CN108630921B - Preparation method of iron oxide/carbon fiber composite lithium ion battery cathode material - Google Patents

Preparation method of iron oxide/carbon fiber composite lithium ion battery cathode material Download PDF

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CN108630921B
CN108630921B CN201810372696.9A CN201810372696A CN108630921B CN 108630921 B CN108630921 B CN 108630921B CN 201810372696 A CN201810372696 A CN 201810372696A CN 108630921 B CN108630921 B CN 108630921B
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carbon fiber
iron oxide
fiber composite
iron
metal organic
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CN108630921A (en
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杜慧玲
曹娜
王金磊
马万里
郗雪艳
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Xian University of Science and Technology
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • 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 discloses a preparation method of an iron oxide/carbon fiber composite lithium ion battery cathode material, which comprises the following steps: mixing an iron-based metal organic framework serving as a precursor with a PAN solution, carrying out electrostatic spinning to obtain metal organic framework/PAN fiber, and carrying out heat treatment on the metal organic framework/PAN fiber in an inert atmosphere to prepare the iron oxide/carbon fiber composite material. The iron oxide/carbon fiber composite material prepared by the invention has good flexibility, conductivity, ordered pore structure and large specific surface area, and has higher first discharge specific capacity, charge specific capacity, first coulombic efficiency, cycling stability and rate capability when being used as a lithium ion battery cathode material.

Description

Preparation method of iron oxide/carbon fiber composite lithium ion battery cathode material
Technical Field
The invention belongs to the field of preparation of electrode materials, and particularly relates to a preparation method of an iron oxide/carbon fiber composite lithium ion battery cathode (material).
Background
The negative electrode material is a main component of the lithium ion battery, and directly influences the performance of the lithium ion battery. At present, the anode material of a commercial lithium ion battery is mainly graphite, but the theoretical specific capacity of the anode material is only 372mA h/g, so that the requirement of a high-capacity and high-power chemical power supply in the field of power such as a new energy electric automobile is difficult to meet. Therefore, the development of a negative electrode material with high specific capacity, high safety and low cost has become one of the hot spots of theoretical research and application research.
The Metal Organic Frameworks (MOFs) are composed of metal ions and organic ligands, have the characteristics of a regular controllable porous structure, an ultra-large specific surface area, high purity and the like, and meanwhile, the MOFs are used as electrode materials, the metal ions are likely to generate redox reaction in the charging and discharging processes, and the pore channels of the three-dimensional structure are beneficial to the storage and transmission of lithium ions in the MOFs, so that the MOFs can be a potential novel lithium ion battery electrode material. However, at present, researches on direct use of metal organic framework materials as lithium ion battery electrode materials are relatively few, and mainly because the MOFs materials have problems of structural collapse, chemical composition change and the like in the charging and discharging processes, the materials have low reversible capacity, low coulombic efficiency, and poor cycle stability and rate capability. The MOFs material contains a large amount of metal central ions and abundant organic ligands, and MOFs is used as a precursor to be calcined at high temperature under a certain atmosphere condition, so that novel metal oxides can be prepared, and the morphological structure characteristics of the MOFs precursor can be reserved to a certain extent. Therefore, the MOFs are used as a precursor template to prepare a novel lithium ion battery anode material, and the interest of researchers at home and abroad is also aroused in recent years. However, the battery negative electrode material obtained by calcining MOFs or carbon fibers cannot be directly used as an electrode, but needs to be coated on a metal current collector by a conductive agent and a binder, so that the electrode manufacturing process is complex, and the electrochemical performance needs to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of an iron oxide/carbon fiber composite lithium ion battery cathode material, wherein an MIL series is selected as a precursor, so that the method has the characteristics of better shape adjustability, simplicity in operation, stable process, good repeatability, high product purity and the like. The iron oxide/carbon fiber composite material prepared by the method can be directly used as a flexible electrode, avoids the use of a conductive agent, a binder and a metal current collector in the traditional electrode preparation process, and shows excellent electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
1) preparing iron-based metal organic framework/polyacrylonitrile fiber: adding 0.03-0.5 g of iron-based metal organic framework into 3-5 mL of dimethylformamide, performing ultrasonic dispersion for 20-30 min to obtain a suspension, adding 0.32-0.52 g of Polyacrylonitrile (PAN) into the suspension to obtain a mixed solution, placing the mixed solution in a water bath at 50-65 ℃, stirring for 18-24 h, taking out, standing at 25-40 ℃ for 4-6 h to obtain a solution, performing electrostatic spinning on the solution, and drying (the drying temperature is 60-80 ℃) to obtain iron-based metal organic framework/polyacrylonitrile fibers;
2) preparing an iron oxide/carbon fiber composite material: pre-oxidizing the iron-based metal organic framework/polyacrylonitrile fiber at 200-250 ℃ for 2-4 h, and then carrying out heat treatment at 400-600 ℃ for 3-6 h in an inert atmosphere to obtain the iron oxide/carbon fiber composite material.
