WO2021196428A1 - Iron oxide nanotube material and preparation method therefor - Google Patents

Iron oxide nanotube material and preparation method therefor Download PDF

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WO2021196428A1
WO2021196428A1 PCT/CN2020/098711 CN2020098711W WO2021196428A1 WO 2021196428 A1 WO2021196428 A1 WO 2021196428A1 CN 2020098711 W CN2020098711 W CN 2020098711W WO 2021196428 A1 WO2021196428 A1 WO 2021196428A1
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iron oxide
feooh
nanotubes
oxide nanotube
nanotube
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赵卫民
林红
刘永
孙建勇
闫福东
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山东海容电源材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

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  • the invention relates to the field of nanocomposite material preparation, in particular to an iron oxide nanotube material and a preparation method thereof.
  • Lithium-ion batteries have attracted widespread attention because of their long cycle life, high energy density, low self-discharge and environmental friendliness.
  • the negative electrode material in lithium ion batteries is mainly commercial graphite, but in recent years, graphite negative electrodes have been continuously improved, making the capacity of storing lithium ions closer and closer to the theoretical capacity of 372mAh/g. Since it is difficult to achieve breakthroughs in the improvement of graphite anode materials, people have turned their attention to transition metal oxides with high specific capacity and excellent safety performance.
  • Fe 2 O 3 in transition metal oxides has a theoretical capacity of 1005 mAh/g, abundant raw materials, and low cost.
  • the modification and improvement of Fe 2 O 3 have broad research prospects.
  • the present invention provides an iron oxide nanotube material with simple and easy reaction, low cost, and suitable for industrial production and a preparation method thereof.
  • An iron oxide nanotube material which is characterized in that: ⁇ -FeOOH nanorods are used as raw materials to obtain ⁇ -FeOOH nanotubes through polyacid etching, and the ⁇ -FeOOH nanotubes are transformed by heating to obtain iron oxide nanometers with stable appearance.
  • the surface of the iron oxide nanotube is a hollow tube.
  • the invention adopts the ⁇ -FeOOH porous nanotubes formed by heating and multi-acid etching to obtain Fe 2 O 3 nanotube materials that maintain the morphology of the nanotubes, which solves the problems of low specific capacity and poor cycle stability of traditional negative electrode materials, and is Fe 2 O 3
  • the method for preparing iron oxide nanotube materials includes the following steps: firstly use phosphotungstic acid to etch ⁇ -FeOOH nanorods to form ⁇ -FeOOH nanotubes; The ⁇ -FeOOH nanotubes are heated at a temperature of °C for 2h to form pure phase iron oxide nanotubes.
  • the phosphotungstic acid etching reaction temperature is 80° C.
  • the reaction time is 1 h
  • the reaction temperature rise rate is 2° C./min.
  • the heating rate of the ⁇ -FeOOH nanotubes is 1-5°C/min; the heating reaction temperature is too high, the nanotube skeleton is easy to collapse; the temperature is too low, the ⁇ -FeOOH nanotubes cannot be fully converted into iron oxide nanotube materials .
  • the advantages of the present invention are that the iron-based nanotubes can be controllably produced by adjusting the polyacid, the skeleton supporting the iron ions can still maintain the stability of the morphology after aerobic combustion, and the obtained iron oxide nanotubes have good uniformity and good stability. It is beneficial to the improvement of electrochemical performance; the iron oxide nanotube material of the present invention is a nano-scale tubular material with high capacity and good cycle performance. Its preparation method has the advantages of low cost, simple process flow, mild reaction conditions and large utilization. Characteristics of mass production.
  • Figure 1 is a thermogravimetric diagram of the ⁇ -FeOOH nanotubes of the present invention
  • Figure 2 is a single crystal X-ray diffraction pattern of the iron oxide nanotube material of the present invention
  • Figure 3 is an ordinary scanning electron microscope map of the iron oxide nanotube material of the present invention.
