WO2024036907A1 - 一种三元正极纤维复合材料及其制备方法 - Google Patents

一种三元正极纤维复合材料及其制备方法 Download PDF

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Publication number
WO2024036907A1
WO2024036907A1 PCT/CN2023/077458 CN2023077458W WO2024036907A1 WO 2024036907 A1 WO2024036907 A1 WO 2024036907A1 CN 2023077458 W CN2023077458 W CN 2023077458W WO 2024036907 A1 WO2024036907 A1 WO 2024036907A1
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source
composite material
fiber composite
ternary cathode
nickel
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PCT/CN2023/077458
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English (en)
French (fr)
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李爱霞
余海军
谢英豪
李长东
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Priority to GBGB2311690.8A priority Critical patent/GB202311690D0/en
Publication of WO2024036907A1 publication Critical patent/WO2024036907A1/zh

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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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 application relates to the field of battery materials, and specifically to a ternary cathode fiber composite material and a preparation method thereof.
  • the ternary cathode material is a lithium nickel cobalt manganate material prepared by adjusting the ratio of nickel source, manganese source and cobalt source according to actual needs. This material has the advantages of low cost, high unit capacity and good safety. However, with the diversification of use scenarios, pure ternary cathode materials can no longer meet the needs of all users due to their shortcomings such as poor heat resistance, short service life, and poor rate performance.
  • ternary cathode materials were structurally modified, especially to give the materials a special morphology.
  • the thermal stability and electrochemical performance of materials can be effectively improved through physical means alone.
  • electrospinning is a commonly used modification and structure construction method for lithium-ion battery materials.
  • This method mainly uses high-voltage static electricity to accelerate charged substances under the action of electric field force and overcome surface tension to form a small jet stream.
  • the solvent evaporates or solidifies, and finally falls on the receiving device to form a non-woven fiber mat.
  • This three-dimensional fiber composite structure can effectively improve the structural stress performance of the product, and at the same time, the specific surface area is significantly larger, making it easier to infiltrate.
  • the electrolyte will also increase the number of lithium deintercalation sites, effectively improving the overall electrochemical activity of the material.
  • the purpose of this application is to provide a method for preparing a ternary cathode fiber composite material.
  • This method pre-constructs a coaxial fiber precursor of a sandwich structure through a coaxial electrospinning method, and then uses a monomer to The polymer grafting method introduces a nitrogen-containing polymer coating layer to coat the fiber surface. After high-temperature sintering, the two-layer structure in the fiber precursor fuses to form a ternary cathode carbon composite material, and the outer layer of nitrogen-containing polymer coating The coating is converted into a nitrogen-containing carbon layer to effectively retain the fiber morphology and effectively improve the conductivity of the overall material.
  • a method for preparing a ternary cathode fiber composite material including the following steps:
  • the preparation method of the ternary cathode fiber composite material described in this application adopts a coaxial electrospinning method to prepare a coaxial fiber precursor with a cobalt source, a nickel source and a manganese source as the inner axis and a lithium source as the outer axis. All with Structural polymers perform morphological fixation. Then the precursor further introduces nitrogen-containing polymer monomers, and uses the structural polymer contained in the precursor as a grafting site to graft a thinner layer of nitrogen-containing polymer on the surface of the precursor.
  • the cobalt source, nickel source and manganese source of the inner shaft and the lithium source of the outer shaft undergo crystallization behavior.
  • the stress trends are opposite, and the overall internal shrinkage stress is significant.
  • the ternary cathode fiber composite material not only has high conductivity, but also retains a relatively complete fiber network structure, a large specific surface area, abundant lithium deintercalation sites, a high proportion of active ternary material content, and excellent electrochemical performance.
  • the cobalt source, nickel source and manganese source are soluble salts;
  • the lithium source is lithium carbonate,
  • the structural polymer is polyimide, and the solution A is N, N-dimethylmethane.
  • Amide (DMF) is N, N-dimethylmethane.
  • the cobalt source is at least one of cobalt acetate and cobalt nitrate
  • the nickel source is at least one of nickel acetate and nickel nitrate
  • the manganese source is manganese acetate
  • cobalt source, nickel source, manganese source and lithium source described in this application can also be selected from other soluble salts that are soluble in solution A, as long as they can be configured for
  • the electrospinning solution and the types of lithium nickel cobalt manganate that can be directly synthesized subsequently are not limited by the above preferred range.
  • the mass concentration of the structural polymer in the spinning liquid I and the spinning liquid II is 5wt% to 15wt%, and the total concentration of cobalt ions, nickel ions, and manganese ions in the spinning liquid I is The concentration of lithium ions in the spinning solution II is 0.4-0.8 mmol/g.
