CN108199014B - Porous nitrogen-doped carbon/Fe2O3Graphene foam flexible composite material, preparation method and application thereof - Google Patents
Porous nitrogen-doped carbon/Fe2O3Graphene foam flexible composite material, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides porous nitrogen-doped carbon/Fe2O3A graphene flexible composite material, a preparation method and application thereof. In the flexible composite material, graphene coats Fe2O3The nanoparticles, nitrogen-doped carbon, have a porous foam structure. The method comprises the following steps: preparing pure melamine foam, calcining in nitrogen to obtain nitrogen-doped carbon foam matrix, and mixing nano Fe2O3Mixing the graphene oxide solution and polyvinylpyrrolidone to prepare a spinning solution, taking a nitrogen-doped carbon foam substrate as a receiving device, and directly spinning the spinning solution on carbon foam by adopting a high-voltage electrostatic spinning technology to obtain porous nitrogen-doped carbon/Fe2O3The flexible composite material is obtained by carbonizing and cooling the/graphene oxide/PVP composite material at a high temperature. The material is used as a negative electrode material of a lithium ion battery, and has the characteristics of good flexibility, high conductivity, high specific capacity and the like.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to porous nitrogen-doped carbon/Fe2O3Graphene foam flexible composite material and preparation method and application thereof.
Background
In recent years, the demand for flexible electronic devices that can be bent and folded has increased year by year, and flexible lithium ion batteries are the core components of flexible electronic devices. The traditional lithium ion battery is mainly formed by mixing and coating an active material, a conductive agent and a binder on a metal current collector and drying and rolling, the electrode material does not have flexibility, and the energy density of the whole material is greatly reduced due to the existence of the current collector. Therefore, there is a need to develop a self-supporting flexible electrode material free of binder, conductive agent and current collector to meet the demand of flexible electronic devices.
Currently, commercial lithium ion negative electrode materials are mainly carbon materials, which have many limitations: the theoretical capacity is low, the potential is close to the metallic lithium, dendrite and the like can be generated on the surface, and the safety performance cannot be ensured. In recent years, Fe2O3The material is considered to be one of the lithium ion battery cathode materials with potential application prospects due to the advantages of high theoretical specific capacity, abundant resources, low cost, safety, no toxicity and the like, but the material is caused by huge volume change in the circulating processThe capacity fade of (a) and the poor rate capability associated with its low electronic conductivity severely hamper its practical application. To improve Fe2O3The material has the circulating stability, and the currently adopted modification means mainly comprise carbon coating, doping and preparation of Fe with a nano porous structure2O3A material. Carbon coating can improve Fe2O3The compatibility of the base composite material and the electrolyte can also improve the conductivity of the composite material. The porous structure may be Fe2O3The volume expansion of the material provides a reserved space, and the volume stress caused by the volume expansion is relieved. The graphene serving as a two-dimensional carbon material has excellent mechanical property and good conductivity, and can react with Fe2O3The material composite can improve the conductivity and electrochemical performance of the composite material.
In summary, the characteristics of the self-supporting flexible electrode and Fe are combined2O3The melamine foam and the Fe2O3And the graphene is subjected to ternary compounding, and the self-supporting flexible composite electrode is used as a lithium ion battery cathode material by utilizing the synergistic effect of the composite material, so that the electrochemical performance of the lithium ion battery cathode material is hopefully and remarkably improved.
Disclosure of Invention
In order to solve the problems, the invention provides porous nitrogen-doped carbon/Fe2O3Graphene flexible composite material, and preparation method and application thereof. The composite material has the characteristics of good flexibility, high conductivity, high specific capacity and the like, and the self-supporting flexible electrode material without an adhesive, a conductive agent and a current collector can obviously improve the energy density of the material and the electrochemical performance under the bending condition.
The invention adopts the following technical scheme: porous nitrogen-doped carbon/Fe2O3A/graphene flexible composite, wherein: graphene coated Fe2O3The nanoparticles, nitrogen-doped carbon, have a three-dimensional porous foam structure.