  • Figure 4 is an elemental analysis spectrum diagram of the iron oxide nanotube material of the present invention.
  • Fig. 5 is a graph showing the rate performance of the iron oxide nanotube material of the present invention.
  • the inventors used the controllable adjustment of the acidity of phosphotungstic acid to generate ⁇ -FeOOH nanotubes.
  • the ⁇ -FeOOH nanotubes were heated aerobic to convert them into Fe 2 O 3 nanotubes.
  • the preparation method of the nano material has the characteristics of low cost, simple process flow, mild reaction conditions and favorable for large-scale promotion.
  • the present invention provides an Fe 2 O 3 nanotubes, based on Fe 2 O 3 structure of the nanotubes, the method further study was prepared according to the present invention, Fe 2 O 3 nanotube material.
  • the preparation method of the iron oxide nanotube material of the present invention includes the following steps:
  • FIG. 1 is the thermogravimetric spectrum of the ⁇ -FeOOH porous nanotubes prepared by the present invention.
  • the heating temperature is selected by measuring the change in mass percentage of the sample as the temperature rises, so as to ensure most of the reaction
  • the substance can be converted into Fe 2 O 3 , and it is necessary to ensure that the nanotube framework remains stable during the reaction process. From the figure, we find that the mass percentage of nanotubes decreases significantly at 250°C, indicating that the skeleton begins to become unstable, but the skeleton does not collapse; at 400°C, the mass percentage of nanotubes tends to stabilize, indicating that the skeleton of the nanotubes is complete Collapse. In order to ensure the complete conversion of the reactants, we select 250°C as the optimal reaction temperature.
  • Figure 2 is the single crystal X-ray diffraction pattern of Fe 2 O 3 nanotube material prepared by the present invention.
  • the basic principle of X-ray diffraction is to make a single monochromatic X-ray incident on the test sample, and different atoms are scattered. X-rays will interfere with each other, which makes strong X-ray diffraction appear in some special directions. According to the orientation and intensity of the diffraction lines in space, it is possible to analyze the close relationship between the structure of the sample and the internal atomic distribution rules. From the figure, we find that the diffraction peaks of the prepared Fe 2 O 3 nanotube material correspond to the characteristic peaks of the standard sample respectively, which means that the obtained sample is pure phase Fe 2 O 3 without other impurities.
  • Figure 3 is an SEM image of the Fe 2 O 3 nanotube material prepared by the present invention. From the figure, an obvious tubular structure can be observed, which shows that the Fe 2 O 3 material still maintains a nanotube structure in the microscopic view. Its length and width are both nanometers. The small microscopic size of nanomaterials effectively alleviates the changes in the volume structure of the material during charging and discharging. The high specific surface area not only enhances the lithium ion intercalation activity, but also the tubular structure can provide a reserved space for volume expansion during the lithiation process.
  • FIG 4 is the elemental analysis spectrum of the Fe 2 O 3 nanotube material prepared by the present invention.
  • the nanotubes are mainly composed of iron and oxygen elements, without tungsten, which indicates that the purity of the Fe 2 O 3 nanotube samples prepared is relatively high.
  • FIG 5 is the rate performance diagram of the Fe 2 O 3 nanotube material prepared by the present invention.
  • the electrochemical test results show that compared with the traditional graphite anode material, the rate performance of the Fe 2 O 3 nanotube material is Improved significantly.
  • the first discharge specific capacity of the material at a rate of 1C/10C is about 1350Ah/g, and the specific capacity of the material is still maintained at about 930Ah/g after 10 cycles. The experiment was done three times in parallel to ensure the accuracy of the data.
  • the present invention obtains a Fe 2 O 3 nanotube material through a two-step hydrothermal-heating method, and the material can be applied to the field of lithium ion battery negative electrodes.
  • the preparation method of the nano material is simple and easy to implement, the raw material price is low, and it is suitable for large-scale production, which provides a reference for the preparation of other nano materials.