  • the introduction of structural polymers not only helps with spinning shape and continuous spinning, It also acts as a carrier for raw materials such as cobalt source and lithium source in the obtained coaxial fiber precursor a. If the content is too small, various raw material solutions will easily cause losses during subsequent processing, and the nitrogen-containing polymer monomer will not be fully accessible. If the content is too high, the spinning liquid will be too viscous, which will easily affect the spinning effect, and may also affect the subsequent crystallization synthesis efficiency of lithium nickel cobalt manganate.
  • the inner diameter of the needle used for outer shaft spinning is 0.8 ⁇ 1.5mm
  • the inner diameter of the needle used for inner shaft spinning is 0.3 ⁇ 0.5mm
  • the injection rate is 0.4 ⁇ 1.5mm.
  • the voltage is set to 18 ⁇ 22kV
  • the spinning receiving distance is 10 ⁇ 25cm.
  • the nitrogen-containing polymerized monomer is pyrrole
  • the catalyst is ferric chloride
  • the solution B is absolute ethanol.
  • the mass ratio of the structural polymer to the nitrogen-containing polymer monomer in the coaxial fiber precursor a is 1: (0.2 ⁇ 0.4).
  • the polymerization reaction in step (3) is performed at -5 to 5°C.
  • Another object of the present application is to provide a ternary cathode fiber composite material prepared by the preparation method of the ternary cathode fiber composite material.
  • Another object of the present application is to provide a lithium-ion battery positive electrode sheet prepared from the ternary positive electrode fiber composite material described in the present application.
  • the ternary cathode fiber composite material described in this application has an excellent three-dimensional fiber structure, a large specific surface area, and many lithium deintercalation sites. It also contains nitrogen doping. When applied to the cathode plate of a lithium-ion battery, it does not It only has good lithium deintercalation efficiency, high conductivity, good cycle stability, and improved service life compared with existing products.
  • this application provides a method for preparing a ternary cathode fiber composite material.
  • This method pre-constructs a coaxial fiber precursor of a sandwich structure through a coaxial electrospinning method, and then connects it through a monomer polymer.
  • the nitrogen-containing polymer coating is introduced on the surface of the fiber through the branch method. After high-temperature sintering, the two-layer structure in the fiber precursor is fused to form a ternary cathode carbon composite material, while the outer nitrogen-containing polymer coating is The transformation into a nitrogen-containing carbon layer effectively retains the fiber morphology and effectively improves the conductivity of the overall material.
  • This application also provides a lithium-ion battery cathode sheet prepared from the ternary cathode fiber composite material.
  • Figure 1 is a transmission electron microscope image of the ternary cathode fiber composite material obtained in Example 1 of the present application.
  • Figure 2 is a transmission electron microscope image of the ternary cathode fiber composite material obtained in Comparative Example 1 of the present application.
  • Figure 3 is a transmission electron microscope image of the ternary cathode fiber composite material obtained in Comparative Example 2 of the present application.
  • the polyimide used in each embodiment and comparative example can be matrimid 5218PI powder.
  • the molar ratio of cobalt element in the cobalt source, nickel element in the nickel source and manganese element in the manganese source is 0.1:0.8:0.1. It should be noted here that the embodiments and comparative examples of the present application are only explained through some specific implementable solutions, but are not limited thereto. Persons skilled in the art should know that, without affecting the feasibility of the overall technical solution, In this case, the polyimide can be selected from other sources, and the molar ratio of the three elements of nickel, cobalt and manganese in the product can be adjusted according to actual needs.
  • the lithium source lithium acetate and the structural polymer polyimide accounting for 10wt% of the total solution mass are dissolved in DMF under stirring 60-80°C water bath conditions to prepare spinning solution II; the cobalt element, nickel in the cobalt source
  • the total concentration of seed ions is 0.6mmol/g; the concentration of lithium ions in the spinning solution II is 0.6mmol/g;
  • the coaxial fiber precursor b is calcined at 850°C for 15 hours under a protective atmosphere to obtain the ternary cathode fiber composite material.
  • Example 1 An embodiment of the ternary cathode fiber composite material and its preparation method described in the present application. The only difference between this embodiment and Example 1 is that in the step (1), the polymer in the spinning liquid I and the spinning liquid II The mass concentration of imide is 5wt%. The total concentration of cobalt ions, nickel ions and manganese ions in the spinning liquid I is 0.8mmol/g. The concentration of lithium ions in the spinning liquid II is 0.8mmol/g.
  • Example 1 An embodiment of the ternary cathode fiber composite material and its preparation method described in the present application.
  • the only difference between this embodiment and Example 1 is that in the step (1), the polymer in the spinning liquid I and the spinning liquid II
  • the mass concentration of imide is 20wt%
  • the total concentration of cobalt ions, nickel ions, and manganese ions in the spinning liquid I is 0.2mmol/g
  • the concentration of lithium ions in the spinning liquid II is 0.2mmol/g.
