CN110323442B - Carbon-coated Fe 3 O 4 Composite material and preparation method and application thereof - Google Patents
Carbon-coated Fe 3 O 4 Composite material and preparation method and application thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention belongs to the field of new energy, and particularly relates to carbon-coated Fe 3 O 4 Composite material and its preparation method and application. Carbon-coated Fe 3 O 4 A composite material having the general structural formula: CNT @ hollow Fe 3 O 4 @ C, where CNT is carbon nanotube, hollow Fe 3 O 4 Is Fe 3 O 4 The hollow pipe is in a hollow tubular structure, and C is coated in hollow Fe 3 O 4 The outermost layer of the carbon shell layer has a layered tubular structure, the outermost layer of the coating layer is the carbon shell layer, and the inner wall of the carbon shell layer is Fe 3 O 4 The hollow tube is composed of carbon nanotubes at the innermost layer, wherein the carbon nanotubes and Fe 3 O 4 A certain gap space is reserved between the tubes to form a tube-in-tube structure, and the material serving as a negative electrode material can be applied to lithium ion batteries, sodium ion batteries or potassium ion batteries.
Description
Technical Field
The invention belongs to the field of new energy, and particularly relates to carbon-coated Fe 3 O 4 A composite material and a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) are the primary power source for portable electronic devices due to their high energy density, long cycle life and good safety. For this reason, new electrode materials with higher energy/power densities and better cyclability are more desirable. Wherein, fe 3 O 4 Is considered to be a promising anode material due to its low cost, environmental friendliness and high theoretical capacity (924 mA h g-1). However, as in the case of conversion-based metal oxide anodes, lithium insertion/extraction of Fe 3 O 4 The large volume change in the process (74%) causes Fe 3 O 4 The agglomeration and pulverization of the anode typically results in rapid capacity fade and poor cycle stability.
To increase Fe 3 O 4 Of the anodeLithium storage performance two main strategies have been developed over the last few years. One strategy is to produce nano-Fe with a mesoporous or hollow structure 3 O 4 A material. Such nanostructured anodes can provide rich active sites, short electron/ion diffusion paths and void space for volume modulation, thereby improving specific capacity and cycling stability. Another strategy is to incorporate Fe 3 O 4 Combined with various carbon nanomaterials (e.g. carbon nanotubes, graphene, mesoporous carbon and carbon coatings) to simultaneously address Fe 3 O 4 Conductive defects and volume changes. For example, jianping Wang et al found Fe coating 3 O 4 The Carbon Nanotubes (CNTs) of (1) showed good cyclability and ranged from 0.1 Ag -1 Keeping 800mAh g after the next 100 cycles -1 Capacity of [ Nano Lett., 13 (2013) 818]. Previous reports respectively prove that graphene/CNT @ Fe is utilized 3 O 4 The addition of a carbon coating to the composite material can mitigate Fe 3 O 4 Thereby extending the battery cycle life [ a.chem.eng.j.,326 (2017) 507; chem.eur.j.,19 (2013) 9866; matter chem.a,3 (2015) 18289]. However, fe due to its large volume change 3 O 4 The problems of aggregation and pulverization still occur during charge and discharge cycles of the base anode, so that the charge and discharge cycle stability is severely limited.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides carbon-coated Fe 3 O 4 Composite material and its preparation method and application.
The technical scheme of the invention is as follows:
carbon-coated Fe 3 O 4 A composite material having the general structural formula: CNT @ hollow Fe 3 O 4 @ C, where CNT is carbon nanotube, hollow Fe 3 O 4 Is Fe 3 O 4 The hollow tube of (A) is in a hollow tubular structure, and C is coated on hollow Fe 3 O 4 The outermost layer of the carbon shell layer has a layered tubular structure, the outermost layer of the coating layer is the carbon shell layer, and the inner wall of the carbon shell layer is Fe 3 O 4 The hollow tube is composed of carbon nanotubes at the innermost layer, wherein the carbon nanotubes and Fe 3 O 4 Certain gap spaces are reserved among the tubes to form a tube-in-tube structure.