Abstract

An iron oxide nanotube material and a preparation method therefor. The iron oxide nanotube material is characterized in that a β-FeOOH nanorod is used as a raw material, a β-FeOOH nanotube is obtained by means of polyacid etching, then the β-FeOOH nanotube is heated and converted to obtain an morphologically stable iron oxide nanotube, and the surface of the iron oxide nanotube is in a hollow tubular shape. The iron oxide nanotube material is a nanoscale tubular material and has the characteristics of high capacity and good cycle performance, and the preparation method therefor has the characteristics of low cost, simple process flow, mild reaction conditions and utilization of large-scale production.

Description

一种氧化铁纳米管材料及其制备方法Iron oxide nanotube material and preparation method thereof (一)技术领域(1) Technical field
本发明涉及纳米复合材料制备领域，特别涉及一种氧化铁纳米管材料及其制备方法。The invention relates to the field of nanocomposite material preparation, in particular to an iron oxide nanotube material and a preparation method thereof.
(二)背景技术(2) Background technology
随着环境问题的日益严重，人们渴望找到可持续能源来满足日益增长的经济要求。锂离子电池因为具有循环寿命长、高能量密度、低自放电和环境友好等优点引起人们的广泛关注。锂离子电池中的负极材料主要是商业化石墨，但是近几年来，石墨负极被不断改进，使得储存锂离子的容量越来越接近理论容量372mAh/g。由于对石墨负极材料的改良难以取得突破，因此人们把目光投向高比容量和安全性能优异的过渡金属氧化物。With the increasingly serious environmental problems, people are eager to find sustainable energy to meet the growing economic requirements. Lithium-ion batteries have attracted widespread attention because of their long cycle life, high energy density, low self-discharge and environmental friendliness. The negative electrode material in lithium ion batteries is mainly commercial graphite, but in recent years, graphite negative electrodes have been continuously improved, making the capacity of storing lithium ions closer and closer to the theoretical capacity of 372mAh/g. Since it is difficult to achieve breakthroughs in the improvement of graphite anode materials, people have turned their attention to transition metal oxides with high specific capacity and excellent safety performance.
在脱嵌锂的过程中，过渡金属氧化物因为过大的体积变化导致碎裂粉化，这使得活性物质失去有效电接触，导致容量衰减，循环寿命变短。为了提高该类材料的电化学性能，人们尝试从以下方面对材料进行改进：①负极材料复合化：通过引入导电性能好且体积效应小的物质来提高电极的电化学性能；②活性材料纳米化：纳米材料的微观尺寸的较小有效缓解了材料充放电过程中的体积结构变化，高比表面积不仅增强了锂离子嵌入活性，而且可以获得高倍率容量。In the process of deintercalating lithium, the transition metal oxides are fragmented and pulverized due to excessive volume changes, which makes the active material lose effective electrical contact, resulting in capacity degradation and shortened cycle life. In order to improve the electrochemical performance of such materials, people try to improve the materials from the following aspects: ① Composite anode material: Improve the electrochemical performance of the electrode by introducing substances with good conductivity and small volume effect; ② Nanometerization of active materials : The small microscopic size of nanomaterials effectively alleviates the changes in the volume structure of the material during charging and discharging. The high specific surface area not only enhances the lithium ion intercalation activity, but also obtains high rate capacity.
过渡金属氧化物中的Fe 2O 3作为负极材料，具有1005mAh/g的理论容量且原料丰富、成本低廉，对Fe 2O 3的修饰改进具有广阔的研究前景。 As a negative electrode material, Fe 2 O 3 in transition metal oxides has a theoretical capacity of 1005 mAh/g, abundant raw materials, and low cost. The modification and improvement of Fe 2 O 3 have broad research prospects.
(三)发明内容(3) Contents of the invention
本发明为了弥补现有技术的不足，提供了一种反应简单易行、成本低廉、适于工业化生产的氧化铁纳米管材料及其制备方法。In order to make up for the deficiencies of the prior art, the present invention provides an iron oxide nanotube material with simple and easy reaction, low cost, and suitable for industrial production and a preparation method thereof.
