CN110649237B - Iron oxide @ carbon nanocomposite and preparation method and application thereof - Google Patents

Iron oxide @ carbon nanocomposite and preparation method and application thereof Download PDF

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CN110649237B
CN110649237B CN201910924391.9A CN201910924391A CN110649237B CN 110649237 B CN110649237 B CN 110649237B CN 201910924391 A CN201910924391 A CN 201910924391A CN 110649237 B CN110649237 B CN 110649237B
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iron oxide
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pyrolysis deposition
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CN110649237A (en
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钟海长
徐敬博
杜子宇
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Xiamen University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
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    • B01J35/40—
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an iron oxide @ carbon nano composite material and a preparation method and application thereof2O3Or Fe3O4. Also discloses a preparation method thereof, and the ferrocene powder is selected as a precursor in the step (1); performing discharge plasma ball milling on ferrocene powder to obtain partial pre-carbonized powder; step (3) carrying out pyrolysis deposition treatment on part of the pre-carbonized powder to obtain Fe with a nano structure3C and a carbon substrate; step (4) of mixing Fe3C is subjected to in-situ oxidation to obtain Fe2O3Or Fe3O4And coating a layer of carbon film on the surface of the iron oxide @ carbon nano composite material, and then naturally cooling to room temperature to obtain the iron oxide @ carbon nano composite material. The invention can be used not only as a lithium ion negative electrode material,it can also be used as the anode material of sodium ion battery and the hydrogen absorbing and releasing catalyst of hydrogen storage material.

Description

Iron oxide @ carbon nanocomposite and preparation method and application thereof
Technical Field
The invention relates to the field of composite material preparation, and particularly relates to an iron oxide @ carbon nanocomposite material and a preparation method and application thereof.
Background
With the rapid development of socio-economy, the conventional fossil energy is rapidly consumed and causes a serious environmental problem, so that the development of new energy and energy storage technology is very urgent. Lithium Ion Batteries (LIBs) are an attractive energy storage device due to their advantages of high specific capacity, no memory effect, long service life, etc. It has been widely used in portable devices such as mobile phones and notebook computers. However, with the increasing abundance and intellectualization of the functions of these terminal electric devices, and the requirement of users for continuous power supply for a long time, especially for developing power batteries for new energy vehicles, higher capacity requirements are provided for lithium ion batteries. The theoretical capacity of the carbon-based negative electrode material is 372 mAh/g, the capacity of the carbon-based negative electrode material which is widely commercialized at present approaches the theoretical capacity limit, and the requirement of new energy automobiles and the like on high capacity is difficult to meet. In recent years, transition metal oxides based on conversion reactions have a higher theoretical specific capacity, such as Fe2O3The theoretical specific capacity of the alloy is 1007 mAh/g, Fe3O4The theoretical capacity of the oxide is 924 mAh/g, and the oxide has the advantages of good physical and chemical stability, easy control of morphology and size, safer lithium intercalation potential and the like, and has received wide attention. In addition, the iron oxide is considered to be a high-capacity negative electrode material with a good application prospect due to rich resources, low price and environmental friendliness. However, its electrochemical properties, especially high rate performance, are affected by its poor electronic conductivity, ionic conductivity and structural stability. The main methods to improve these problems include preparation of nano-structured active materials, design and preparation of carbon-coated materials, or mixing or doping of active materials with highly conductive materials, etc. However, the problem of pulverization caused by volume change caused by charging and discharging of the iron oxide is not fundamentally solved. High first irreversible capacity, severe voltage hysteresis, low first coulombic efficiency, poor cycle lifeThe problems of poor rate performance and the like still exist.
Therefore, the inventors further studied and developed an iron oxide @ carbon nanocomposite, a preparation method and applications thereof, and the present application was made thereby.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the iron oxide @ carbon nanocomposite material, and the preparation method and the application thereof, wherein the iron oxide @ carbon nanocomposite material can be used as a lithium ion negative electrode material, a positive electrode material of a sodium ion battery and a hydrogen absorption and desorption catalyst of a hydrogen storage material.
In order to solve the technical problems, the technical solution of the invention is as follows:
an iron oxide @ carbon nano composite material is characterized in that iron oxide nano particles are in a core-shell structure, a carbon film is wrapped on the surface of the iron oxide nano particles and dispersed in a carbon matrix, and the iron oxide is Fe2O3Or Fe3O4。
Further, the particle size of the iron oxide nanoparticles is 20-200 nm.
Further, the thickness of the carbon film is in the range of 4 to 6 nm, and preferably 5 nm.
Further, the carbon matrix is in the form of carbon nanotubes, carbon nanorods or graphite nanoplatelets.
