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WO2017121113A1 - 一种碳包覆铁酸锌电极材料及其制备方法与应用 - Google Patents

一种碳包覆铁酸锌电极材料及其制备方法与应用 Download PDF

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WO2017121113A1
WO2017121113A1 PCT/CN2016/095922 CN2016095922W WO2017121113A1 WO 2017121113 A1 WO2017121113 A1 WO 2017121113A1 CN 2016095922 W CN2016095922 W CN 2016095922W WO 2017121113 A1 WO2017121113 A1 WO 2017121113A1
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zinc ferrite
electrode material
carbon
coated zinc
ferrite electrode
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PCT/CN2016/095922
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English (en)
French (fr)
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侯贤华
屈丽娜
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华南师范大学
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • 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
    • 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
    • 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 invention belongs to the technical field of new energy materials, and particularly relates to a carbon coated zinc ferrite electrode material and a preparation method and application thereof.
  • lithium-ion batteries have been widely used in various small portable electronics due to their high voltage platform, high energy density, low self-discharge, good cycle performance, light weight and environmental friendliness.
  • Electrode materials are the key factors determining the overall performance of lithium-ion batteries.
  • Commercial graphite is currently used as a common anode material for lithium-ion batteries. It has good reversibility, high capacity and low discharge platform, but the actual specific capacity is close to the theory.
  • the specific capacity of 372mAh/g, pure graphite can not meet the demand of high energy density battery; on the other hand, the lithium-embedded potential platform of graphite is close to the deposition potential of metallic lithium, and it is prone to "deposition of lithium" during rapid charging or low-temperature charging. Therefore, safety hazards are caused; in addition, the graphite material has poor solvent compatibility, and is easily peeled off in a low-temperature electrolyte containing propylene carbonate or the like to cause capacity degradation. Therefore, the development of a lithium ion battery anode material with high capacity, long life, safety and reliability has become one of the key factors for improving battery performance.
  • the metal oxide lithium storage anode material has a high theoretical capacity and can form various alloys with lithium.
  • the lithium insertion potential is higher than the electrode potential of the graphite anode material, and it is difficult to cause surface lithium deposition during charging, and the safety is poor.
  • As a negative electrode material for lithium ion batteries zinc ferrite (ZnFe 2 O 4 ), a soft magnetic material with excellent performance, has great commercial value.
  • ZnFe 2 O 4 material has a high theoretical capacity (1486 mAh/g), and is inexpensive and free.
  • the advantages of poisoning can be used as a hot spot for replacing graphite electrode materials. At the same time, it has a stable potential platform (about 0.8v), which does not cause lithium deposition, which greatly improves the safety of the battery.
  • the structure of zinc ferrite is stable, which makes the material have good cycle performance as a negative electrode material, which is the basis for developing high-performance zinc ferrite storage electrode materials.
  • the disadvantages and disadvantages of zinc ferrite are: first, low conductivity, resulting in poor high-rate charge and discharge performance, and low actual specific capacity; second, low efficiency for the first time, during the first lithium intercalation reaction, a large number
  • the irreversible Li 2 O and the formation of the dead lithium phase material cause the active lithium ions to be consumed, so that they cannot be reduced to effective active lithium ions during the subsequent delithiation reaction, thereby reducing the first cycle efficiency, in the actual battery design process. Can not effectively match the positive electrode material and other issues.
  • a primary object of the present invention is to provide a method for preparing a carbon coated zinc ferrite electrode material.
  • Another object of the present invention is to provide a carbon-coated zinc ferrite electrode material prepared by the above preparation method.
  • a method for preparing a carbon-coated zinc ferrite electrode material comprises the following steps:
  • step (3) The dried product in the step (2) is calcined at 300 to 600 ° C for 3 to 6 hours in an air atmosphere; a carbon coated zinc ferrite electrode material is obtained;
  • the zinc ferrite described in the step (1) is preferably nanorod zinc ferrite
  • the method for preparing zinc ferrite described in the step (1) preferably comprises the following steps:
  • the acid precipitant with the dispersing agent and stirring for 0.5 to 5 hours; then adding the soluble zinc salt and the ferrous salt to be uniformly mixed, stirring for 18 to 24 hours; washing and drying to obtain nano-rod zinc ferrite;
  • the zinc salt is Zinc sulfate, zinc chloride or zinc nitrate;
  • the divalent iron salt is ferrous sulfate or ferrous chloride;
  • the molar ratio of zinc ions and ferrous ions in the soluble zinc salt and the divalent iron salt is preferably 1:2;
  • the dispersing agent is a mixture of ethylene glycol, cyclohexane, cetyltrimethylammonium bromide and water;
  • the acid precipitating agent is citric acid, oxalic acid or acetic acid;
  • the washing method is preferably washed with anhydrous ethanol and deionized water
  • the drying condition is preferably dried at 50 to 80 ° C for 5 to 10 hours;
  • the ethanol aqueous solution described in the step (1) the mass ratio of ethanol to water is preferably 9:1;
