CN115376840A - Graphene-carbon nanofiber composite aerogel electrode material, and preparation method and application thereof - Google Patents
Graphene-carbon nanofiber composite aerogel electrode material, and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a graphene-carbon nanofiber composite aerogel electrode material and a preparation method and application thereof. The preparation method comprises the following steps: s1, freeze-drying a bacterial cellulose membrane; s2, carbonizing the freeze-dried bacterial cellulose to obtain carbon nano fibers; s3, ultrasonically mixing the carbon nano fiber obtained in the step S2 and graphene oxide in deionized water according to a certain mass ratio to prepare a dispersion liquid; and S4, carrying out hydrothermal reaction on the dispersion liquid to form graphene-carbon nanofiber composite hydrogel, and freeze-drying to form the graphene-carbon nanofiber composite aerogel electrode material. The prepared stone material can be used for the anode or the cathode of a lithium ion capacitor, and can also be used for the anode and the cathode of the lithium ion capacitor. When the electrode material is applied to the anode and the cathode of a lithium ion capacitor, the high specific capacity of 95 mAh/g and 1428mAh/g, excellent cycle performance and ultrahigh rate performance are respectively shown.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a graphene-carbon nanofiber composite aerogel electrode material and a preparation method and application thereof.
Background
In the case of electrode materials for lithium ion capacitors, carbon materials such as are frequently usedThe theoretical specific capacity of the graphite cathode material is only 372mAh/g, and common conductive polymers such as polyaniline, polypyrrole, polythiophene and the like can cause serious pollution, harm to human bodies and the like, so that the application of the graphite cathode material in lithium ion capacitors is limited. The multi-element metal oxide and the transition metal oxide have a conversion type or alloy type reaction mechanism, have the advantages of low cost, high theoretical specific capacity and the like, but have poor conductivity and are easy to generate volume expansion, rupture and excessive consumption of Li in a circulation process + An excessively thick SEI film is formed, which in turn causes poor cycle stability, limiting its application in electrode materials.
Graphene is used as a new pet in a carbon material, has excellent conductivity and has an ultrahigh theoretical specific surface area. The graphene aerogel has considerable application prospect in lithium ion electrode and super capacitor electrode materials, is suitable for physical adsorption and desorption reactions of the anode of a lithium ion capacitor due to the huge specific surface area, but can cause a large amount of Li due to the overlarge specific surface area when being used as the cathode of a lithium ion battery + A large amount of oxygen-containing functional groups and Li are remained on the surface of the carbon material while an SEI film is formed in an excessive thickness + Irreversible side reactions occur, increasing internal resistance, affecting reversible Li + The intercalation and deintercalation reaction forms 'dead lithium', which is easy to cause the reduction of the cycle life, the 'water jump' of the electrode capacity and even the internal short circuit.
Disclosure of Invention
The invention aims to provide a graphene-carbon nanofiber composite aerogel electrode material, a preparation method and application aiming at the defects in the prior art.
The preparation method of the graphene-carbon nanofiber composite aerogel electrode material comprises the following steps:
s1, freeze-drying a bacterial cellulose membrane at a certain temperature to obtain freeze-dried bacterial cellulose;
s2, carbonizing the freeze-dried bacterial cellulose obtained in the step S1 in an inert atmosphere to obtain carbon nano fibers;
s3, ultrasonically mixing the carbon nanofiber obtained in the step S2 and graphene oxide in deionized water according to a certain mass ratio to prepare a dispersion liquid;
and S4, carrying out hydrothermal reaction on the dispersion liquid obtained in the step S3 to form graphene-carbon nanofiber composite hydrogel, and freeze-drying to form the graphene-carbon nanofiber composite aerogel electrode material.
Further, in step S1, the bacterial cellulose membrane can be in a dispersion or colloidal membrane shape, the solid content of the bacterial cellulose membrane is 1-20%, the diameter is 50-100 nm, the length is less than 50 μm, the bacterial cellulose membrane is pre-frozen by adopting a refrigerator or liquid nitrogen freezing, and the freeze-drying temperature is-80-25 ℃.