Porous nitrogen-doped carbon/Fe2O3The preparation method of the graphene flexible composite material comprises the following steps:
(1) preparing pure melamine foam;
(2) transferring the melamine foam prepared in the step (1) into a tubular furnace, calcining in nitrogen atmosphere at the calcining temperature of 300-1200 ℃ for 1-10 hours to obtain a nitrogen-doped carbon foam substrate; preferably, the calcining temperature of the melamine foam is 800-1200 ℃, and the calcining time is 3-10 hours;
(3) mixing nano Fe2O3Mixing the graphene oxide solution according to a certain proportion, stirring the mixture evenly, adding polyvinylpyrrolidone with the mass being 5-10% of the mixed solution, preferably 8-10%, continuously stirring the mixture, and standing the mixture to obtain a spinning solution;
(4) directly spinning the spinning stock solution in the step (3) on carbon foam by using the nitrogen-doped carbon foam substrate prepared in the step (2) as a receiving device and adopting a high-voltage electrostatic spinning technology to obtain porous nitrogen-doped carbon/Fe2O3Graphene oxide/PVP composite material;
(5) mixing the porous nitrogen-doped carbon/Fe obtained in the step (4)2O3Transferring the/graphene oxide/PVP composite material into a high-temperature tubular resistance furnace for high-temperature carbonization, and cooling to obtain porous nitrogen-doped carbon/Fe2O3A graphene flexible composite material.
Preferably, the step (1) for preparing the pure melamine foam is specifically as follows: soaking melamine foam in 1mol/L diluted hydrochloric acid for 6 hours, then transferring the melamine foam into a mixed solution of absolute ethyl alcohol/acetone for soaking for 3 hours, then cleaning the obtained melamine foam with absolute ethyl alcohol and deionized water, and then drying the melamine foam in a drying oven to obtain pure melamine foam; further preferably, the dried product is dried in a 60 ℃ drying oven for 12 hours.
Preferably, in the step (3), the nano Fe2O3The mass ratio of the graphene oxide to the graphene oxide is 1 (1-5), and more preferably 1 (3-5).
Preferably, in the step (4), the spinning voltage of the high-voltage electrostatic spinning technology is 10000-40000V, the spinning speed is 1-5mL/h, the distance between the spinning nozzle and the foamed nickel is 5-20cm, and more preferably, the distance between the spinning nozzle and the foamed nickel is 10-20 cm.
Preferably, in the step (5), under the protection of the mixed atmosphere of argon and hydrogen, heating to 400-900 ℃ at a heating rate of 3-7 ℃/min, carbonizing for 1-5 h, and naturally cooling to room temperature; more preferably, the carbonization temperature is 550-900 ℃ and the time is 1-3 h.
Preferably, in step (3), the Fe2O3The powder is in nanometer grade, and the particle size is 300-500 nm; the method comprises the steps of oxidizing graphite powder into graphite oxide by using concentrated sulfuric acid and potassium permanganate as oxidants, and stripping the graphite oxide into graphene oxide by ultrasonic stripping.
The porous nitrogen-doped carbon/Fe2O3The graphene flexible composite material is used as a negative electrode material of the lithium ion battery, after the lithium ion battery is prepared, the battery is charged and discharged at a current density of 0.1A/g, the first discharge capacity of the battery reaches 1195mAh/g, the discharge capacity after 60 cycles reaches over 951mAh/g, and the battery has the characteristics of good flexibility, high conductivity, high specific capacity and the like.
Compared with the prior art, the invention has the following outstanding beneficial effects:
(1) the prepared flexible composite electrode material does not need additives such as a metal current collector, a binder, conductive carbon and the like, and can be directly used as an electrode material, so that the energy density and the power density of the electrode can be improved.
(2) The nitrogen-doped carbon has a porous foam structure, and can effectively relieve the nano Fe2O3The volume effect of the porous nitrogen-doped carbon/Fe can be improved, the energy band structure of the material can be changed by nitrogen doping, the diffusion rate of lithium ions is reduced, the structural defects of the material are caused, the lithium storage performance of the material is improved, and the prepared porous nitrogen-doped carbon/Fe2O3The flexible graphene composite material is used as a battery cathode to prepare a 2025 type button battery, the battery is charged and discharged at a current density of 0.1A/g, the first discharge capacity of the battery can reach 1195mAh/g, the discharge capacity after 60 cycles can reach 951mAh/g, and the battery has the characteristics of high conductivity and high specific capacity.
(3) The porous nitrogen-doped carbon/Fe prepared by the invention2O3In the graphene flexible composite material, the graphene is coated with Fe2O3Nanoparticles, effective in relieving nano-Fe2O3Volume effect of (1), improvement of Fe2O3Is used for the electrical conductivity of (1).