  • the uniformity of the dispersion described in the step (1) is preferably uniform by stirring and stirring, wherein the stirring speed is preferably 200 to 400 rpm, the stirring time is preferably 10 to 30 minutes, and the zinc ferrite is sufficiently mixed and dispersed uniformly by stirring, which is advantageous for coupling with the coupling agent. Grafting, the more uniform and finer the dispersion, the more the surface of the particles can be graft polymerized, and the area of the polymerization coating is increased;
  • the silane coupling agent described in the step (1) is KH570 or KH560;
  • the amount of the silane coupling agent described in the step (1) is not more than 5% by mass of the zinc ferrite;
  • the silane coupling agent described in the step (1) is preferably added to the reaction system by dropwise addition; the dropping speed is preferably 5 to 10 d / min;
  • the time of the surface treatment described in the step (1) is preferably 2 to 12 h;
  • the initiator described in the step (2) is benzoyl peroxide or azobisisobutyronitrile
  • the amount of the initiator described in the step (2) is 0.8% to 1.2% of the mass of the mixed monomer
  • the mixed monomer described in the step (2) is styrene and acrylonitrile, wherein the mass ratio of styrene to acrylonitrile is (3:7) to (7:3); the mass ratio of styrene to acrylonitrile is preferred. 7:3;
  • the mass ratio of the zinc ferrite to the mixed monomer in the step (2) is 1: (1 to 3); too much mixed monomer causes mutual polymerization before the polymer, agglomeration causes the particles to increase, and Affect the coating effect;
  • the mass ratio of the zinc ferrite to the mixed monomer in the step (2) is preferably 1:1;
  • the dispersing agent described in the step (2) is polyvinylpyrrolidone
  • the dispersant is used in the step (2) in an amount of 10% to 20% by mass of the mixed monomer; if the amount of the dispersant is too small, the dispersion is uneven, and since the dispersant PVP is a nonionic polymer, the amount is too large. Will also increase the viscosity of the reaction, which is not conducive to the reaction;
  • the speed of the dropwise addition described in the step (2) is preferably 5 to 10 d / min;
  • the time of the in-situ graft copolymerization reaction described in the step (2) is preferably from 12 h to 24 h;
  • the drying condition described in the step (2) is preferably: drying at 50 to 80 ° C for 5 to 10 hours;
  • a carbon-coated zinc ferrite electrode material prepared by the above preparation method
  • the carbon-coated zinc ferrite electrode material has good dispersibility, small outer layer coating particle size and uniform particles;
  • the carbon coated zinc ferrite electrode material can be applied to the field of lithium ion battery preparation
  • the invention disperses zinc ferrite uniformly in an aqueous solution of ethanol, and then adds a silane coupling agent for surface treatment: the silane coupling agent undergoes hydrolysis reaction under water condition, and the hydrolyzed silane One type of coupling agent will produce a hydroxyl group at one end, and this hydroxyl group will have a hydrogen bond with the zinc ferrite, that is, the hydroxyl group on the surface of the precursor, and in the subsequent heating process, the dehydration condensation bond is formed to function as a graft;
  • the benzoyl peroxide contains a peroxy group (—O—O—), and after heating, the —O—O— bond is broken and splits into two corresponding radicals, thereby initiating polymerization of the monomer.
  • —O—O— peroxy group
  • the invention firstly adds an initiator, and when the half life is reached, the monomer which is dripped is more completely polymerized, which is equivalent to less monomer in the atmosphere of more initiator radicals, The titrated monomer is fully polymerized. Further, after the initiator is added, the mixed monomer is added dropwise, and the grafting reaction is completed, and then the polymerization is carried out to obtain the polymer-coated zinc ferrite particles (Fig. 1);
  • the invention adopts the method of coprecipitation and in-situ graft copolymerization to prepare nanometer-polymer coated zinc ferrite particles, and the product has uniform dispersion and good crystallinity, and the aspect ratio is 2:1 to 3: 1.
  • the outer coating is evenly distributed, the particle size is small, the electrochemical performance is excellent, the first charging and discharging efficiency is high, the cycle performance is good, and the specific capacity is high (for the first time, it is more than 1600mAh/g, and the theoretical commercial capacity of graphite is 372mAh. /g), thereby solving the problem of the first inefficiency, large irreversible capacity loss, and poor conductivity of the zinc ferrite electrode material.
  • FIG. 1 is a schematic view showing the preparation of a carbon-coated zinc ferrite electrode material of the present invention.
  • Example 2 is an XRD pattern of a carbon-coated zinc ferrite electrode material prepared in Example 1.
  • Example 3 is an SEM chart of a carbon-coated zinc ferrite electrode material prepared in Example 1.
  • Example 4 is a graph showing the charge and discharge cycle performance of the carbon-coated zinc ferrite electrode material obtained in Example 1.
  • Example 5 is an XRD pattern of a carbon-coated zinc ferrite electrode material prepared in Example 2.
  • Example 6 is a SEM image of a carbon-coated zinc ferrite electrode material prepared in Example 2.
  • Fig. 7 is a graph showing the charge and discharge cycle performance of the carbon-coated zinc ferrite electrode material obtained in Example 2.
  • Example 8 is an XRD pattern of a carbon-coated zinc ferrite electrode material prepared in Example 3.
  • Example 9 is a SEM image of a carbon-coated zinc ferrite electrode material prepared in Example 3.
  • Fig. 10 is a graph showing the charge and discharge cycle performance of the carbon-coated zinc ferrite electrode material obtained in Example 3.
  • Figure 11 is a SEM image of a carbon coated zinc ferrite electrode material prepared in Comparative Example.
  • precursor zinc ferrite 100 mL of cyclohexane, 16.5 mL of ethylene glycol and 16.5 mL of deionized water were separately mixed, and then 10.68 g of cetyltrimethylammonium bromide was added, and the mixture was stirred for 30 minutes; Then add 10 g of oxalic acid as a precipitant and continue to stir for 1 h; then weigh 1.15 g of zinc sulfate, respectively.