A preparation method of an iron oxide @ carbon nanocomposite comprises the following specific steps:
step (1): selecting ferrocene powder as a precursor;
step (2): performing discharge plasma ball milling on the ferrocene powder to obtain partial pre-carbonized powder;
and (3): carrying out pyrolysis deposition treatment on part of the pre-carbonized powder to obtain Fe with a nano structure3C and a carbon substrate;
and (4): mixing Fe3C is subjected to in-situ oxidation to obtain Fe2O3Or Fe3O4And coating a layer of carbon film on the surface of the iron oxide @ carbon nano composite material, and then naturally cooling to room temperature to obtain the iron oxide @ carbon nano composite material.
Further, in the step (2), the ball milling time of the ferrocene powder is 2-3 hours, the ball-to-material ratio of the discharge plasma assisted ball milling is 50:1, meanwhile, the pressure is kept at 0.1 atmosphere and the pressure is low, the discharge current is 2-3A, and the discharge voltage is 10-25 kV.
Further, when pyrolysis deposition is carried out in the step (3), argon is introduced as protective gas, the temperature of the pyrolysis deposition is 500-600 ℃, the time of the pyrolysis deposition is 5-40 minutes, and the carbon matrix is a carbon nano tube/rod or a graphite nano sheet.
Further, in the step (4), before in-situ oxidation, the temperature is reduced to 100-300 ℃, and the temperature is kept for 10-60 minutes by introducing the atmosphere.
Further, in the step (3), the pyrolysis deposition temperature is 600 ℃, the pyrolysis deposition time is 30 minutes, the temperature is reduced to 300 ℃ in the step (4), and the temperature is maintained for 30 minutes by introducing the atmosphere.
An application of iron oxide @ carbon nanocomposite is used as a negative electrode material of a lithium ion battery or a hydrogen absorption and desorption catalyst of a hydrogen storage material.
The invention designs and develops a simple and efficient preparation method of an iron oxide-carbon core-shell structure nano composite material and a preparation method thereof based on the problems of iron oxide serving as a lithium ion battery cathode material. Compared with other chemical methods, the method is based on a physical chemical vapor deposition method, has low requirement on equipment, is easy to operate, does not need to use any toxic and harmful gas, does not generate any toxic and harmful by-product, and is easy to realize large-scale preparation. The preparation of the nano-composites with various morphological characteristics can also be realized by regulating and controlling a temperature field.
The invention has the following advantages:
(1) the selected raw materials have wide sources and low price, and the cost can be effectively reduced;
(2) the preparation process flow is simple, and the operation and the batch production are easy to realize;
(3) the used equipment is simple and is very suitable for industrial application;
(4) in the preparation process, any other additive is not needed, and toxic and harmful byproducts are not generated, so that the preparation process is very environment-friendly;
(5) the same equipment and process are adopted, and the control of the product appearance can be easily realized only by changing the temperature condition;
(6) the prepared composite material is used as a negative electrode material of a lithium ion battery, and has high specific capacity, good rate capability and charge-discharge stability;
(7) it can also be used as hydrogen absorbing and releasing catalyst of hydrogen storage material.
Drawings
FIG. 1 is Fe of a sample prepared in example 1 of the present invention2O3XRD pattern of (a);
FIG. 2 is an SEM micrograph of a prepared sample at a pyrolytic deposition temperature of 600 ℃;
FIG. 3 is a high power SEM image of a sample prepared at a pyrolytic deposition temperature of 600 ℃;
FIG. 4 is an SEM micrograph of a prepared sample at a pyrolytic deposition temperature of 500 ℃;
FIG. 5 is a STEM microtopography of a prepared sample at a pyrolytic deposition temperature of 550 ℃;
FIG. 6 is a high power STEM plot of samples prepared at a pyrolytic deposition temperature of 550 ℃;
FIG. 7 is a STEM of the in situ oxidation at 300 ℃ of the prepared sample at 500 ℃ for pyrolytic deposition;
FIG. 8 is a graph of rate performance of the sample of example 4 as a negative electrode material for a lithium ion battery;
FIG. 9 is a schematic flow diagram of the present invention;
FIG. 10 shows Fe of a sample prepared in example 5 of the present invention3O4XRD pattern of (a).
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. The invention discloses an iron oxide @ carbon nano composite material and a preparation method and application thereof, as shown in figure 2, iron oxide nano particles are in a core-shell structure (also called as a spherical structure), the surface of the iron oxide nano particles is coated with a carbon film and dispersed in a carbon matrix, and iron oxide Fe2O3。
Further, Fe is selected according to the pyrolysis temperature and treatment time2O3Or Fe3O4The particle size of the nano particles is 20-200 nm.
Further, the thickness of the carbon film is in a range of 4 to 6 nm. In this embodiment, the preferred thickness of the carbon film is 5 nm.
Further, the carbon matrix is in the form of carbon nanotubes, carbon nanorods or graphite nanoplatelets.