  • a ternary cathode fiber composite material and its preparation method including the following steps:
  • the total concentration of lithium ions is 0.6mmol/g; the concentration of lithium ions is 0.6mmol/g;
  • the coaxial fiber precursor b is calcined at 850°C for 15 hours under a protective atmosphere to obtain the ternary cathode fiber composite material.
  • a ternary cathode fiber composite material and its preparation method including the following steps:
  • the lithium source lithium acetate and the structural polymer polyimide accounting for 10wt% of the total solution mass are dissolved in DMF under stirring 60-80°C water bath conditions to prepare spinning solution II; the cobalt element, nickel in the cobalt source
  • the total concentration of seed ions is 0.6mmol/g; the concentration of lithium ions in the spinning solution II is 0.6mmol/g;
  • the coaxial fiber precursor a is calcined at 850°C for 15 hours under a protective atmosphere to obtain the ternary cathode fiber composite material.
  • a ternary cathode fiber composite material and its preparation method including the following steps:
  • the lithium source lithium acetate and the structural polymer polyimide accounting for 10wt% of the total solution mass are dissolved in DMF under stirring 60-80°C water bath conditions to prepare spinning solution II; the cobalt element, nickel in the cobalt source
  • the total concentration of seed ions is 0.6mmol/g; the concentration of lithium ions in the spinning solution II is 0.6mmol/g;
  • the coaxial fiber precursor b is calcined at 850°C for 15 hours under a protective atmosphere to obtain the ternary cathode fiber composite material.
  • each ternary cathode fiber composite material of this application the products of each example and comparative example were used for the preparation of positive electrode sheets of lithium ion batteries: the products of each example and comparative example were mixed with carbon black and PVDF respectively. The mass ratio is 8:1:1, mixed and stirred to make a slurry, then coated on aluminum foil and cut to prepare pole pieces.
  • the obtained electrode piece is used as the positive electrode piece, and the lithium piece is used as the counter electrode piece.