(4) In the preparation process, porous nitrogen is doped with carbon/Fe2O3Graphene oxide/PVP composite as precursor product, wherein polyvinylpyrrolidone (PVP) can increase graphene/nano Fe2O3The bonding force with the carbon foam substrate keeps the structural stability of the flexible material.
Drawings
FIG. 1 shows porous N-doped carbon/Fe samples of example 1 of the present invention2O3And testing the flexibility of the graphene flexible composite material.
FIG. 2 is a scanning electron micrograph of a nitrogen-doped carbon foam sample according to example 1 of the present invention.
FIG. 3 shows porous N-doped carbon/Fe samples of example 1 of the present invention2O3A/graphene flexible composite material cycle performance curve.
Detailed Description
Example 1
Porous nitrogen-doped carbon/Fe2O3The preparation method of the graphene flexible composite material comprises the following steps:
(1) the preparation method comprises the steps of soaking melamine foam in 1mol/L diluted hydrochloric acid for 6 hours, transferring the melamine foam into a mixed solution of absolute ethyl alcohol/acetone (1:1) to soak for 3 hours, cleaning the obtained melamine foam for 3-5 times with absolute ethyl alcohol and deionized water, and drying in a drying oven at 60 ℃ for 12 hours to obtain pure melamine foam.
(2) And (2) transferring the melamine foam obtained in the step (1) into a tubular furnace, and calcining in a nitrogen atmosphere at 800 ℃ for 3 hours to obtain the nitrogen-doped carbon foam substrate.
(3) Mixing nano Fe2O3And mixing the graphene oxide solution according to a certain proportion, and stirring the mixture until the mixture is uniform. Adding polyvinylpyrrolidone (PVP) with the mass of 10% of the mixed solution, continuously stirring for 4 hours, and standing for 2 hours to obtain spinning stock solution; therein is provided withRice Fe2O3The mass ratio of the graphene oxide to the graphene oxide is 1: 3; said Fe2O3The powder is in nanometer grade, and the particle size is 300-500 nm; the method comprises the steps of oxidizing graphite powder into graphite oxide by using concentrated sulfuric acid and potassium permanganate as oxidants, and stripping the graphite oxide into graphene oxide by ultrasonic stripping.
(4) Directly spinning the spinning solution obtained in the step (3) on carbon foam by using the nitrogen-doped carbon foam prepared in the step (2) as a receiving device and adopting a high-voltage electrostatic spinning technology to obtain porous nitrogen-doped carbon/Fe2O3Graphene oxide/PVP flexible composite material; wherein the spinning voltage of the high-voltage electrostatic spinning technology is 40000V, the spinning speed is 1mL/h, and the distance between the spinneret and the foamed nickel is 10 cm.
(5) Mixing the porous nitrogen-doped carbon/Fe obtained in the step (4)2O3Transferring the/graphene oxide/PVP flexible composite material into a high-temperature tubular resistance furnace, heating to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon-hydrogen gas, carbonizing for 3 hours, and naturally cooling to room temperature in the argon-hydrogen gas to obtain porous nitrogen-doped carbon/Fe2O3A graphene flexible composite material.
FIG. 1 is a flexibility test of the composite material obtained in this example, and it can be seen that the composite material exhibits excellent mechanical flexibility.
Fig. 2 is a scanning electron micrograph of the nitrogen-doped carbon foam obtained in this example, which shows that the nitrogen-doped carbon foam has a three-dimensional porous structure.
Further, the porous nitrogen-doped carbon/Fe obtained in the example2O3The flexible graphene composite material is used as a working electrode, a lithium sheet is used as an auxiliary electrode and a reference electrode, the electrolyte is a universal lithium ion battery electrolyte, a 2025 type button battery is prepared, the battery is charged and discharged at a current density of 0.1A/g, the cycle performance curve of the electrode material is shown in figure 3, it can be seen that the first discharge capacity of the composite material can reach 1195mAh/g, and the discharge capacity after 60 cycles is 951.1 mAh/g.
Example 2
Porous nitrogen-doped carbon/Fe2O3StoneThe preparation method of the flexible graphene composite material comprises the following steps:
(1) the melamine foam prepared in step (1) in example 1 was transferred to a tube furnace and calcined in a nitrogen atmosphere at 300 ℃ for 10 hours to obtain a nitrogen-doped carbon foam substrate.