  • ferrous sulfate 2.23 g of ferrous sulfate is dissolved in the above mixed solution, wherein the molar concentration of zinc sulfate is 0.08 mol/liter, the molar concentration of ferrous sulfate is 0.16 mol/liter, and the molar ratio of zinc sulfate to ferrous sulfate is 1:2.
  • the mixture was stirred at room temperature for 24 hours; the yellow liquid after the stirring was alternately washed with anhydrous ethanol and deionized water for 3 times, and then dried in an oven at 60 ° C for 8 hours to obtain a yellow zinc ferrite powder;
  • the dried product in the step (3) is sintered in a muffle furnace at 450 ° C for 5 hours in an air atmosphere to obtain a carbon-coated zinc ferrite electrode material; wherein, FIG. 2 is obtained in the present embodiment.
  • the XRD pattern of the carbon-coated zinc ferrite electrode material is consistent with the zinc ferrite standard card JCPDSno.22-1012, and there is no diffraction peak of impurities such as ZnO or Fe 2 O 3 , and the crystallinity is good.
  • 3 is a scanning electron micrograph of the carbon-coated zinc ferrite electrode material prepared in the present embodiment, which shows that the coated zinc ferrite surface coating particles are uniform and have good dispersibility, and the average diameter is 20 to 50 nm.
  • the carbon-coated zinc ferrite electrode material prepared in the present embodiment is used as a negative electrode active material, and is mixed with a binder LA132 and a conductive agent Super-P in a weight ratio of 5:2:3 to prepare a slurry and coated thereon. On a copper foil, vacuum drying, rolling, and slicing were carried out to prepare a negative electrode sheet.
  • the cycle performance was tested using a constant current charge and discharge test using a current of 100 mA, and the charge and discharge voltage ranged from 0.01 V to 3 V.
  • the electrochemical performance of the experimental battery fabricated by the carbon coated zinc ferrite electrode material prepared in this example was tested by LAND battery test system (Wuhan Jinnuo Electronics Co., Ltd.) and tested under normal temperature conditions.
  • 4 is a graph showing the charge-discharge cycle performance of a carbon-coated zinc ferrite electrode material prepared in the present embodiment as a negative electrode material for a lithium ion battery, which can be obtained from FIG. 4, and the coated zinc ferrite nano-powder material is used as a lithium battery.
  • the specific capacity of the negative electrode material is high, the first discharge specific capacity is 1644 mAh/g, the first charge specific capacity is 1280 mAh/g, and the first cycle efficiency is 77.86%. After circulating for 20 weeks, the specific capacity was maintained at 1100 mAh/g or more, and the cycle performance was excellent.
  • the dried product in the step (3) is sintered in a muffle furnace at 300 ° C for 6 hours in an air atmosphere to obtain a carbon-coated zinc ferrite electrode material; wherein, FIG. 5 is obtained in the present embodiment.
  • the XRD pattern of the carbon-coated zinc ferrite electrode material is consistent with the zinc ferrite standard card JCPDSno.22-1012, and there is no diffraction peak of impurities such as ZnO and Fe2O3, and the crystallinity is good.
  • 6 is a scanning electron micrograph of the carbon-coated zinc ferrite electrode material prepared in the present embodiment, which shows that the surface of the coated zinc ferrite has uniform particles and good dispersibility, and the average diameter is 20 to 50 nm.
  • the carbon-coated zinc ferrite electrode material prepared in the present embodiment is used as a negative electrode active material, and is mixed with a binder LA132 and a conductive agent Super-P in a weight ratio of 5:2:3 to prepare a slurry and coated thereon. On a copper foil, vacuum drying, rolling, and slicing were carried out to prepare a negative electrode sheet.
  • the cycle performance was tested using a constant current charge and discharge test using a current of 100 mA, and the charge and discharge voltage ranged from 0.01 V to 3 V.
  • the electrochemical performance of the experimental battery fabricated by the carbon coated zinc ferrite electrode material prepared in this example was tested using a LAND battery test system (Wuhan Jinnuo Electronics Co., Ltd.) and tested under normal temperature conditions.
  • 7 is a graph showing the charge and discharge cycle performance of a carbon-coated zinc ferrite electrode material prepared in the present embodiment as a negative electrode material for a lithium ion battery, which can be obtained from FIG. 7 , and the polymer coated zinc ferrite material is used as a lithium battery.
  • the specific capacity of the negative electrode material is high.
  • the first specific capacity is 1364 mAh/g
  • the first charge specific capacity is 1084 mAh/g
  • the first cycle efficiency is 79.47%.
  • the specific capacity is increasing.
  • the charge-discharge specific capacity is average.
  • the cycle performance is excellent.
  • precursor zinc ferrite 100 mL of cyclohexane, 16.5 mL of ethylene glycol and 16.5 mL of deionized water were separately mixed, and 10.68 g of cetyltrimethylammonium bromide was added thereto, and the mixture was stirred for 30 minutes and uniformly mixed.
  • step (3) in the air atmosphere, the dried product in step (3) is sintered in a muffle furnace at 600 ° C for 3 h to obtain a carbon coated zinc ferrite electrode material;
  • FIG. 8 is an XRD pattern of the carbon-coated zinc ferrite electrode material prepared in the present embodiment, which is consistent with the zinc ferrite standard card JCPDSno. 22-1012, and has no diffraction peak of impurities such as ZnO and Fe 2 O 3 , The crystallinity of the product was good.
  • 9 is a scanning electron micrograph of the carbon-coated zinc ferrite electrode material prepared in the present embodiment, which shows that the surface of the coated zinc ferrite has uniform particles and good dispersibility, and the average particle diameter is 20 to 50 nm.