  • a commercial separator and a commercial lithium hexafluorophosphate series electrolyte are used to prepare a button-type lithium-ion half-battery.
  • the obtained battery is cyclically charged and discharged at an operating voltage of 3 to 4.5V and a rate of 0.1C. 100 times; at the same time, prepare another batch of samples in parallel for rate performance testing: first charge and discharge at a rate of 0.1C at the same voltage for 10 times, then cycle at a high rate of 2C for 50 times, and then return to 0.1C rate to calculate the capacity retention rate.
  • the test results are shown in Table 1.
  • the lithium nickel cobalt manganate in the material can achieve the original state during the sintering synthesis process. Crystallization will not have much impact on the fiber structure of the product.
  • the overall product has a large specific surface area, showing a good three-dimensional fiber structure, high stability and many lithium deintercalation sites, which can effectively infiltrate the electrolyte; at the same time, in the nitrogen In the case of doping, the conductivity of the product is improved.
  • the initial discharge specific capacity of the resulting ternary cathode fiber composite material can reach 160 ⁇ 185mAh/g.
  • Example 1 The discharge after 100 cycles The specific ease can also reach 140 ⁇ 165%, and the capacity retention rate after the rate test can reach up to 92%. It can be seen from the comparison between Example 1 and Examples 2 to 9 that changes in the addition ratio of structural polymer, conductive polymer (i.e. polypyrrole) or ternary materials will lead to the discharge capacity, The cycle stability and rate performance change, so they need to be maintained in a better range. In contrast, the product of Comparative Example 1 does not use coaxial spinning method to process precursors.

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Abstract

本申请公开了一种三元正极纤维复合材料及其制备方法，属于电池材料领域。本申请所述方法三元正极纤维复合材料的制备方法通过同轴静电纺丝法预先构建夹心结构的同轴纤维前驱体，随后通过单体聚合物接枝的方法引入含氮聚合物包覆层包覆在纤维表面，经高温烧结后纤维前驱体中的两层结构融合形成三元正极碳复合材料，而外层的含氮聚合物无包覆层则转化为含氮碳层有效保留纤维形貌，同时有效提升整体材料的导电性。本申请还公开了所述三元正极纤维复合材料制备的锂离子电池正极极片。

Description

一种三元正极纤维复合材料及其制备方法 技术领域
本申请涉及电池材料领域，具体涉及一种三元正极纤维复合材料及其制备方法。