Preferably, the iron-based metal organic framework is selected from MIL-88A, MIL-88B, MIL-53, MIL-100 or MIL-101.
Preferably, the iron-based metal organic framework is rod-shaped or spherical, and the size of the iron-based metal organic framework is 20-500 nm.
Preferably, the adding amount of the iron-based metal organic framework is 10-60% of the total mass of the iron-based metal organic framework and the polyacrylonitrile.
Preferably, the iron oxide/carbon fiber composite material is a flexible and foldable fiber membrane.
Preferably, in the iron oxide/carbon fiber composite material, the diameter of carbon fiber is 0.8-10 μm; the iron oxide is Fe with rod-shaped or spherical shape characteristics2O3Distributed in the carbon fiber (for example, iron oxide is distributed on the surface of the carbon fiber experimentally observed), and rod-shaped Fe2O3Has a length of 1 to 2 μm and a diameter of 15 to 500nm, and is spherical Fe2O3The size of (A) is 15 to 500 nm.
Preferably, the electrostatic spinning conditions are as follows: the voltage is 10-15 kV, the receiving distance is 10-16 cm, and the solution flow rate is 150-300 mu L/min.
Preferably, the preparation method of the iron-based metal organic framework comprises the following steps: 0.351 to 1.053g of fumaric acid, terephthalic acid or trimesic acid and 0.81 to 2.43g of FeCl3·6H2And mixing the O in water, putting the mixture into a reaction kettle, putting the reaction kettle into an oven with the temperature of 100-150 ℃ for reaction for 10-12 hours, and cleaning the precipitate obtained by the reaction with deionized water and then drying to obtain the iron-based metal organic framework.
The invention has the beneficial effects that:
the iron-based metal organic framework/polyacrylonitrile fiber is prepared by an electrostatic spinning method, and then the iron oxide/carbon fiber composite material is obtained by heat treatment.
The iron oxide/carbon fiber composite material prepared by the invention is a flexible foldable fiber membrane and can be directly used as a lithium ion battery cathode (flexible electrode), so that the use of a conductive agent, a binder and a metal current collector in the traditional electrode preparation process is avoided, the electrode preparation process is simplified, the energy density of the battery is obviously improved, and the excellent electrochemical performance is shown.
The iron oxide/carbon fiber composite lithium ion battery cathode prepared by the invention has the first discharge specific capacity of 902.9mAh/g, the charge specific capacity of 562mAh/g and the first coulomb efficiency of 66%. After circulating for 50 times, the specific discharge capacity of the lithium ion battery can still reach 375 mAh/g.
Drawings
Fig. 1 is an XRD profile of the iron oxide/carbon fiber composite material prepared in example 1 of the present invention.
Fig. 2 is an SEM photograph of the iron oxide/carbon fiber composite material prepared in example 1 of the present invention.
Fig. 3 is a charge-discharge curve of the iron oxide/carbon fiber composite material prepared in example 1 of the present invention as a negative electrode of a lithium ion battery.
Fig. 4 is an SEM photograph of the iron oxide/carbon fiber composite material prepared in example 2 of the present invention.
Fig. 5 is a charge-discharge curve of the iron oxide/carbon fiber composite material prepared in example 2 of the present invention as a negative electrode of a lithium ion battery.
Figure 6 is an SEM photograph of the iron oxide/carbon fiber composite prepared in example 3 of the present invention.
Fig. 7 is a charge-discharge curve of the iron oxide/carbon fiber composite material prepared in example 3 of the present invention as a negative electrode of a lithium ion battery.
Figure 8 is an SEM photograph of the iron oxide/carbon fiber composite prepared in example 4 of the present invention.