  • the microporous membrane is a membrane and assembled into a half-cell.
  • the cycle performance was tested using a constant current charge and discharge test using a current of 100 mA, and the charge and discharge voltage ranged from 0.01 V to 3 V.
  • the electrochemical performance of the experimental battery fabricated by the carbon coated zinc ferrite electrode material prepared in this example was tested by LAND battery test system (Wuhan Jinnuo Electronics Co., Ltd.) and tested under normal temperature conditions.
  • Figure 10 is a graph showing the charge-discharge cycle performance of a carbon-coated zinc ferrite electrode material prepared in the present embodiment as a negative electrode material for a lithium ion battery, which is obtained from Figure 10, and the polymer coated zinc ferrite nano-powder material As the anode material of the lithium battery, the specific capacity is high, the first specific capacity is 1619 mAh/g, the first charge specific capacity is 1255 mAh/g, and the first cycle efficiency is 77.52%. After 20 weeks, the specific capacity was maintained at 1100 mAh/g or more, and the cycle performance was excellent.
  • precursor zinc ferrite 100 mL of cyclohexane, 16.5 mL of ethylene glycol and 16.5 mL of deionized water were separately mixed, and 10.68 g of cetyltrimethylammonium bromide was added thereto, and the mixture was stirred for 30 minutes and uniformly mixed.
  • step (3) in the air atmosphere, the dried product in step (3) is sintered in a muffle furnace at 450 ° C for 5 h to obtain a carbon coated zinc ferrite electrode material;
  • FIG. 11 is a scanning electron micrograph of the carbon-coated zinc ferrite electrode material prepared in the present embodiment, showing The coated surface of the zinc ferrite surface coating is not uniform, and many particles are agglomerated together, the dispersibility is not good, and the morphology is not good. Moreover, the charge-discharge cycle performance of the carbon-coated zinc ferrite electrode material as a negative electrode material for a lithium ion battery is significantly lower than that of the first embodiment.

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Abstract