背景技术
三元正极材料是以镍源、锰源和钴源根据实际需要调节比例而制备的镍钴锰酸锂材料，该材料具有成本低廉、单位容量高、安全性好的优点。然而，随着使用场景的多样化，纯三元正极材料由于其耐热性差、使用寿命短、倍率性能差等缺陷已经不能满足所有使用者的需求。
基于纯三元正极材料的固有缺陷，人们开始采用一些改性手段进行优化，主要包括元素掺杂和结构改性，而对三元正极材料进行结构改性，特别是赋予材料特殊的形貌，可以仅通过物理手段便有效提升材料的热稳定性及电化学性能。
现有技术中，静电纺丝法是锂离子电池材料的常用改性及结构构建方法，该方法主要是通过高压静电将带电物质在电场力作用下加速并克服表面张力形成喷射细流，该细流在喷射过程中溶剂蒸发或固化，最终落在接收装置上形成类似非织造的纤维毡，这种三维纤维复合结构可以有效提升产品的结构受力性能，同时比表面积显著变大，更加容易浸润电解液，锂脱嵌位点也会增多，有效提升材料的整体电化学活性。然而，由于静电纺丝过程耗时较长，含固-液相的原料容易发生静置分层，在纺丝过程中堵塞针头，因此现有配制的静电纺丝原料多为纯液相。对于三元正极材料而言，虽然可以采用可溶性盐作为原料进行静电纺丝形貌构建，但这些前驱体原料在后续烧结过程中将发生明显的结晶行为，导致在先构建的纤维形貌发生内部收缩并最终破碎损坏。
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。
基于现有技术的不足，本申请的目的在于提供了一种三元正极纤维复合材料的制备方法，该方法通过同轴静电纺丝法预先构建夹心结构的同轴纤维前驱体，随后通过单体聚合物接枝的方法引入含氮聚合物包覆层包覆在纤维表面，经高温烧结后纤维前驱体中的两层结构融合形成三元正极碳复合材料，而外层的含氮聚合物包覆层则转化为含氮碳层有效保留纤维形貌，同时有效提升整体材料的导电性。
为了达到上述目的，本申请采取的技术方案为：
一种三元正极纤维复合材料的制备方法，包括以下步骤：
(1)将钴源、镍源和锰源和结构聚合物溶于溶液A制备纺丝液I，将锂源和结构聚合物溶于溶液A制备纺丝液II；
(2)以纺丝液I为内轴纺丝液，纺丝液II为外轴纺丝液采用同轴结构针头进行静电纺丝处理，所得纤维布经干燥处理后，得同轴纤维前驱体a；
(3)将含氮聚合单体溶于溶液B中，随后将同轴纤维前驱体a置入溶液中浸泡完全，加入催化剂引发含氮聚合单体发生聚合反应，待反应完全后过滤并干燥，得同轴纤维前驱体b；所述钴源、镍源、锰源、锂源和结构聚合物不溶于溶液B；
(4)将同轴纤维前驱体b经保护气氛下700～900℃煅烧10～15h，即得所述三元正极纤维复合材料。
本申请所述三元正极纤维复合材料的制备方法采用同轴静电纺丝法制备以钴源、镍源和锰源为内轴、锂源为外轴的同轴纤维前驱体，同时内外两轴都以 结构聚合物进行形态固定。随后该前驱体进一步引入含氮的聚合物单体，并以前驱体含有的结构聚合物作为接枝位点在前驱体表面接枝一层较薄的含氮聚合物，当该前驱体在高温烧结生成镍钴锰酸锂时，内轴的钴源、镍源和锰源和外轴的锂源发生结晶行为，但由于两者处于不同的结构位置，应力趋势相反，整体的内部收缩应力显著降低，内外轴发生融合，而接枝在外层的含氮聚合物在高温烧结时一边碳化成高导电率的含氮碳层，一边也会有效牵引同轴纤维协助其保持形貌，最终制备的三元正极纤维复合材料不仅导电性高，同时纤维网络结构保留较完整，比表面积大，锂脱嵌位点丰富，活性三元材料含量比例高，电化学性能优异。
可选地，所述钴源、镍源和锰源为可溶性盐；所述锂源为碳酸锂，所述结构聚合物为聚酰亚胺，所述溶液A为N，N-二甲基甲酰胺(DMF)。
可选地，所述钴源为醋酸钴、硝酸钴中的至少一种，所述镍源为醋酸镍、硝酸镍中的至少一种，所述锰源为醋酸锰。
需要特别说明的是，本申请所述钴源、镍源、锰源及锂源除了上述说明的优选种类外，也可选用其他可溶于溶液A的其他可溶性盐，只要是可配置成用于静电纺丝的溶液且后续可直接合成镍钴锰酸锂的种类均不受上述优选范围限制。
可选地，所述钴源中钴元素、镍源中镍元素和锰源中锰元素的摩尔之比为x：y：(1-x-y)，其中x＝0.01～0.1。
可选地，所述纺丝液I和纺丝液II中结构聚合物的质量浓度为5wt％～15wt％，所述纺丝液I中钴离子、镍离子、锰离子三种离子的总浓度为0.4～0.8mmol/g，所述纺丝液II中锂离子的浓度为0.4～0.8mmol/g。
在静电纺丝过程中，结构聚合物的引入除了帮助纺丝定型及持续喷丝外， 还充当了所得同轴纤维前驱体a中钴源、锂源等原料的负载体，若含量太少，各种原料溶液在后续处理过程中容易造成损失，同时含氮聚合单体也无法充分接枝聚合，而如果含量太多，纺丝液过粘稠，容易影响纺丝效果，同时也可能会影响后续镍钴锰酸锂的结晶合成效率。
可选地，所述步骤(2)中静电纺丝处理时，外轴纺丝所用针头的内径为0.8～1.5mm，内轴纺丝所用针头的内径为0.3～0.5mm，注射速率为0.4～0.6mL/h，电压设置为18～22kV，纺丝接收距离为10～25cm。
可选地，所述含氮聚合单体为吡咯，所述催化剂为三氯化铁，所述溶液B为无水乙醇。
可选地，同轴纤维前驱体a中结构聚合物与含氮聚合单体的质量之比为1：(0.2～0.4)。
