WO2015051627A1 - Rod-shaped nano iron oxide electrode material, and preparation method therefor and application thereof - Google Patents

Rod-shaped nano iron oxide electrode material, and preparation method therefor and application thereof Download PDF

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WO2015051627A1
WO2015051627A1 PCT/CN2014/075130 CN2014075130W WO2015051627A1 WO 2015051627 A1 WO2015051627 A1 WO 2015051627A1 CN 2014075130 W CN2014075130 W CN 2014075130W WO 2015051627 A1 WO2015051627 A1 WO 2015051627A1
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iron oxide
rod
shaped nano
preparation
electrode material
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PCT/CN2014/075130
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French (fr)
Chinese (zh)
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曾宏
武英
戚雯
况春江
周少雄
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安泰科技股份有限公司
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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
    • H01M4/48—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
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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)
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—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
    • 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
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • 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
    • 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
    • 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

  • Rod-shaped nano-iron oxide electrode material preparation method and application thereof
  • the invention belongs to the technical field of preparation of electrode materials for lithium ion batteries, and particularly relates to a rod-shaped nano-iron oxide electrode material, a preparation method and application thereof, the rod-shaped nano-iron oxide has regular shape, uniform size, high purity, and can be used as positive and negative Electrode material. Background technique
  • lithium-ion battery As a new type of high-energy battery, lithium-ion battery has the advantages of high energy density, long service life, good cycle performance and no memory effect. It is widely used in mobile electronic products such as mobile phones, notebook computers, digital cameras and so on. In recent years, lithium-ion batteries have become one of the most valuable energy storage devices in the 21st century in the fields of electric vehicles, power tools, smart power grids, distributed energy systems, aerospace, and defense.
  • iron oxide nanomaterials Due to its high theoretical specific capacity, abundant reserves, easy preparation, non-toxicity, environmental friendliness and low cost, iron oxide nanomaterials have become a research hotspot in the field of lithium ion battery materials.
  • Common methods for synthesizing nano-iron oxides include mechanical ball milling, hydrothermal reaction, or synthesis of iron oxide nanomaterials by layer-by-layer self-assembly and subsequent heat treatment using FeOOH nanorods as precursors.
  • the mechanical ball milling method has the following drawbacks despite the simple method:
  • the obtained material has low purity, contains other impurities, and the prepared material is generally granular and the particle distribution is uneven.
  • a method for preparing nanometer iron oxide by using FeOOH nanorods as a precursor generally adding a base, It is polluted by the environment.
  • the obtained materials must be annealed at about 600 degrees, the process flow is long, the operation steps are cumbersome, the efficiency is low, and the energy consumption is high.
  • nano-iron oxide prepared by the above method is generally used as a negative electrode material for a lithium ion battery, and is basically not used as a positive electrode material, and a lithium salt such as lithium iron phosphate is usually used as a positive electrode material.
  • the main constituent materials of lithium-ion battery include electrolyte, isolation material, positive and negative materials, etc.
  • the positive electrode material occupies a large proportion (the mass ratio of positive and negative materials is 3:1 ⁇ 4:1), and the cost directly determines the battery cost. High and low. Therefore, the development of low-cost cathode materials is a market demand.
  • One of the objects of the present invention is to provide a method for preparing a rod-shaped nano-iron oxide electrode material in view of the defects existing in the prior art. This method is simple and easy.
  • Another object of the present invention is to provide a rod-shaped nano-iron oxide electrode material prepared by the above method and its use in a lithium ion battery.
  • the obtained rod-shaped nano-iron oxide not only has a relatively large specific surface area, a regular morphology, a uniform size, and good electrochemical performance.
  • a method for preparing a rod-shaped nanometer iron oxide electrode material wherein a hydrothermal reaction is carried out by using FeCl 3 «6H 2 0, ammonium dihydrogen phosphate (NH 4 H 2 P0 4 ) and water as raw materials, and the resulting precipitate is washed to obtain a rod shape.
  • Nano-iron oxide powder
  • FeCl 3 «6H 2 0 FeCl 3 +6H 2 0
  • the hydrothermal reaction temperature is 200-240 ° C, and the hydrothermal reaction time is 1-10 h.
  • the temperature of the hydrothermal reaction is 202 ° C, 210 ° C, 218 ° C, 225 ° C, 230 ° C, 235 ° C or 238.
  • hydrothermal reaction time is 1.5h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h, 8h, 8.5h or 9.5h. More preferably, the temperature of the hydrothermal reaction is 210-230 ° C, and the time of the hydrothermal reaction is 4-5 h.
  • the molar ratio of FeCl 3 «6H 2 0 to ammonium dihydrogen phosphate in the raw material is 26: 1-30: 1, exemplarily Can be 26.5: 1, 27: 1, 28: 1, 29: 1 or 29.5: 1.
  • the molar ratio of FeCl 3 *6H 2 0 to ammonium dihydrogen phosphate in the raw material is 27: 1-28: 1.
  • the precipitate is washed successively with deionized water and alcohol.
  • a rod-shaped nano-iron oxide electrode material prepared by the above method has a rod shape, an average diameter of 60-80 nm, a length of 250-300 nm, a purity of 99.9% or more, and a crystal phase of a-Fe 2 0 3 .
  • the above rod-shaped nano-iron oxide electrode material is used in a lithium ion battery, and the rod-shaped nano-iron oxide electrode material is used as an active material of a positive electrode or a negative electrode of a lithium ion battery.
  • the specific method of the application is as follows:
  • a binder and a conductive agent are added to the rod-shaped nano-iron oxide powder, thoroughly mixed by grinding, and then the mixed slurry is filtered to obtain a uniform pre-coated refining slurry;
  • the pre-coated refining slurry is applied to the surface current collector of the aluminum foil surface and the current collector of the copper foil, and dried to form a battery positive electrode sheet and a battery negative electrode sheet having an active material.
  • the mass percentage of the binder, the conductive agent and the rod-shaped nano iron oxide powder is: binder: 10-20%; conductive agent : 10-30%; rod-shaped nano iron oxide powder: 50-80%. More preferably, the binder: 10; a conductive agent: 20%; a rod-shaped nano iron oxide powder: 70%.
  • the grinding time is 40-60 min, and exemplarily, the grinding time is 42 min, 45 min, 50 min, 55 min. Or 58min.
  • the drying temperature is 100-120 ° C, and the drying time is 18-24 h.
  • the drying temperature is 105 ° C, 110. C, 102. C, 108. C or 120. C
  • drying time is 18.5h, 20h, 21h, 22h, 23h or 23.5h.
  • the binder and the conductive agent are reagents commonly used in the art.
  • the binder may be polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC) or polyolefin (PP, PE and other copolymers:
  • the conductive agent may be Carbon black super P, conductive graphite, ketjen black, carbon nanotubes or nano carbon fibers.
  • the present invention has the following beneficial effects:
  • the preparation method of the rod-shaped nano iron oxide powder of the invention is easy to obtain and non-toxic; the reactant can have a wide concentration range and is easy to control; the toxic substance is not used in the whole reaction, and the reaction does not need to add a surfactant, Catalyst, etc., no pollution to the environment; easy to separate products, few impurities, high purity; simple preparation process, convenient operation, easy to large-scale industrial production.
  • the rod-shaped nano-iron oxide powder obtained by the above method has uniform shape and uniform size, and has a rod shape, and the average diameter is about 60-80 nm, and the length is about 250-300 nm, and the purity of the material is high.
  • the above rod-shaped nano-iron oxide powder is used as a positive and negative electrode active material of a lithium ion battery, and has low cost, good electrochemical performance, good chemical stability of the electrode material, high specific capacity, and low polarization of the charge and discharge platform. It has been proved by experiments that the positive and negative electrodes made of the iron oxide nanorods have good charge and discharge cycles and can be used as electrode materials for lithium ion batteries. The iron oxide nanorod negative electrode materials are charged and discharged under the current of 100mAh/g for the first time.
  • the discharge capacity reaches 1030 mAh/g, the first charge capacity reaches 723 mAh/ g; the iron oxide nanorod positive electrode has a current discharge capacity of 222.4 mAh/g at a current of 20 mAh/g, and the first charge capacity is 175 mAh/g.
  • Figure 1 is a hydrothermal method for synthesizing iron oxide (Fe 2 O 3 ) nanorods (ie, rod-shaped nano-iron oxides, hereinafter referred to as iron oxide nanorods) by a hydrothermal reaction temperature (low-magnification SEM photograph), specifically hydrothermal reaction temperature Scanning electron micrograph (low-magnification SEM photograph) of iron oxide (Fe 2 O 3 ) nanorods prepared at 220 ° C (ie, Example 1); as can be seen from the above picture, the obtained nanomaterials are uniform in size and rod-shaped. The diameters are all about 60-80 nm, and the lengths are about 250-300 nm.