本发明属于新型能源材料技术领域，具体涉及一种碳包覆铁酸锌电极材料及其制备方法与应用。本发明将铁酸锌均匀分散在乙醇水溶液中，加入硅烷类偶联剂进行表面处理；然后将反应体系加热到50℃～80℃，加入引发剂混匀；再滴加混合单体和分散剂进行原位接枝共聚反应，收集产物，洗涤，干燥，煅烧；得到碳包覆铁酸锌电极材料。本发明制备方法简单、成本低廉、效率高、包覆效果好；采用共沉淀法和原位接枝共聚的方法制得的碳包覆铁酸锌电极材料外层包覆物颗粒分布均匀、粒径小，表现出了优异的电化学性能、良好的循环稳定性以及电导性。

Description

一种碳包覆铁酸锌电极材料及其制备方法与应用 技术领域
本发明属于新型能源材料技术领域，具体涉及一种碳包覆铁酸锌电极材料及其制备方法与应用。
背景技术
在过去的十几年里，作为可充电电池，锂离子电池具有电压平台高，能量密度大、自放电小、循环性能好、重量轻和环境友好等优点而被广泛应用于各种小型便携式电子设备，电动车和混合动力电动汽车领域。电极材料是决定锂离子电池综合性能优劣的关键因素，目前商业化的石墨作为常见的锂离子电池负极材料，具有可逆性好、容量高和放电平台低等特点，但实际比容量已接近理论比容量372mAh/g，单纯的石墨已经不能满足高能量密度电池的需求；另一方面，石墨的嵌锂电位平台接近金属锂的沉积电势，快速充电或者低温充电过程中容易发生“析锂”现象从而引发安全隐患；此外，石墨材料的溶剂相容性较差，在含碳酸丙烯脂等的低温电解液中容易发生剥离导致容量衰减。因此，开发出具有高容量、长寿命、安全可靠的锂离子电池负极材料成为提高电池性能的关键因素之一。
金属类氧化物储锂负极材料具有较高的理论容量，能够与锂形成多种形式的合金，嵌锂电位均高于石墨负极材料的电极电势，在充电时难以引起表面锂沉积现象,安全性差。作为锂离子电池负极材料，性能优异的软磁性材料铁酸锌(ZnFe2O4)，表现出了巨大的商业价值，ZnFe2O4材料具有理论容量高(1486mAh/g)、价格便宜、无毒等优点可作为替代石墨的电极材料成为研究的热点，同时，具有有稳定的电位平台(0.8v左右)，不会产生析锂现象，从而大大提高了电池的安全性。同时，在充放电过程中，铁酸锌结构稳定，使得该材料作为负极材料具有良好的循环性能，这是开发高性能铁酸锌储锂电极材料的基础。
作为锂离子电池负极材料铁酸锌存在的缺点与不足是：一是电导率低，导致高倍率充放电性能差，实际比容量低；二是首次效率低，在首次嵌锂反应过程中，大量的不可逆Li2O以及死锂相物质生成使得活性锂离子被消耗，使得在随后的脱锂反应过程中不能还原为有效的活性锂离子，从而降低了首次循环效 率，在实际的电池设计过程中不能有效与正极材料进行匹配等问题。
发明内容
为了克服现有技术的不足和缺点，本发明的首要目的在于提供一种碳包覆铁酸锌电极材料的制备方法。
本发明的另一目的在于提供上述制备方法制备得到的碳包覆铁酸锌电极材料。
本发明的再一目的在于提供上述碳包覆铁酸锌电极材料的应用。
本发明的目的通过下述技术方案实现：
一种碳包覆铁酸锌电极材料的制备方法，包含如下步骤：
(1)将铁酸锌均匀分散在乙醇水溶液中；然后加入硅烷类偶联剂进行表面处理；
(2)将步骤(1)中的反应体系加热到50℃～80℃，加入引发剂混匀；然后滴加混合单体和分散剂进行原位接枝共聚反应，然后收集产物，洗涤，干燥；
(3)将步骤(2)中干燥后的产物在空气氛围中300～600℃煅烧3～6h；得到碳包覆铁酸锌电极材料；
步骤(1)中所述的铁酸锌优选为纳米棒状铁酸锌；
步骤(1)中所述的铁酸锌的制备方法(共沉淀法)，优选包含如下步骤：
将酸根沉淀剂与分散剂混合，搅拌0.5～5小时；然后加入可溶性锌盐、二价铁盐混合均匀，搅拌18～24h；洗涤、干燥，得到纳米棒状铁酸锌；所述的锌盐为硫酸锌、氯化锌或硝酸锌；所述的二价铁盐为硫酸亚铁或氯化亚铁；
所述的可溶性锌盐和二价铁盐中锌离子和亚铁离子的摩尔比优选为1：2；
所述的分散剂为乙二醇、环己烷、十六烷基三甲基溴化铵和水的混合物；
所述的酸根沉淀剂为柠檬酸、草酸或乙酸；
所述的洗涤的方式优选为采用无水乙醇和去离子水洗涤；
所述的干燥的条件优选为50～80℃干燥5～10h；
步骤(1)中所述的乙醇水溶液中，乙醇和水的质量比优选为9:1；
步骤(1)中所述的分散均匀优选采用搅拌分散均匀，其中，搅拌速度优选为200～400rpm，搅拌时间优选为10～30min，搅拌使铁酸锌充分混合分散均匀，有利于与偶联剂进行接枝，分散的越均匀越细，就可以使越多的颗粒表面发生接枝聚合，增大聚合包覆面积；
步骤(1)中所述的硅烷类偶联剂为KH570或KH560；
步骤(1)中所述的硅烷类偶联剂的用量不超过铁酸锌质量的5％；
步骤(1)中所述的硅烷类偶联剂优选通过滴加的方式加入反应体系；滴加的速度优选为5～10d/min；
步骤(1)中所述的表面处理的时间优选为2～12h；
步骤(2)中所述的引发剂为过氧化苯甲酰或偶氮二异丁腈；
步骤(2)中所述的引发剂的用量为混合单体质量的0.8％～1.2％；
步骤(2)中所述的混合单体为苯乙烯和丙烯腈，其中，苯乙烯和丙烯晴的质量比为(3:7)～(7:3)；苯乙烯和丙烯晴的质量比优选为7:3；
步骤(2)中所述的铁酸锌与混合单体的质量比为1:(1～3)；混合单体太多会导致聚合物之前的相互聚合，会团聚使颗粒增大，并且会影响包覆效果；
步骤(2)中所述的铁酸锌与混合单体的质量比优选为1:1；
步骤(2)中所述的分散剂为聚乙烯吡咯烷酮；