含氮聚合单体的引入量过多，虽然在聚合过程中能形成更多量的聚吡咯，但并非能全部接枝至同轴纤维前驱体a上，对于最终产品的稳定性提升程度有限，还可能造成整体产品的活性物质分布不均匀；而如果引入量过少，则很难有效发挥牵引作用，保障最终产品的纤维形貌，同时氮元素掺杂量不足，对产品导电性提升程度不足。
可选地，所述步骤(3)中的聚合反应在-5～5℃下进行。
本申请的另一目的在于提供所述三元正极纤维复合材料的制备方法制备得到的三元正极纤维复合材料。
本申请的再一目的在于提供一种锂离子电池正极极片，由本申请所述三元正极纤维复合材料制备得到。
本申请所述三元正极纤维复合材料具有优异的三维纤维结构，比表面积大，脱嵌锂位点多，同时含有氮元素的掺杂，当应用在锂离子电池正极极片时，不 仅具有良好的脱嵌锂效率，导电性高，同时循环稳定性好，使用寿命相比于现有产品有所提升。
本申请的有益效果在于，本申请提供了一种三元正极纤维复合材料的制备方法，该方法通过同轴静电纺丝法预先构建夹心结构的同轴纤维前驱体，随后通过单体聚合物接枝的方法引入含氮聚合物包覆层包覆在纤维表面，经高温烧结后纤维前驱体中的两层结构融合形成三元正极碳复合材料，而外层的含氮聚合物包覆层则转化为含氮碳层有效保留纤维形貌，同时有效提升整体材料的导电性。本申请还提供了所述三元正极纤维复合材料制备的锂离子电池正极极片。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。
图1为本申请实施例1所得三元正极纤维复合材料的透射电镜图。
图2为本申请对比例1所得三元正极纤维复合材料的透射电镜图。
图3为本申请对比例2所得三元正极纤维复合材料的透射电镜图。
具体实施方式
为了更好地说明本申请的目的、技术方案和优点，下面将结合具体实施例及对比例对本申请作进一步说明，其目的在于详细地理解本申请的内容，而不是对本申请的限制。本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请的保护范围。本申请实施、对比例所设计的实验试剂、原料及仪器，除非特别说明，均为常用的普通试剂、原料及仪器。
可选地，各实施例及对比例所用聚酰亚胺可选用matrimid 5218PI粉，所用 钴源中钴元素、镍源中镍元素和锰源中锰元素的摩尔之比为0.1：0.8：0.1。在此需要说明的是，本申请各实施例和对比例仅仅通过具体的一些可实现方案进行阐述说明，但并不局限于此，本领域技术人员应当知悉，在不影响整体技术方案可行性的情况下，所述聚酰亚胺可以选用其他来源的种类，所述产品中镍钴锰三种元素的摩尔比可以根据实际需要进行调整。
实施例1
本申请所述三元正极纤维复合材料及其制备方法的一种实施例，包括以下步骤：
(1)将钴源醋酸钴、镍源醋酸镍和锰源醋酸锰和占总溶液质量10wt％结构聚合物聚酰亚胺，在搅拌60～80℃水浴条件下溶于DMF中制备纺丝液I，将锂源醋酸锂和占总溶液质量10wt％结构聚合物聚酰亚胺，在搅拌60～80℃水浴条件下溶于DMF中制备纺丝液II；所述钴源中钴元素、镍源中镍元素和锰源中锰元素的摩尔之比为x：y：(1-x-y)，其中x＝0.1，y＝0.8；所述纺丝液I中钴离子、镍离子、锰离子三种离子的总浓度为0.6mmol/g；所述纺丝液II中锂离子的浓度为0.6mmol/g；
(2)以纺丝液I为内轴纺丝液，纺丝液II为外轴纺丝液采用同轴结构针头进行静电纺丝处理，所得纤维布经80℃干燥处理24h后，得同轴纤维前驱体a；其中，具体采用的参数为：外轴纺丝所用针头的内径为1.2mm，内轴纺丝所用针头的内径为0.3mm，注射速率为0.5mL/h，电压设置为19kV，纺丝接收距离为22cm；
(3)将含氮聚合单体吡咯溶于无水乙醇中，随后将同轴纤维前驱体a置入溶液中浸泡完全，调整溶液温度降低至0℃，加入适量三氯化铁引发含氮聚合单体吡咯发生聚合反应，待反应完全后过滤并置于60℃环境下干燥24h，得同轴 纤维前驱体b；其中吡咯的添加量为：聚酰亚胺总添加质量：吡咯添加质量＝1:0.3；
(4)将同轴纤维前驱体b经保护气氛下850℃煅烧15h，即得所述三元正极纤维复合材料。
实施例2
本申请所述三元正极纤维复合材料及其制备方法的一种实施例，本实施例与实施例1的差别仅在于，所述步骤(1)中纺丝液I和纺丝液II中聚酰亚胺的质量浓度均为15wt％，所述纺丝液I中钴离子、镍离子、锰离子三种离子的总浓度为0.4mmol/g，所述纺丝液II中锂离子的浓度为0.4mmol/g。
实施例3
本申请所述三元正极纤维复合材料及其制备方法的一种实施例，本实施例与实施例1的差别仅在于，所述步骤(1)中纺丝液I和纺丝液II中聚酰亚胺的质量浓度均为5wt％，所述纺丝液I中钴离子、镍离子、锰离子三种离子的总浓度为0.8mmol/g，所述纺丝液II中锂离子的浓度为0.8mmol/g。
实施例4
本申请所述三元正极纤维复合材料及其制备方法的一种实施例，本实施例与实施例1的差别仅在于，所述步骤(1)中纺丝液I和纺丝液II中聚酰亚胺的质量浓度均为20wt％，所述纺丝液I中钴离子、镍离子、锰离子三种离子的总浓度为0.2mmol/g，所述纺丝液II中锂离子的浓度为0.2mmol/g。
实施例5
本申请所述三元正极纤维复合材料及其制备方法的一种实施例，本实施例与实施例1的差别仅在于，所述步骤(1)中纺丝液I和纺丝液II中聚酰亚胺的质量浓度均为3wt％，所述纺丝液I中钴离子、镍离子、锰离子三种离子的总浓度 为1mmol/g，所述纺丝液II中锂离子的浓度为1mmol/g。