Further, in step S2, the carbonization atmosphere can be Ar or Ar/H 2 、N 2 、N 2 /H 2 、Ar/N 2 。
Further, in the step S2, the heating rate is 2-10 ℃, the heat preservation temperatures are 400-700 ℃ and 800-1200 ℃ respectively, and the corresponding heat preservation time is 30 min-3 h.
Further, in step S3, the mass ratio of the graphene oxide to the carbon nanofibers is 20: (1-10), in the dispersion liquid, the concentration of the graphene oxide is 0.5-2 mg/ml, the ultrasonic power is 500-800W, and the ultrasonic time is 10-100 min.
Further, in step S3, the solvent includes any one or more of water, absolute ethanol, and ethylene glycol.
Further, in the step S4, the capacity of the polytetrafluoroethylene lining is 50-250 ml, the heat preservation temperature of the oven is 150-210 ℃, the heat preservation time is 6-12 h, and the obtained hydrogel is freeze-dried to obtain the graphene-carbon nanofiber composite aerogel electrode material.
The graphene-carbon nanofiber composite aerogel electrode material prepared by the preparation method is provided.
A lithium ion capacitor adopts the graphene-carbon nanofiber composite aerogel electrode material to prepare the positive electrode and the negative electrode of the lithium ion capacitor.
Further, the specific process for preparing the anode and the cathode is as follows: mixing the graphene-carbon nanofiber composite aerogel electrode material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of (6): (0.5 1.5): (0.5) grinding and mixing the raw materials in N-methyl pyrrolidone to prepare slurry; coating the slurry on a 15-micron single-sided smooth-thick copper foil, drying at 70 ℃ for 1024 hours to obtain a lithium ion capacitor negative electrode, coating the slurry on a 24-micron thick double-sided carbon-coated aluminum foil, and drying at 50 ℃ for 2448 hours to obtain a lithium ion capacitor positive electrode.
In the invention, the bacterial cellulose membrane is subjected to freeze-drying carbonization treatment to obtain the carbon nanofiber. Carrying out ultrasonic mixing on graphene oxide and a carbon nanofiber material in a solvent according to a preset mass ratio to obtain a uniformly mixed dispersion liquid with a preset concentration, pouring the dispersion liquid into a hydrothermal kettle with a polytetrafluoroethylene lining, carrying out hydrothermal self-assembly at a certain temperature to form graphene-carbon nanofiber composite hydrogel, and carrying out freeze drying to form graphene-carbon nanofiber composite aerogel. In the process of obtaining the three-dimensional hydrogel by one-step hydrothermal self-assembly of the carbon nanofibers and the graphene oxide, the one-dimensional carbon nanofibers are effectively connected with each cavity of the three-dimensional graphene-based hydrogel to form Li + And diffusion channels for electrons, and improves Li under high current density + And the accessibility of electrons, thereby improving the rate performance of the electrolyte, avoiding the deposition of 'dead lithium' and the problem of internal short circuit caused by the deposition of 'dead lithium', relieving the irreversible side reaction between the electrolyte and the surface of the electrode, and leading the capacity of the electrolyte to be increased or decreased (3000 circles and the capacity retention rate of 130%) when the electrolyte is used as a cathode in the circulation process, from the non-circulation to the capacity increase after the circulation. The preparation process has no addition of other chemical reagents, does not need complex, time-consuming and uncontrollable washing and impurity removal steps, does not generate toxic and environment-polluting waste liquid, can obtain the graphene-carbon nanofiber composite aerogel after direct freeze-drying, has more pores and larger specific surface area, and can show high capacity when being used for the positive electrode and the negative electrode of a lithium ion capacitor. The preparation process has the advantages of no addition of other chemical reagents, simple process, low cost, short preparation period and high electrochemical performance, and is suitable for large-scale industrial production.
The graphene-carbon nanofiber composite aerogel electrode material prepared by the method can be used for the positive electrode or the negative electrode of a lithium ion capacitor, and can also be used for preparing a composite aerogel electrode material for a lithium ion capacitorThe lithium ion capacitor anode and cathode are used. When the graphene-carbon nanofiber composite aerogel electrode material is applied to the positive electrode and the negative electrode of a lithium ion capacitor, the high specific capacity of 95 mAh/g and 1428mAh/g, excellent cycle performance and ultrahigh rate performance are respectively shown. The lithium ion capacitor assembled by the anode and the cathode can reach 181Wh kg 1 High energy density of 24.4kW kg 1 High power density.
