WO2025000367A1 - 一种正极材料及其制备方法和应用 - Google Patents

一种正极材料及其制备方法和应用 Download PDF

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WO2025000367A1
WO2025000367A1 PCT/CN2023/103984 CN2023103984W WO2025000367A1 WO 2025000367 A1 WO2025000367 A1 WO 2025000367A1 CN 2023103984 W CN2023103984 W CN 2023103984W WO 2025000367 A1 WO2025000367 A1 WO 2025000367A1
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positive electrode
electrode material
preparing
material according
rgo
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French (fr)
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李爱霞
余海军
谢英豪
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202380010053.9A priority Critical patent/CN117083733B/zh
Priority to PCT/CN2023/103984 priority patent/WO2025000367A1/zh
Publication of WO2025000367A1 publication Critical patent/WO2025000367A1/zh
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    • 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

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  • the present invention belongs to the technical field of positive electrode materials, and in particular relates to a positive electrode material and a preparation method and application thereof.
  • the main commercial cathode materials for lithium-ion batteries include lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, and nickel cobalt manganese oxide.
  • lithium cobalt oxide has a high cost and poses a safety hazard when overcharged; layered lithium manganese oxide has poor structural stability, spinel lithium manganese oxide has a low specific capacity, and its structural stability at high temperatures needs to be improved.
  • Lithium iron phosphate has poor processing performance, low tap density, and low energy density; in contrast, nickel cobalt manganese oxide materials have the advantages of low cost, good high temperature performance, high energy density, and excellent processing performance, and are therefore used in large quantities and widely.
  • the present disclosure aims to solve at least one of the technical problems existing in the related art.
  • the present disclosure provides a positive electrode material and a preparation method and application thereof, the positive electrode material having good high rate performance and cycle stability, and being able to meet the increasingly high technical requirements of existing lithium ion batteries.
  • a positive electrode material comprises a core and a wrapping layer, wherein the wrapping layer is wrapped on the core, the core comprises a nickel cobalt lithium manganese oxide material, and the wrapping layer comprises a MOFs material and a V 2 O 5 /rGO material.
  • the molecular formula of the lithium nickel cobalt manganese oxide material is LiNi x Co y Mn 1-xy O 2 , 1>x ⁇ 0.8, y ⁇ 0 and 1-xy>0.
  • the mass ratio of the core to the wrapping layer is 1:(0.15-0.25).
  • the mass ratio of V 2 O 5 /rGO material to MOFs material in the encapsulating layer is 1:(0.01-0.1).
  • a method for preparing the positive electrode material as described above comprises the following steps:
  • step (2) (2) soaking the V 2 O 5 /rGO material obtained in step (1) in a MOFs generation solution, taking it out, and heating it to generate MOFs material on the surface and inside of the V 2 O 5 /rGO material, thereby obtaining a coating layer material;
  • step (3) The coating layer material obtained in step (2) is mixed with lithium nickel cobalt manganese oxide and heated to obtain the positive electrode material.
  • the vanadium source is at least one of ammonium vanadate, vanadium acetylacetonate and vanadyl acetylacetonate.
  • the acid is at least one of oxalic acid and citric acid.
  • the surfactant is at least one of hexamethylenetetramine and dodecyl alcohol amide.
  • step (1) the molar ratio of the vanadium source, the acid and the surfactant is 1:1:(0.1-0.5).
  • the mass of rGO added is 1.5-3 times the mass of the vanadium source.
  • the stirring speed in the stirring state is 600-1000 r/min.
  • step (1) the temperature of the temperature-raising reaction is 300-350° C., and the reaction time is 10-20 hours.
  • step (1) the sintering is performed by heating the temperature to 600-800° C. at a rate of 15-20° C./min and sintering for 3-5 hours.
  • the MOFs generating solution in step (2) is prepared by dissolving Cr(NO 3 ) 3 and sodium benzoate in methanol in a molar ratio of (3-7):(2-5), and the ratio of Cr(NO 3 ) 3 to methanol is 5g:(50-100)ml.