实施例6
本申请所述三元正极纤维复合材料及其制备方法的一种实施例，本实施例与实施例1的差别仅在于，所述步骤(3)中吡咯的添加量为：聚酰亚胺总添加质量：吡咯添加质量＝1:0.2。
实施例7
本申请所述三元正极纤维复合材料及其制备方法的一种实施例，本实施例与实施例1的差别仅在于，所述步骤(3)中吡咯的添加量为：聚酰亚胺总添加质量：吡咯添加质量＝1:0.4。
实施例8
本申请所述三元正极纤维复合材料及其制备方法的一种实施例，本实施例与实施例1的差别仅在于，所述步骤(3)中吡咯的添加量为：聚酰亚胺总添加质量：吡咯添加质量＝1:0.1。
实施例9
本申请所述三元正极纤维复合材料及其制备方法的一种实施例，本实施例与实施例1的差别仅在于，所述步骤(3)中吡咯的添加量为：聚酰亚胺总添加质量：吡咯添加质量＝1:0.5。
对比例1
一种三元正极纤维复合材料及其制备方法，包括以下步骤：
(1)将锂源醋酸锂、钴源醋酸钴、镍源醋酸镍和锰源醋酸锰和占总溶液质量20wt％结构聚合物聚酰亚胺，在搅拌60～80℃水浴条件下溶于DMF中制备纺丝液，所述钴源中钴元素、镍源中镍元素和锰源中锰元素的摩尔之比为x：y：(1-x-y)，其中x＝0.1，y＝0.8；所述纺丝液中钴离子、镍离子、锰离子三种离子 的总浓度为0.6mmol/g；所述锂离子的浓度为0.6mmol/g；
(2)以纺丝液进行静电纺丝处理，所得纤维布经80℃干燥处理24h后，得纤维前驱体a；其中，具体采用的参数为：纺丝所用针头的内径，注射速率为0.3mL/h，电压设置为20kV，纺丝接收距离为22cm；
(3)将含氮聚合单体吡咯溶于无水乙醇中，随后将纤维前驱体a置入溶液中浸泡完全，调整溶液温度降低至0℃，加入适量三氯化铁引发含氮聚合单体吡咯发生聚合反应，待反应完全后过滤并置于60℃环境下干燥24h，得同轴纤维前驱体b；其中吡咯的添加量为：聚酰亚胺添加质量：吡咯添加质量＝1:0.3；
(4)将同轴纤维前驱体b经保护气氛下850℃煅烧15h，即得所述三元正极纤维复合材料。
对比例2
一种三元正极纤维复合材料及其制备方法，包括以下步骤：
(1)将钴源醋酸钴、镍源醋酸镍和锰源醋酸锰和占总溶液质量10wt％结构聚合物聚酰亚胺，在搅拌60～80℃水浴条件下溶于DMF中制备纺丝液I，将锂源醋酸锂和占总溶液质量10wt％结构聚合物聚酰亚胺，在搅拌60～80℃水浴条件下溶于DMF中制备纺丝液II；所述钴源中钴元素、镍源中镍元素和锰源中锰元素的摩尔之比为x：y：(1-x-y)，其中x＝0.1，y＝0.8；所述纺丝液I中钴离子、镍离子、锰离子三种离子的总浓度为0.6mmol/g；所述纺丝液II中锂离子的浓度为0.6mmol/g；
(2)以纺丝液I为内轴纺丝液，纺丝液II为外轴纺丝液采用同轴结构针头进行静电纺丝处理，所得纤维布经80℃干燥处理24h后，得同轴纤维前驱体a；其中，具体采用的参数为：外轴纺丝所用针头的内径为1.2mm，内轴纺丝所用针头的内径为0.3mm，注射速率为0.5mL/h，电压设置为19kV，纺丝接收距离 为22cm；
(3)将同轴纤维前驱体a经保护气氛下850℃煅烧15h，即得所述三元正极纤维复合材料。
对比例3
一种三元正极纤维复合材料及其制备方法，包括以下步骤：
(1)将钴源醋酸钴、镍源醋酸镍和锰源醋酸锰和占总溶液质量10wt％结构聚合物聚酰亚胺，在搅拌60～80℃水浴条件下溶于DMF中制备纺丝液I，将锂源醋酸锂和占总溶液质量10wt％结构聚合物聚酰亚胺，在搅拌60～80℃水浴条件下溶于DMF中制备纺丝液II；所述钴源中钴元素、镍源中镍元素和锰源中锰元素的摩尔之比为x：y：(1-x-y)，其中x＝0.1，y＝0.8；所述纺丝液I中钴离子、镍离子、锰离子三种离子的总浓度为0.6mmol/g；所述纺丝液II中锂离子的浓度为0.6mmol/g；
(2)以纺丝液I为内轴纺丝液，纺丝液II为外轴纺丝液采用同轴结构针头进行静电纺丝处理，所得纤维布经80℃干燥处理24h后，得同轴纤维前驱体a；其中，具体采用的参数为：外轴纺丝所用针头的内径为1.2mm，内轴纺丝所用针头的内径为0.3mm，注射速率为0.5mL/h，电压设置为19kV，纺丝接收距离为22cm；
(3)将采用HUMMER法制备还原氧化石墨烯rGO置于无水乙醇中，随后将同轴纤维前驱体a置入溶液中浸泡完全，在超声环境以50rpm的速率搅拌将rGO及同轴纤维前驱体a混合均匀，过滤并置于60℃环境下干燥24h，得同轴纤维前驱体b；其中吡咯的添加量为：聚酰亚胺总添加质量：吡咯添加质量＝1:0.3；
(4)将同轴纤维前驱体b经保护气氛下850℃煅烧15h，即得所述三元正极纤维复合材料。
效果例1
为了验证本申请各三元正极纤维复合材料的制备方法的优选性，将实施例1、对比例1和对比例2产品进行透射电镜观察，测试结果如图1～3所示，可以看出，在本申请所述制备方法的优选下，所得产品具有良好的纤维形貌，在三元正极材料烧结形成过程中由于两种聚合物的作用，整体纤维结构没有崩塌；相比之下，对比例1产品制备过程中没有采用同轴纺丝工艺，三元正极材料在烧结结晶过程中破坏了预先构建的纤维形貌，而对比例2产品由于没有外层包覆的含氮聚合物，同样难以在高温烧结时维持良好的三维纤维网络结构，在烧结后存在明显的纤维断裂现象。