Fig. 9 is a charge-discharge curve of the iron oxide/carbon fiber composite material prepared in example 4 of the present invention as a negative electrode of a lithium ion battery.
Fig. 10 is a charge-discharge curve of individual MOFs calcined as a negative electrode material for a lithium ion battery (taking into account a conductive agent, a binder, and a current collector).
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
First, the reference prepares precursor MIL-88A: dissolving 0.702g of fumaric acid in deionized water, stirring uniformly, and adding 1.62g of FeCl3·6H2And O, fully mixing the materials, putting the mixture into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven with the temperature of 100 ℃ for reaction for 12 hours, washing the reactant (the red brown precipitate) with deionized water for multiple times, and drying to obtain the red brown MIL-88A.
MIL-53 or MIL-100 can be prepared by replacing fumaric acid with terephthalic acid or trimesic acid. Such MOFs are all capable of being converted to porous iron oxides after pyrolysis at high temperatures.
Example 1
(1) Preparation of MIL-88A/PAN composite fiber
0.480g of MIL-88A was dissolved in 3mL of Dimethylformamide (DMF) (i.e., MIL-88A content: 60 wt%), and ultrasonic dispersion was carried out for 20min to obtain a suspension. Weighing 0.32g of PAN and dissolving in the suspension, then placing the mixed solution in a water bath kettle at 65 ℃ for stirring for 18h, taking out, standing at room temperature for 4h, and then carrying out electrostatic spinning on the solution, wherein the process conditions of the electrostatic spinning are set as follows: the voltage is 15kV, the receiving distance is 16cm, the solution flow rate is 200 mu L/min, and the fiber is dried in a drying box at the temperature of 80 ℃ to prepare the MIL-88A/PAN fiber.
(2) Preparation of iron oxide/carbon fiber
MIL-88A/PAN fiber is placed in a tubular furnace, and pre-oxidation is carried out by keeping the temperature of 250 ℃ for 2h under the air conditionThen, nitrogen (N) is introduced2>99.99 percent) and preserving heat for 3 hours at 400 ℃ for heat treatment, and then naturally cooling to room temperature to obtain the iron oxide/carbon fiber composite material. The XRD pattern of the composite material is shown in FIG. 1, and the position of the diffraction peak is compared with that of a standard card (JCPDF 33-0664), which indicates that the prepared sample is Fe2O3Carbon fiber (Fe)2O3/CF) composite material and high purity. As can be seen from FIG. 2, iron oxide is uniformly distributed on the surface of the carbon fiber, the diameter of the carbon fiber is about 4 μm, and Fe2O3Effectively retains the rod-shaped morphology characteristic of MIL-88A, the length is about 1.2 mu m, and the diameter is about 300 nm.
(3) Lithium ion battery assembly
The prepared iron oxide/carbon fiber composite material is directly used as a working electrode (the negative electrode of the iron oxide/carbon fiber composite lithium ion battery) without using a conductive agent and a binder, a lithium sheet is used as a counter electrode and a reference electrode, and 1mol/L LiPF6The mixed solution of diethyl carbonate and ethylene carbonate (volume ratio 1:1) is used as an electrolyte. All assembly was performed in an argon filled glove box.
As can be seen from the charge-discharge curve shown in FIG. 3, the first specific discharge capacity of the iron oxide/carbon fiber composite lithium ion battery cathode reaches 850mAh/g, the specific charge capacity reaches 562mAh/g, the first coulombic efficiency reaches 66%, and after 50 times of circulation, the specific discharge capacity can still reach 375 mAh/g.
Example 2
0.0355g of MIL-88A was dissolved in 3mL of dimethylformamide (i.e., MIL-88A content of 10 wt%), and dispersed with ultrasound for 20min to obtain a suspension. Weighing 0.32g of PAN and dissolving in the suspension, then placing the mixed solution in a water bath kettle at 65 ℃ for stirring for 18h, taking out, standing at room temperature for 4h, and then carrying out electrostatic spinning on the solution, wherein the process conditions of the electrostatic spinning are set as follows: the voltage is 10kV, the receiving distance is 12cm, the solution flow rate is 200 mu L/min, and the fiber is dried in a drying box at the temperature of 80 ℃ to prepare the MIL-88A/PAN fiber.