Drawings
Fig. 1 is a scanning electron microscope image of a graphene-carbon nanofiber composite aerogel electrode material prepared in example 1 of the present invention;
fig. 2 is a graph showing energy density and power density of a lithium ion capacitor constructed by the positive electrode and the negative electrode of the lithium ion capacitor obtained in example 1 of the present invention.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.
The invention provides a graphene-carbon nanofiber composite aerogel electrode material which comprises the following steps:
step S1, freeze-drying a bacterial cellulose membrane at a certain temperature to obtain freeze-dried bacterial cellulose;
s2, carbonizing the freeze-dried bacterial cellulose obtained in the step S1 in a tube furnace under inert atmosphere at a certain heating rate, heat preservation temperature and heat preservation time to obtain carbon nano fibers;
s3, ultrasonically mixing the carbon nanofibers obtained in the step S2 and graphene oxide in deionized water according to a certain mass ratio to prepare a dispersion liquid;
and S4, pouring the dispersion liquid obtained in the step S3 into a hydrothermal kettle with a polytetrafluoroethylene lining (the capacity of the polytetrafluoroethylene lining is 50-250 ml), keeping the temperature in an oven for a period of time at a certain temperature, cooling the oven to room temperature to form graphene-carbon nanofiber composite hydrogel, and freeze-drying the graphene-carbon nanofiber composite aerogel electrode material to form the graphene-carbon nanofiber composite aerogel electrode material.
The bacterial cellulose membrane is freeze-dried at a certain temperature, and after freeze-drying, the bacterial cellulose membrane is heated to X ℃ at a certain heating rate in a tube furnace inert atmosphere, and is insulated for a certain time, and then the bacterial cellulose membrane is heated to Y ℃ at a certain heating rate, is insulated for a certain time, and is cooled to room temperature in the furnace, so that the fibrous structure of the carbon nanofiber is obtained. Carrying out ultrasonic mixing on graphene oxide and a carbon nanofiber material in a solvent according to a preset mass ratio to obtain a uniformly mixed dispersion liquid with a preset concentration, pouring the dispersion liquid into a hydrothermal kettle with a polytetrafluoroethylene lining, keeping the temperature in an oven for a period of time, cooling the oven to room temperature to form graphene-carbon nanofiber composite hydrogel, and carrying out freeze drying to form the graphene-carbon nanofiber composite aerogel electrode material.
According to the invention, the bacterial cellulose membrane which is a green, cheap and mass-prepared raw material is adopted, the bacterial cellulose membrane and the graphene are formed into hydrogel under hydrothermal conditions by utilizing the fiber structure energy storage characteristic of the carbonized bacterial cellulose membrane through a simple carbonization process, and in the process of the three-dimensional hydrogel obtained by one-step hydrothermal self-assembly of the carbon nanofiber and the graphene oxide, the one-dimensional carbon nanofiber is effectively connected with each cavity of the three-dimensional graphene-based hydrogel to form Li + And diffusion channels for electrons, and improves Li under high current density + And electron accessibility, thereby improving the rate capability thereof. The graphene-carbon nanofiber composite aerogel electrode material with high performance is prepared through the simple and convenient reaction which can be prepared in a large scale.
The technical solutions and advantages of the present invention will be described in detail below with reference to specific examples and comparative examples.
And (3) graphene oxide: the modified Hummers method is selected for preparation.
Example 1
Freeze-drying the bacterial cellulose membrane at a certain temperature, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min in a tube furnace inert atmosphere after freeze-drying, preserving the heat for 1h, raising the temperature to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling the furnace to room temperature to obtain the carbon nanofiber. And ultrasonically mixing the graphene oxide and the carbon nanofiber material in deionized water according to a mass ratio of 60mg. And obtaining the uniformly mixed dispersion liquid with preset concentration. Pouring the dispersion liquid into a 100ml of a hydrothermal kettle with a polytetrafluoroethylene lining, keeping the temperature in an oven at 180 ℃ for 10 hours, cooling the oven to room temperature to form graphene-carbon nanofiber composite hydrogel, and freeze-drying at a certain temperature to form graphene-carbon nanofiber composite aerogel; preparing a graphene-carbon nanofiber composite aerogel electrode material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 8:1:1, grinding and mixing the raw materials in N-methyl pyrrolidone to prepare slurry; coating the slurry on a 15-micron single-sided smooth-thick copper foil, drying at 70 ℃ for 1024 hours to obtain a lithium ion capacitor negative electrode, coating the slurry on a 24-micron thick double-sided carbon-coated aluminum foil, and drying at 50 ℃ for 2448 hours to obtain a lithium ion capacitor positive electrode.