效果例2
为了验证本申请各三元正极纤维复合材料的性能优选性，将各实施例和对比例产品用于锂离子电池正极极片的制备：将各实施例和对比例产品分别和炭黑、PVDF按质量比8:1:1混合搅拌制浆，随后涂覆在铝箔上经裁切制备极片。
所得极片作为正极极片，以锂片为对电极片，采用商用隔膜及商用六氟磷酸锂系电解液制备扣式锂离子半电池，所得电池在3～4.5V工作电压、0.1C倍率下循环充放电100次；同时，平行制备另一批样品进行倍率性能测试：在相同电压下先以0.1C倍率循环充放电10次，随后在2C倍率下大倍率循环充放电50次，随后在返回至0.1C倍率，计算容量保留率。测试结果如表1所示。
表1

从表1可以看出，由于前驱体在制备过程中采用同轴纺丝处理，以及结构聚合物、导电聚合物的稳定作用下，材料中的镍钴锰酸锂在烧结合成过程中能够实现原位结晶，不会对产品的纤维结构产生太大影响，整体产品的比表面积较大，呈现良好的三维纤维结构，稳定性高且锂脱嵌位点多，可有效浸润电解液；同时在氮掺杂的情况下，产品的导电性有所提升，当用在低倍率循环过程中，所得三元正极纤维复合材料的初始放电比容量可达160～185mAh/g，经过100次循环后的放电比容易也同样可达到140～165％，在倍率测试后的容量保持率最高可达到92％。从实施例1与实施例2～9对比可以看出，无论是结构聚合物、导电聚合物(即聚吡咯)亦或是三元材料的添加比例发生变化，均会导致最终产品的放电容量、循环稳定性以及倍率性能发生变化，因此需要维持在一个较好的范围。相比之下，对比例1产品中并没有采用同轴纺丝法进行前驱体 的制备，经过后续负载及烧结步骤后产品难以维持预先构建的纤维结构，产品的循环稳定性及倍率性能差；对比例2产品虽然采用了同轴纺丝法制备前驱体，但并没有进一步引入外层的含氮聚合物包覆层，最终得到的产品的形貌结构同样不理想，同时由于没有氮元素的掺杂，产品导电性不足，放电比容量较低；对比例3产品在制备过程中采用常见的碳改性材料还原石墨烯代替实施例中的聚吡咯包覆层，但由于紧靠简单的物理分散很难将还原石墨烯结合至前驱体上，因此产品虽相比对比例2产品其综合性能均有一定提升，但总体效果依然不如实施例产品。
最后所应当说明的是，以上实施例仅用以说明本申请的技术方案而非对本申请保护范围的限制，尽管参照较佳实施例对本申请作了详细说明，本领域的普通技术人员应当理解，可以对本申请的技术方案进行修改或者等同替换，而不脱离本申请技术方案的实质和范围。

Claims (10)

  1. 一种三元正极纤维复合材料的制备方法，其中，包括以下步骤：
    (1)将钴源、镍源和锰源和结构聚合物溶于溶液A制备纺丝液I，将锂源和结构聚合物溶于溶液A制备纺丝液II；
    (2)以纺丝液I为内轴纺丝液，纺丝液II为外轴纺丝液采用同轴结构针头进行静电纺丝处理，所得纤维布经干燥处理后，得同轴纤维前驱体a；
    (3)将含氮聚合单体溶于溶液B中，随后将同轴纤维前驱体a置入溶液中浸泡完全，加入催化剂引发含氮聚合单体发生聚合反应，待反应完全后过滤并干燥，得同轴纤维前驱体b；所述钴源、镍源、锰源、锂源和结构聚合物不溶于溶液B；
    (4)将同轴纤维前驱体b经保护气氛下700～900℃煅烧10～15h，即得所述三元正极纤维复合材料。
  2. 如权利要求1所述三元正极纤维复合材料的制备方法，其中，所述钴源、镍源和锰源为可溶性盐；所述锂源为碳酸锂，所述结构聚合物为聚酰亚胺，所述溶液A为N，N-二甲基甲酰胺。
  3. 如权利要求2所述三元正极纤维复合材料的制备方法，其中，所述钴源为醋酸钴、硝酸钴中的至少一种，所述镍源为醋酸镍、硝酸镍中的至少一种，所述锰源为醋酸锰。
  4. 如权利要求3所述三元正极纤维复合材料的制备方法，其中，所述钴源中钴元素、镍源中镍元素和锰源中锰元素的摩尔之比为x：y：(1-x-y)，其中x＝0.01～0.1。
  5. 如权利要求1所述三元正极纤维复合材料的制备方法，其中，所述纺丝液I和纺丝液II中结构聚合物的质量浓度为5wt％～15wt％，所述纺丝液I中钴离子、镍离子、锰离子三种离子的总浓度为0.4～0.8mmol/g，所述纺丝液II中锂 离子的浓度为0.4～0.8mmol/g。
  6. 如权利要求1所述三元正极纤维复合材料的制备方法，其中，所述步骤(2)中静电纺丝处理时，外轴纺丝所用针头的内径为0.8～1.5mm，内轴纺丝所用针头的内径为0.3～0.5mm，注射速率为0.4～0.6mL/h，电压设置为18～22kV，纺丝接收距离为10～25cm。
  7. 如权利要求1所述三元正极纤维复合材料的制备方法，其中，所述含氮聚合单体为吡咯，所述催化剂为三氯化铁，所述溶液B为无水乙醇。
  8. 如权利要求1所述三元正极纤维复合材料的制备方法，其中，同轴纤维前驱体a中结构聚合物与含氮聚合单体的质量之比为1：(0.2～0.4)。
  9. 如权利要求1～8任一项所述三元正极纤维复合材料的制备方法制备得到的三元正极纤维复合材料。
  10. 一种锂离子电池正极极片，其中，由权利要求9所述三元正极纤维复合材料制备得到。
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