Furthermore, the carbon nano tube is selected from one of multi-wall carbon nano tube, single-wall carbon nano tube and single-wall carbon nano tube bundle;
furthermore, the pipe diameters of the single-walled carbon nanotube bundle and the multi-walled carbon nanotube are both selected from 5-50nm;
furthermore, the pipe diameters of the single-walled carbon nanotube bundles and the multi-walled carbon nanotubes are both selected from 20-50nm;
further, the carbon nanotube and Fe 3 O 4 A certain clearance space volume which is larger than or equal to Fe is reserved between the pipes 3 O 4 Fe in hollow tube 3 O 4 74% of the volume of the substance;
further, the coating is made of hollow Fe 3 O 4 The thickness of the surface carbon shell layer is selected from 1-15nm, preferably 3-6nm;
further, the carbon nanotube, fe 3 O 4 And the content of C is preferably selected from 15.6wt%,68.6wt% and 15.8wt%, respectively;
the pipe diameter of the composite material is 60nm-450nm, and the length is 50nm-10um;
the pipe diameter of the composite material is 100-200nm, and the length of the composite material is 500nm-3um;
the pore volume of the composite material is 0.27cm 3 /g；
Said Fe 3 O 4 The phase of the substance is consistent with that of the JCPDS No.19-0629 standard card;
said Fe 3 O 4 Is in the shape of nano strip, each strip Fe 3 O 4 Cross-linked together to form porous Fe 3 O 4 A hollow tube.
Carbon-coated Fe 3 O 4 The composite material is applied as a negative electrode material to a lithium ion battery, a sodium ion battery or a potassium ion battery.
Containing the carbon-coated Fe 3 O 4 Of composite materialsThe secondary battery comprises a lithium ion battery, a sodium ion battery or a potassium ion battery, and the lithium ion battery, the sodium ion battery or the potassium ion battery comprises a positive electrode, a negative electrode and electrolyte; the negative electrode includes: a current collector and a negative electrode material supported on the current collector; wherein the negative electrode material contains the composite material.
Carbon-coated Fe 3 O 4 The preparation method of the composite material comprises the following steps:
1) Preparing a carboxylated carbon nanotube: placing the carbon nano tube in concentrated nitric acid for refluxing for 1-6h, cooling, filtering, washing with deionized water to be neutral, and drying for later use; the carbon nano-tube is selected from one of multi-wall carbon nano-tube or single-wall carbon nano-tube; the pipe diameter of the multi-wall carbon nano-tube is selected from 5-50nm.
2) Preparation of CNT @ C composite nanomaterial: dispersing the carboxylated carbon nanotubes, sodium dodecyl sulfate and glucose in deionized water, and performing ultrasonic dispersion uniformly to obtain a mixture solution A; the mass ratio of the carboxylated carbon nanotubes to the sodium dodecyl sulfate to the glucose is 20:2: (400-800). Transferring the mixture solution A into the inner liner of a stainless steel reaction kettle for hydrothermal reaction, and keeping the temperature at 160-200 ℃ for more than 3-48 h. And naturally cooling the reaction kettle to room temperature, collecting a brown product, repeatedly washing the brown product with deionized water and ethanol for several times, and drying to obtain the CNT @ C composite nano material.
The structure of CNT @ C is that a carbon nano tube is coated with a carbon layer.
The temperature and time of the hydrothermal reaction are further preferably 180-190 ℃, and the time is 12-15 h;
3) Preparation of CNT @ C @ FeOOH composite: dissolving CNT @ C in a mixed solution of ethanol and deionized water, adding ferric salt and urea after uniform ultrasonic dispersion, and continuing ultrasonic dispersion to obtain a mixed solution B. Heating and stirring the mixed solution B at 60-80 ℃ for more than 24 h. Filtering, washing and drying to obtain the CNT @ C @ FeOOH composite material. The CNT @ C FeOOH composite material has the structure that the CNT @ C outer layer is coated with FeOOH; the volume ratio of the ethanol to the water is 32:5.3; the FeOOH is nano particles with the particle size of 3-10nm. The CNT @ C @ FeOOH material has a multilayer coating structure, the axis of the innermost core is a carbon nano tube, the surface of the carbon nano tube is coated with a carbon layer, and the carbon layer is further coated with a layer of FeOOH.
4)CNT@hollow Fe 2 O 3 The preparation of (1): placing CNT @ C @ FeOOH in air, burning until all intermediate carbon layers in CNT @ C @ FeOOH are selectively removed, and finally obtaining CNT @ hollow Fe 2 O 3 A composite material; the burning temperature in the air is 230-550 ℃, and the time is 0.5-12h; preferably, the temperature is raised to 400 ℃ in air at a rate of 1-20 ℃/min and maintained for 2h.