Example 2
Freeze-drying the bacterial cellulose membrane at a certain temperature, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min in a tube furnace inert atmosphere after freeze-drying, preserving the heat for 1h, raising the temperature to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling the furnace to room temperature to obtain the carbon nanofiber. And ultrasonically mixing the graphene oxide and the carbon nanofiber material in deionized water according to a mass ratio of 60mg. Obtaining the dispersion liquid with preset concentration and even mixing. Pouring the dispersion liquid into a 100ml of hydrothermal kettle with a polytetrafluoroethylene lining, keeping the temperature in an oven at 180 ℃ for 10 hours, cooling the oven to room temperature to form graphene-carbon nanofiber composite hydrogel, and freeze-drying the graphene-carbon nanofiber composite aerogel at a certain temperature; preparing a graphene-carbon nanofiber composite aerogel electrode material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 8:1:1, grinding and mixing the raw materials in N-methyl pyrrolidone to prepare slurry; coating the slurry on a 15-micron single-sided smooth copper foil, drying for 1024 hours at 70 ℃ to obtain a lithium ion capacitor cathode, coating the slurry on a 24-micron thick double-sided carbon-coated aluminum foil, and drying for 2448 hours at 50 ℃ to obtain a lithium ion capacitor anode.
Example 3
Freeze-drying the bacterial cellulose membrane at a certain temperature, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min in a tube furnace inert atmosphere after freeze-drying, preserving heat for 1h, raising the temperature to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and cooling the furnace to room temperature to obtain the carbon nanofiber. And ultrasonically mixing the graphene oxide and the carbon nanofiber material in deionized water according to a mass ratio of 60mg. Obtaining the dispersion liquid with preset concentration and even mixing. Pouring the dispersion liquid into a 50ml of hydrothermal kettle with a polytetrafluoroethylene lining, keeping the temperature in an oven at 180 ℃ for 10 hours, cooling the oven to room temperature to form graphene-carbon nanofiber composite hydrogel, and freeze-drying the graphene-carbon nanofiber composite aerogel at a certain temperature; preparing a graphene-carbon nanofiber composite aerogel electrode material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 8:1:1, grinding and mixing the raw materials in N-methyl pyrrolidone to prepare slurry; coating the slurry on a 15-micron single-sided smooth copper foil, drying for 1024 hours at 70 ℃ to obtain a lithium ion capacitor cathode, coating the slurry on a 24-micron thick double-sided carbon-coated aluminum foil, and drying for 2448 hours at 50 ℃ to obtain a lithium ion capacitor anode.
Example 4
Freeze-drying the bacterial cellulose membrane at a certain temperature, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min in a tube furnace inert atmosphere after freeze-drying, preserving the heat for 1h, raising the temperature to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling the furnace to room temperature to obtain the carbon nanofiber. And ultrasonically mixing the graphene oxide and the carbon nanofiber material in deionized water according to a mass ratio of 60mg. And obtaining the uniformly mixed dispersion liquid with preset concentration. Pouring the dispersion liquid into a 100ml of a hydrothermal kettle with a polytetrafluoroethylene lining, keeping the temperature in an oven at 150 ℃ for 10 hours, cooling the oven to room temperature to form graphene-carbon nanofiber composite hydrogel, and freeze-drying at a certain temperature to form graphene-carbon nanofiber composite aerogel; preparing a graphene-carbon nanofiber composite aerogel electrode material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 8:1:1 in N methyl pyrrolidone to prepare slurry; coating the slurry on a 15-micron single-sided smooth copper foil, drying for 1024 hours at 70 ℃ to obtain a lithium ion capacitor cathode, coating the slurry on a 24-micron thick double-sided carbon-coated aluminum foil, and drying for 2448 hours at 50 ℃ to obtain a lithium ion capacitor anode.