  • FIG. 2 is a topographical view (high-power SEM photograph) of a hydrothermally synthesized iron oxide (Fe 2 O 3 ) nanorod, specifically an iron oxide prepared by a hydrothermal reaction temperature of 220 ° C (ie, Example 1).
  • 2 0 3 Scanning electron micrograph of nanorods (high magnification SEM photograph).
  • the obtained nanomaterials are uniform in size and have a rod shape with a diameter of about 60-80 nm and a length of about 250-300 nm.
  • Figure 3 is a hydrothermal synthetic iron oxide (Fe 2 0 3) XRD pattern, particularly the hydrothermal reaction temperature is detected XRD pattern of synthetic iron oxide (Fe 2 0 3) when the 220 ° C (i.e. Example 1 embodiment), It is found from the figure that the diffraction peaks of the prepared nanomaterials are all XRD of Fe 2 0 3 nanorods. The XRD spectrum can confirm that the product is a-Fe 2 0 3 phase, and the characteristic peak is obvious.
  • FIG. 4 is a Raman spectrum of iron oxide nanorods, specifically a Raman spectrum of iron oxide (Fe 2 0 3 ) synthesized at a hydrothermal reaction temperature of 220 ° C (ie, Example 1), and the prepared nanomaterials are found from the map.
  • the diffraction peaks are all Raman peaks of Fe 2 0 3 nanorods.
  • the Raman structure of iron oxide nanorods is characterized by typical iron oxide. The product was confirmed to be Fe 2 0 3 by Raman spectrum.
  • Example 5 is a capacity-voltage curve of a button cell assembled with the iron oxide nanorods prepared in Example 1 as a negative electrode material. It can be seen from the figure that under the test condition of 0.1C, the iron oxide nanorod negative electrode has a first discharge capacity of 1030 mAh/ g in the voltage range of 0.01 to 3 V ; the first charge capacity reaches 723 mAh/g.
  • Example 6 is a capacity-cycle number and coulombic efficiency curve of a button cell assembled with the iron oxide nanorods prepared in Example 1 as a negative electrode material. As can be seen from the figure, except for the first to the 18th Coulomb efficiency In addition, the coulombic efficiency of other cycles is close to 100%.
  • Fig. 7 is a capacity-voltage curve of a button cell assembled by using iron oxide nanorods prepared in Example 1 as a positive electrode material. It can be seen from the figure that under the test condition of 0.1C, the iron oxide nanorod positive electrode has a first discharge capacity of 222.4 mAh/g in the voltage range of 1.5-4.5V, the first charging capacity is 175mAh/g, and the second discharge capacity is 144.4. mAh/g.
  • Fig. 8 is a capacity (coulombic efficiency) - cycle curve of a button cell assembled with the iron oxide nanorods prepared in Example 1 as a positive electrode material. As can be seen from the figure, in addition to the first to the 10th Coulomb efficiency, the Coulomb efficiency at other cycle times is close to 100%.
  • the obtained nanomaterials are uniform in size and rod-shaped, and the average diameters are all about 60-80 nm, and the lengths are about 250-300 nm. It can be confirmed from Fig. 3 and Fig. 4 that the product is an a-Fe 2 0 3 phase, and the characteristic peak is conspicuous.
  • the prepared rod-shaped nano-iron oxide powder, the binder polytetrafluoroethylene (PTFE) and the conductive agent carbon black Super P were uniformly mixed according to the mass ratio of 7: 1:2, ground for 45 minutes, and then filtered to obtain a uniform pre-preparation.
  • the anode electrode sheet of the electrode active material battery was obtained by holding at a temperature of 110 ° C for 24 h.
  • the slurry was directly applied to a copper foil surface current collector, and incubated at 110 ° C for 24 h in a vacuum oven to obtain an electrode active material battery negative electrode sheet.
  • the battery is subjected to constant current charge and discharge experiments.
  • the electrical performance test results are shown in Figure 5 and Figure 6.
  • the first discharge capacity reaches 1030 mAh/ g at a current density of 0.01 to 3 V and a current density of 100 mAh/ g; the first charge capacity is reached. At 723 mAh/g, it can still be maintained at 90 mAh/g after 100 cycles of charge and discharge.
  • the coulombic efficiency of other cycles is close to 100% except for the first to 18th coulombic efficiency.
  • the positive electrode sheet prepared in this embodiment the lithium sheet is a negative electrode sheet, and PE (polyethylene) is a separator.
  • the battery is subjected to constant current charge and discharge experiments.
  • the electrical performance test results are shown in Figure 7 and Figure 8.
  • the first discharge capacity reaches 222.4 mAh/g and the first charge capacity in the voltage range of 1.5-4.5V and 100mA/g current density. 175mAh/g, the second discharge capacity is 144.4mAh/g, and can still be maintained at HOmAh/g after 20 cycles of charge and discharge.
  • the coulombic efficiency is close to 100% except for the first to the 10th Coulomb efficiency. .
  • Example 2 Example 2
  • the molar ratio of ferric chloride to ammonium dihydrogen phosphate is 30:1 and deionized water (120g), all of which are placed in a hydrothermal reaction kettle. At 220 °C, the hydrothermal reaction time is 2 h. Then naturally cool to room temperature. The precipitate was washed three times with deionized water and twice with alcohol, and after separation, a rod-shaped nano-iron oxide powder was obtained, and the purity by HPLC was 99.9%.
  • the obtained nanomaterials are uniform in size and rod-shaped, with diameters of about 60-80. Around nanometer, the length is about 250-300 nanometers.
  • the product was confirmed to be a-Fe 2 0 3 phase by XRD analysis at 33 °, 35.7 °, 53.9. Significant a-Fe 2 0 3 characteristic peaks were observed at the position.
  • the battery was subjected to a constant current charge and discharge test.
  • the initial discharge capacity reached 1384 mAh/ g at a current density of 0.01 mA/ g at a current density of 0.01 mA/ g; the first charge capacity reached 773 mAh/g, and the charge and discharge cycle was still 100 times.
  • Maintained at 200 mAh/g the coulombic efficiency of the other cycles is close to 100%, except for the first to third coulombic efficiency.
  • the positive electrode sheet prepared in this embodiment the lithium sheet is a negative electrode sheet, and PE (polyethylene) is a separator.
  • the battery was subjected to a constant current charge and discharge test.
  • the initial discharge capacity reached 197 mAh/g at a current density of 1.5 mA/g at a current range of 1.5-4.5 V, and the first charge capacity was 169 mAh/g.
  • the obtained nanomaterials are uniform in size and rod-shaped, with diameters of about 60-80 nm and lengths of about 250-300 nm.
  • the product was confirmed to be a-Fe 2 0 3 phase by XRD analysis at 33.1 °, 35.6 °, 53.8. Significant a-Fe 2 0 3 characteristic peaks were observed at the position.
  • PE polyethylene
  • the first discharge capacity reached 1281mAh / g in the voltage range of 0.013V, 100mA / g current density ; the first charge capacity reached 781mAh / g, after the charge and discharge cycle 50 times can still maintain at 330mAh /g, except for the first to second coulombic efficiency, the coulombic efficiency of the other cycles is close to 100%.
  • the positive electrode sheet prepared in this embodiment the lithium sheet is a negative electrode sheet, and PE (polyethylene) is a separator.
  • the battery was subjected to constant current charge and discharge experiments.
  • the initial discharge capacity reached 183 mAh/g and the first charge capacity was 174 mAh/g in the voltage range of 1.5-4.5 V and 100 mA/g current density.
  • the obtained nanomaterials are uniform in size and rod-shaped, with diameters of about 60-80 nm and lengths of about 250-300 nm.
  • the product was confirmed to be a-Fe 2 0 3 phase by XRD analysis at 33 °, 35.7 °, 53.9. Significant a-Fe 2 0 3 characteristic peaks were observed at the position.
  • the battery was subjected to a constant current charge and discharge test.
  • the initial discharge capacity reached 1083 mAh/g at a current density of 0.01 mA/ g at a current density of 0.01 to 3 V.
  • the first charge capacity reached 730 mAh/g, and the charge and discharge cycle was still 50 times. Maintained at 260 mAh/g, the coulombic efficiency of the other cycles is close to 100%, except for the first to second coulombic efficiency.
  • the positive electrode sheet prepared in this embodiment the lithium sheet is a negative electrode sheet, and PE (polyethylene) is a separator.
  • the battery was subjected to a constant current charge-discharge test.