(2) Mixing nano Fe2O3And mixing the graphene oxide solution according to a certain proportion, stirring the mixture evenly, adding polyvinylpyrrolidone (PVP) with the mass being 5% of that of the mixed solution, continuously stirring the mixture for 4 hours, and standing the mixture for 2 hours to obtain the spinning solution. Wherein the nanometer Fe2O3The mass ratio of the graphene oxide to the graphene oxide is 1: 1; said Fe2O3The powder is in nanometer grade, and the particle size is 300-500 nm; the method comprises the steps of oxidizing graphite powder into graphite oxide by using concentrated sulfuric acid and potassium permanganate as oxidants, and stripping the graphite oxide into graphene oxide by ultrasonic stripping.
(3) Directly spinning the spinning solution obtained in the step (3) on carbon foam by using the nitrogen-doped carbon foam prepared in the step (1) as a receiving device and adopting a high-voltage electrostatic spinning technology to obtain porous nitrogen-doped carbon/Fe2O3Graphene oxide/PVP flexible composite material; wherein the spinning voltage of the high-voltage electrostatic spinning technology is 30000V, the spinning speed is 5mL/h, and the distance between a spinning nozzle and foamed nickel is 20 cm;
(4) mixing the porous nitrogen-doped carbon/Fe obtained in the step (3)2O3Transferring the/graphene oxide/PVP flexible composite material into a high-temperature tubular resistance furnace, heating to 900 ℃ at a heating rate of 7 ℃/min under the protection of argon-hydrogen gas, carbonizing for 1h, and naturally cooling to room temperature in the argon-hydrogen gas to obtain porous nitrogen-doped carbon/Fe2O3A graphene flexible composite material.
The electrochemical performance test of the material of this example was performed according to the procedure described in example 1, and the test results were: the discharge capacity after 60 cycles was 642.2mAh/g at a current density of 0.1A/g.
Example 3
Porous nitrogen-doped carbon/Fe2O3Preparation of/graphene flexible composite materialThe preparation method comprises the following steps:
(1) the melamine foam prepared in step (1) in example 1 was transferred to a tube furnace and calcined in a nitrogen atmosphere at 1200 ℃ for 1 hour to obtain a nitrogen-doped carbon foam substrate.
(2) Mixing nano Fe2O3Mixing the graphene oxide solution according to a certain proportion, stirring the mixture evenly, adding polyvinylpyrrolidone (PVP) with the mass being 8% of that of the mixed solution, continuously stirring the mixture for 4 hours, standing the mixture for 2 hours to obtain spinning solution, wherein nano Fe2O3The mass ratio of the graphene oxide to the graphene oxide is 1: 5; said Fe2O3The powder is in nanometer grade, and the particle size is 300-500 nm; the method comprises the steps of oxidizing graphite powder into graphite oxide by using concentrated sulfuric acid and potassium permanganate as oxidants, and stripping the graphite oxide into graphene oxide by ultrasonic stripping.
(3) Directly spinning the spinning solution obtained in the step (3) on carbon foam by using the nitrogen-doped carbon foam prepared in the step (1) as a receiving device and adopting a high-voltage electrostatic spinning technology to obtain porous nitrogen-doped carbon/Fe2O3Graphene oxide/PVP flexible composite material; wherein the spinning voltage of the high-voltage electrostatic spinning technology is 10000V, the spinning speed is 2mL/h, and the distance between a spinning nozzle and foamed nickel is 16 cm;
(4) mixing the porous nitrogen-doped carbon/Fe obtained in the step (3)2O3Transferring the/graphene oxide/PVP flexible composite material into a high-temperature tubular resistance furnace, heating to 400 ℃ at a heating rate of 3 ℃/min under the protection of argon-hydrogen gas, carbonizing for 5 hours, and naturally cooling to room temperature in the argon-hydrogen gas to obtain porous nitrogen-doped carbon/Fe2O3A graphene flexible composite material.