Example 5
Freeze-drying the bacterial cellulose membrane at a certain temperature, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min in a tube furnace inert atmosphere after freeze-drying, preserving the heat for 1h, raising the temperature to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling the furnace to room temperature to obtain the carbon nanofiber. And ultrasonically mixing the graphene oxide and the carbon nanofiber material in deionized water according to a mass ratio of 60mg. Obtaining the dispersion liquid with preset concentration and even mixing. Pouring the dispersion liquid into a 100ml of a hydrothermal kettle with a polytetrafluoroethylene lining, keeping the temperature in an oven at 180 ℃ for 20 hours, cooling the oven to room temperature to form graphene-carbon nanofiber composite hydrogel, and freeze-drying at a certain temperature to form graphene-carbon nanofiber composite aerogel; preparing a graphene-carbon nanofiber composite aerogel electrode material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 8:1:1 in N methyl pyrrolidone to prepare slurry; coating the slurry on a 15-micron single-sided smooth-thick copper foil, drying at 70 ℃ for 1024 hours to obtain a lithium ion capacitor negative electrode, coating the slurry on a 24-micron thick double-sided carbon-coated aluminum foil, and drying at 50 ℃ for 2448 hours to obtain a lithium ion capacitor positive electrode.
Comparative example 1
And (3) carrying out ultrasonic dispersion on 60mg of graphene oxide in deionized water, wherein the ultrasonic power is 600W, and the ultrasonic time is 60min. Obtaining the uniform dispersion liquid with preset concentration. Pouring the dispersion into a 100ml of a hydrothermal kettle with a polytetrafluoroethylene lining, keeping the temperature in an oven at 180 ℃ for 10 hours, cooling the oven to room temperature to form graphene hydrogel, and freeze-drying at a certain temperature to form graphene aerogel; preparing a graphene aerogel electrode material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 8:1:1 in N methyl pyrrolidone to prepare slurry; coating the slurry on a 15-micron single-sided smooth-thick copper foil, drying at 70 ℃ for 1024 hours to obtain a lithium ion capacitor negative electrode, coating the slurry on a 24-micron thick double-sided carbon-coated aluminum foil, and drying at 50 ℃ for 2448 hours to obtain a lithium ion capacitor positive electrode.
Comparative example 2
And ultrasonically mixing graphene oxide and commercial carbon nanofibers in deionized water according to a mass ratio of 60mg. And obtaining the uniformly mixed dispersion liquid with preset concentration. Pouring the dispersion liquid into a 100ml of hydrothermal kettle with a polytetrafluoroethylene lining, keeping the temperature in an oven at 180 ℃ for 10 hours, cooling the oven to room temperature to form graphene-carbon nanofiber composite hydrogel, and freeze-drying the graphene-carbon nanofiber composite aerogel at a certain temperature; preparing a graphene-carbon nanofiber composite aerogel electrode material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 8:1:1, grinding and mixing the raw materials in N-methyl pyrrolidone to prepare slurry; coating the slurry on a 15-micron single-sided smooth-thick copper foil, drying at 70 ℃ for 1024 hours to obtain a lithium ion capacitor negative electrode, coating the slurry on a 24-micron thick double-sided carbon-coated aluminum foil, and drying at 50 ℃ for 2448 hours to obtain a lithium ion capacitor positive electrode.