  • the initial discharge capacity reached 206 mAh/g at a current density of 1.5 mA/g at a current range of 1.5-4.5 V, and the first charge capacity was 181 mAh/g.
  • Maintained at 106 mAh/g, the coulombic efficiency at other cycle times is close to 100%, except for the first to second coulombic efficiency.

Abstract

Disclosed in the present invention are a rod-shaped nano iron oxide electrode material and a preparation method therefor. The preparation method is: using FeCl3?6H2O, ammonium dihydrogen phosphate and water for hydrothermal reaction as raw materials, and washing the resulting precipitates to obtain rod-shaped nano iron oxide. The nano iron oxide is in a rod shape with an average diameter of 60-80 nm, a length of 250-300 nm, a purity of more than 99.9% and a crystal phase α-Fe2O3. The rod-shaped nano iron oxide electrode material can be used not only as a positive electrode active material for lithium ion batteries, but also as a negative electrode active material for lithium ion batteries. The raw materials used in the preparation method are easily available, nontoxic and free from environmental pollution; the preparation process is simple and convenient to operate, and suitable for large-scale industrial production. The use of the rod-shaped nano iron oxide electrode material as the positive or negative electrode active material for lithium ion batteries leads to such advantages as low cost, excellent electrochemical performances, good chemical stability of the electrode material, high specific capacity, and small polarization of the charge and discharge platform.

Description

棒状纳米氧化铁电极材料及其制备方法和应用 技术领域  Rod-shaped nano-iron oxide electrode material, preparation method and application thereof
本发明属于锂离子电池电极材料的制备技术领域， 特别涉及一种棒状纳 米氧化铁电极材料及其制备方法和应用， 该棒状纳米氧化铁形貌规则、 尺寸 均一、 纯度高， 而且可作为正负电极材料。 背景技术  The invention belongs to the technical field of preparation of electrode materials for lithium ion batteries, and particularly relates to a rod-shaped nano-iron oxide electrode material, a preparation method and application thereof, the rod-shaped nano-iron oxide has regular shape, uniform size, high purity, and can be used as positive and negative Electrode material. Background technique
锂离子电池作为一种新型的高能蓄电池具有能量密度高、 使用寿命长、 循环性能好且无记忆效应等优点， 被广泛应用于移动电子产品如手机、 笔记 本电脑、 数码相机等。 近年来， 锂离子电池已应于电动汽车、 电动工具、 智 能电网、 分布式能源***、 航空航天、 国防等领域， 成为 21 世纪最有应用 价值的储能器件之一。  As a new type of high-energy battery, lithium-ion battery has the advantages of high energy density, long service life, good cycle performance and no memory effect. It is widely used in mobile electronic products such as mobile phones, notebook computers, digital cameras and so on. In recent years, lithium-ion batteries have become one of the most valuable energy storage devices in the 21st century in the fields of electric vehicles, power tools, smart power grids, distributed energy systems, aerospace, and defense.
氧化铁纳米材料由于具有高理论比容量、 丰富储量、 容易制备、 无毒、 环境友好、 成本低， 成为锂离子电池材料领域的研究热点。 常见的纳米氧化 铁的合成方法有机械球磨法、 水热反应或者以 FeOOH纳米棒为前驱体通过 层层自组装法及随后的热处理等方法合成了氧化铁纳米材料。  Due to its high theoretical specific capacity, abundant reserves, easy preparation, non-toxicity, environmental friendliness and low cost, iron oxide nanomaterials have become a research hotspot in the field of lithium ion battery materials. Common methods for synthesizing nano-iron oxides include mechanical ball milling, hydrothermal reaction, or synthesis of iron oxide nanomaterials by layer-by-layer self-assembly and subsequent heat treatment using FeOOH nanorods as precursors.
机械球磨法尽管方法简单但是存在以下缺陷： 获得的材料纯度低， 含有 其它杂质， 并且制备的材料一般为颗粒状， 颗粒分布不均匀。  The mechanical ball milling method has the following drawbacks despite the simple method: The obtained material has low purity, contains other impurities, and the prepared material is generally granular and the particle distribution is uneven.
在现有的通过水热反应合成纳米氧化铁的方法中， 一般存在如下缺陷： 原料的获取不容易， 比如公开号为 CN102674472A的专利申请中将六水合氯 化铁加入纳米纤维素中， 该纳米纤维素还需要使用特别的方法进行制备， 所 以原料的获取上较复杂； 原料中含有有毒的有机成分， 污染环境等。  In the existing method for synthesizing nanometer iron oxide by hydrothermal reaction, there are generally the following defects: the acquisition of the raw material is not easy, for example, the patent application disclosed in CN102674472A incorporates ferric chloride hexahydrate into the nanocellulose, the nanometer. Cellulose also needs to be prepared by a special method, so the acquisition of raw materials is complicated; the raw materials contain toxic organic components, pollute the environment and the like.
以 FeOOH纳米棒为前驱体来制备纳米氧化铁的方法， 一般要加入碱， 对环境有污染， 另外， 获得的材料必须在 600度左右退火， 工艺流程较长， 操作歩骤繁琐， 效率低， 而且能耗高。 A method for preparing nanometer iron oxide by using FeOOH nanorods as a precursor, generally adding a base, It is polluted by the environment. In addition, the obtained materials must be annealed at about 600 degrees, the process flow is long, the operation steps are cumbersome, the efficiency is low, and the energy consumption is high.
目前通过上述方法制备的纳米氧化铁一般作为锂离子电池负极材料使 用， 基本不作为正极材料使用， 正极材料通常使用锂盐比如磷酸铁锂。 锂离 子电池的主要构成材料包括电解液、 隔离材料、 正负极材料等， 正极材料占 有较大比例（正负极材料的质量比为 3: 1~4： 1 ) ， 其成本直接决定电池成本 高低。 因此研发低成本的正极材料是市场的需求。  At present, nano-iron oxide prepared by the above method is generally used as a negative electrode material for a lithium ion battery, and is basically not used as a positive electrode material, and a lithium salt such as lithium iron phosphate is usually used as a positive electrode material. The main constituent materials of lithium-ion battery include electrolyte, isolation material, positive and negative materials, etc. The positive electrode material occupies a large proportion (the mass ratio of positive and negative materials is 3:1~4:1), and the cost directly determines the battery cost. High and low. Therefore, the development of low-cost cathode materials is a market demand.
发明内容 Summary of the invention
针对现有技术中存在的缺陷， 本发明的目的之一在于提供一种棒状纳米 氧化铁电极材料的制备方法。 该方法简单易行。  One of the objects of the present invention is to provide a method for preparing a rod-shaped nano-iron oxide electrode material in view of the defects existing in the prior art. This method is simple and easy.
本发明的目的之二在于提供一种采用上述方法制备的棒状纳米氧化铁 电极材料及其在锂离子电池中应用。 得到的棒状纳米氧化铁不仅具有比较大 的比表面积、 形貌规则、 尺寸比较均一， 而且电化学性能良好。  Another object of the present invention is to provide a rod-shaped nano-iron oxide electrode material prepared by the above method and its use in a lithium ion battery. The obtained rod-shaped nano-iron oxide not only has a relatively large specific surface area, a regular morphology, a uniform size, and good electrochemical performance.
为了实现上述目的， 本发明采用以下技术方案：  In order to achieve the above object, the present invention adopts the following technical solutions:
一种棒状纳米氧化铁电极材料的制备方法， 以 FeCl3«6H20、 磷酸二氢铵 (NH4H2P04)和水为原料进行水热反应，产生的沉淀物经洗涤后获得棒状纳 米氧化铁粉体。 A method for preparing a rod-shaped nanometer iron oxide electrode material, wherein a hydrothermal reaction is carried out by using FeCl 3 «6H 2 0, ammonium dihydrogen phosphate (NH 4 H 2 P0 4 ) and water as raw materials, and the resulting precipitate is washed to obtain a rod shape. Nano-iron oxide powder.