步骤(2)中所述的分散剂的用量为混合单体质量的10％～20％；分散剂用量过少会分散不均，并且由于分散剂PVP是非离子型高分子聚合物，用量太多也会使反应粘度增大，不利于反应；
步骤(2)中所述的滴加的速度优选为5～10d/min；
步骤(2)中所述的原位接枝共聚反应的时间优选为12h～24h；
步骤(2)中所述的干燥的条件优选为：50～80℃干燥5～10h；
一种碳包覆铁酸锌电极材料，通过上述制备方法制备得到；
所述的碳包覆铁酸锌电极材料分散性好、外层包覆物粒径小、颗粒均匀；
所述的碳包覆铁酸锌电极材料可以应用于锂离子电池制备领域；
本发明的原理：本发明将铁酸锌均匀分散在乙醇水溶液中，然后加入硅烷类偶联剂进行表面处理：硅烷类偶联剂在有水的条件下，会进行水解反应，水解后的硅烷类偶联剂一端会产生羟基，这个羟基会与铁酸锌即前驱体表面的羟基有一个氢键的结合，在后续加热过程中，进行脱水缩合成键，起到接枝的作用；
在后续加热过程中，过氧化苯甲酰中含有过氧基(—O—O—)，受热后—O—O—键断裂，分裂成两个相应的自由基，从而引发单体聚合，进而形成聚合物包覆铁酸锌棒状颗粒这一独特结构；在此过程中，引发剂并不能直接引发反应而需要分解为自由基之后才引发反应，而链引发又是决速步，所以引发剂的半衰期有很大意义。本发明先加入引发剂，在半衰期到达的时候会使滴下来的单体聚合更完全，相当于是较少的单体在较多的引发剂自由基氛围中，可以 使滴定下来的单体充分进行聚合，此外，先加入引发剂后滴加混合单体，可以使得接枝反应完全后再进行聚合进而得到聚合物包覆铁酸锌颗粒(图1)；
本发明相对于现有技术具有如下的优点及效果：
(1)本发明采用共沉淀法和原位接枝共聚的方法制备出了纳米级聚合物包覆的铁酸锌颗粒，产物分散均匀，结晶性好，长径比为2:1到3:1，外层包覆物分布均匀、颗粒粒径小，电化学性能优异、首次充放电效率高、循环性能好，比容量高(首次达1600mAh/g以上，目前商业化的石墨理论容量为372mAh/g)，从而解决铁酸锌电极材料存在的首次效率低、不可逆容量损失大和导电性能差的问题。
(2)本发明制备方法简单、成本低廉、绿色环保。
附图说明
图1是本发明碳包覆铁酸锌电极材料的制备原理图。
图2是实施例1制得的碳包覆铁酸锌电极材料的XRD图谱图。
图3是实施例1制得的碳包覆铁酸锌电极材料的SEM图谱图。
图4是实施例1制得的碳包覆铁酸锌电极材料的充放电循环性能图。
图5是实施例2制得的碳包覆铁酸锌电极材料的XRD图谱图。
图6是实施例2制得的碳包覆铁酸锌电极材料的SEM图谱图。
图7是实施例2制得的碳包覆铁酸锌电极材料的充放电循环性能图。
图8是实施例3制得的碳包覆铁酸锌电极材料的XRD图谱图。
图9是实施例3制得的碳包覆铁酸锌电极材料的SEM图谱图。
图10是实施例3制得的碳包覆铁酸锌电极材料的充放电循环性能图。
图11是对比实施例制得的碳包覆铁酸锌电极材料的SEM图谱图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
(1)前驱体铁酸锌的制备：分别取100mL环己烷、16.5mL乙二醇和16.5mL去离子水混合，再加入10.68g十六烷基三甲基溴化铵，搅拌30min混合均匀；再加入10g草酸作为沉淀剂，继续搅拌1h；随后分别称取1.15g硫酸锌、 2.23g硫酸亚铁溶解在上述混合溶液中，其中硫酸锌的摩尔浓度为0.08摩尔/升，硫酸亚铁的摩尔浓度为0.16摩尔/升，硫酸锌与硫酸亚铁的摩尔比为1：2，继续在常温下搅拌24h；搅拌完毕后的黄色液体用无水乙醇和去离子水交替洗3遍后在60℃烘箱中干燥8h，得到铁酸锌黄色粉末；
(2)取5g步骤(1)制得的纳米铁酸锌粉末与乙醇水溶液(45g无水乙醇和5g去离子水混合均匀得到)混合，300rpm搅拌10min，使铁酸锌均匀分散在乙醇水溶液中；然后滴加KH570乙醇溶液(0.25g KH570溶于5g无水乙醇中得到)，滴加速度为10d/min，滴加完毕后搅拌进行表面处理12h；
(3)将步骤(2)中的反应体系加热到70℃，加入过氧化苯甲酰乙醇溶液(0.05g过氧化苯甲酰溶于5g无水乙醇中得到)，300rpm搅拌10min混匀；然后将混合单体5g(3.5g苯乙烯和1.5g丙烯腈)和2.3g质量分数为25.18％的聚乙烯吡咯烷酮溶于10g无水乙醇中，以6d/min的速度滴加到上述反应体系中，70℃原位接枝共聚反应24h；反应完全后产物用乙醇和去离子水交替清洗3遍，并在60℃下干燥8h；
(4)在空气氛围中，将步骤(3)中干燥后的产物在马弗炉中450℃下烧结5h，得到碳包覆铁酸锌电极材料；其中，图2是本实施例制得的碳包覆铁酸锌电极材料的XRD图谱，该图谱与铁酸锌标准卡片JCPDSno.22-1012相吻合，没有ZnO、Fe2O3等杂质的衍射峰，结晶性良好。图3是本实施例制得的碳包覆铁酸锌电极材料的扫描电镜图，表明包覆后的铁酸锌表面包覆物颗粒均匀，分散性好，平均直径为20～50nm。