The graphene-carbon nanofiber composite aerogel electrode materials prepared in example 1 and comparative example 1 were subjected to performance tests, and the results are shown in table 1:
table 1 table of properties of graphene-based composite carbon electrode materials obtained in examples
As can be seen from the above examples and comparative examples, the ratio of graphene oxide to carbon nanofibers, hydrothermal temperature, hydrothermal incubation time, polytetrafluoroethylene lining capacity, and the source of carbon nanofibers have a large influence on the specific capacity of the obtained electrode material. The direct hydrothermal treatment of graphene oxide in comparative example 1 shows that the capacity of the graphene oxide as a negative electrode is lower and is only 536mAh/g, capacity 'diving' occurs in the circulation process, the capacity of the graphene oxide is increased by nearly three times due to the addition of carbonized bacterial cellulose, and the circulation performance is improved (3000 circles, the capacity retention rate is 130%) because of the carbon nanofibers and the carbon nanofibersIn the process of obtaining the three-dimensional hydrogel by one-step hydrothermal self-assembly of the graphene oxide, the one-dimensional carbon nanofibers are effectively connected with each cavity of the three-dimensional graphene-based hydrogel to form Li + And diffusion channel of electrons, and improves Li under high current density + And the accessibility of electrons, thereby improving the rate capability of the lithium battery and avoiding the deposition of 'dead lithium' and the problem of internal short circuit caused by the deposition of 'dead lithium'. When the carbon nanofiber is used for an anode, the capacity is improved, the specific capacity of the carbon nanofiber used as the anode is reduced to some extent, the specific capacity of the carbon nanofiber used as a cathode is improved to some extent, but the specific capacity improvement effect is good without carbonization of the bacterial cellulose membrane, and only about 58% of the specific capacity improvement effect is achieved. The reason for this is probably that the structure of the connection between different carbon nanofibers and graphene is slightly different after hydrothermal treatment, and the thickness, length, structure, conductivity and ion transmission efficiency of different carbon nanofibers are different.
The invention provides a graphene-carbon nanofiber composite aerogel electrode material, which is prepared according to the preparation method of the graphene-carbon nanofiber composite aerogel electrode material. Since all technical schemes of all the embodiments are adopted in the graphene-carbon nanofiber composite aerogel electrode material, the graphene-carbon nanofiber composite aerogel electrode material at least has the beneficial effects brought by the technical schemes of the embodiments, and the details are not repeated here.
The invention also provides a lithium ion capacitor electrode, and the graphene-carbon nanofiber composite aerogel electrode material is used as the positive electrode and the negative electrode of the lithium ion capacitor electrode.
The prepared graphene-carbon nanofiber composite aerogel electrode material can be used for a positive electrode or a negative electrode of a lithium ion capacitor, and can also be used for the positive electrode and the negative electrode of the lithium ion capacitor. When used in the anode of a lithium ion capacitor, the weight ratio is 0.1A g -1 Can reach 95mAh g under the current density -1 Specific capacity of (a); 5Ag -1 More than 10000 cycles of the circulating capacity is maintained to be 99% of the initial capacity. When used in a negative electrode, the content of the organic acid is 0.1A g -1 Can reach 1428mAh g at the current density -1 The capacity of (c); as shown in FIG. 2, 2Ag -1 Under the current of (3), the capacity is kept above 130% after more than 3000 circles of circulation, and the capacity of a full battery assembled by the positive electrode and the negative electrode can reach-181 Wh kg -1 Energy density of 24.4kW kg -1 The power density of (a).
In this embodiment, the graphene-carbon nanofiber composite aerogel electrode material, that is, the graphene-carbon nanofiber composite electrode material, when applied to the positive electrode and the negative electrode of a lithium ion capacitor, shows excellent capacity characteristics, cycle performance and ultrahigh rate performance. The total battery assembled by the positive electrode and the negative electrode can reach 181Wh kg -1 The energy density of (2).
Fig. 1 is a scanning electron microscope image of a graphene-carbon nanofiber composite aerogel electrode material prepared in example 1 of the present invention, and as can be seen from fig. 1, the electrode material after hydrothermal treatment has a large number of thin yarn-like and micron-sized pores with wrinkles and curls, because a large number of oxygen-containing functional groups of GO drop off in the hydrothermal process, under pi-pi conjugate interaction, carbon nanofibers and graphene sheets are connected with each other by self-assembly, are interlaced and stacked to form a three-dimensional interconnected network structure, and one-dimensional carbon nanofibers connect each cavity of three-dimensional graphene, thereby forming a diffusion path of Li + and electrons.
Since the lithium ion capacitor electrode adopts all technical solutions of all the embodiments, the lithium ion capacitor electrode at least has the beneficial effects brought by the technical solutions of the embodiments, and details are not repeated herein.