上述水热反应的机理为：  The mechanism of the above hydrothermal reaction is:
NH4H2P04= NH3 ++H3P04" NH 4 H 2 P0 4 = NH 3 + +H 3 P0 4 "
H3P04" +H20= H3P04+OH" H 3 P0 4 " +H 2 0= H 3 P0 4 +OH"
FeCl3«6H20= FeCl3 +6H20 FeCl 3 «6H 2 0= FeCl 3 +6H 2 0
3 OH_ + Fe3+ = Fe(OH)3| 3 OH _ + Fe 3+ = Fe(OH) 3 |
2Fe(OH)3= Fe203|+3H20 2Fe(OH) 3 = Fe 2 0 3 |+3H 2 0
在上述棒状纳米氧化铁电极材料的制备方法中， 作为一种优选实施方 式， 所述水热反应的温度为 200-240 °C， 水热反应的时间为 1-10 h。 示例性 地， 所述水热反应的温度为 202°C、 210°C、 218°C、 225°C、 230°C、 235°C 或 238。C， 水热反应的时间为 1.5h、 2h、 2.5h、 3h、 4h、 5h、 6h、 7h、 8h、 8.5h或 9.5h。 更优选地， 所述水热反应的温度为 210-230 °C， 水热反应的时 间为 4-5h。 In the above preparation method of the rod-shaped nano-iron oxide electrode material, as a preferred embodiment, the hydrothermal reaction temperature is 200-240 ° C, and the hydrothermal reaction time is 1-10 h. Exemplary The temperature of the hydrothermal reaction is 202 ° C, 210 ° C, 218 ° C, 225 ° C, 230 ° C, 235 ° C or 238. C, hydrothermal reaction time is 1.5h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h, 8h, 8.5h or 9.5h. More preferably, the temperature of the hydrothermal reaction is 210-230 ° C, and the time of the hydrothermal reaction is 4-5 h.
在上述棒状纳米氧化铁电极材料的制备方法中， 作为一种优选实施方 式， 所述原料中 FeCl3«6H20与磷酸二氢铵的摩尔比为 26: 1-30: 1， 示例性地 可以为 26.5: 1、 27: 1、 28: 1、 29: 1或 29.5: 1。 优选地， 所述原料中 FeCl3*6H20 与磷酸二氢铵的摩尔比为 27: 1-28: 1。 In the above preparation method of the rod-shaped nano-iron oxide electrode material, as a preferred embodiment, the molar ratio of FeCl 3 «6H 2 0 to ammonium dihydrogen phosphate in the raw material is 26: 1-30: 1, exemplarily Can be 26.5: 1, 27: 1, 28: 1, 29: 1 or 29.5: 1. Preferably, the molar ratio of FeCl 3 *6H 2 0 to ammonium dihydrogen phosphate in the raw material is 27: 1-28: 1.
在上述棒状纳米氧化铁电极材料的制备方法中， 作为一种优选实施方 式， 所述沉淀物依次采用去离子水和酒精进行洗涤。  In the above method for producing a rod-shaped nano-iron oxide electrode material, as a preferred embodiment, the precipitate is washed successively with deionized water and alcohol.
一种通过上述方法制备的棒状纳米氧化铁电极材料， 呈棒状， 平均直径 为 60-80纳米， 长度为 250-300纳米， 纯度为 99.9%以上， 晶相为 a - Fe203。 A rod-shaped nano-iron oxide electrode material prepared by the above method has a rod shape, an average diameter of 60-80 nm, a length of 250-300 nm, a purity of 99.9% or more, and a crystal phase of a-Fe 2 0 3 .
上述棒状纳米氧化铁电极材料在锂离子电池中的应用， 所述棒状纳米氧 化铁电极材料作为锂离子电池的正极或负极的活性材料。 优选地， 所述应用 的具体方法如下：  The above rod-shaped nano-iron oxide electrode material is used in a lithium ion battery, and the rod-shaped nano-iron oxide electrode material is used as an active material of a positive electrode or a negative electrode of a lithium ion battery. Preferably, the specific method of the application is as follows:
歩骤一， 将粘结剂和导电剂加入上述棒状纳米氧化铁粉体中， 通过研磨 进行充分混合， 然后将混合后浆料进行过滤， 以得到均匀的预涂精制浆液； 歩骤二， 将所述预涂精制浆液分别涂布于铝箔表面集流体和铜箔表面集 流体， 经烘干后制成具有活性材料的电池正极电极片和电池负极电极片。  First, a binder and a conductive agent are added to the rod-shaped nano-iron oxide powder, thoroughly mixed by grinding, and then the mixed slurry is filtered to obtain a uniform pre-coated refining slurry; The pre-coated refining slurry is applied to the surface current collector of the aluminum foil surface and the current collector of the copper foil, and dried to form a battery positive electrode sheet and a battery negative electrode sheet having an active material.
在上述应用中， 作为一种优选实施方式，在所述歩骤一中，所述粘结剂、 导电剂和棒状纳米氧化铁粉末的质量百分比为： 粘结剂： 10-20%; 导电剂： 10-30%； 棒状纳米氧化铁粉体： 50-80%。 更优选地， 粘结剂： 10; 导电剂： 20%； 棒状纳米氧化铁粉末： 70%。  In the above application, as a preferred embodiment, in the first step, the mass percentage of the binder, the conductive agent and the rod-shaped nano iron oxide powder is: binder: 10-20%; conductive agent : 10-30%; rod-shaped nano iron oxide powder: 50-80%. More preferably, the binder: 10; a conductive agent: 20%; a rod-shaped nano iron oxide powder: 70%.
在上述应用中， 作为一种优选实施方式， 在所述歩骤一中， 所述研磨时 间为 40-60min， 示例性地， 所述研磨时间为 42min、 45min、 50min、 55min 或 58min。 In the above application, as a preferred embodiment, in the first step, the grinding time is 40-60 min, and exemplarily, the grinding time is 42 min, 45 min, 50 min, 55 min. Or 58min.
在上述应用中， 作为一种优选实施方式， 在所述歩骤二中， 所述烘干的 温度为 100-120°C， 烘干时间为 18-24 h。示例性地， 所述烘干温度为 105°C、 110。C、 102。C、 108。C或 120。C， 烘干时间为 18.5h、 20h、 21h、 22h、 23h 或 23.5h。  In the above application, as a preferred embodiment, in the second step, the drying temperature is 100-120 ° C, and the drying time is 18-24 h. Illustratively, the drying temperature is 105 ° C, 110. C, 102. C, 108. C or 120. C, drying time is 18.5h, 20h, 21h, 22h, 23h or 23.5h.
在上述应用中， 所述粘结剂和导电剂为本领域常用试剂。 其中， 粘结剂 可以为聚四氟乙烯（PTFE)、聚偏氟乙烯（PVDF)、羧甲基纤维素钠 (CMC) 或聚烯烃类 (PP， PE以及其他的共聚物: 导电剂可以为炭黑 super P、 导电 石墨、 科琴黑、 碳纳米管或纳米碳纤维。  In the above applications, the binder and the conductive agent are reagents commonly used in the art. Wherein, the binder may be polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC) or polyolefin (PP, PE and other copolymers: the conductive agent may be Carbon black super P, conductive graphite, ketjen black, carbon nanotubes or nano carbon fibers.
与现有技术相比， 本发明具有如下有益效果：  Compared with the prior art, the present invention has the following beneficial effects:
1 ) 本发明棒状纳米氧化铁粉末的制备方法， 原料易得、 无毒； 反应物 可以有很宽的浓度范围， 易于控制； 整个反应中未采用有毒物质， 反应也不 需要加入表面活性剂、催化剂等， 对环境无污染； 产物易于分离， 杂质很少、 纯度高； 制备工艺简单、 操作方便， 易于大规模的工业化生产。  1) The preparation method of the rod-shaped nano iron oxide powder of the invention, the raw material is easy to obtain and non-toxic; the reactant can have a wide concentration range and is easy to control; the toxic substance is not used in the whole reaction, and the reaction does not need to add a surfactant, Catalyst, etc., no pollution to the environment; easy to separate products, few impurities, high purity; simple preparation process, convenient operation, easy to large-scale industrial production.
2 )采用上述方法得到的棒状纳米氧化铁粉末形貌规则、尺寸比较均一， 呈棒状， 平均直径均约在 60-80纳米左右， 长度均约 250-300纳米左右， 材 料的纯度高。  2) The rod-shaped nano-iron oxide powder obtained by the above method has uniform shape and uniform size, and has a rod shape, and the average diameter is about 60-80 nm, and the length is about 250-300 nm, and the purity of the material is high.