采用本实施例制得的碳包覆铁酸锌电极材料作为负极活性物质，与粘结剂LA132、导电剂Super-P按照5:2:3的重量比混合，调成浆料，涂布在铜箔上，并进行真空干燥、辊压、切片，制成负极片，使用1mol/L LiPF6的三组分混合溶剂EC：DMC：EMC＝1：1：1，v/v/v溶液为电解液，聚丙烯微孔膜为隔膜，组装成半电池。使用100mA电流进行恒流充放电实验测试循环性能，充放电电压的范围是0.01V到3V。采用(武汉金诺电子有限公司)LAND电池测试系统测试本实施例制得的碳包覆铁酸锌电极材料制作的实验电池的电化学性能，在常温条件下测试。图4是本实施例制得的碳包覆铁酸锌电极材料做成锂离子电池负极材料的充放电循环性能图，由图4可得，包覆后铁酸锌纳米粉体材料作为锂电池负极材料比容量高，首次放电比容量为1644mAh/g，首次充电比容量是1280mAh/g，首次循环效率为77.86％。循环20周，比容量还保持在1100mAh/g以上，循环性能优异。
实施例2
(1)前驱体铁酸锌的制备：分别取100mL环己烷、16.5mL乙二醇和16.5mL去离子水混合，再加入10.68g十六烷基三甲基溴化铵，搅拌30min混合均匀；再加入10g草酸作为沉淀剂，继续搅拌2h；随后分别称取1.15g硫酸锌、2.23g硫酸亚铁溶解在上述混合溶液中，其中硫酸锌的摩尔浓度为0.08摩尔/升，硫酸亚铁的摩尔浓度为0.16摩尔/升，硫酸锌与硫酸亚铁的摩尔比为1：2，继续在常温下搅拌24h；搅拌完毕后的黄色液体用无水乙醇和去离子水交替洗3遍后在60℃度烘箱中干燥8h，得到铁酸锌黄色粉末；
(2)取2g步骤(1)制得的纳米铁酸锌粉末与乙醇水溶液(45g无水乙醇和5g去离子水混合均匀得到)混合，400rpm搅拌15min，使铁酸锌均匀分散在乙醇水溶液中；然后滴加KH570乙醇溶液(0.1g KH570溶于5g无水乙醇得到)，滴加速度为8d/min，滴加完毕后搅拌进行表面处理10h；
(3)将步骤(2)中的反应体系加热到80℃，加入过氧化苯甲酰乙醇溶液(0.04g过氧化苯甲酰溶于5g无水乙醇中得到)，300rpm搅拌10min混匀；然后取混合单体4g(2.8g苯乙烯和1.2g丙烯腈)和1.9g质量分数为25.18％的聚乙烯吡咯烷酮剂于10g无水乙醇，以6d/min的速度滴加到上述反应体系中，60℃原位接枝共聚反应18h；反应完全后产物用乙醇和去离子水交替清洗3遍并在60℃下干燥8h；
(4)在空气氛围中，将步骤(3)中干燥后的产物在马弗炉中300℃下烧结6h，得到碳包覆铁酸锌电极材料；其中，图5是本实施例制得的碳包覆铁酸锌电极材料的XRD图谱，该图谱与铁酸锌标准卡片JCPDSno.22-1012相吻合，没有ZnO、Fe2O3等杂质的衍射峰，结晶性良好。图6是本实施例制得的碳包覆铁酸锌电极材料的扫描电镜图，表明包覆后的铁酸锌表面颗粒均匀，分散性好，平均直径为20～50nm。
采用本实施例制得的碳包覆铁酸锌电极材料作为负极活性物质，与粘结剂LA132、导电剂Super-P按照5:2:3的重量比混合，调成浆料，涂布在铜箔上，并进行真空干燥、辊压、切片，制成负极片，使用1mol/L LiPF6的三组分混合溶剂EC：DMC：EMC＝1：1：1，v/v/v溶液为电解液，聚丙烯微孔膜为隔膜，组装成半电池。使用100mA电流进行恒流充放电实验测试循环性能，充放电电压的范围是0.01V到3V。采用(武汉金诺电子有限公司)LAND电池测试系统测试本实施例制得的碳包覆铁酸锌电极材料制作的实验电池的电化学性能，在 常温条件下测试。图7是本实施例制得的碳包覆铁酸锌电极材料做成锂离子电池负极材料的充放电循环性能图，由图7可得，聚合物包覆后的铁酸锌材料作为锂电池负极材料比容量高，首次的比容量为1364mAh/g，首次充电比容量是1084mAh/g，首次循环效率为79.47％，经过5周，比容量呈上升趋势，经过20周，充放电比容量均在1100mAh/g以上，循环性能优异。
实施例3
(1)前驱体铁酸锌的制备：分别取100mL环己烷、16.5mL乙二醇和16.5mL去离子水混合，再加入10.68g十六烷基三甲基溴化铵，搅拌30min混合均匀。再加入10g草酸作为沉淀剂，继续搅拌1h；随后分别称取1.15g硫酸锌、2.23g硫酸亚铁溶解在上述混合溶液中，其中硫酸锌的摩尔浓度为0.08摩尔/升，硫酸亚铁的摩尔浓度为0.16摩尔/升，硫酸锌与硫酸亚铁的摩尔比为1：2，继续在常温下搅拌24h；搅拌完毕后的黄色液体用无水乙醇和去离子水交替洗3遍后在60℃烘箱中干燥8h，得到铁酸锌黄色粉末；
(2)取1g步骤(1)制得的纳米铁酸锌粉末与乙醇水溶液(45g无水乙醇和5g去离子水混合均匀得到)混合，200rpm搅拌30min，使铁酸锌均匀分散在乙醇水溶液中；然后滴加KH570乙醇溶液(0.05g KH570溶于5g无水乙醇中得到)，滴加速度为5d/min，滴加完毕后搅拌2h；
(3)将步骤(2)中的反应体系加热到60℃，加入过氧化苯甲酰乙醇溶液(0.03g过氧化苯甲酰溶于5g无水乙醇中得到)，300rpm搅拌10min混匀；然后将混合单体(2.1g苯乙烯和0.9g丙烯腈)和1.4g质量分数为25.18％的聚乙烯吡咯烷酮溶于10g无水乙醇，以6d/min的速度滴加到上述反应体系中，70℃原位接枝共聚反应12h；反应完全后产物用乙醇和去离子水交替清洗3遍并在60℃下干燥8h；
(4)在空气氛围中，将步骤(3)中干燥后的产物在马弗炉中600℃下烧结3h，得到碳包覆铁酸锌电极材料；
图8是本实施例制得的碳包覆铁酸锌电极材料的XRD图谱，该图谱与铁酸锌标准卡片JCPDSno.22-1012相吻合，没有ZnO、Fe2O3等杂质的衍射峰，产物的结晶性良好。图9是本实施例制得的碳包覆铁酸锌电极材料的扫描电镜图，表明包覆后的铁酸锌表面颗粒均匀，分散性好，平均粒径为20～50nm。