Putting MIL-88A/PAN fiber into a tube furnace, pre-oxidizing at 250 ℃ for 2h under the air condition, and introducing nitrogen (N)2>99.99 percent) and heat treatment is carried out for 3 hours at 400 ℃, and then the mixture is naturally cooledCooling to room temperature to obtain iron oxide/carbon fiber (Fe)2O3/CF) composite material. It can be seen from fig. 4 that rod-shaped iron oxide is distributed on the surface of the carbon fiber.
The prepared iron oxide/carbon fiber composite material is directly used as a working electrode (the negative electrode of the iron oxide/carbon fiber composite lithium ion battery) without using a conductive agent and a binder. As can be seen from the charge-discharge curve shown in FIG. 5, the first specific discharge capacity of the negative electrode of the iron oxide/carbon fiber composite lithium ion battery reaches 582.1mAh/g, the specific charge capacity reaches 300.2mAh/g, the first coulombic efficiency reaches 52%, and after 50 times of circulation, the specific discharge capacity can still reach 204.3 mAh/g.
Example 3
0.080g of MIL-88A was dissolved in 3mL of dimethylformamide (i.e., MIL-88A content: 20 wt%), and dispersed with ultrasound for 20min to obtain a suspension. Weighing 0.32g of PAN and dissolving in the suspension, then placing the mixed solution in a water bath kettle at 65 ℃ for stirring for 18h, taking out, standing at room temperature for 4h, and then carrying out electrostatic spinning on the solution, wherein the process conditions of the electrostatic spinning are set as follows: the voltage is 13kV, the receiving distance is 10cm, the solution flow rate is 200 mu L/min, and the fiber is dried in a drying box at the temperature of 80 ℃ to prepare the MIL-88A/PAN fiber.
Putting MIL-88A/PAN fiber into a tube furnace, pre-oxidizing at 250 ℃ for 2h under the air condition, and introducing nitrogen (N)2>99.99 percent) is heated for 3 hours at 400 ℃ and then naturally cooled to room temperature to obtain the iron oxide/carbon fiber (Fe)2O3/CF) composite material. It can be seen from fig. 6 that rod-shaped iron oxide is distributed on the surface of the carbon fiber.
The prepared iron oxide/carbon fiber composite material is directly used as a working electrode (the negative electrode of the iron oxide/carbon fiber composite lithium ion battery) without using a conductive agent and a binder. As can be seen from the charge-discharge curve shown in FIG. 7, the first discharge specific capacity of the iron oxide/carbon fiber composite lithium ion battery cathode reaches 902.9mAh/g, the charge specific capacity reaches 426.9mAh/g, the first coulombic efficiency reaches 47%, and after 50 times of circulation, the discharge specific capacity can still reach 238.5 mAh/g.
Example 4
0.215g of MIL-88A was dissolved in 3mL of dimethylformamide (i.e., MIL-88A content: 40 wt%), and dispersed with ultrasound for 20min to obtain a suspension. Weighing 0.32g of PAN and dissolving in the suspension, then placing the mixed solution in a water bath kettle at 65 ℃ for stirring for 18h, taking out, standing at room temperature for 4h, and then carrying out electrostatic spinning on the solution, wherein the process conditions of the electrostatic spinning are set as follows: the voltage is 13kV, the receiving distance is 15cm, the solution flow rate is 200 mu L/min, and the fiber is dried in a drying box at the temperature of 80 ℃ to prepare the MIL-88A/PAN fiber.
Putting MIL-88A/PAN fiber into a tube furnace, pre-oxidizing at 250 ℃ for 2h under the air condition, and introducing nitrogen (N)2>99.99 percent) is heated for 3 hours at 400 ℃ and then naturally cooled to room temperature to obtain the iron oxide/carbon fiber (Fe)2O3/CF) composite material. It can be seen from fig. 8 that rod-shaped iron oxide is distributed on the surface of the carbon fiber, and the rod-shaped iron oxide is perpendicular to the surface of the carbon fiber.
The prepared iron oxide/carbon fiber composite material is directly used as a working electrode (the negative electrode of the iron oxide/carbon fiber composite lithium ion battery) without using a conductive agent and a binder. As can be seen from the charge-discharge curve shown in FIG. 9, the first discharge specific capacity of the negative electrode of the iron oxide/carbon fiber composite lithium ion battery reaches 813.5mAh/g, the charge specific capacity reaches 506.1mAh/g, the first coulombic efficiency reaches 62%, and after 50 times of circulation, the discharge specific capacity can still reach 297.7 mAh/g.