3 ) 将上述棒状纳米氧化铁粉末作为锂离子电池的正负极活性材料， 成本低、 电化学性能良好、 电极材料化学稳定性好、 比容量高、 充放电 平台的极化小。 经试验证明， 该氧化铁纳米棒制成的正、 负电极， 具有 良好的充放电循环， 可作为锂离子电池的电极材料； 氧化铁纳米棒负极 材料在电流 100mAh/g充放电条件下， 首次放电容量达到 1030 mAh/g， 首次 充电容量达到 723mAh/g; 氧化铁纳米棒正极在电流 20mAh/g下， 首次放电 容量达到 222.4 mAh/g, 第 1次充电容量 175mAh/g。 附图说明 3) The above rod-shaped nano-iron oxide powder is used as a positive and negative electrode active material of a lithium ion battery, and has low cost, good electrochemical performance, good chemical stability of the electrode material, high specific capacity, and low polarization of the charge and discharge platform. It has been proved by experiments that the positive and negative electrodes made of the iron oxide nanorods have good charge and discharge cycles and can be used as electrode materials for lithium ion batteries. The iron oxide nanorod negative electrode materials are charged and discharged under the current of 100mAh/g for the first time. The discharge capacity reaches 1030 mAh/g, the first charge capacity reaches 723 mAh/ g; the iron oxide nanorod positive electrode has a current discharge capacity of 222.4 mAh/g at a current of 20 mAh/g, and the first charge capacity is 175 mAh/g. DRAWINGS
图 1是水热方法合成氧化铁 （Fe203 ) 纳米棒 （即棒状纳米氧化铁， 以 下均简称为氧化铁纳米棒） 的形貌图 （低倍 SEM照片） ， 具体为水热反应 温度为 220 °C时 （即实施例 1 ) 制备的氧化铁 （Fe203 ) 纳米棒的扫描电子 显微镜照片 （低倍 SEM照片） ； 从上述图片可以看出， 所得纳米材料尺寸 均一， 呈棒状， 直径均约在 60-80纳米左右， 长度均约 250-300纳米左右。 Figure 1 is a hydrothermal method for synthesizing iron oxide (Fe 2 O 3 ) nanorods (ie, rod-shaped nano-iron oxides, hereinafter referred to as iron oxide nanorods) by a hydrothermal reaction temperature (low-magnification SEM photograph), specifically hydrothermal reaction temperature Scanning electron micrograph (low-magnification SEM photograph) of iron oxide (Fe 2 O 3 ) nanorods prepared at 220 ° C (ie, Example 1); as can be seen from the above picture, the obtained nanomaterials are uniform in size and rod-shaped. The diameters are all about 60-80 nm, and the lengths are about 250-300 nm.
图 2是水热方法合成氧化铁 (Fe203 )纳米棒的形貌图（高倍 SEM照片） ， 具体为水热反应温度为 220 °C时 （即实施例 1 ) 制备的氧化铁 （Fe203 ) 纳 米棒的扫描电子显微镜照片 （高倍 SEM照片） 。 从上述图片可以看出， 所 得纳米材料尺寸均一， 呈棒状， 直径约在 60-80纳米左右， 长度约 250-300 纳米左右。 2 is a topographical view (high-power SEM photograph) of a hydrothermally synthesized iron oxide (Fe 2 O 3 ) nanorod, specifically an iron oxide prepared by a hydrothermal reaction temperature of 220 ° C (ie, Example 1). 2 0 3 ) Scanning electron micrograph of nanorods (high magnification SEM photograph). As can be seen from the above picture, the obtained nanomaterials are uniform in size and have a rod shape with a diameter of about 60-80 nm and a length of about 250-300 nm.
图 3是水热方法合成氧化铁（Fe203 ) 的 XRD图谱， 具体为水热反应温 度为 220 °C时 （即实施例 1 ) 合成氧化铁（Fe203 ) 的 XRD检测图谱， 从图 中发现制备的纳米材料的衍射峰均为 Fe203纳米棒的 XRD, 通过 XRD谱图 可以确认产物为 a -Fe203相， 特征峰明显。 Figure 3 is a hydrothermal synthetic iron oxide (Fe 2 0 3) XRD pattern, particularly the hydrothermal reaction temperature is detected XRD pattern of synthetic iron oxide (Fe 2 0 3) when the 220 ° C (i.e. Example 1 embodiment), It is found from the figure that the diffraction peaks of the prepared nanomaterials are all XRD of Fe 2 0 3 nanorods. The XRD spectrum can confirm that the product is a-Fe 2 0 3 phase, and the characteristic peak is obvious.
图 4是氧化铁纳米棒的 Raman图谱， 具体为水热反应温度为 220 °C时 (即实施例 1 ) 合成氧化铁 （Fe203 ) 的 Raman 图谱， 从图谱中发现制备的 纳米材料的衍射峰均为 Fe203纳米棒的 Raman峰值。氧化铁纳米棒的 Raman 结构表征为典型的氧化铁特点。 通过 Raman谱图可以确认产物为 Fe203。 4 is a Raman spectrum of iron oxide nanorods, specifically a Raman spectrum of iron oxide (Fe 2 0 3 ) synthesized at a hydrothermal reaction temperature of 220 ° C (ie, Example 1), and the prepared nanomaterials are found from the map. The diffraction peaks are all Raman peaks of Fe 2 0 3 nanorods. The Raman structure of iron oxide nanorods is characterized by typical iron oxide. The product was confirmed to be Fe 2 0 3 by Raman spectrum.
图 5是以实施例 1制备的氧化铁纳米棒为负极材料组装的扣式电池 的容量 -电压曲线。 从图中可知， 0.1C 的测试条件下氧化铁纳米棒负极， 在电压范围 0.01-3V内， 首次放电容量达到 1030 mAh/g; 第 1次充电容量达 到 723mAh/g。 5 is a capacity-voltage curve of a button cell assembled with the iron oxide nanorods prepared in Example 1 as a negative electrode material. It can be seen from the figure that under the test condition of 0.1C, the iron oxide nanorod negative electrode has a first discharge capacity of 1030 mAh/ g in the voltage range of 0.01 to 3 V ; the first charge capacity reaches 723 mAh/g.
图 6是以实施例 1制备的氧化铁纳米棒为负极材料组装的扣式电池的 容量 -循环次数、 库伦效率曲线。 从图中可知， 除首次到第 18次的库仑效率 夕卜， 其他循环的库仑效率接近 100%。 6 is a capacity-cycle number and coulombic efficiency curve of a button cell assembled with the iron oxide nanorods prepared in Example 1 as a negative electrode material. As can be seen from the figure, except for the first to the 18th Coulomb efficiency In addition, the coulombic efficiency of other cycles is close to 100%.
图 7是以实施例 1制备的氧化铁纳米棒为正极材料组装扣式电池的 容量 -电压曲线。 从图中可知， 0.1C 的测试条件下氧化铁纳米棒正极， 在 电压范围 1.5-4.5V 内首次放电容量达到 222.4 mAh/g, 第 1 次充电容量 175mAh/g， 第 2次放电电容量 144.4mAh/g。  Fig. 7 is a capacity-voltage curve of a button cell assembled by using iron oxide nanorods prepared in Example 1 as a positive electrode material. It can be seen from the figure that under the test condition of 0.1C, the iron oxide nanorod positive electrode has a first discharge capacity of 222.4 mAh/g in the voltage range of 1.5-4.5V, the first charging capacity is 175mAh/g, and the second discharge capacity is 144.4. mAh/g.
图 8是以实施例 1制备的氧化铁纳米棒为正极材料组装扣式电池的 容量 （库仑效率） -循环曲线。 从图中可知， 除首次到第 10次的库仑效率 夕卜， 其他循环次数下的库仑效率接近 100%。  Fig. 8 is a capacity (coulombic efficiency) - cycle curve of a button cell assembled with the iron oxide nanorods prepared in Example 1 as a positive electrode material. As can be seen from the figure, in addition to the first to the 10th Coulomb efficiency, the Coulomb efficiency at other cycle times is close to 100%.
具体实施方式 detailed description
下面通过实施例对本发明进行详细说明， 但本发明并不限于此。  The invention will be described in detail below by way of examples, but the invention is not limited thereto.
实施例 1  Example 1
棒状纳米氧化铁粉体的制备：  Preparation of rod-shaped nano-iron oxide powder:
称取六水三氯化铁 （FeCl3'6H20 ) 0.972g, 磷酸二氢铵 （NH4H2P04 ) 0.01485g (六水三氯化铁与磷酸二氢铵摩尔比例为 26: 1 )和去离子水 160g， 将其全部放入水热反应釜中， 在 220 °C条件下， 水热反应时间 2 h， 然后自 然冷却到室温。 再将沉淀物依次通过去离子水洗涤 3次、 酒精洗涤 2次， 分 离后获得棒状纳米氧化铁粉体， HPLC检测纯度为 99.9%。 Weigh 0.972g of ferric chloride (FeCl 3 '6H 2 0 ) and 0.01485g of ammonium dihydrogen phosphate (NH 4 H 2 P0 4 ) (the molar ratio of ferric chloride to diammonium phosphate is 26: 1) and 160 g of deionized water, all of which were placed in a hydrothermal reaction kettle at 220 ° C for 2 h of hydrothermal reaction time, and then naturally cooled to room temperature. The precipitate was washed three times with deionized water and twice with alcohol, and after separation, a rod-shaped nano-iron oxide powder was obtained, and the purity by HPLC was 99.9%.