The invention can be used as the cathode material of the lithium ion battery or the hydrogen absorbing and releasing catalyst of the hydrogen storage material. The lithium ion battery cathode material has high capacity, good cycle performance and good rate performance. After 100 charge-discharge cycles with a current density of 0.2A/g, the specific capacity is about 1000 mAh/g; under the charge-discharge current density of 0.5A/g, the specific capacity after 300 cycles of charge-discharge is kept above 560 mAh/g; and under the current density of 1A/g, after 500 times of charge-discharge cycles, the high specific capacity of 400 mAh/g is still maintained.
As shown in fig. 9, a preparation method of an iron oxide @ carbon nanocomposite comprises the following specific steps:
step (1): selecting ferrocene powder as a precursor.
Step (2): and ball-milling the ferrocene powder by adopting a discharge plasma ball-milling method to obtain partial pre-carbonized powder. In the step (2), the discharge plasma is adopted to assist ball milling, the precursor is pre-carbonized, the volatilization of the precursor in the step (3) in the temperature rising process is reduced and ensured to escape from a target temperature zone, and the yield of the pyrolysis deposition product is improved.
And (3): performing pyrolysis deposition treatment on partial pre-carbonized powder prepared by discharge plasma ball milling in a vacuum tube furnace at the pyrolysis deposition temperature of 500-600 ℃ for 5-40 minutes to obtain Fe with a nano structure3And C and carbon nano tube/rod or graphite nano sheet. The pyrolysis deposition temperature can be selected within the temperature range of 500-600 ℃, different forms of carbon from lichen to nanotube/rod can be changed by selecting different temperatures, and the carbon can be simultaneously adjustedControlled intermediate Fe3The particle size of C is very distributed.
And (4): after the step (3) is finished, reducing the temperature to 100-300 ℃, introducing air, keeping the temperature for 10-60 minutes, and adding Fe3C is subjected to in-situ oxidation to obtain Fe2O3Or controlling the oxygen content and the oxidation time, and under the anoxic condition, Fe can be formed3O4And maintaining the nano structure, coating a layer of carbon film on the surface of the nano structure, and naturally cooling to room temperature to obtain the nano composite material. The in-situ oxidation temperature is 300 ℃, so that the loss of carbon can be effectively reduced.
Further, in the step (2), the ball milling time of the ferrocene powder is 2-3 hours. The ball-material ratio of the discharge plasma assisted ball milling is 50:1, meanwhile, the pressure is kept low at 0.1 atmosphere, the discharge current is 2-3A, and the discharge voltage is about 13 kV.
Further, in the step (3), during pyrolysis deposition, argon is introduced as a protective gas (i.e., the ambient atmosphere is protected by argon), so that carbon can be prevented from being oxidized into CO and CO2。
Example 1
A preparation method of an iron oxide @ carbon nanocomposite comprises the following specific steps:
step (1): with ferrocene (C)10H10Fe) as precursor.
Step (2): adopting a discharge plasma ball milling method to mix ferrocene (C)10H10Fe) is mixed in a stainless steel grinding ball according to the ball-to-material ratio of 50:1 (mass ratio), and the ferrocene powder is ball-milled for 2-3 hours while keeping the pressure of 0.1 atmosphere low, the discharge current is 2-3A, and the discharge voltage is about 13kV, so that partial pre-carbonized powder is obtained.
And (3): and taking out part of the pre-carbonized powder prepared by the discharge plasma ball milling, putting the pre-carbonized powder into a porcelain boat, wrapping the pre-carbonized powder by using aluminum foil paper, putting the wrapped pre-carbonized powder into a vacuum tube furnace, and introducing argon atmosphere for protection to perform pyrolysis deposition treatment. The temperature of the pyrolysis deposition treatment in the vacuum tube furnace was 600 ℃.
As shown in the lower part (a) of fig. 1) As shown in the figure, the intermediate Fe is obtained by pyrolysis deposition at 600 DEG C3C and carbon composite powder. As shown in fig. 2, performing pyrolytic deposition at 600 degrees will obtain a composite powder with a tube/rib structure. From FIG. 3 of the high power SEM, it can be seen that the intermediate Fe3C is embedded in the carbon tubes/rods.
And (4): after the completion of the above step (3), the temperature is lowered to 300 ℃ and the temperature is maintained for 30 minutes by introducing the atmosphere, as shown in the upper part (b) of FIG. 1, after the in-situ oxidation at 300 ℃, the intermediate Fe3C is subjected to in-situ oxidation to obtain Fe2O3And then naturally cooling to room temperature to obtain the nano composite material.
Example 2
The difference from example 1 is that: the temperature of the pyrolysis deposition treatment in the vacuum tube furnace was 500 ℃.