采用本实施例制得的碳包覆铁酸锌电极材料作为负极活性物质，与粘结剂LA132、导电剂Super-P按照5:2:3的重量比混合，调成浆料，涂布在铜箔上， 并进行真空干燥、辊压、切片，制成负极片，使用1mol/L LiPF6的三组分混合溶剂EC：DMC：EMC＝1：1：1，v/v/v溶液为电解液，聚丙烯微孔膜为隔膜，组装成半电池。使用100mA电流进行恒流充放电实验测试循环性能，充放电电压的范围是0.01V到3V。采用(武汉金诺电子有限公司)LAND电池测试系统测试本实施例制得的碳包覆铁酸锌电极材料制作的实验电池的电化学性能，在常温条件下测试。图10是本实施例制得的碳包覆铁酸锌电极材料做成锂离子电池负极材料的充放电循环性能图，由图10可得，聚合物包覆后的铁酸锌纳米粉体材料作为锂电池负极材料比容量高，首次的比容量为1619mAh/g，首次充电比容量是1255mAh/g，首次循环效率为77.52％。经过20周，比容量还保持在1100mAh/g以上，循环性能优异。
对比实施例1
(1)前驱体铁酸锌的制备：分别取100mL环己烷、16.5mL乙二醇和16.5mL去离子水混合，再加入10.68g十六烷基三甲基溴化铵，搅拌30min混合均匀。再加入10g草酸作为沉淀剂，继续搅拌1h；随后分别称取1.15g硫酸锌、2.23g硫酸亚铁溶解在上述混合溶液中，其中硫酸锌的摩尔浓度为0.08摩尔/升，硫酸亚铁的摩尔浓度为0.16摩尔/升，硫酸锌与硫酸亚铁的摩尔比为1：2，继续在常温下搅拌24h；搅拌完毕后的黄色液体用无水乙醇和去离子水交替洗3遍后在60℃烘箱中干燥8h，得到铁酸锌黄色粉末；
(2)取1g步骤(1)制得的纳米铁酸锌粉末与乙醇水溶液(45g无水乙醇和5g去离子水混合均匀得到)混合，300rpm搅拌10min，使铁酸锌均匀分散在乙醇水溶液中；然后滴加KH570乙醇溶液(0.25g KH570溶于5g无水乙醇中得到)，滴加速度为10d/min，滴加完毕后搅拌12h；
(3)将步骤(2)中的反应体系加热到70℃，加入过氧化苯甲酰乙醇溶液(0.05g过氧化苯甲酰溶于5g无水乙醇中得到)，300rpm搅拌10min混匀；然后将混合单体5g(3.5g苯乙烯和1.5g丙烯腈)和2.3g质量分数为25.18％的聚乙烯吡咯烷酮溶于10g无水乙醇中，以6d/min的速度滴加到上述反应体系中，70℃原位接枝共聚反应24h；反应完全后产物用乙醇和去离子水交替清洗3遍，并在60℃下干燥8h；
(4)在空气氛围中，将步骤(3)中干燥后的产物在马弗炉中450℃下烧结5h，得到碳包覆铁酸锌电极材料；
其中，图11是本实施例制得的碳包覆铁酸锌电极材料的扫描电镜图，表明 包覆后的铁酸锌表面包覆物颗粒不均匀，有很多颗粒团聚在一起，分散性不好，形貌不好。且，该碳包覆铁酸锌电极材料做成锂离子电池负极材料的充放电循环性能显著低于实施例1。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种碳包覆铁酸锌电极材料的制备方法，其特征在于包含如下步骤：
    (1)将铁酸锌均匀分散在乙醇水溶液中；然后加入硅烷类偶联剂进行表面处理；
    (2)将步骤(1)中的反应体系加热到50℃～80℃，加入引发剂混匀；然后滴加混合单体和分散剂进行原位接枝共聚反应，然后收集产物，洗涤，干燥；
    (3)将步骤(2)中干燥后的产物在空气氛围中300～600℃煅烧3～6h；得到碳包覆铁酸锌电极材料。
  2. 根据权利要求1所述的碳包覆铁酸锌电极材料的制备方法，其特征在于：步骤(1)中所述的硅烷类偶联剂为KH570或KH560；所述的硅烷类偶联剂的用量不超过铁酸锌质量的5％。
  3. 根据权利要求1所述的碳包覆铁酸锌电极材料的制备方法，其特征在于：
    步骤(2)中所述的引发剂为过氧化苯甲酰或偶氮二异丁腈；所述的引发剂的用量为混合单体质量的0.8％～1.2％。
  4. 根据权利要求1所述的碳包覆铁酸锌电极材料的制备方法，其特征在于：
    步骤(2)中所述的混合单体为苯乙烯和丙烯腈，其中，苯乙烯和丙烯晴的质量比为(3:7)～(7:3)；步骤(2)中所述的铁酸锌与混合单体的质量比为1:(1～3)。
  5. 根据权利要求1所述的碳包覆铁酸锌电极材料的制备方法，其特征在于：
    步骤(2)中所述的铁酸锌与混合单体的质量比为1:1。
  6. 根据权利要求1所述的碳包覆铁酸锌电极材料的制备方法，其特征在于：
    步骤(2)中所述的分散剂为聚乙烯吡咯烷酮；所述的分散剂的用量为混合单体质量的10％～20％。
  7. 根据权利要求1所述的碳包覆铁酸锌电极材料的制备方法，其特征在于：
    步骤(2)中所述的原位接枝共聚反应的时间为12h～24h。
  8. 根据权利要求1所述的碳包覆铁酸锌电极材料的制备方法，其特征在于：步骤(1)中所述的表面处理的时间为2～12h。
  9. 一种碳包覆铁酸锌电极材料，其特征在于：通过权利要求1～8任一项所述的制备方法制备得到。
  10. 权利要求9所述的碳包覆铁酸锌电极材料在锂离子电池领域中的应用。
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