从图 1和图 2中可看出， 所得纳米材料尺寸均一， 呈棒状， 平均直径均 约在 60-80纳米左右， 长度均约 250-300纳米左右。 从图 3和图 4中可以确 认产物为 a -Fe203相， 特征峰明显。 As can be seen from Fig. 1 and Fig. 2, the obtained nanomaterials are uniform in size and rod-shaped, and the average diameters are all about 60-80 nm, and the lengths are about 250-300 nm. It can be confirmed from Fig. 3 and Fig. 4 that the product is an a-Fe 2 0 3 phase, and the characteristic peak is conspicuous.
具有上述电极活性材料的电池正极和负极电极片的制备：  Preparation of battery positive and negative electrode sheets having the above electrode active material:
按照 7: 1:2 的质量比将制备的棒状纳米氧化铁粉体、 粘结剂聚四氟乙烯 (PTFE) 和导电剂炭黑 Super P均匀混合， 研磨 45分钟， 然后过滤， 得到 均匀的预涂精制浆液； 将该浆液直接涂布于铝箔表面集流体， 并在真空烘箱 中以 110°C的温度保温 24 h， 得到电极活性材料电池正极电极片。 将该浆液 直接涂布于铜箔表面集流体， 并在真空烘箱中以 110°C的温度保温 24 h， 得 到电极活性材料电池负极电极片。 The prepared rod-shaped nano-iron oxide powder, the binder polytetrafluoroethylene (PTFE) and the conductive agent carbon black Super P were uniformly mixed according to the mass ratio of 7: 1:2, ground for 45 minutes, and then filtered to obtain a uniform pre-preparation. Coating the refined slurry; directly applying the slurry to the surface collector of the aluminum foil, and in a vacuum oven The anode electrode sheet of the electrode active material battery was obtained by holding at a temperature of 110 ° C for 24 h. The slurry was directly applied to a copper foil surface current collector, and incubated at 110 ° C for 24 h in a vacuum oven to obtain an electrode active material battery negative electrode sheet.
以该实施例制备的负极电极片、 锂片为正极片、 PE (聚乙烯） 为隔膜、 LiPF6 lmol/1 DMC:EC:EMC=1 :1: 1为电解液组装成扣式电池 1-A。对电池进行 恒流充放电实验， 电性能测试结果参见图 5和图 6， 在电压范围 0.01-3V内、 lOOmA/g电流密度下， 首次放电容量达到 1030 mAh/g; 第 1次充电容量达到 723mAh/g, 充放电循环 100次后仍能维持在 90mAh/g， 除首次到第 18次的 库仑效率外， 其他循环的库仑效率接近 100%。 The negative electrode sheet prepared in this example, the lithium sheet is a positive electrode sheet, PE (polyethylene) is a separator, LiPF 6 lmol/1 DMC:EC:EMC=1:1:1 is an electrolyte assembled into a button battery 1- A. The battery is subjected to constant current charge and discharge experiments. The electrical performance test results are shown in Figure 5 and Figure 6. The first discharge capacity reaches 1030 mAh/ g at a current density of 0.01 to 3 V and a current density of 100 mAh/ g; the first charge capacity is reached. At 723 mAh/g, it can still be maintained at 90 mAh/g after 100 cycles of charge and discharge. The coulombic efficiency of other cycles is close to 100% except for the first to 18th coulombic efficiency.
以该实施例制备的正极电极片、 锂片为负极片、 PE (聚乙烯） 为隔膜、 The positive electrode sheet prepared in this embodiment, the lithium sheet is a negative electrode sheet, and PE (polyethylene) is a separator.
LiPF6 lmol/1 DMC:EC:EMC=1 :1: 1为电解液组装成扣式电池 1-B。对电池进行 恒流充放电实验， 电性能测试结果参见图 7和图 8，在电压范围 1.5-4.5V内、 lOOmA/g 电流密度下， 首次放电容量达到 222.4 mAh/g, 第 1 次充电容量 175mAh/g, 第 2次放电电容量 144.4mAh/g， 充放电循环 20次后仍能维持在 HOmAh/g, 除首次到第 10次的库仑效率外， 其他循环次数下的库仑效率接 近 100%。 实施例 2 LiPF 6 lmol/1 DMC: EC: EMC = 1: 1: 1 is assembled into a button battery 1-B. The battery is subjected to constant current charge and discharge experiments. The electrical performance test results are shown in Figure 7 and Figure 8. The first discharge capacity reaches 222.4 mAh/g and the first charge capacity in the voltage range of 1.5-4.5V and 100mA/g current density. 175mAh/g, the second discharge capacity is 144.4mAh/g, and can still be maintained at HOmAh/g after 20 cycles of charge and discharge. The coulombic efficiency is close to 100% except for the first to the 10th Coulomb efficiency. . Example 2
棒状纳米氧化铁粉体的制备：  Preparation of rod-shaped nano-iron oxide powder:
称取六水三氯化铁（FeCl3*6H20) 0.695g，磷酸二氢铵（NH4H2P04) O.OlgWeigh ferric chloride (FeCl 3 *6H 2 0) 0.695g, ammonium dihydrogen phosphate (NH 4 H 2 P0 4 ) O.Olg
(六水三氯化铁与磷酸二氢铵摩尔比例为 30: 1 ) 和去离子水 120g， 将其全 部放入水热反应釜中， 在 220 °C条件下， 水热反应时间 2 h， 然后自然冷却 到室温。 再将沉淀物依次通过去离子水洗涤 3次、 酒精洗涤 2次， 分离后获 得棒状纳米氧化铁粉体， HPLC检测纯度为 99.9%。 (The molar ratio of ferric chloride to ammonium dihydrogen phosphate is 30:1) and deionized water (120g), all of which are placed in a hydrothermal reaction kettle. At 220 °C, the hydrothermal reaction time is 2 h. Then naturally cool to room temperature. The precipitate was washed three times with deionized water and twice with alcohol, and after separation, a rod-shaped nano-iron oxide powder was obtained, and the purity by HPLC was 99.9%.
经低倍 SEM分析， 所得纳米材料尺寸均一， 呈棒状， 直径均约在 60-80 纳米左右，长度均约 250-300纳米左右。经 XRD分析可以确认产物为 a -Fe203 相， 在 33 °、 35.7 °、 53.9 。位置可观察到明显 a -Fe203特征峰。 After low-magnification SEM analysis, the obtained nanomaterials are uniform in size and rod-shaped, with diameters of about 60-80. Around nanometer, the length is about 250-300 nanometers. The product was confirmed to be a-Fe 2 0 3 phase by XRD analysis at 33 °, 35.7 °, 53.9. Significant a-Fe 2 0 3 characteristic peaks were observed at the position.
具有上述电极活性材料的电池正极和负极电极片的制备： 同实施例 1。 以该实施例制备的负极电极片、 锂片为正极片、 PE (聚乙烯） 为隔膜、 LiPF6 lmol/1 DMC:EC:EMC=1 :1: 1为电解液组装成扣式电池 2-A。对电池进行 恒流充放电实验， 在电压范围 0.01-3V内、 100mA/g电流密度下， 首次放电 容量达到 1384mAh/g; 第 1次充电容量达到 773mAh/g， 充放电循环 100次 后仍能维持在 200mAh/g， 除首次到第 3次的库仑效率外， 其他循环的库仑 效率接近 100%。 Preparation of battery positive and negative electrode sheets having the above electrode active material: Same as in Example 1. The negative electrode sheet prepared in this example, the lithium sheet is a positive electrode sheet, PE (polyethylene) is a separator, LiPF 6 lmol/1 DMC:EC:EMC=1:1:1 is an electrolyte assembled into a button battery 2 A. The battery was subjected to a constant current charge and discharge test. The initial discharge capacity reached 1384 mAh/ g at a current density of 0.01 mA/ g at a current density of 0.01 mA/ g; the first charge capacity reached 773 mAh/g, and the charge and discharge cycle was still 100 times. Maintained at 200 mAh/g, the coulombic efficiency of the other cycles is close to 100%, except for the first to third coulombic efficiency.
以该实施例制备的正极电极片、 锂片为负极片、 PE (聚乙烯） 为隔膜、 The positive electrode sheet prepared in this embodiment, the lithium sheet is a negative electrode sheet, and PE (polyethylene) is a separator.