  • the reaction mechanism is as follows: sodium benzoate is partially protonated in methanol to produce benzoic acid and sodium ions, Cr(NO 3 ) 3 is dissolved in methanol to release Cr 3+ ions and NO 3- ions, Cr 3+ ions react with benzoic acid to form a Cr-benzoic acid complex, and Cr- The benzoic acid complexes formed crystal nuclei and gradually grew to form MOFs.
  • step (2) the soaking time is 6-12 hours.
  • the heating temperature is 130-160° C.
  • the heating time is 12-24 hours.
  • the heating temperature is 100-200° C.
  • the heating time is 2-12 hours.
  • a lithium ion battery comprises the positive electrode material as described above.
  • the coating layer of the positive electrode material of the present disclosure is formed by mixing MOFs material and V 2 O 5 /rGO material;
  • the MOFs material has the advantages of high porosity, low density, large specific surface area, regular pores, adjustable pore size, topological structure diversity and tailorability;
  • the V 2 O 5 /rGO material is modified by MOFs material to expand the specific surface area of the V 2 O 5 /rGO material, improve its spatial structure, and promote the insertion/extraction of lithium ions;
  • the MOFs material is loaded on the surface and inside of the V 2 O 5 /rGO material, the conductivity and stability of the MOFs material are promoted, so that the surface coating layer of the positive electrode material of the present disclosure can avoid direct contact between the ternary nickel cobalt manganese oxide material as the core and the electrolyte, reducing the occurrence of side reactions; at the same time, the surface coating layer significantly improves the high rate performance and cycle stability of the ternary nickel co
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • a positive electrode material comprises a core and a wrapping layer, wherein the wrapping layer is wrapped on the core, the core is a nickel cobalt manganese oxide material, the wrapping layer is a mixture of MOFs material and V 2 O 5 /rGO material, the molecular formula of the nickel cobalt manganese oxide material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 , the mass ratio of the core to the wrapping layer is 1:0.15, and the mass ratio of the V 2 O 5 /rGO material to the MOFs material in the wrapping layer is 1:0.01.
  • the method for preparing the above-mentioned positive electrode material comprises the following steps:
  • ammonium vanadate, oxalic acid and hexamethylenetetramine were dissolved in water at a molar ratio of 1:1:0.1, rGO was added, the mass of the added rGO was 1.5 times the mass of the ammonium vanadate, the mixture was stirred at a speed of 600 r/min, the temperature was raised to 300°C under stirring, the reaction was carried out for 20 h, the precipitate was washed with water, dried, the temperature was raised to 600°C at a rate of 15°C/min, sintered for 3 h, and cooled to obtain V 2 O 5 /rGO material;
  • step (2) The coating material prepared in step (2) is mixed with lithium nickel cobalt manganese oxide having a molecular formula of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and heated at 100° C. for 12 h to obtain a positive electrode material.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • a positive electrode material comprises a core and a wrapping layer, wherein the wrapping layer is wrapped on the core, the core is a nickel cobalt manganese oxide material, the wrapping layer is a mixture of MOFs material and V 2 O 5 /rGO material, the molecular formula of the nickel cobalt manganese oxide material is LiNi 0.9 Co 0.05 Mn 0.05 O 2 , the mass ratio of the core to the wrapping layer is 1:0.25, and the mass ratio of the V 2 O 5 /rGO material to the MOFs material in the wrapping layer is 1:0.1.
  • the method for preparing the above-mentioned positive electrode material comprises the following steps:
  • ammonium vanadate, oxalic acid and hexamethylenetetramine were dissolved in water at a molar ratio of 1:1:0.5, rGO was added, and the mass of the added rGO was 3 times the mass of the ammonium vanadate, and the mixture was stirred at a speed of 1000 r/min, heated to 350°C under stirring for 10 h, and the precipitate was washed with water, dried, and heated to 800°C at a rate of 20°C/min, sintered for 5 h, and cooled to obtain V 2 O 5 /rGO material;
  • step (3) The coating layer material prepared in step (2) is mixed with lithium nickel cobalt manganese oxide having a molecular formula of LiNi 0.9 Co 0.05 Mn 0.05 O 2 , and heated at a temperature of 200° C. for 2 h to obtain a positive electrode material.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • a positive electrode material comprises a core and a wrapping layer, wherein the wrapping layer is wrapped on the core, the core is a nickel cobalt manganese oxide material, the wrapping layer is a mixture of MOFs material and V 2 O 5 /rGO material, the molecular formula of the nickel cobalt manganese oxide material is LiNi 0.9 Co 0.05 Mn 0.05 O 2 , the mass ratio of the core to the wrapping layer is 1:0.2, and the mass ratio of the V 2 O 5 /rGO material to the MOFs material in the wrapping layer is 1:0.05.