5)CNT@hollow Fe 3 O 4 Preparation of @ C: mixing CNT @ hollow Fe 2 O 3 Dispersing deionized water, performing ultrasonic treatment to form a uniform solution, adding Cetyl Trimethyl Ammonium Bromide (CTAB) and ammonia water, continuing to perform ultrasonic dispersion uniformly, adding resorcinol and formaldehyde solution to obtain a mixed solution C, and continuing to stir for more than 16h. Filtering, washing with water and ethanol several times, and drying to obtain CNT @ hollow Fe 2 O 3 @ RF composite. Mixing CNT @ hollow Fe 2 O 3 @ RF is put in a tube furnace, carbonized at high temperature under inert atmosphere and naturally cooled to room temperature to obtain the CNT @ hollow Fe 3 O 4 @ C composite.
The RF is phenolic resin, the CNT is hydroxyl Fe 2 O 3 @ RF composite material is CNT @ hollow Fe 2 O 3 The outer layer is coated with a phenolic resin layer, and the outer layer is coated with CNT @ hollow Fe 3 O 4 The structure of @ C being Fe in the form of a hollow tubular structure 3 O 4 Sleeving outer CNT layer with Fe 3 O 4 A clearance space is reserved between the wall of the hollow tube and the outer CNT layer, and Fe is contained in the clearance space 3 O 4 A carbon layer is coated outside the substrate. The temperature of the high-temperature carbonization is 450-600 ℃, and the holding time is 1-5h. Said Fe 3 O 4 Is in the shape of nano strip, each strip Fe 3 O 4 Cross-linked together to form a porous hollow tube.
Compared with the prior art, the carbon-coated Fe provided by the invention 3 O 4 Composite material with layered tubeThe structure is characterized in that the outermost coating layer is a carbon shell, and the inner wall of the carbon shell is Fe 3 O 4 The hollow nano-tube composed of nano-particles is a carbon nano-tube at the innermost layer, wherein the carbon nano-tube and Fe 3 O 4 Certain gap spaces are reserved among the nanotubes to form a tube-in-tube structure. The material with the structure is used as a negative electrode material of a lithium ion battery, a sodium ion battery or a potassium ion battery, the electrical conductivity of the material can be greatly improved due to the existence of the carbon nano tube on the innermost layer, and the carbon nano tube and Fe 3 O 4 The space reserved between the nanotubes is favorable for buffering the change of the volume caused by ion de-intercalation in the battery, and the external carbon layer can buffer the damage, agglomeration and crushing phenomena of the volume change of the active material to the overall structure of the material, so that the structural stability of the electrode material is improved, and the charge-discharge cycle stability of the battery is further improved. In addition, the structure is more innovative in that the active ingredient Fe 3 O 4 Is in a hollow tube structure, not only ensures the space for reserving the volume change of the active material, but also ensures the active ingredient Fe 3 O 4 And the carbon layer can be directly contacted with the outermost layer, so that the ion migration path is more favorably shortened, and the rate capability of the battery is improved.
The invention provides carbon-coated Fe 3 O 4 The preparation method of the composite material has the technical key points that:
step 2) in the preparation of the CNT @ C composite nano material, the thickness of the C layer can be effectively controlled by adjusting the dosage proportion of glucose and the hydrothermal reaction temperature and time, so that the carbon nano tube and Fe can be effectively regulated and controlled 3 O 4 The space volume reserved between the nanotubes can realize the optimal reserved space volume. The hydrothermal temperature and time directly affect the thickness of the carbon layer coated on the outer layer of the carbon nanotube, and too high temperature or too long time can cause the thickness of the carbon layer to be too thick, thereby causing Fe to be formed in the subsequent steps 3 O 4 The interstitial space between the hollow tube walls and the outer CNT layer is too large to affect the cell performance of the final product.
The innovation of the step 4) is that the temperature of air burning and the burning process are accurately controlled to ensure that the C layer in the CNT @ C material is removed and the CNT is reserved. Preferably, the temperature is raised to 400 ℃ in air at a rate of 1-20 ℃/min and maintained for 2h.