本发明是通过如下技术方案实现的：The present invention is realized through the following technical solutions:
一种氧化铁纳米管材料，其特征在于：以β-FeOOH纳米棒为原料，通过多酸刻蚀得到β-FeOOH纳米管，β-FeOOH纳米管再经加热转化得到形貌稳定的氧化铁纳米管，该氧化铁纳米管表面呈中空管状。An iron oxide nanotube material, which is characterized in that: β-FeOOH nanorods are used as raw materials to obtain β-FeOOH nanotubes through polyacid etching, and the β-FeOOH nanotubes are transformed by heating to obtain iron oxide nanometers with stable appearance. The surface of the iron oxide nanotube is a hollow tube.
本发明采用加热多酸刻蚀形成的β-FeOOH多孔纳米管得到保持纳米管形貌的Fe 2O 3纳米管材料，解决了传统负极材料比容量低和循环稳定性差的问题，为Fe 2O 3纳米管负极材料的推广应用奠定了基础。 The invention adopts the β-FeOOH porous nanotubes formed by heating and multi-acid etching to obtain Fe 2 O 3 nanotube materials that maintain the morphology of the nanotubes, which solves the problems of low specific capacity and poor cycle stability of traditional negative electrode materials, and is Fe 2 O 3 The popularization and application of nanotube anode materials laid the foundation.
基于上述发明构思，氧化铁纳米管材料的制备方法，其步骤为：首先利用磷钨酸来刻蚀β-FeOOH纳米棒，形成β-FeOOH纳米管；其次通过控制加热温度，在空气中以250℃、保温2h的条件加热β-FeOOH纳米管，形成纯相氧化铁纳米管。Based on the above-mentioned inventive concept, the method for preparing iron oxide nanotube materials includes the following steps: firstly use phosphotungstic acid to etch β-FeOOH nanorods to form β-FeOOH nanotubes; The β-FeOOH nanotubes are heated at a temperature of ℃ for 2h to form pure phase iron oxide nanotubes.
本发明的更优技术方案为：The more optimal technical scheme of the present invention is:
所述磷钨酸刻蚀反应温度为80℃，反应时间为1h，反应升温速率为2℃/min。The phosphotungstic acid etching reaction temperature is 80° C., the reaction time is 1 h, and the reaction temperature rise rate is 2° C./min.
所述β-FeOOH纳米管的加热升温速率为1-5℃/min；该加热反应温度过高，纳米管骨架容易坍塌；温度过低，β-FeOOH纳米管不能充分转化为氧化铁纳米管材料。The heating rate of the β-FeOOH nanotubes is 1-5°C/min; the heating reaction temperature is too high, the nanotube skeleton is easy to collapse; the temperature is too low, the β-FeOOH nanotubes cannot be fully converted into iron oxide nanotube materials .
进一步的，本发明的更具体反应步骤为：Further, the more specific reaction steps of the present invention are:
将1.622g氯化铁加入25mL蒸馏水中，加入100μL的浓盐酸防 止水解，之后加入43mg的磷钨酸搅拌均匀，置于反应釜中加热，冷却离心后，用超纯水和乙醇反复冲洗，干燥后得到β-FeOOH纳米管固体；Add 1.622g of ferric chloride to 25mL of distilled water, add 100μL of concentrated hydrochloric acid to prevent hydrolysis, then add 43mg of phosphotungstic acid and stir evenly, place it in the reactor to heat, cool and centrifuge, rinse repeatedly with ultrapure water and ethanol, and dry Then obtain β-FeOOH nanotube solid;
取50mgβ-FeOOH纳米管放入马弗炉中加热，冷却后用蒸馏水和乙醇反复清洗，过滤后得到黑色产品。Take 50mg of β-FeOOH nanotubes and put them in a muffle furnace for heating, and after cooling, they are repeatedly washed with distilled water and ethanol, and a black product is obtained after filtration.