  • the method for preparing the above-mentioned positive electrode material comprises the following steps:
  • step (3) The coating layer material prepared in step (2) is mixed with lithium nickel cobalt manganese oxide having a molecular formula of LiNi 0.9 Co 0.05 Mn 0.05 O 2 , and heated at a temperature of 150° C. for 8 h to obtain a positive electrode material.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • a positive electrode material comprises a core and a wrapping layer, wherein the wrapping layer is wrapped on the core, the core is a nickel cobalt manganese oxide material, the wrapping layer is a mixture of MOFs material and V 2 O 5 /rGO material, the molecular formula of the nickel cobalt manganese oxide material is LiNi 0.9 Co 0.05 Mn 0.05 O 2 , the mass ratio of the core to the wrapping layer is 1:0.18, and the mass ratio of V 2 O 5 /rGO material to MOFs material in the wrapping layer is 1:0.06.
  • the method for preparing the above-mentioned positive electrode material comprises the following steps:
  • Vanadyl acetylacetonate, citric acid and dodecyl alcohol amide were dissolved in water at a molar ratio of 1:1:0.3, rGO was added, and the mass of the added rGO was 1.6 times the mass of the vanadyl acetylacetonate, and the mixture was stirred at a speed of 800 r/min, heated to 320°C under stirring for 15 h, washed with water, dried, heated to 700°C at a rate of 18°C/min, sintered for 4 h, and cooled to obtain V 2 O 5 /rGO material;
  • step (3) The coating layer material prepared in step (2) is mixed with lithium nickel cobalt manganese oxide having a molecular formula of LiNi 0.9 Co 0.05 Mn 0.05 O 2 , and heated at a temperature of 150° C. for 8 h to obtain a positive electrode material.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • a positive electrode material comprises a core and a coating layer, wherein the coating layer is coated on the core, the core is a nickel cobalt manganese oxide material, the coating layer is a mixture of MOFs material and V 2 O 5 /rGO material, the molecular formula of the nickel cobalt manganese oxide material is LiNi 0.9 Co 0.05 Mn 0.05 O 2 , the mass ratio of the core to the coating layer is 1:0.16, and the coating layer is The mass ratio of V 2 O 5 /rGO material to MOFs material is 1:0.03.
  • the method for preparing the above-mentioned positive electrode material comprises the following steps:
  • Vanadium acetylacetonate, citric acid and hexamethylenetetramine were dissolved in water at a molar ratio of 1:1:0.2, rGO was added, and the mass of the added rGO was 1.8 times the mass of the vanadium acetylacetonate, and the mixture was stirred at a speed of 800 r/min, heated to 320°C under stirring for 15 h, washed with water, dried, heated to 700°C at a rate of 18°C/min, sintered for 4 h, and cooled to obtain V 2 O 5 /rGO material;
  • step (3) The coating layer material prepared in step (2) is mixed with lithium nickel cobalt manganese oxide having a molecular formula of LiNi 0.9 Co 0.05 Mn 0.05 O 2 , and heated at a temperature of 150° C. for 8 h to obtain a positive electrode material.
  • Comparative Example 1 (Compared with Example 3, the only difference is that the encapsulation layer does not contain MOFs material)
  • a positive electrode material comprises a core and a wrapping layer, wherein the wrapping layer is wrapped on the core, the core is a nickel cobalt manganese oxide material, the wrapping layer is a V 2 O 5 /rGO material, the molecular formula of the nickel cobalt manganese oxide material is LiNi 0.9 Co 0.05 Mn 0.05 O 2 , the mass ratio of the core to the wrapping layer is 1:0.2, and the mass ratio of the V 2 O 5 /rGO material to the MOFs material in the wrapping layer is 1:0.05.