The innovation of the step 5) is that the RF quantity and the carbonization temperature are accurately controlled, the thickness of the outermost coating carbon layer can be realized, the battery performance of the electrode material can be directly influenced by the thickness of the carbon layer, the ion transmission rate is slowed down by the excessively thick carbon layer, and the carbon layer is easily damaged in the volume change process of the active material due to the excessively thin carbon layer. The thickness of the carbon layer is selected from the range of 1-15nm, preferably 3-6nm.
The invention provides carbon-coated Fe 3 O 4 The composite material is used as a lithium ion negative electrode material, and shows high specific capacity, excellent rate performance and excellent cycling stability. At 0.2 and 4A g -1 Respectively, and exhibits 859 and 428mA h g -1 At 0.2 ag -1 After the next 500 cycles, the mixture still keeps 758mA h g -1 In addition, the specific capacity of the catalyst is 1.5Ag -1 Has 409mA h g after 1000 cycles at a high rate -1 The specific capacity of the resin composition is high, and the resin composition has long-life cycle performance.
Drawings
FIG. 1 is a schematic diagram of the preparation of carbon-coated Fe 3 O 4 The composite material has a schematic flow chart, wherein the flow chart 1 shows that a carbon layer is coated on the outer surface of the carbon nano tube, the flow chart 2 shows that a layer of FeOOH is coated on the coated carbon layer, the flow chart 3 shows that the intermediate carbon layer is completely removed, and simultaneously the FeOOH is converted into Fe 2 O 3 Scheme 4 shows that the outermost layer is coated with a carbon layer and Fe 2 O 3 Conversion to higher capacity density Fe 3 O 4 。
FIG. 2 is a graph of MWNT @ C (a, b, c), MWNT @ C @ FeOOH (d, e, f), MWNT @ hold Fe prepared in example 1 2 O 3 (g, h, i) representative scanning electron micrographs and transmission electron micrographs of the composite.
FIG. 3 shows the carbon-coated Fe prepared in this example 3 O 4 Scanning electron micrographs (a, b) and transmission electron micrographs (c, d) of the composite.
FIG. 4 shows the carbon-coated Fe prepared in this example 3 O 4 Powder X-ray diffraction pattern (XRD) of the composite material.
FIG. 5 shows the present exampleMWNT @ hollow Fe prepared in examples 2 O 3 Composite material and MWNT @ hollow Fe 3 O 4 Thermogravimetric plot of @ C.
FIG. 6 is a thermogram of MWNT @ C composite material prepared in this example.
FIG. 7 is an XRD pattern of MWNT @ C @ FeOOH composite material prepared in this example.
FIG. 8 shows MWNT @ hold Fe prepared in this example 2 O 3 XRD pattern of the composite.
FIG. 9 shows MWNT @ hollow Fe prepared in this example 3 O 4 The nitrogen isothermal adsorption and desorption curve of the @ C composite material.
FIGS. 10 and 11 show MWNT @ hollow Fe prepared in this example 3 O 4 A graph of the charging and discharging cycle performance of the @ C composite material as an ion battery negative electrode.
FIG. 12 is a diagram showing a lithium ion battery assembled in the same manner as in example 1 in comparative example and commercially prepared Fe tested in the same test method 3 O 4 And Fe 2 O 3 The charge-discharge cycle performance of (1).
Detailed Description
Example 1:
1) Multiwall carbon nanotubes (MWNTs) of size 5-50nm were first selected for carboxylation with concentrated nitric acid (65 wt%) under reflux in an oil bath at 140 ℃ for 6h prior to use. After cooling to room temperature, filtering and washing until neutral, and drying for later use.
2) Dispersing carboxylated MWNTs, sodium dodecyl sulfate and glucose in deionized water, and performing ultrasonic dispersion uniformly to obtain a mixture solution A. The specific mass ratio of carboxylated MWNTs, sodium dodecyl sulfate and glucose is 20mg: 400-800 mg.
3) The mixture solution A was transferred to a 25ml stainless steel reactor liner, sealed and kept at 190 ℃ for 15h for hydrothermal reaction. And after the reaction kettle is naturally cooled to room temperature, collecting a brown product, repeatedly washing the brown product by using deionized water and ethanol for several times, and finally drying the brown product at 80 ℃ for 12 hours to obtain the MWNT @ C composite nanomaterial.