本发明的优点在于可以通过调节多酸来可控生成铁基纳米管，支撑铁离子的骨架经过有氧燃烧，依然能保持形貌的稳定，得到的氧化铁纳米管均一性好、稳定性好，有利于电化学性能的提高；本发明的氧化铁纳米管材料是纳米级管状材料，具有容量高、循环性能良好的特地，其制备方法具有成本低、工艺流程简单、反应条件温和以及利用大规模生产的特点。The advantages of the present invention are that the iron-based nanotubes can be controllably produced by adjusting the polyacid, the skeleton supporting the iron ions can still maintain the stability of the morphology after aerobic combustion, and the obtained iron oxide nanotubes have good uniformity and good stability. It is beneficial to the improvement of electrochemical performance; the iron oxide nanotube material of the present invention is a nano-scale tubular material with high capacity and good cycle performance. Its preparation method has the advantages of low cost, simple process flow, mild reaction conditions and large utilization. Characteristics of mass production.
(四)附图说明(4) Description of the drawings
下面结合附图对本发明作进一步的说明。The present invention will be further described below in conjunction with the accompanying drawings.
图1为本发明β-FeOOH纳米管的热重图谱；Figure 1 is a thermogravimetric diagram of the β-FeOOH nanotubes of the present invention;
图2为本发明氧化铁纳米管材料单晶X射线衍射图谱；Figure 2 is a single crystal X-ray diffraction pattern of the iron oxide nanotube material of the present invention;
图3为本发明氧化铁纳米管材料普通扫描电子显微镜图谱；Figure 3 is an ordinary scanning electron microscope map of the iron oxide nanotube material of the present invention;
图4为本发明氧化铁纳米管材料元素分析谱图；Figure 4 is an elemental analysis spectrum diagram of the iron oxide nanotube material of the present invention;
图5为本发明氧化铁纳米管材料的倍率性能图。Fig. 5 is a graph showing the rate performance of the iron oxide nanotube material of the present invention.
(五)具体实施方式(5) Specific implementation methods
为了更好地理解和实施，下面结合附图详细说明本发明。For a better understanding and implementation, the present invention will be described in detail below in conjunction with the accompanying drawings.
本发明人在研究锂离子电池负极材料时发现应用非常广泛的碳负极材料容量开发已经进入瓶颈期，需要进一步开发新型负极材料。 因此，申请人通过对Fe 2O 3的研究发现其具有非常高的理论储锂容量，但是反应过程中过大的体积变化导致其容易碎裂粉化，这极大的影响其在电化学方面的应用。通过研究发现，纳米材料的微观尺寸较小有效缓解了材料充放电过程中的体积结构变化。 The inventor found that the capacity development of carbon anode materials, which is widely used, has entered a bottleneck period when studying anode materials for lithium-ion batteries, and it is necessary to further develop new anode materials. Therefore, the applicant found through research on Fe 2 O 3 that it has a very high theoretical lithium storage capacity, but the excessive volume change during the reaction causes it to be easily broken and pulverized, which greatly affects its electrochemical aspects. Applications. Through research, it is found that the small microscopic size of nanomaterials effectively alleviates the volume structure changes during the charging and discharging process of the materials.
进一步，发明人利用磷钨酸的酸性可控调节生成β-FeOOH纳米管，通过控制温度，有氧加热β-FeOOH纳米管使其转变为Fe 2O 3纳米管。该纳米材料制备方法具有成本廉价、工艺流程简单、反应条件温和以及利于大规模推广的特点。 Furthermore, the inventors used the controllable adjustment of the acidity of phosphotungstic acid to generate β-FeOOH nanotubes. By controlling the temperature, the β-FeOOH nanotubes were heated aerobic to convert them into Fe 2 O 3 nanotubes. The preparation method of the nano material has the characteristics of low cost, simple process flow, mild reaction conditions and favorable for large-scale promotion.
