覆三元正极材料及其制备方法
CN114864886A (zh) * 2022-04-02 2022-08-05 万华化学集团股份有限公司 一种正极材料及其制备方法

Also Published As

Publication number Publication date
CN116848662B (zh) 2025-11-14
CN116848662A (zh) 2023-10-03

Similar Documents

Publication Publication Date Title
CN109768231B (zh) 一种单晶型高镍三元正极材料及其制备方法
KR102811223B1 (ko) 페로보론 합금 코팅 리튬인산철의 제조 방법
CN108767226B (zh) 一种金属酞菁化合物包覆的三元正极材料及其制备方法
CN1595689A (zh) 锰系正极材料及其制备与用途
CN109449429B (zh) 一种磷酸铁锂/碳化硅复合型材料及其制备方法
CN110233249A (zh) 磷酸铁锂纳米粉末包覆高镍三元正极材料及其制备方法和应用
CN105914358A (zh) 蛋黄-蛋壳结构氮掺杂碳包覆四氧化三铁@二氧化锡磁性纳米盒子的制备方法
CN113809319B (zh) 一种高性能动力电池镍钴锰酸锂正极材料及其制备方法
CN107946578B (zh) 一种钴酸锂包覆的镍钴铝酸锂正极材料及其制备方法
CN108987683A (zh) 一种碳包覆三元正极材料的制备方法
CN111952554A (zh) 一种锂离子电池三元正极材料及其制备方法
CN111081994A (zh) 一种表面修饰的富锂层状过渡金属氧化物及其制备方法和应用
CN115504524B (zh) 一种单晶高镍材料及其制备方法和应用
CN108417796A (zh) 一种低表面碱性的镍钴铝酸锂正极材料及其制备方法
CN118289724B (zh) 一种磷酸预处理与离子掺杂共改性磷酸铁锂正极材料的制备方法
CN106099092A (zh) 一种用于锂离子电池负极材料的钒酸铜的制备方法
CN116848662B (zh) 包覆型正极材料及其制备方法和应用
CN107749478A (zh) 一种锰酸锂‑三元动力锂离子电池
CN107749465A (zh) 一种磷酸铁锂‑ncm三元材料动力锂离子电池
CN117832427B (zh) 一种磷酸铁锂复合材料的制备方法和应用
CN120015811A (zh) 硅酸铋包覆的磷酸铁锰锂材料及其制备方法、锂离子电池
CN113666432A (zh) 碳包覆的镍锰二元无钴正极材料、其制备方法及锂离子电池
CN115367723B (zh) 一种LiFe2F6包覆磷酸铁锂正极材料的制备方法
CN102891310A (zh) 钛硅碳改性的锂离子电池三元正极材料及其制备方法
CN115010181B (zh) 一种富锂锰基正极材料及其改性方法和应用

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 202380009468.4

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23935925

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23935925

Country of ref document: EP

Kind code of ref document: A1