4) 160mg MWNT @ C was dissolved in a mixed solution of ethanol and deionized water (ethanol andthe volume ratio of water is 32ml:5.3 ml), after uniform ultrasonic dispersion, 540mg of FeCl was added 3 ·6H 2 And continuously performing ultrasonic dispersion on the O and 1.2g of urea to obtain a mixed solution B.
5) The mixed solution B was transferred to a 50ml flask. The mixture solution was heated and stirred for 60 hours under an oil bath at 60 ℃. After filtration, washing and drying, MWNT @ C @ FeOOH is obtained.
6) The resulting MWNT @ C @ FeOOH was placed in a muffle furnace and heated to 400 ℃ in air at a rate of 1 ℃/min, and held for 2h. Cooling at room temperature to obtain MWNT @ hollow Fe 2 O 3 A composite material.
7) MWNT @ hollow Fe 2 O 3 Dispersing deionized water, performing ultrasonic treatment to form a uniform solution, adding 0.6ml of 0.01M CTAB and 48 mu l of ammonia water, performing ultrasonic treatment for 0.5h, adding 24mg of resorcinol and 33.6 mu l of formaldehyde solution to obtain a mixed solution C, and stirring for 16h. Filtering, washing with water and ethanol several times, and drying to obtain MWNT @ hollow Fe 2 O 3 @ RF composite.
8) Mixing MWNT @ hollow Fe 2 O 3 @ RF was placed in a tube furnace and calcined at 550 ℃ for 2h under an argon atmosphere for carbonization. Naturally cooling to room temperature to obtain MWNT @ hollow Fe 3 O 4 @ C composite material.
9) And (3) putting the product (80 wt%), conductive carbon black (10 wt%) and carboxymethyl cellulose (CMC 10 wt%) obtained in the step 8) into an agate mortar for grinding, wherein deionized water is used as a dispersing agent, and foamed nickel is used as a current collector. Uniformly coating the ground slurry on the weighed dry foamed nickel, drying for 12 hours at 80 ℃ in vacuum, flattening and weighing the electrode plates, and obtaining the mass of the slurry on each electrode plate according to the mass difference before and after coating of the current collector. And continuously vacuum-drying the electrode plates for 2h at 80 ℃, and then putting the electrode plates into a glove box to be assembled with a button cell.
10 Assembling a button cell in a glove box filled with argon, wherein the counter electrode is a metal lithium sheet, the diaphragm is a Celgard 2300 membrane, and the manufactured electrode plate is a working electrode. The electrolyte is 1M LiPF 6 In Ethylene Carbonate (EC): ethyl Methyl Carbonate (EMC): dimethyl carbonate (DMC) (volume ratio 1
11 Constant current charge and discharge test mainly examines the charge and discharge specific capacity, the cycle performance and the rate performance of the lithium ion half-cell under different current densities. Constant current discharging is firstly carried out on the lithium ion half battery to 0.05V, so that lithium ions in the metal lithium sheet are embedded into the working electrode material; then the constant current is charged to 3V, and the test is carried out in a circulating way.
FIG. 2 shows MWNT @ C (a, b, c), MWNT @ C @ FeOOH (d, e, f), MWNT @ holow Fe prepared in this example 2 O 3 (g, h, i) the representative scanning electron micrograph and transmission electron micrograph of the composite material, from the observation result, MWNT's pipe diameter 5-50nm, mainly distribute in 20-50nm, MWNT @ C carbon bed is coated outside the carbon nanotube, the thickness of the coated carbon bed is all in 20nm-200nm, the carbon bed thickness mainly concentrated in 40-80nm, MWNT @ C can be regulated and controlled through controlling the amount of glucose and the condition of hydrothermal reaction, increase the consumption of glucose and reaction time theoretically can make the carbon bed thickness achieve more than 1 micron, MWNT @ C length is all in 50nm-10um, mainly concentrate on 500nm-3um, MWNT @ C length is controlled by the length of the carbon nanotube used, therefore the length of the carbon nanotube put into can be chosen wantonly, therefore the length of MWNT @ C can also be controlled wantonly. MWNT @ C @ FeOOH is a layer of FeOOH nano-particles coated on the basis of MWNT @ C structure; the pipe diameters of MWNT @ C @ FeOOH are all 60nm-450nm, and are mainly concentrated at 100 nm-200 nm; MWNT @ C @ FeOOH has a length of 50nm-10um, and is mainly concentrated at 500nm-3um. MWNT @ hollow Fe 2 O 3 Is converted from MWNT @ C @ FeOOH after removing C layer by high-temperature burning, fe 2 O 3 Forming a hollow tube, the CNT @ hold Fe 2 O 3 The material has a tube-in-tube structure, the inner tube is made of carbon nano tube, the outer tube is made of Fe 2 O 3 Hollow tube, CNT @ hold Fe 2 O 3 The pipe diameters of the materials are all 60nm-450nm, mainly concentrated at 100-200nm, the lengths are all 50nm-10um, and mainly concentrated at 500nm-3um.