The electrochemical performance of the material of this example was tested as described in example 1, and the discharge capacity after 60 cycles was 786.5mAh/g at a current density of 0.1A/g.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (14)
1. Porous nitrogen-doped carbon/Fe2O3The preparation method of the graphene flexible composite material is characterized by comprising the following steps: the porous nitrogen-doped carbon/Fe2O3The graphene flexible composite material comprises: graphene coated Fe2O3The nano particles and the nitrogen-doped carbon are of three-dimensional porous foam structures;
the preparation method comprises the following steps:
(1) preparing pure melamine foam;
(2) transferring the melamine foam prepared in the step (1) into a tubular furnace, calcining in nitrogen atmosphere at the calcining temperature of 300-1200 ℃ for 1-10 hours to obtain a nitrogen-doped carbon foam substrate;
(3) mixing nano Fe2O3Mixing the graphene oxide solution according to a certain proportion, stirring the mixture evenly, adding polyvinylpyrrolidone (PVP) with the mass being 5-10% of that of the mixed solution, continuously stirring the mixture, and standing the mixture to obtain a spinning solution;
(4) directly spinning the spinning solution in the step (3) on the carbon foam substrate by using the nitrogen-doped carbon foam substrate prepared in the step (2) as a receiving device and adopting a high-voltage electrostatic spinning technology to obtain porous nitrogen-doped carbon/Fe2O3Graphene oxide/PVP composite material;
(5) mixing the porous nitrogen-doped carbon/Fe obtained in the step (4)2O3Transferring the/graphene oxide/PVP composite material into a high-temperature tubular resistance furnace for high-temperature carbonization, and cooling to obtain porous nitrogen-doped carbon/Fe2O3A graphene flexible composite material.
2. The method of claim 1, wherein: the step (1) of preparing the pure melamine foam specifically comprises the following steps: the preparation method comprises the steps of taking melamine foam, soaking the melamine foam in 1mol/L diluted hydrochloric acid for 6 hours, transferring the melamine foam into a mixed solution of absolute ethyl alcohol/acetone, soaking for 3 hours, cleaning the obtained melamine foam with absolute ethyl alcohol and deionized water, and then drying in a drying oven to obtain pure melamine foam.
3. The method of claim 2, wherein: drying in a drying oven at 60 deg.C for 12 hr.
4. The method according to claim 1 or 2, characterized in that: in the step (2), the calcining temperature of the melamine foam is 800-1200 ℃, and the calcining time is 3-10 hours.
5. The method according to claim 1 or 2, characterized in that: in the step (3), the nano Fe2O3The mass ratio of the graphene oxide to the graphene oxide is 1 (1-5).
6. The method of claim 4, wherein the nano-Fe2O3The mass ratio of the graphene oxide to the graphene oxide is 1 (3-5).
7. The method according to claim 1 or 2, characterized in that: in the step (3), the mass of the polyvinylpyrrolidone (PVP) is 8-10% of that of the mixed solution.
8. The method according to claim 1 or 2, characterized in that: in the step (4), the spinning voltage of the high-voltage electrostatic spinning technology is 10000-40000V, the spinning speed is 1-5mL/h, and the distance between a spinning nozzle and the foamed nickel is 5-20 cm.
9. The method of claim 8, wherein the distance between the spinneret and the nickel foam is 10-20 cm.
10. The method according to claim 1 or 2, characterized in that: in the step (5), under the protection of the mixed atmosphere of argon and hydrogen, the temperature is raised to 400-900 ℃ at the heating rate of 3-7 ℃/min, carbonization is carried out for 1-5 h, and then natural cooling is carried out to the room temperature.
11. The method according to claim 10, wherein the carbonization temperature is 550 to 900 ℃ and the carbonization time is 1 to 3 hours.
12. The method of claim 1, wherein: the nano Fe2O3Is in nanometer level, the particle size is 300-500 nanometers; the method comprises the steps of oxidizing graphite powder into graphite oxide by using concentrated sulfuric acid and potassium permanganate as oxidants, and stripping the graphite oxide into graphene oxide by ultrasonic stripping.
13. Porous nitrogen-doped carbon/Fe obtained by the preparation method of claim 12O3The application of the graphene flexible composite material is characterized in that: a negative electrode material for a lithium ion battery.
14. Use according to claim 13, characterized in that: after the lithium ion battery is prepared from the flexible composite material, the lithium ion battery is charged and discharged at a current density of 0.1A/g, the first discharge capacity of the lithium ion battery reaches 1195mAh/g, and the discharge capacity after 60 cycles reaches 951 mAh/g.
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| CN109698341B (en) * | 2018-12-27 | 2023-10-27 | 格力钛新能源股份有限公司 | Electrode preparation method, electrode and battery |
| CN110918007B (en) * | 2019-11-04 | 2022-04-22 | 江苏一夫新材料产业技术研究院有限公司 | PVP polymerized SnO2-graphene aerogels and method for the production thereof |
| CN111215111B (en) * | 2020-01-13 | 2022-07-19 | 山西大学 | Carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies and preparation method and application thereof |
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