LiPF6 lmol/1 DMC:EC:EMC=1 :1: 1为电解液组装成扣式电池 2-B。对电池进行 恒流充放电实验， 在电压范围 1.5-4.5V内、 100mA/g电流密度下， 首次放电 容量达到 197mAh/g， 第 1次充电容量 169mAh/g， 充放电循环 20次后仍能 维持在 98mAh/g， 除首次到第 2次的库仑效率外， 其他循环次数下的库仑效 率接近 100%。 实施例 3 LiPF 6 lmol/1 DMC: EC: EMC=1:1: 1 is assembled into a button battery 2-B. The battery was subjected to a constant current charge and discharge test. The initial discharge capacity reached 197 mAh/g at a current density of 1.5 mA/g at a current range of 1.5-4.5 V, and the first charge capacity was 169 mAh/g. Maintained at 98 mAh/g, the coulombic efficiency at other cycle times is close to 100%, except for the first to second coulombic efficiency. Example 3
棒状纳米氧化铁粉体的制备： 除水热反应条件为 205 °C、反应时间为 8h 夕卜， 其他均与实施例 1的棒状纳米氧化铁粉体的制备方法相同。  Preparation of rod-shaped nano-iron oxide powder: The preparation method of the rod-shaped nano-iron oxide powder of Example 1 was the same except that the hydrothermal reaction condition was 205 ° C and the reaction time was 8 h.
经低倍 SEM分析， 所得纳米材料尺寸均一， 呈棒状， 直径均约在 60-80 纳米左右，长度均约 250-300纳米左右。经 XRD分析可以确认产物为 a -Fe203 相， 在 33.1 °、 35.6 °、 53.8 。位置可观察到明显 a -Fe203特征峰。 After low-magnification SEM analysis, the obtained nanomaterials are uniform in size and rod-shaped, with diameters of about 60-80 nm and lengths of about 250-300 nm. The product was confirmed to be a-Fe 2 0 3 phase by XRD analysis at 33.1 °, 35.6 °, 53.8. Significant a-Fe 2 0 3 characteristic peaks were observed at the position.
具有上述电极活性材料的电池正极和负极电极片的制备： 同实施例 1。 以该实施例制备的负极电极片、 锂片为正极片、 PE (聚乙烯） 为隔膜、 LiPF6 lmol/1 DMC:EC:EMC=1 :1: 1为电解液组装成扣式电池 3-A。对电池进行 恒流充放电实验， 在电压范围 0.01-3V内、 100mA/g电流密度下， 首次放电 容量达到 1281mAh/g; 第 1次充电容量达到 781mAh/g， 充放电循环 50次后 仍能维持在 330mAh/g， 除首次到第 2次的库仑效率外， 其他循环的库仑效 率接近 100%。 Preparation of battery positive and negative electrode sheets having the above electrode active material: Same as in Example 1. The negative electrode sheet prepared in this example, the lithium sheet is a positive electrode sheet, PE (polyethylene) is a separator, LiPF 6 lmol/1 DMC:EC:EMC=1:1:1 is an electrolyte assembled into a button battery 3- A. Carry out the battery Constant current charge and discharge test, the first discharge capacity reached 1281mAh / g in the voltage range of 0.013V, 100mA / g current density ; the first charge capacity reached 781mAh / g, after the charge and discharge cycle 50 times can still maintain at 330mAh /g, except for the first to second coulombic efficiency, the coulombic efficiency of the other cycles is close to 100%.
以该实施例制备的正极电极片、 锂片为负极片、 PE (聚乙烯） 为隔膜、 The positive electrode sheet prepared in this embodiment, the lithium sheet is a negative electrode sheet, and PE (polyethylene) is a separator.
LiPF6 lmol/1 DMC:EC:EMC=1 :1: 1为电解液组装成扣式电池 3-B。对电池进行 恒流充放电实验， 在电压范围 1.5-4.5V内、 100mA/g电流密度下， 首次放电 容量达到 183mAh/g， 第 1次充电容量 174mAh/g， 充放电循环 20次后仍能 维持在 83mAh/g， 除首次到第 2次的库仑效率外， 其他循环次数下的库仑效 率接近 100%。 实施例 4 LiPF 6 lmol/1 DMC: EC: EMC=1:1: 1 is assembled into a button battery 3-B. The battery was subjected to constant current charge and discharge experiments. The initial discharge capacity reached 183 mAh/g and the first charge capacity was 174 mAh/g in the voltage range of 1.5-4.5 V and 100 mA/g current density. Maintained at 83 mAh/g, the coulombic efficiency at other cycle times is close to 100%, except for the first to second coulombic efficiency. Example 4
棒状纳米氧化铁粉体的制备： 除水热反应条件为 240 °C、反应时间为 4h 夕卜， 其他均与实施例 1的棒状纳米氧化铁粉体的制备方法相同。  Preparation of rod-shaped nano-iron oxide powder: The preparation method of the rod-shaped nano-iron oxide powder of Example 1 was the same except that the hydrothermal reaction condition was 240 ° C and the reaction time was 4 h.
经低倍 SEM分析， 所得纳米材料尺寸均一， 呈棒状， 直径均约在 60-80 纳米左右，长度均约 250-300纳米左右。经 XRD分析可以确认产物为 a -Fe203 相， 在 33 °、 35.7 °、 53.9 。位置可观察到明显 a -Fe203特征峰。 After low-magnification SEM analysis, the obtained nanomaterials are uniform in size and rod-shaped, with diameters of about 60-80 nm and lengths of about 250-300 nm. The product was confirmed to be a-Fe 2 0 3 phase by XRD analysis at 33 °, 35.7 °, 53.9. Significant a-Fe 2 0 3 characteristic peaks were observed at the position.
具有上述电极活性材料的电池正极和负极电极片的制备： 同实施例 1。 以该实施例制备的负极电极片、 锂片为正极片、 PE (聚乙烯） 为隔膜、 LiPF6 lmol/1 DMC:EC:EMC=1 :1: 1为电解液组装成扣式电池 4-A。对电池进行 恒流充放电实验， 在电压范围 0.01-3V内、 100mA/g电流密度下， 首次放电 容量达到 1083mAh/g， 第 1次充电容量达到 730mAh/g， 充放电循环 50次后 仍能维持在 260mAh/g， 除首次到第 2次的库仑效率外， 其他循环的库仑效 率接近 100%。 Preparation of battery positive and negative electrode sheets having the above electrode active material: Same as in Example 1. The negative electrode sheet prepared in this example, the lithium sheet is a positive electrode sheet, PE (polyethylene) is a separator, LiPF 6 lmol/1 DMC:EC:EMC=1:1:1 is an electrolyte assembled into a button battery 4- A. The battery was subjected to a constant current charge and discharge test. The initial discharge capacity reached 1083 mAh/g at a current density of 0.01 mA/ g at a current density of 0.01 to 3 V. The first charge capacity reached 730 mAh/g, and the charge and discharge cycle was still 50 times. Maintained at 260 mAh/g, the coulombic efficiency of the other cycles is close to 100%, except for the first to second coulombic efficiency.
以该实施例制备的正极电极片、 锂片为负极片、 PE (聚乙烯） 为隔膜、 LiPF6 lmol/1 DMC:EC:EMC=1 :1: 1为电解液组装成扣式电池 4-B。对电池进行 恒流充放电实验， 在电压范围 1.5-4.5V内、 100mA/g电流密度下， 首次放电 容量达到 206mAh/g， 第 1次充电容量 181mAh/g， 充放电循环 20次后仍能 维持在 106mAh/g， 除首次到第 2次的库仑效率外， 其他循环次数下的库仑 效率接近 100%。 The positive electrode sheet prepared in this embodiment, the lithium sheet is a negative electrode sheet, and PE (polyethylene) is a separator. LiPF 6 lmol/1 DMC: EC: EMC=1:1: 1 is assembled into a button battery 4-B. The battery was subjected to a constant current charge-discharge test. The initial discharge capacity reached 206 mAh/g at a current density of 1.5 mA/g at a current range of 1.5-4.5 V, and the first charge capacity was 181 mAh/g. Maintained at 106 mAh/g, the coulombic efficiency at other cycle times is close to 100%, except for the first to second coulombic efficiency.
应当理解， 这些实施例的用途仅用于说明本发明而非意欲限制本发明的 保护范围。 此外， 也应理解， 在阅读了本发明的技术内容之后， 本领域技术 人员可以对本发明作各种改动、修改和 /或变型， 所有的这些等价形式同样落 于本申请所附权利要求书所限定的保护范围之内。  It is to be understood that the use of these embodiments is merely illustrative of the invention and is not intended to limit the scope of the invention. In addition, it should be understood that various changes, modifications, and/or variations of the invention may be made by those skilled in the art in the appended claims. Within the limits of protection defined.