FIG. 3 shows the carbon-coated Fe prepared in this example 3 O 4 The composite material can be observed to have a layered tubular structure in scanning electron micrographs (a, b) and transmission electron micrographs (c, d), wherein the outermost coating layer is a carbon shell and the inner layer of the carbon shell is a carbon shellThe wall being Fe 3 O 4 The hollow nanotube is formed with carbon nanotube in the innermost layer, and the carbon nanotube and Fe are mixed 3 O 4 A certain gap space is reserved among the nanotubes to form a tube-in-tube structure; the pipe diameters are all between 60nm and 450nm, the pipe diameters are mainly concentrated between 100 nm and 200nm, the lengths are all between 50nm and 10um, the pipe diameters are mainly concentrated between 500nm and 3um, the thickness of the outermost layer carbon layer is between 1nm and 15nm, and the pipe diameters are mainly concentrated between 3 nm and 6nm. e, f are respectively carbon-coated Fe 3 O 4 The high-resolution transmission electron microscope picture and the crystal diffraction pattern of the composite material show that the active substance of the composite material is Fe 3 O 4 ，Fe 3 O 4 Is in the shape of nano strip, each strip Fe 3 O 4 Cross-linked together to form a porous hollow tube.
FIG. 4 shows carbon-coated Fe prepared in this example 3 O 4 Powder X-ray diffraction (XRD) pattern of a composite material in which the active ingredient is Fe 3 O 4 The phase of the card is consistent with that of the JCPDS No.19-0629 standard card.
FIG. 5 is MWNT @ hollow Fe prepared in this example 2 O 3 Composite material and MWNT @ hollow Fe 3 O 4 Thermogram of @ C, in which Fe is calculated 2 O 3 Content of (2 wt.%), MWNT @ hollow Fe 3 O 4 In @ C, the content of Fe3O4 is 68.6wt%, the content of the multi-wall carbon nano tube is 15.6wt%, and the content of the carbon layer is 15.8wt%.
FIG. 6 is a thermogravimetric plot of the MWNT @ C composite material prepared in this example, in which it can be determined that the temperature for removing the carbon layer is between 230-550nm, and 400 ℃ is the most preferable.
FIG. 7 is an XRD pattern of MWNT @ C @ FeOOH composite material prepared in this example, in which the phase of FeOOH can be confirmed to be consistent with that on JCPDS No.34-1266 standard card.
FIG. 8 is MWNT @ hollow Fe prepared in this example 2 O 3 The XRD pattern of the composite material can confirm that the phase of Fe2O3 is consistent with that on JCPDS No.33-0664 standard card.
FIG. 9 shows MWNT @ hollow Fe prepared in this example 3 O 4 Isothermal nitrogen desorption of @ C compositeAttached curve, MWNT @ hollow Fe calculated by analysis 3 O 4 The pore volume of the @ C composite was 0.27cm 3 /g。
FIGS. 10 and 11 are MWNT @ hollow Fe prepared in this example 3 O 4 The @ C composite material has a charge-discharge cycle performance chart of 0.2 and 4A g as the negative electrode of the ion battery -1 Respectively, 859 and 428mA h g -1 High specific capacity of (2). At 0.2A g -1 758mA h g after the next 500 cycles -1 The specific capacity of (A). In addition, in 1.5Ag -1 Has a high rate of 409mA h g after 1000 cycles -1 The specific capacity of the resin is high, and the cycle performance of the resin is long in service life; as a comparative example, MWNT @ hollow Fe with outermost layer not coated with C layer 2 O 3 When the ionic cell cathode is used, the charge-discharge cycle performance is obviously inferior to that of MWNT @ hollow Fe 3 O 4 @C，MWNT@hollow Fe 2 O 3 At 0.2A g -1 Only 450mA h g remained after 130 times of lower circulation -1 The specific capacity of (A).