As shown in FIG. 4, it can be seen that the sample prepared at the temperature has a novel structural feature of 'lichen', namely intermediate Fe3C is embedded in the carbon matrix.
Example 3
The difference from example 1 is that: the temperature of the pyrolytic deposition treatment in the vacuum tube furnace was 550 ℃.
As shown in fig. 5 and 6, the composite powder of a transition form obtained by pyrolysis deposition at 550 ℃ is intermediate between the samples prepared at 500 ℃ and 600 ℃. The tendency of the sample morphology to shift from "lichen" to tube/rod. The STEM profile in FIGS. 5 and 6 shows the intermediate Fe3The C is in a superfine nano particle structure and is highly dispersed and distributed in the carbon matrix.
Example 4
The difference from example 1 is that: the temperature of the pyrolysis deposition treatment in the vacuum tube furnace was 500 ℃.
As shown in FIG. 7, Fe can be seen from the graph2O3The nano particles are in a core-shell structure, and a layer of carbon film is wrapped on the surface of the nano particles and is dispersed in the carbon matrix.
As shown in fig. 8, it is a charge and discharge rate diagram using the 500 ℃ pyrolytic deposition sample as a negative electrode of a lithium ion battery. It can be seen that the lithium ion battery anode material has good rate capability.
Example 5
The difference from example 1 is that: and (4): after the step (3) is finished, reducing the temperature to 200 ℃, introducing the atmosphere for heat preservation for 40 minutes, controlling the oxygen content and the oxidation time, and under the anoxic condition, adding Fe3C is subjected to in-situ oxidation to obtain Fe3O4And keeping the nano structure, wrapping a carbon film on the surface of the nano structure, and naturally cooling to room temperature to obtain the nano composite material, as shown in FIG. 10.
From the above examples, it can be seen that the control of the morphology of the sample can be easily achieved by merely adjusting the temperature of the pyrolytic deposition process. The lithium ion battery cathode material has high specific capacity, good claims rate performance and cycling stability. But the application is not limited to the lithium ion battery cathode material, and the catalyst can also be used as the sodium ion battery anode material and the hydrogen storage material hydrogen absorption and desorption catalyst.
The above-mentioned embodiments are only preferred embodiments of the present invention, and do not limit the technical scope of the present invention, so that the changes and modifications made by the claims and the specification of the present invention should fall within the scope of the present invention.

Claims (8)

1. A preparation method of an iron oxide @ carbon nanocomposite is characterized by comprising the following steps: the method comprises the following specific steps: step (1): selecting ferrocene powder as a precursor; step (2): performing discharge plasma ball milling on the ferrocene powder to obtain partial pre-carbonized powder; and (3): carrying out pyrolysis deposition treatment on part of the pre-carbonized powder to obtain Fe with a nano structure3C, and a carbon matrix, wherein during pyrolysis deposition, argon is introduced as a protective gas, the temperature of the pyrolysis deposition is 500-600 ℃, the time of the pyrolysis deposition is 5-40 minutes, and the carbon matrix is a carbon nano tube or a carbon nano rod; and (4): mixing Fe3C is subjected to in-situ oxidation to obtain Fe2O3Or Fe3O4Coating a layer of carbon film on its surface, and naturally cooling to room temperature to obtain ferriteThe compound @ carbon nanocomposite has a core-shell structure of iron oxide nanoparticles.
2. The method of claim 1, wherein: in the step (2), the ball milling time of the ferrocene powder is 2-3 hours, the ball-to-material ratio of the discharge plasma assisted ball milling is 50:1, meanwhile, the pressure is kept at 0.1 atmosphere and the pressure is low, the discharge current is 2-3A, and the discharge voltage is 10-25 kV.
3. The method of claim 1, wherein: in the step (4), before in-situ oxidation, the temperature is reduced to 100-300 ℃, and the temperature is kept for 10-60 minutes by introducing the atmosphere.
4. The method of claim 1, wherein: in the step (3), the pyrolysis deposition temperature is 600 ℃, the pyrolysis deposition time is 30 minutes, in the step (4), the temperature is reduced to 300 ℃, and the temperature is kept for 30 minutes by introducing the atmosphere.
5. An iron oxide @ carbon nanocomposite prepared by the process of claim 1, wherein: the particle size of the iron oxide nanoparticles is 20-200 nanometers.
6. The iron oxide @ carbon nanocomposite as claimed in claim 5, wherein: the thickness range of the carbon film is 4-6 nanometers.
7. The iron oxide @ carbon nanocomposite as claimed in claim 6, wherein: the carbon film thickness was 5 nm.
8. Use of the iron oxide @ carbon nanocomposite as defined in claim 5 or 6, wherein: used as the cathode material of lithium ion battery or as the hydrogen absorbing and releasing catalyst of hydrogen storage material.
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