In order to further embody the significance of the invention, calcined materials of single MOFs (MIL-88A) are used as working electrodes (iron oxide lithium ion battery cathodes), carbon black is used as a conductive agent, PVDF is used as a binder, lithium sheets are used as a counter electrode and a reference electrode, and 1mol/L LiPF is used6And assembling the button cell by using a mixed solution (volume ratio is 1:1) of diethyl carbonate and ethylene carbonate as an electrolyte, and testing the electrochemical performance of the button cell.
It can be seen from the charge-discharge curve shown in fig. 10 that the first discharge specific capacity of the negative electrode of the iron oxide lithium ion battery, which takes the factors of the conductive agent, the binder, the current collector and the like into consideration, reaches 116.6mAh/g, the charge specific capacity reaches 89.5mAh/g, the first coulombic efficiency reaches 77%, and after 50 cycles, the discharge specific capacity is still 87.3 mAh/g. Compared with the material calcined by single MOFs, the electrochemical performance of the iron oxide/carbon fiber composite material is obviously improved, which shows that the method has certain progress significance.

Claims (10)

1. A preparation method of an iron oxide/carbon fiber composite material is characterized by comprising the following steps: the method comprises the following steps:
1) preparing iron-based metal organic framework/polyacrylonitrile fiber: adding 0.03-0.5 g of iron-based metal organic framework into 3-5 mL of dimethylformamide, performing ultrasonic dispersion for 20-30 min to obtain a suspension, adding 0.32-0.52 g of polyacrylonitrile into the suspension to obtain a mixed solution, placing the mixed solution in a water bath at 50-65 ℃, stirring for 18-24 h, taking out, standing at 25-40 ℃ for 4-6 h to obtain a solution, and performing electrostatic spinning on the solution to obtain iron-based metal organic framework/polyacrylonitrile fibers;
2) preparing an iron oxide/carbon fiber composite material: pre-oxidizing the iron-based metal organic framework/polyacrylonitrile fiber at 200-250 ℃ for 2-4 h, and then carrying out heat treatment at 400-600 ℃ for 3-6 h in an inert atmosphere to obtain the iron oxide/carbon fiber composite material.
2. The method of claim 1, wherein the iron oxide/carbon fiber composite is prepared by: the iron-based metal organic framework is selected from MIL-88A, MIL-88B, MIL-53, MIL-100 or MIL-101.
3. The method of claim 1, wherein the iron oxide/carbon fiber composite is prepared by: the iron-based metal organic framework is rod-shaped or spherical.
4. The method of claim 1, wherein the iron oxide/carbon fiber composite is prepared by: the adding amount of the iron-based metal organic framework is 10-60% of the total mass of the iron-based metal organic framework and the polyacrylonitrile.
5. The method of claim 1, wherein the iron oxide/carbon fiber composite is prepared by: the iron oxide/carbon fiber composite material is a flexible and foldable fiber membrane.
6. The method of claim 1, wherein the iron oxide/carbon fiber composite is prepared by: in the iron oxide/carbon fiber composite material, iron oxide is distributed on the surface of carbon fiber.
7. The method of claim 1, wherein the iron oxide/carbon fiber composite is prepared by: the electrostatic spinning conditions are as follows: the voltage is 10-15 kV, the receiving distance is 10-16 cm, and the solution flow rate is 150-300 mu L/min.
8. The method of claim 1, wherein the iron oxide/carbon fiber composite is prepared by: the preparation method of the iron-based metal organic framework comprises the following steps: 0.351 to 1.053g of fumaric acid, terephthalic acid or trimesic acid and 0.81 to 2.43g of FeCl3·6H2And mixing the O in water, putting the mixture into a reaction kettle, putting the reaction kettle into an oven with the temperature of 100-150 ℃ for reaction for 10-12 hours, and cleaning the precipitate obtained by the reaction with deionized water and then drying to obtain the iron-based metal organic framework.
9. Use of the iron oxide/carbon fiber composite material of claim 1 in the preparation of a negative electrode for a lithium ion battery.
10. Use of the iron oxide/carbon fiber composite material of claim 1 in the preparation of a flexible electrode.
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