FIG. 12 shows a lithium ion battery assembled by the same method as in example 1 in comparative example and commercially prepared Fe tested by the same test method 3 O 4 And Fe 2 O 3 In the charge-discharge cycle characteristics chart of (1), they are respectively 0.15 ag -1 The specific capacity of the alloy is obviously lower than MWNT @ hollow Fe after 150 times of circulation under the current density 2 O 3 And MWNT @ hollow Fe 3 O 4 @C。
Example 2
The present embodiment is different from embodiment 1 in that: step 3) the hydrothermal reaction conditions are respectively 200 ℃ for 3h,160 ℃ for 48h and 180 ℃ for 12h; and 8) selecting the high-temperature carbonization temperature from 450-600 ℃, the time from 1-5h, and the atmosphere from nitrogen.
Example 3
The present embodiment is different from embodiment 1 in that: step 6), the burning temperature in the air is 230-550 ℃, and the time is 0.5-12h under the temperature.
Claims (23)
1. Carbon-coated Fe 3 O 4 Composite material, characterized in thatThe composite material has the following structural general formula: CNT @ hollow Fe 3 O 4 @ C, wherein CNT is carbon nanotube, hollow Fe 3 O 4 Is Fe 3 O 4 The hollow tube is in a hollow tubular structure, and C is coated in hollow Fe 3 O 4 The outermost layer of the carbon shell layer has a layered tubular structure, the outermost layer of the coating layer is the carbon shell layer, and the inner wall of the carbon shell layer is Fe 3 O 4 The hollow tube is composed of carbon nanotubes at the innermost layer, wherein the carbon nanotubes and Fe 3 O 4 A certain gap space is reserved between the pipes to form a pipe-in-pipe structure;
said Fe 3 O 4 Is in the shape of nano strip, each strip Fe 3 O 4 Cross-linked together to form porous Fe 3 O 4 A hollow tube.
2. The composite material of claim 1, wherein the carbon nanotubes are one of multi-walled carbon nanotubes, single-walled carbon nanotubes, or bundles of single-walled carbon nanotubes.
3. The composite material of claim 2, wherein the tube diameter of each of the single-walled carbon nanotube bundle and the multi-walled carbon nanotube is 5-50nm.
4. The composite material of claim 3, wherein the tube bundle of single-walled carbon nanotubes and the multi-walled carbon nanotubes each have a tube diameter of 20 to 50nm.
5. The composite material of claim 1, wherein the carbon nanotubes are Fe 3 O 4 The volume of a certain clearance space reserved between the tubes is larger than or equal to Fe 3 O 4 Fe in hollow tube 3 O 4 74% of the material volume.
6. The composite material as claimed in claim 1, wherein said coating is hollow Fe 3 O 4 Of (2)The thickness of the outer carbon shell layer is 1-15nm.
7. The composite material as claimed in claim 1, wherein said coating is hollow Fe 3 O 4 The thickness of the outermost carbon shell layer is 3-6nm.
8. The composite material of claim 1, wherein the composite material has a tube diameter of 60nm to 450nm and a length of 50nm to 10um.
9. The composite material of claim 1, wherein the composite material has a tube diameter of 100-200nm and a length of 500nm-3um.
10. Carbon coated Fe according to any one of claims 1 to 9 3 O 4 The preparation method of the composite material comprises the following steps:
mixing CNT @ hollow Fe 2 O 3 Dispersing the material into deionized water to obtain a uniform solution, adding Cetyl Trimethyl Ammonium Bromide (CTAB) and ammonia water, uniformly dispersing, adding resorcinol and formaldehyde solution to obtain a mixed solution, continuously stirring for more than 16h, filtering, washing, and drying to obtain CNT @ hollow Fe 2 O 3 @ RF composite; mixing CNT with hollow Fe 2 O 3 Carbonizing at 450-600 deg.C for 1-5h under RF inert atmosphere to obtain CNT @ hollow Fe 3 O 4 The @ C composite material is the carbon-coated Fe 3 O 4 A composite material;
the CNT @ hold Fe 2 O 3 The material has a tube-in-tube structure, the inner tube is carbon nanotube, the outer tube is Fe 2 O 3 A hollow tube; the carbon nano tube is one of a multi-wall carbon nano tube or a single-wall carbon nano tube;
the RF is phenolic resin, the CNT is hydroxyl Fe 2 O 3 The @ RF composite material is CNT @ hollow Fe 2 O 3 The outer layer is coated with a phenolic resin layer;
the inert atmosphere refers to one or more of high-purity nitrogen, high-purity argon, high-purity helium, high-purity neon and high-purity krypton.