本发明提供一种Fe 2O 3纳米管材料，基于该Fe 2O 3纳米管材料的结构，进一步研究得到本发明的Fe 2O 3纳米管材料的制备方法。以下，通过实施例进一步的详细说明。本发明氧化铁纳米管材料的制备方法包括如下步骤： The present invention provides an Fe 2 O 3 nanotubes, based on Fe 2 O 3 structure of the nanotubes, the method further study was prepared according to the present invention, Fe 2 O 3 nanotube material. Hereinafter, it will be described in further detail through examples. The preparation method of the iron oxide nanotube material of the present invention includes the following steps:
(1)制备磷钨酸诱导的β-FeOOH多孔纳米管：将1.622g FeCl 3加入25mL蒸馏水中，加入100μL的HCl防止水解。加入43mg的磷钨酸搅拌均匀，放入反应釜中加热，冷却离心后，用超纯水和乙醇反复清洗，干燥后得到固体； (1) Preparation of β-FeOOH porous nanotubes induced by phosphotungstic acid: 1.622 g of FeCl 3 was added to 25 mL of distilled water, and 100 μL of HCl was added to prevent hydrolysis. Add 43mg of phosphotungstic acid and stir evenly, put it into the reactor and heat, after cooling and centrifuging, repeatedly washing with ultrapure water and ethanol, and drying to obtain a solid;
(2)制备Fe 2O 3纳米管材料：取50mg S1步骤中制备的样品，放入马弗炉中加热，冷却后用蒸馏水和乙醇反复清洗，过滤后得到黑色样品。 (2) Preparation of Fe 2 O 3 nanotube material: Take 50 mg of the sample prepared in step S1, heat it in a muffle furnace, and wash it repeatedly with distilled water and ethanol after cooling, and obtain a black sample after filtering.
实施例1：Example 1:
请参阅附图1，其是本发明制备的β-FeOOH多孔纳米管的热重图谱，通过测定样品随着温度的升高，质量百分比的变化情况来选择 加热温度，既要保证大部分的反应物能够转化为Fe 2O 3，又要保证反应过程中纳米管骨架保持稳定。从图中我们发现250℃时，纳米管质量百分比下降明显，表明其骨架开始变得不稳定，但是骨架并没有坍塌；400℃时，纳米管质量百分比趋于稳定，说明纳米管的骨架已经完全坍塌。为了保证反应物转化完全，我们从中选取250℃作为最佳反应温度。 Please refer to attached Figure 1, which is the thermogravimetric spectrum of the β-FeOOH porous nanotubes prepared by the present invention. The heating temperature is selected by measuring the change in mass percentage of the sample as the temperature rises, so as to ensure most of the reaction The substance can be converted into Fe 2 O 3 , and it is necessary to ensure that the nanotube framework remains stable during the reaction process. From the figure, we find that the mass percentage of nanotubes decreases significantly at 250°C, indicating that the skeleton begins to become unstable, but the skeleton does not collapse; at 400°C, the mass percentage of nanotubes tends to stabilize, indicating that the skeleton of the nanotubes is complete Collapse. In order to ensure the complete conversion of the reactants, we select 250°C as the optimal reaction temperature.
实施例2：Example 2:
请参阅附图2，其是本发明制备的Fe 2O 3纳米管材料单晶X射线衍射图谱，X射线衍射的基本原理是让一束单色X射线入射到测试样品上，不同原子散射的X射线会相互干涉，这使得在某些特殊方向上会出现强X射线衍射，根据衍射线在空间分布的方位和强度，能够分析出样品的结构密切相关和内部的原子分配规律。从图中我们发现制备的Fe 2O 3纳米管材料的衍射峰与标准样品的特征峰分别对应，这表示得到的样品是纯相Fe 2O 3，并无其他杂质。 Please refer to Figure 2, which is the single crystal X-ray diffraction pattern of Fe 2 O 3 nanotube material prepared by the present invention. The basic principle of X-ray diffraction is to make a single monochromatic X-ray incident on the test sample, and different atoms are scattered. X-rays will interfere with each other, which makes strong X-ray diffraction appear in some special directions. According to the orientation and intensity of the diffraction lines in space, it is possible to analyze the close relationship between the structure of the sample and the internal atomic distribution rules. From the figure, we find that the diffraction peaks of the prepared Fe 2 O 3 nanotube material correspond to the characteristic peaks of the standard sample respectively, which means that the obtained sample is pure phase Fe 2 O 3 without other impurities.