  • the method for preparing the above-mentioned positive electrode material comprises the following steps:
  • ammonium vanadate, oxalic acid and hexamethylenetetramine were dissolved in water at a molar ratio of 1:1:0.4, rGO was added, and the mass of the added rGO was twice the mass of the ammonium vanadate, and the mixture was stirred at a speed of 800 r/min, heated to 320°C under stirring for 15 h, and the precipitate was washed with water, dried, and heated to 700°C at a rate of 18°C/min, sintered for 4 h, and cooled to obtain V 2 O 5 /rGO material;
  • V 2 O 5 /rGO material prepared in step (1) is mixed with lithium nickel cobalt manganese oxide having a molecular formula of LiNi 0.9 Co 0.05 Mn 0.05 O 2 , and heated at 150° C. for 8 h to obtain a positive electrode material.
  • the lithium sheet was used as the negative electrode sheet, and a CR2430 button half-cell was assembled in an inert gas glove box, and the battery was tested for performance.
  • the test results are shown in Table 1.
  • the 0.1C gram capacity of the lithium battery made of the positive electrode material disclosed in the present invention can reach more than 199.56 mAh/g, the rate performance at 0.5C/0.1C can reach more than 90.39%, the rate performance at 1C/0.1C can reach more than 82.28%, the rate performance at 2C/0.1C can reach more than 70.11%, and the capacity retention rate after 100 cycles can reach more than 90.23%.
  • Example 3 In addition, by comparing Example 3 with Comparative Example 1, it can be seen that when the encapsulation layer does not contain MOFs material, the rate performance and 100 cycle capacity retention rate of the final battery will be significantly reduced. By comparing Example 3 with Comparative Example 2, it can be seen that the lithium battery made of the positive electrode material disclosed in the present invention has better high rate performance and cycle stability than the lithium battery made of a single ternary lithium cobalt manganese oxide material.