Claims

权 利 要 求 书 claims
1、 一种棒状纳米氧化铁电极材料的制备方法， 其特征在于， 以 FeCl3-6H20, 磷酸二氢铵和水为原料进行水热反应， 产生的沉淀物经洗涤后 获得棒状纳米氧化铁粉体。 1. A method for preparing rod-shaped nano-iron oxide electrode materials, which is characterized in that FeCl 3 -6H 2 0, ammonium dihydrogen phosphate and water are used as raw materials to perform a hydrothermal reaction, and the resulting precipitate is washed to obtain rod-shaped nano-iron oxide. Iron powder.
2、 根据权利要求 1 所述的制备方法， 其特征在于， 所述水热反应的温 度为 200-240 °C， 水热反应的时间为 1-10 h。 优选地， 所述水热反应的温度 为 210-230 °C， 水热反应的时间为 5-6h。 2. The preparation method according to claim 1, characterized in that the temperature of the hydrothermal reaction is 200-240 °C, and the time of the hydrothermal reaction is 1-10 h. Preferably, the temperature of the hydrothermal reaction is 210-230 °C, and the time of the hydrothermal reaction is 5-6 h.
3、根据权利要求 1所述的制备方法，其特征在于，所述原料中 FeCl3«6H20 与磷酸二氢铵的摩尔比为 26: 1-30: 1， 3. The preparation method according to claim 1, characterized in that the molar ratio of FeCl 3 «6H 2 0 and ammonium dihydrogen phosphate in the raw material is 26: 1-30: 1,
4、根据权利要求 3所述的制备方法，其特征在于，所述原料中 FeCl3«6H20 与磷酸二氢铵的摩尔比为 27: 1-28: 1。 4. The preparation method according to claim 3, characterized in that the molar ratio of FeCl 3 «6H 2 0 and ammonium dihydrogen phosphate in the raw material is 27: 1-28: 1.
5、 根据权利要求 1 所述的制备方法， 其特征在于， 所述沉淀物依次采 用去离子水和酒精进行洗涤。 5. The preparation method according to claim 1, characterized in that the precipitate is washed with deionized water and alcohol in sequence.
6、 一种通过权利要求 1-5 任一所述方法制备的棒状纳米氧化铁电极材 料， 其特征在于， 呈棒状， 平均直径为 60-80纳米， 长度为 250-300纳米， 纯度为 99.9%以上， 晶相为 a - Fe203。 6. A rod-shaped nano-iron oxide electrode material prepared by the method of any one of claims 1-5, characterized in that it is rod-shaped, with an average diameter of 60-80 nanometers, a length of 250-300 nanometers, and a purity of 99.9% Above, the crystal phase is a-Fe 2 0 3 .
7、 权利要求 6所述棒状纳米氧化铁电极材料在锂离子电池中的应用， 其特征在于， 所述棒状纳米氧化铁电极材料作为锂离子电池的正极和负极的 活性材料。 7. The application of the rod-shaped nano-iron oxide electrode material in lithium-ion batteries according to claim 6, characterized in that the rod-shaped nano-iron oxide electrode material serves as the active material of the positive electrode and negative electrode of the lithium-ion battery.
8、 根据权利要求 7所述的应用， 其特征在于， 具体的应用方法如下： 歩骤一， 将粘结剂和导电剂加入上述棒状纳米氧化铁粉体中， 通过研磨 进行充分混合， 然后将混合后浆料进行过滤， 以得到均匀的预涂精制浆液； 歩骤二， 将所述预涂精制浆液分别涂布于铝箔表面集流体和铜箔表面集 流体， 经烘干后制成具有活性材料的电池正极电极片和电池负极电极片。 8. The application according to claim 7, characterized in that the specific application method is as follows: Step 1: Add the binder and conductive agent to the above-mentioned rod-shaped nano-iron oxide powder, mix thoroughly by grinding, and then mix After mixing, the slurry is filtered to obtain a uniform pre-coated refined slurry; Step 2: Apply the pre-coated refined slurry to the aluminum foil surface current collector and the copper foil surface current collector respectively, and then dry them to form an active The battery positive electrode sheet and the battery negative electrode sheet are made of materials.
9、 根据权利要求 8所述的应用， 其特征在于， 在所述歩骤一中， 所述 粘结剂、 导电剂和棒状纳米氧化铁粉末的质量百分比为： 粘结剂： 10-20%; 导电剂： 10-30%; 棒状纳米氧化铁粉体： 50-80%。 优选地， 粘结剂： 10%; 导电剂： 20%; 棒状纳米氧化铁粉末： 70%。 9. The application according to claim 8, characterized in that, in the step one, the mass percentage of the binder, conductive agent and rod-shaped nano-iron oxide powder is: Binder: 10-20% ; Conductive agent: 10-30%; Rod-shaped nano-iron oxide powder: 50-80%. Preferably, binder: 10%; conductive agent: 20%; rod-shaped nano-iron oxide powder: 70%.
10、 根据权利要求 8所述的应用， 其特征在于， 在所述歩骤一中， 所述 研磨时间为 40-60min; 在所述歩骤二中， 所述烘干的温度为 100-120°C， 烘 干时间为 18-24 h。 10. The application according to claim 8, characterized in that, in the first step, the grinding time is 40-60min; in the second step, the drying temperature is 100-120 °C, drying time is 18-24 h.
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Publication number Priority date Publication date Assignee Title
CN103606672A (en) * 2013-10-12 2014-02-26 安泰科技股份有限公司 Rod-shaped nano iron oxide electrode material, and preparation method and application thereof
CN104815658B (en) * 2015-04-09 2017-04-12 太原理工大学 Tetrahexahedron iron oxide nanocrystalline catalyst, preparation method and application thereof
CN106972152A (en) * 2017-04-07 2017-07-21 深圳市佩成科技有限责任公司 Lithium ion cell electrode preparation and the assemble method of battery
WO2018184183A1 (en) * 2017-04-07 2018-10-11 深圳市佩成科技有限责任公司 Method of manufacturing lithium-ion battery electrode and assembling battery
CN107313065B (en) * 2017-07-14 2019-01-04 西南大学 Iron phosphide modified alpha type iron oxide vermiform nano-structure array light anode and its preparation method and application
CN108390046B (en) * 2018-03-16 2020-06-12 福州大学 Preparation method of rod-shaped α -ferric oxide/GN lithium battery negative electrode material
CN108383167A (en) * 2018-04-18 2018-08-10 中国科学院青海盐湖研究所 A kind of preparation method of rodlike alpha-type ferric oxide
CN112951619B (en) * 2021-01-29 2022-05-03 多助科技(武汉)有限公司 Iron oxide @ manganese dioxide core-shell structure material and preparation and application thereof
CN113184914B (en) * 2021-04-20 2022-10-18 广东工业大学 Porous capsule-shaped Fe 2 O 3 Nano material and preparation method and application thereof
CN114394626A (en) * 2022-01-20 2022-04-26 西南石油大学 Preparation method of rod-like ferric oxide negative electrode material of lithium ion battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102259933A (en) * 2011-05-09 2011-11-30 中国矿业大学 Preparation method and application of rice-grain alpha-iron trioxide
CN103013441A (en) * 2013-01-10 2013-04-03 贵州大学 Method for growing low helical carbon nanotube composite microwave absorbing material by in-situ catalysis
CN103606672A (en) * 2013-10-12 2014-02-26 安泰科技股份有限公司 Rod-shaped nano iron oxide electrode material, and preparation method and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101355151A (en) * 2007-07-25 2009-01-28 比亚迪股份有限公司 Battery anode and primary cell as well as preparation method thereof
CN102544457B (en) * 2012-02-17 2014-12-03 合肥工业大学 Method for preparing graphene oxide-iron sesquioxide nanotube composite material by using in-situ method
CN102637869A (en) * 2012-05-02 2012-08-15 中国科学院长春应用化学研究所 Fe2O3 nanorod and manufacturing method and usages of Fe2O3 nanorod

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102259933A (en) * 2011-05-09 2011-11-30 中国矿业大学 Preparation method and application of rice-grain alpha-iron trioxide
CN103013441A (en) * 2013-01-10 2013-04-03 贵州大学 Method for growing low helical carbon nanotube composite microwave absorbing material by in-situ catalysis
CN103606672A (en) * 2013-10-12 2014-02-26 安泰科技股份有限公司 Rod-shaped nano iron oxide electrode material, and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIU, HAO ET AL.: "Electrochemical performance of a-Fe203 nanorods as anode material for lithium-ion cells", ELECTROCHIMICAACTA, vol. 54, 17 October 2008 (2008-10-17), pages 1733 *

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