实施例3：Example 3:
请参阅附图3，其是本发明制备的Fe 2O 3纳米管材料的SEM图像，从图中可以观察到明显的管状结构，这表明Fe 2O 3材料在微观上依然保持纳米管状结构，其长度和宽度均呈纳米级。纳米材料的微观尺寸较小有效缓解了材料充放电过程中的体积结构变化，高比表面积不仅增强了锂离子嵌入活性，而且管状结构可以为锂化过程中体积膨胀提供预留的空间。 Please refer to Figure 3, which is an SEM image of the Fe 2 O 3 nanotube material prepared by the present invention. From the figure, an obvious tubular structure can be observed, which shows that the Fe 2 O 3 material still maintains a nanotube structure in the microscopic view. Its length and width are both nanometers. The small microscopic size of nanomaterials effectively alleviates the changes in the volume structure of the material during charging and discharging. The high specific surface area not only enhances the lithium ion intercalation activity, but also the tubular structure can provide a reserved space for volume expansion during the lithiation process.
实施例4：Example 4:
请参阅附图4，其是本发明制备的Fe 2O 3纳米管材料元素分析谱图，由于水热法合成β-FeOOH多孔纳米管过程中需要用到磷钨酸来进行刻蚀，尽管反应后进行清洗，但还是可能存在一部分磷钨酸附着在β-FeOOH多孔纳米管上，经过空气中加热过程，生成钨磷氧化物影响产物的纯度，从图中可以清晰的看到Fe 2O 3纳米管主要是由铁元素和氧元素组成，并无钨元素，这表明制得的Fe 2O 3纳米管样品的纯度比较高。 Please refer to Figure 4, which is the elemental analysis spectrum of the Fe 2 O 3 nanotube material prepared by the present invention. As the process of hydrothermal synthesis of β-FeOOH porous nanotubes requires phosphotungstic acid for etching, although the reaction After cleaning, there may still be a part of phosphotungstic acid attached to the β-FeOOH porous nanotubes. After heating in the air, tungsten phosphorous oxide is generated and the purity of the product is affected. Fe 2 O 3 can be clearly seen from the figure. The nanotubes are mainly composed of iron and oxygen elements, without tungsten, which indicates that the purity of the Fe 2 O 3 nanotube samples prepared is relatively high.
实施例5：Example 5:
请参阅附图5，其是本发明制备的Fe 2O 3纳米管材料的倍率性能图，电化学测试结果显示，与传统的石墨负极材料相比，Fe 2O 3纳米管材料的倍率性能有显著的提高。1C/10C的倍率下材料的首次放电比容量为1350Ah/g左右，循环10次后该材料的比容量仍然维持在930Ah/g左右。该实验平行做三次，保证数据的准确性。 Please refer to Figure 5, which is the rate performance diagram of the Fe 2 O 3 nanotube material prepared by the present invention. The electrochemical test results show that compared with the traditional graphite anode material, the rate performance of the Fe 2 O 3 nanotube material is Improved significantly. The first discharge specific capacity of the material at a rate of 1C/10C is about 1350Ah/g, and the specific capacity of the material is still maintained at about 930Ah/g after 10 cycles. The experiment was done three times in parallel to ensure the accuracy of the data.