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Abstract

本公开公开了一种正极材料，该正极材料包括芯核及包裹层，包裹层包裹在芯核上，芯核包括镍钴锰酸锂材料，包裹层包括MOFs材料与V2O5/rGO材料。

Description

一种正极材料及其制备方法和应用 技术领域
本公开属于正极材料技术领域，特别涉及一种正极材料及其制备方法和应用。
背景技术
商品化的锂离子电池正极材料主要有钴酸锂、锰酸锂、磷酸铁锂以及镍钴锰酸锂等，其中钴酸锂成本较高，过充电时，存在安全隐患；层状锰酸锂结构稳定性差，尖晶石型锰酸锂比容量低，高温下结构稳定性有待提高。磷酸铁锂加工性能差、振实密度低、能量密度低；相比之下，镍钴锰酸锂材料具有成本低、高温性能好、能量密度高以及加工性能优良等优点，进而被大量和广泛的使用。但是在使用过程中，发现镍钴锰酸锂材料的高倍率性能和循环稳定性相对于钴酸锂较差。因此，亟需改善现有钴锰酸锂材料的电化学性能来满足锂离子电池越来越高的技术要求。
发明内容
本公开旨在至少解决相关技术中存在的技术问题之一。为此，本公开提出一种正极材料及其制备方法和应用，该正极材料具有较好的高倍率性能和循环稳定性，能满足现有锂离子电池越来越高的的技术要求。
本公开的上述技术目的是通过以下技术方案得以实现的：
一种正极材料，所述正极材料包括芯核及包裹层，所述包裹层包裹在所述芯核上，所述芯核包括镍钴锰酸锂材料，所述包裹层包括MOFs材料与V2O5/rGO材料。
在一实施例，所述镍钴锰酸锂材料的分子式为LiNixCoyMn1-x-yO2，1＞x≥0.8，y≥0且1-x-y＞0。
在一实施例，所述芯核与所述包裹层的质量比为1：(0.15-0.25)。
在一实施例，所述包裹层中V2O5/rGO材料与MOFs材料质量比为1：(0.01-0.1)。
一种如上所述正极材料的制备方法，包括以下步骤：
(1)将钒源、酸及表面活性剂溶于水中，加入rGO后，搅拌状态下升温反应，洗涤，干燥，烧结，冷却，得到V2O5/rGO材料，表面活性剂能够在水中形成胶束结构，构成一定的界面张力，能够包裹钒源、酸及rGO，使得它们在水中更加均匀地混合，同时升温反应时，可以促进反应的进行，加快V2O5的生成，使反应更加充分，防止V2O5及rGO的不均匀沉淀，使V2O5及rGO混合的更加均匀；
(2)将步骤(1)制到的V2O5/rGO材料放入到MOFs生成溶液中浸泡，取出，加热，使所述V2O5/rGO材料表面及内部生成MOFs材料，制得包裹层材料；
(3)将步骤(2)制到的包裹层材料与镍钴锰酸锂混合，加热，即得所述正极材料。
在一实施例，步骤(1)中，所述钒源为钒酸铵、乙酰丙酮钒及乙酰丙酮氧钒中的至少一种。
在一实施例，步骤(1)中，所述酸为乙二酸及柠檬酸中的至少一种。
在一实施例，步骤(1)中，所述表面活性剂为六次甲基四胺及十二烷基醇酰胺中的至少一种。
在一实施例，步骤(1)中，所述钒源、酸及表面活性剂的摩尔比为1：1：(0.1-0.5)。
在一实施例，步骤(1)中，加入rGO的质量为钒源质量的1.5-3倍。
在一实施例，步骤(1)中，所述搅拌状态下中搅拌速度为600-1000r/min。
在一实施例，步骤(1)中，所述升温反应的温度为300-350℃，反应时间为10-20h。
在一实施例，步骤(1)中，所述烧结是以速率15-20℃/min升温至600-800℃，烧结3-5h。
在一实施例，步骤(2)中所述MOFs生成溶液为将Cr(NO3)3及苯甲酸钠按照摩尔比(3-7)：(2-5)溶于甲醇中制得，Cr(NO3)3与甲醇的配比为5g:(50-100)ml，其反应机理为：苯甲酸钠在甲醇中部分质子化，产生苯甲酸和钠离子，Cr(NO3)3在甲醇中溶解，释放出Cr3+离子和NO3-离子，Cr3+离子与苯甲酸产生配位反应，形成Cr-苯甲酸配合物，Cr- 苯甲酸配合物形成晶体核并逐渐生长，可以形成MOFs。
在一实施例，步骤(2)中，所述浸泡的时间为6-12h。
在一实施例，步骤(2)中，所述加热的温度为130-160℃，加热的时间为12-24h。
在一实施例，步骤(3)中，所述加热的温度为100-200℃，加热的时间为2-12h。
一种锂离子电池，包括如上所述的正极材料。