11. The method as claimed in claim 10, wherein CNT @ hold Fe 2 O 3 The preparation method of the material comprises the following steps:
placing CNT @ C @ FeOOH in air, burning until all intermediate carbon layers in CNT @ C @ FeOOH are selectively removed, and finally obtaining CNT @ hollow Fe 2 O 3 A composite material;
the CNT @ C @ FeOOH structure is of a multilayer coating structure, the shaft center of the innermost core is a carbon nano tube, the surface of the carbon nano tube is coated with a carbon layer, and the carbon layer is coated with a layer of FeOOH.
12. The method of claim 11, wherein the FeOOH is a nanoparticle having a size of 3-10nm.
13. The method of claim 11, wherein the air is burned at a temperature selected from the group consisting of 230 ℃ to 550 ℃ for a period of 0.5 to 12 hours.
14. The method of claim 11, wherein the burning in the air is selected from raising the temperature to 400 ℃ at a rate of 1-20 ℃/min for a period of 2 hours.
15. The method according to any one of claims 11-14, wherein the method for preparing cnt @ c @ feooh comprises the steps of:
1) Preparing a carboxylated carbon nanotube;
2) Preparing CNT @ C composite nano material;
3) Preparation of CNT @ C @ FeOOH composite: dissolving the CNT @ C composite nano material in a mixed solution of ethanol and deionized water, adding ferric salt and urea after uniform ultrasonic dispersion, and continuing ultrasonic dispersion to obtain a mixed solution B; heating and stirring the mixed solution B at 60-80 ℃ for more than 24 h; filtering, washing and drying to obtain the CNT @ C @ FeOOH composite material;
the CNT @ C composite nano material is structurally characterized in that a carbon nano tube is coated with a carbon layer;
the carboxylated carbon nano tube is a carbon nano tube of which the surface contains carboxyl groups.
16. The method of claim 15, wherein the volume ratio of ethanol to deionized water is selected from the group consisting of 32.
17. The method of claim 15, wherein the method for preparing carboxylated carbon nanotubes comprises the steps of: and (3) putting the carbon nano tube in concentrated nitric acid for refluxing for 1-6h, cooling, filtering, washing with deionized water to be neutral, and drying for later use.
18. The method of claim 15, wherein the cnt @ c composite nanomaterial preparation method comprises the steps of: drying for later use, dispersing the carboxylated carbon nanotubes, sodium dodecyl sulfate and glucose in deionized water, and uniformly dispersing to obtain a mixture solution A; transferring the mixture solution A into a reactor for hydrothermal reaction, keeping the temperature at 160-200 ℃ for 3-48 h, filtering, washing and drying after the reaction is finished to obtain the CNT @ C composite nano material;
the mass ratio of the carboxylated carbon nanotubes to the sodium dodecyl sulfate to the glucose is 20:2: (400-800).
19. The method according to claim 18, wherein the temperature of the hydrothermal reaction is selected from 180 to 190 ℃ and the holding time is selected from 12 to 15 hours.
20. The method of claim 15, wherein the thickness of the carbon layer in the cnt @ c composite nanomaterial is greater than 1nm.
21. The method of claim 15, wherein the thickness of the carbon layer in the cnt @ c composite nanomaterial is greater than 20-40nm.
22. Carbon-coated Fe as defined in any one of claims 1 to 9 3 O 4 The composite material is applied to a primary or secondary electrochemical generator, a high-energy generator and an electrochemical luminescence modulation system, and is characterized in that the composite material is applied to a lithium ion battery, a sodium ion battery or a potassium ion battery as a negative electrode material.
23. A carbon-coated Fe comprising any one of claims 1 to 9 3 O 4 The secondary battery comprises a lithium ion battery, a sodium ion battery or a potassium ion battery, wherein the lithium ion battery, the sodium ion battery or the potassium ion battery comprises a positive electrode, a negative electrode and electrolyte; the negative electrode includes: a current collector and a negative electrode material supported on the current collector; wherein the negative electrode material contains the composite material.
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