相对于现有技术，本发明通过水热-加热两步法得到了一种Fe 2O 3纳米管材料，并可把该材料运用到锂离子电池负极领域。该纳米材料的制备方法简单易行，原料价格低廉，适合大规模生产，这为其他纳米材料的制备提供了借鉴。 Compared with the prior art, the present invention obtains a Fe 2 O 3 nanotube material through a two-step hydrothermal-heating method, and the material can be applied to the field of lithium ion battery negative electrodes. The preparation method of the nano material is simple and easy to implement, the raw material price is low, and it is suitable for large-scale production, which provides a reference for the preparation of other nano materials.
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above are only the embodiments of the present invention, which do not limit the scope of the present invention. Any equivalent structure or equivalent process transformation made by using the content of the description and drawings of the present invention, or directly or indirectly applied to other related technologies In the same way, all fields are included in the scope of patent protection of the present invention.

Claims (6)

  1. 一种氧化铁纳米管材料，其特征在于：以β-FeOOH纳米棒为原料，通过多酸刻蚀得到β-FeOOH纳米管，β-FeOOH纳米管再经加热转化得到形貌稳定的氧化铁纳米管，该氧化铁纳米管表面呈中空管状。An iron oxide nanotube material, which is characterized in that: β-FeOOH nanorods are used as raw materials to obtain β-FeOOH nanotubes through polyacid etching, and the β-FeOOH nanotubes are transformed by heating to obtain iron oxide nanometers with stable appearance. The surface of the iron oxide nanotube is a hollow tube.
  2. 根据权利要求1所述的氧化铁纳米管材料的制备方法，其特征在于：首先利用磷钨酸来刻蚀β-FeOOH纳米棒，形成β-FeOOH纳米管；其次通过控制加热温度，在空气中以250℃、保温2h的条件加热β-FeOOH纳米管，形成纯相氧化铁纳米管。The method for preparing iron oxide nanotube materials according to claim 1, characterized in that: firstly, phosphotungstic acid is used to etch β-FeOOH nanorods to form β-FeOOH nanotubes; secondly, by controlling the heating temperature, in the air The β-FeOOH nanotubes were heated at 250°C for 2h to form pure phase iron oxide nanotubes.
  3. 根据权利要求2所述的氧化铁纳米管材料的制备方法，其特征在于：所述磷钨酸刻蚀反应温度为80℃，反应时间为1h，反应升温速率为2℃/min。The method for preparing iron oxide nanotube material according to claim 2, wherein the phosphotungstic acid etching reaction temperature is 80°C, the reaction time is 1 h, and the reaction temperature rise rate is 2°C/min.
  4. 根据权利要求2所述的氧化铁纳米管材料的制备方法，其特征在于：所述β-FeOOH纳米管的加热升温速率为1-5℃/min。The method for preparing iron oxide nanotube materials according to claim 2, wherein the heating rate of the β-FeOOH nanotubes is 1-5°C/min.
  5. 根据权利要求2所述的氧化铁纳米管材料的制备方法，其特征在于：将1.622g氯化铁加入25mL蒸馏水中，加入100μL的浓盐酸，之后加入43mg的磷钨酸搅拌均匀，置于反应釜中加热，冷却离心后，用超纯水和乙醇反复冲洗，干燥后得到β-FeOOH纳米管固体。The method for preparing iron oxide nanotube material according to claim 2, characterized in that: 1.622g of ferric chloride is added to 25mL of distilled water, 100μL of concentrated hydrochloric acid is added, and then 43mg of phosphotungstic acid is added, stirred evenly, and placed in the reaction The kettle is heated, cooled and centrifuged, washed repeatedly with ultrapure water and ethanol, and dried to obtain β-FeOOH nanotube solids.
  6. 根据权利要求2所述的氧化铁纳米管材料的制备方法，其特征在于：取50mgβ-FeOOH纳米管放入马弗炉中加热，冷却后用蒸馏水和乙醇反复清洗，过滤后得到黑色产品。The method for preparing iron oxide nanotube material according to claim 2, characterized in that: 50 mg of β-FeOOH nanotubes are heated in a muffle furnace, and after cooling, they are repeatedly washed with distilled water and ethanol, and a black product is obtained after filtration.
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