本公开的有益效果是：本公开的正极材料的包裹层由MOFs材料与V2O5/rGO材料混合而成，MOFs材料具有高孔隙率、低密度、大比表面积、孔道规则、孔径可调以及拓扑结构多样性和可裁剪性等优点，通过MOFs材料对V2O5/rGO材料进行改性，扩大V2O5/rGO材料的比表面积，改进其空间结构，促进锂离子嵌入/脱出，同时由于MOFs材料负载在V2O5/rGO材料表面及内部，促进MOFs材料的导电性与稳定性，从而使得本公开的正极材料的表面包覆层能够避免作为芯核的三元镍钴锰酸锂材料与电解液直接接触，减少了副反应的发生，同时表面包覆层对三元镍钴锰酸锂材料的高倍率性能和循环稳定性能起到显著提升的作用。
具体实施方式
下面结合具体实施例对本公开做进一步的说明。
实施例1：
一种正极材料，包括芯核及包裹层，包裹层包裹在芯核上，芯核为镍钴锰酸锂材料，包裹层由MOFs材料与V2O5/rGO材料混合而成，镍钴锰酸锂材料的分子式为LiNi0.8Co0.1Mn0.1O2，芯核与包裹层的质量比为1：0.15，包裹层中V2O5/rGO材料与MOFs材料质量比为1：0.01。
上述正极材料的制备方法，包括以下步骤：
(1)将钒酸铵、乙二酸及六次甲基四胺以摩尔比1：1：0.1溶于水中，加入rGO，加入的rGO的质量为钒酸铵质量的1.5倍，以600r/min的速度搅拌，搅拌状态下升温至300℃反应20h，用水洗涤沉淀物，干燥，以速率15℃/min升温至600℃，烧结3h，冷却，得到V2O5/rGO材料；
(2)将Cr(NO3)3及苯甲酸钠按照摩尔比3：2溶于甲醇中制得MOFs 生成溶液，Cr(NO3)3与甲醇的配比为5g:50ml，将步骤(1)制到的V2O5/rGO材料放入到MOFs生成溶液中浸泡6h，取出，以130℃的温度加热24h，使V2O5/rGO材料表面及内部生成MOFs材料，制得包裹层材料；
(3)将步骤(2)制到的包裹层材料与分子式为LiNi0.8Co0.1Mn0.1O2的镍钴锰酸锂混合，以100℃的温度加热12h，即得正极材料。
实施例2：
一种正极材料，包括芯核及包裹层，包裹层包裹在芯核上，芯核为镍钴锰酸锂材料，包裹层由MOFs材料与V2O5/rGO材料混合而成，镍钴锰酸锂材料的分子式为LiNi0.9Co0.05Mn0.05O2，芯核与包裹层的质量比为1：0.25，包裹层中V2O5/rGO材料与MOFs材料质量比为1：0.1。
上述正极材料的制备方法，包括以下步骤：
(1)将钒酸铵、乙二酸及六次甲基四胺以摩尔比1：1：0.5溶于水中，加入rGO，加入的rGO的质量为钒酸铵质量的3倍，以1000r/min的速度搅拌，搅拌状态下升温至350℃反应10h，用水洗涤沉淀物，干燥，以速率20℃/min升温至800℃，烧结5h，冷却，得到V2O5/rGO材料；
(2)将Cr(NO3)3及苯甲酸钠按照摩尔比7：5溶于甲醇中制得MOFs生成溶液，Cr(NO3)3与甲醇的配比为5g:100ml，将步骤(1)制到的V2O5/rGO材料放入到MOFs生成溶液中浸泡12h，取出，以160℃的温度加热12h，使V2O5/rGO材料表面及内部生成MOFs材料，制得包裹层材料；
(3)将步骤(2)制到的包裹层材料与分子式为LiNi0.9Co0.05Mn0.05O2的镍钴锰酸锂混合，以200℃的温度加热2h，即得正极材料。
实施例3：
一种正极材料，包括芯核及包裹层，包裹层包裹在芯核上，芯核为镍钴锰酸锂材料，包裹层由MOFs材料与V2O5/rGO材料混合而成，镍钴锰酸锂材料的分子式为LiNi0.9Co0.05Mn0.05O2，芯核与包裹层的质量比为1：0.2，包裹层中V2O5/rGO材料与MOFs材料质量比为1：0.05。
上述正极材料的制备方法，包括以下步骤：
(1)将钒酸铵、乙二酸及六次甲基四胺以摩尔比1：1：0.4溶于水中，加入rGO，加入的rGO的质量为钒酸铵质量的2倍，以800r/min的速度 搅拌，搅拌状态下升温至320℃反应15h，用水洗涤沉淀物，干燥，以速率18℃/min升温至700℃，烧结4h，冷却，得到V2O5/rGO材料；
(2)将Cr(NO3)3及苯甲酸钠按照摩尔比5：4溶于甲醇中制得MOFs生成溶液，Cr(NO3)3与甲醇的配比为5g:80ml，将步骤(1)制到的V2O5/rGO材料放入到MOFs生成溶液中浸泡10h，取出，以150℃的温度加热20h，使V2O5/rGO材料表面及内部生成MOFs材料，制得包裹层材料；