The above is not relevant and is applicable to the prior art.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it will be understood by those skilled in the art that the foregoing is illustrative only and is not limiting of the scope of the invention, as various modifications or additions may be made to the specific embodiments described and substituted in a similar manner by those skilled in the art without departing from the scope of the invention as defined in the appending claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. A preparation method of a graphene-carbon nanofiber composite aerogel electrode material is characterized by comprising the following steps: the method comprises the following steps:
s1, freeze-drying a bacterial cellulose membrane at a certain temperature to obtain freeze-dried bacterial cellulose;
s2, carbonizing the freeze-dried bacterial cellulose obtained in the step S1 in an inert atmosphere to obtain carbon nanofibers;
s3, ultrasonically mixing the carbon nanofiber obtained in the step S2 and graphene oxide in deionized water according to a certain mass ratio to prepare a dispersion liquid;
and S4, carrying out hydrothermal reaction on the dispersion liquid obtained in the step S3 to form graphene-carbon nanofiber composite hydrogel, and freeze-drying to form the graphene-carbon nanofiber composite aerogel electrode material.
2. The method for preparing the graphene-carbon nanofiber composite aerogel electrode material as claimed in claim 1, wherein the method comprises the following steps: in the step S1, the bacterial cellulose membrane can be in a dispersion liquid or colloidal membrane shape, the solid content of the bacterial cellulose membrane is 1-20%, the diameter is 50-100 nm, the length is 50-50 mu m, the bacterial cellulose membrane is frozen in a pre-freezing mode by adopting a refrigerator or liquid nitrogen, and the freeze-drying temperature is-80-25 ℃.
3. The method for preparing the graphene-carbon nanofiber composite aerogel electrode material as claimed in claim 1, wherein the method comprises the following steps: in step S2, the carbonization atmosphere can be Ar or Ar/H 2 、N 2 、N 2 /H 2 、Ar/N 2 。
4. The method for preparing the graphene-carbon nanofiber composite aerogel electrode material as claimed in claim 1, wherein the method comprises the following steps: in the step S2, the temperature rise rate of the carbonization treatment is 2-10 ℃, the heat preservation temperature is 400-700 ℃ and 800-1200 ℃ respectively, and the corresponding heat preservation time is 30 min-3 h.
5. The method for preparing the graphene-carbon nanofiber composite aerogel electrode material as claimed in claim 1, wherein the method comprises the following steps: in the step S3, the mass ratio of the graphene oxide to the carbon nanofibers is 20: (1-10), in the dispersion liquid, the concentration of the graphene oxide is 0.5-2 mg/ml, the ultrasonic power is 500-800W, and the ultrasonic time is 10-100 min.
6. The method for preparing the graphene-carbon nanofiber composite aerogel electrode material as claimed in claim 1, wherein the method comprises the following steps: in step S3, the solvent includes any one or more of water, absolute ethanol, and ethylene glycol.
7. The method for preparing the graphene-carbon nanofiber composite aerogel electrode material as claimed in claim 1, wherein the method comprises the following steps: and S4, performing hydrothermal reaction at the temperature of 150-210 ℃ for 6-12 h, and freeze-drying the obtained hydrogel to obtain the graphene-carbon nanofiber composite aerogel electrode material.
8. A graphene-carbon nanofiber composite aerogel electrode material prepared by the preparation method as set forth in any one of claims 1.
9. A lithium ion capacitor, characterized by: preparing the positive and negative electrodes of the lithium ion capacitor by using the graphene-carbon nanofiber composite aerogel electrode material as claimed in claim 8.
10. The lithium ion capacitor of claim 9, wherein: the specific process for preparing the anode and the cathode is as follows: mixing the graphene-carbon nanofiber composite aerogel electrode material, conductive carbon black and polyvinylidene fluoride according to the ratio of (6): (0.5 1.5): (0.5) grinding and mixing the raw materials in N-methyl pyrrolidone to prepare slurry; coating the slurry on a 15-micron single-sided smooth thick copper foil, drying at 70 ℃ for 10 hours to obtain a lithium ion capacitor negative electrode, coating the slurry on a 24-micron thick double-sided carbon-coated aluminum foil, and drying at 50 ℃ for 24 hours to obtain a lithium ion capacitor positive electrode.
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