(3)将步骤(2)制到的包裹层材料与分子式为LiNi0.9Co0.05Mn0.05O2的镍钴锰酸锂混合，以150℃的温度加热8h，即得正极材料。
实施例4：
一种正极材料，包括芯核及包裹层，包裹层包裹在芯核上，芯核为镍钴锰酸锂材料，包裹层由MOFs材料与V2O5/rGO材料混合而成，镍钴锰酸锂材料的分子式为LiNi0.9Co0.05Mn0.05O2，芯核与包裹层的质量比为1：0.18，包裹层中V2O5/rGO材料与MOFs材料质量比为1：0.06。
上述正极材料的制备方法，包括以下步骤：
(1)将乙酰丙酮氧钒、柠檬酸及十二烷基醇酰胺以摩尔比1：1：0.3溶于水中，加入rGO，加入的rGO的质量为乙酰丙酮氧钒质量的1.6倍，以800r/min的速度搅拌，搅拌状态下升温至320℃反应15h，用水洗涤沉淀物，干燥，以速率18℃/min升温至700℃，烧结4h，冷却，得到V2O5/rGO材料；
(2)将Cr(NO3)3及苯甲酸钠按照摩尔比5：3溶于甲醇中制得MOFs生成溶液，Cr(NO3)3与甲醇的配比为5g:80ml，将步骤(1)制到的V2O5/rGO材料放入到MOFs生成溶液中浸泡10h，取出，以150℃的温度加热20h，使V2O5/rGO材料表面及内部生成MOFs材料，制得包裹层材料；
(3)将步骤(2)制到的包裹层材料与分子式为LiNi0.9Co0.05Mn0.05O2的镍钴锰酸锂混合，以150℃的温度加热8h，即得正极材料。
实施例5：
一种正极材料，包括芯核及包裹层，包裹层包裹在芯核上，芯核为镍钴锰酸锂材料，包裹层由MOFs材料与V2O5/rGO材料混合而成，镍钴锰酸锂材料的分子式为LiNi0.9Co0.05Mn0.05O2，芯核与包裹层的质量比为1：0.16，包裹层中 V2O5/rGO材料与MOFs材料质量比为1：0.03。
上述正极材料的制备方法，包括以下步骤：
(1)将乙酰丙酮钒、柠檬酸及六次甲基四胺以摩尔比1：1：0.2溶于水中，加入rGO，加入的rGO的质量为乙酰丙酮钒质量的1.8倍，以800r/min的速度搅拌，搅拌状态下升温至320℃反应15h，用水洗涤沉淀物，干燥，以速率18℃/min升温至700℃，烧结4h，冷却，得到V2O5/rGO材料；
(2)将Cr(NO3)3及苯甲酸钠按照摩尔比5：3溶于甲醇中制得MOFs生成溶液，Cr(NO3)3与甲醇的配比为5g:80ml，将步骤(1)制到的V2O5/rGO材料放入到MOFs生成溶液中浸泡10h，取出，以150℃的温度加热20h，使V2O5/rGO材料表面及内部生成MOFs材料，制得包裹层材料；
(3)将步骤(2)制到的包裹层材料与分子式为LiNi0.9Co0.05Mn0.05O2的镍钴锰酸锂混合，以150℃的温度加热8h，即得正极材料。
对比例1：(与实施例3相比，区别仅在于包裹层中不含MOFs材料)
一种正极材料，包括芯核及包裹层，包裹层包裹在芯核上，芯核为镍钴锰酸锂材料，包裹层为V2O5/rGO材料，镍钴锰酸锂材料的分子式为LiNi0.9Co0.05Mn0.05O2，芯核与包裹层的质量比为1：0.2，包裹层中V2O5/rGO材料与MOFs材料质量比为1：0.05。
上述正极材料的制备方法，包括以下步骤：
(1)将钒酸铵、乙二酸及六次甲基四胺以摩尔比1：1：0.4溶于水中，加入rGO，加入的rGO的质量为钒酸铵质量的2倍，以800r/min的速度搅拌，搅拌状态下升温至320℃反应15h，用水洗涤沉淀物，干燥，以速率18℃/min升温至700℃，烧结4h，冷却，得到V2O5/rGO材料；
(2)将步骤(1)制到的V2O5/rGO材料与分子式为LiNi0.9Co0.05Mn0.05O2的镍钴锰酸锂混合，以150℃的温度加热8h，即得正极材料。
对比例2：
称取1kg三元正极活性材料LiNi0.9Co0.05Mn0.05O2，将其置于气流粉碎机中破碎，得到的三元正极材料颗粒的粒径D50＝5μm，将其作为正极材料。
试验例：
分别将实施例1-5及对比例1-2的正极材料作为锂离子电池正极材料，按照质量比正极材料：乙炔黑：聚偏二氟乙烯＝96:5:5比例混合制浆后，均匀涂布至光铝箔上制得正极片。以锂片为负极片，在惰性气体手套箱内组装成CR2430扣式半电池，并对电池进行性能测试，测试结果如表1所示。
表1：电池性能测试结果：
由表1可知，本公开的正极材料制成的锂电池0.1C克容量能达到199.56mAh/g以上，在0.5C/0.1C下的倍率性能能达到90.39％以上，在1C/0.1C下的倍率性能能达到82.28％以上，在2C/0.1C下的倍率性能能达到70.11％以上，100次循环容量保持率能达到90.23％以上。
此外，通过对比实施例3与对比例1可知，当包裹层中不含MOFs材料，最终制得的电池的倍率性能及100次循环容量保持率均会较大幅度下降，通过对比实施例3与对比例2可知，本公开的正极材料制成的锂电池相比单独的三元钴锰酸锂材料制成的锂电池具有更加优异的高倍率性能和循环稳定性能。

Claims (18)

  1. 一种正极材料，其特征在于：所述正极材料包括芯核及包裹层，所述包裹层包裹在所述芯核上，所述芯核包括镍钴锰酸锂材料，所述包裹层包括MOFs材料与V2O5/rGO材料。
  2. 根据权利要求1所述的一种正极材料，其特征在于：所述镍钴锰酸锂材料的分子式为LiNixCoyMn1-x-yO2，1＞x≥0.8，y≥0且1-x-y＞0。
  3. 根据权利要求1所述的一种正极材料，其特征在于：所述芯核与所述包裹层的质量比为1：(0.15-0.25)。
  4. 根据权利要求1所述的一种正极材料，其特征在于：所述包裹层中V2O5/rGO材料与MOFs材料质量比为1：(0.01-0.1)。
  5. 一种如权利要求1至4任一项所述正极材料的制备方法，其特征在于：包括以下步骤：
    (1)将钒源、酸及表面活性剂溶于水中，加入rGO后，搅拌状态下升温反应，洗涤，干燥，烧结，冷却，得到V2O5/rGO材料；
    (2)将步骤(1)制到的V2O5/rGO材料放入到MOFs生成溶液中浸泡，取出，加热，使所述V2O5/rGO材料表面及内部生成MOFs材料，制得包裹层材料；
    (3)将步骤(2)制到的包裹层材料与镍钴锰酸锂混合，加热，即得所述正极材料。
  6. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(1)中，所述钒源为钒酸铵、乙酰丙酮钒及乙酰丙酮氧钒中的至少一种。
  7. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(1)中，所述酸为乙二酸及柠檬酸中的至少一种。
  8. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(1)中，所述表面活性剂为六次甲基四胺及十二烷基醇酰胺中的至少一种。
  9. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(1)中，所述钒源、酸及表面活性剂的摩尔比为1：1：(0.1-0.5)。
  10. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(1)中，加入rGO的质量为钒源质量的1.5-3倍。
  11. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(1)中，所述搅拌状态下中搅拌速度为600-1000r/min。
  12. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(1)中，所述升温反应的温度为300-350℃，反应时间为10-20h。
  13. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(1)中，所述烧结是以速率15-20℃/min升温至600-800℃，烧结3-5h。
  14. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(2)中所述MOFs生成溶液为将Cr(NO3)3及苯甲酸钠按照摩尔比(3-7)：(2-5)溶于甲醇中制得，Cr(NO3)3与甲醇的配比为5g:(50-100)ml。
  15. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(2)中，所述浸泡的时间为6-12h。
  16. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(2)中，所述加热的温度为130-160℃，加热时的间为12-24h。
  17. 根据权利要求5所述的一种正极材料的制备方法，其特征在于：步骤(3)中，所述加热的温度为100-200℃，加热的时间为2-12h。
  18. 一种锂离子电池，其特征在于，包括权利要求1至4任一项所述的正极材料。
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