CN113871209B - Carbon-coated graphene-ferric oxide composite electrode material and preparation method and application thereof - Google Patents
Carbon-coated graphene-ferric oxide composite electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a carbon-coated graphene-ferric oxide composite electrode material, and a preparation method and application thereof. And after the graphene oxide is ultrasonically dispersed in a solvent, adding an iron precursor and a morphology regulator, stirring and mixing, performing solvothermal treatment, filtering, washing and freeze-drying to obtain a graphene/iron oxide composite material, mixing the graphene/iron oxide composite material with a carbon source in an aqueous solution, freeze-drying, and annealing at a high temperature in inert gas to obtain the carbon-coated graphene-iron oxide composite electrode material. The preparation method has the advantages of wide sources of raw materials, simpler method, no use of strong acid or strong alkali, less environmental pollution and mass production. The lithium ion capacitor cathode prepared by the material has high specific capacity, excellent multiplying power performance and good cycle stability.
Description
Technical Field
The invention relates to the field of manufacturing of lithium ion battery devices, in particular to a carbon-coated graphene-ferric oxide composite electrode material, and a preparation method and application thereof.
Background
With the rapid development of global economy and the increasing consumption of fossil fuels and environmental pollution, efficient, green and renewable clean energy is favored, and meanwhile, the construction of novel chemical power sources is widely focused and studied. Among them, lithium ion batteries and supercapacitors are currently very promising electrochemical energy storage systems. Lithium ion batteries generally have the advantages of high energy density, high operating voltage and no memory effect, but their main limiting factors are low power density and poor cycle performance. Supercapacitors, in contrast, have great advantages in terms of power density and cycle life, but are still limited by low energy density. In the aspect of practical electric equipment such as electric automobiles, electronic storage equipment and power grid energy storage, the energy storage equipment is highly expected to have the excellent performances of high energy density, high power density and long cycle life.
High performance lithium ion capacitors (also known as hybrid supercapacitors) are considered to be one of the most promising electrochemical energy storage systems today, due to the higher power density and longer cycle life of lithium ion batteries, as well as the higher energy density than supercapacitors, which consist of a pre-lithiated battery type negative electrode, a capacitive positive electrode and an organic electrolyte containing a lithium salt. The preparation of the high-performance negative electrode material is important to the construction of the high-performance lithium ion capacitor. In the electrode material of the lithium ion capacitor, the development and application of the lithium ion capacitor are limited to a great extent due to the low specific capacitance of the carbon material, such as the theoretical specific capacitance of 372mAh/g of the traditional graphite negative electrode material, the poor cycle performance of the conductive polymer, serious pollution and the like. The transition metal oxide (1000 mAh/g) has a conversion reaction mechanism, has the advantages of environmental friendliness, lower cost, high theoretical specific capacity and the like, becomes a good choice for researchers, but has poor electrical conductivity, poor cycle stability and poor rate capability caused by severe volume expansion phenomenon in the charge and discharge process, and restricts practical application.
Therefore, how to provide a lithium ion capacitor negative electrode material with high capacity and excellent cycle stability and rate performance is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims at providing a carbon-coated graphene-ferric oxide composite electrode material, a preparation method thereof and a lithium ion capacitor cathode, aiming at the defects in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of a carbon-coated graphene-ferric oxide composite electrode material, which comprises the following steps:
s1, after graphene oxide is ultrasonically dispersed in a solvent, adding an iron precursor and a morphology regulator, stirring and mixing, performing solvothermal treatment, and performing suction filtration washing and freeze drying to obtain a graphene/iron oxide composite material;
s2, mixing the graphene/ferric oxide composite material obtained in the step S1 with a carbon source in an aqueous solution, and carrying out high-temperature annealing in inert gas after freeze drying to obtain the carbon-coated graphene/ferric oxide composite electrode material.
Further, in step S1, the iron precursor includes any one or more of ferric trichloride, ferrous lactate, ferric citrate, ferric glycine, ferric sulfate and ferric nitrate.
Further, in step S1, the solvent includes any one or more of water, absolute ethanol, isopropanol, ethylene glycol, propylene glycol, and glycerol.
Further, in step S1, the morphology regulator is composed of sulfate and phosphate in a certain proportion, wherein the sulfate includes any one or more of sodium sulfate, ammonium sulfate and potassium sulfate, and the phosphate includes any one or more of disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, monoammonium phosphate, sodium polyphosphate and ammonium polyphosphate.
In step S1, the temperature of the solvothermal treatment is 160-220 ℃ and the solvothermal treatment time is 10-20 h.
Further, in step S1, the mass ratio of the graphene oxide, the iron precursor and the morphology regulator is (3-6): 65: (1-2).
Further, in the step S2, the annealing temperature is 500-900 ℃, the annealing time is 1-10h, and the heating rate is 1-10 ℃/min.
The invention also provides a carbon-coated graphene-ferric oxide composite electrode material which is prepared by adopting the preparation method.
The invention also provides a lithium ion capacitor negative electrode, which comprises the carbon-coated graphene-ferric oxide composite electrode material, wherein the lithium ion capacitor negative electrode is prepared from the carbon-coated graphene-ferric oxide composite electrode material, conductive carbon black and polyvinylidene fluoride according to the following steps of (7-8): (1-2): the mass ratio of (1-2) is configured into slurry; and (3) coating the slurry on a copper foil, drying at 50 ℃ for 0-6h, heating to 70 ℃ and continuously drying for 12-18h to obtain the copper foil.
The technical scheme provided by the invention has the beneficial effects that:
(1) According to the carbon-coated graphene-ferric oxide composite electrode material, graphene oxide is ultrasonically dispersed in a solvent, an iron precursor and a morphology regulator are added under magnetic stirring, so that a uniformly mixed dispersion liquid with preset concentration is obtained, and as graphene oxide is negatively charged due to oxygen-containing functional groups and the like, positively charged iron ions are closely attached to graphene oxide sheets due to electrostatic interaction; and then transferring the dispersion liquid into a hydrothermal kettle for solvothermal treatment, in the solvothermal treatment process, forming and growing iron oxide crystals on graphene oxide sheets, adding a morphology regulator, wherein the iron oxide tends to form nano shuttle-shaped particles with uniform size and regular morphology, and more abundant active sites for contact and reaction with lithium ions and electrolyte, and meanwhile, the graphene oxide can be reduced to a certain extent in the solvothermal process and self-assembled to form a three-dimensional conductive network due to pi-pi conjugation, so that the conductivity of the iron oxide is improved, the volume expansion of the iron oxide particles can be relieved as a flexible substrate in the repeated charge-discharge cycle process, and meanwhile, the iron oxide shuttle-shaped particles also serve as spacers for preventing spontaneous re-stacking of the graphene sheets, increasing the interlayer spacing and facilitating rapid electron and ion transmission between the graphene sheets. And then mixing the carbon source with the carbon source in the solution, and freeze-drying the mixture, so that the carbon source is uniformly coated on the ferric oxide shuttle particles and the graphene substrate, and the particle agglomeration phenomenon can be effectively avoided. Finally, through high-temperature annealing treatment, the carbon source can be carbonized into a thin carbon shell layer with high conductivity coated on the ferric oxide and the graphene in situ, and simultaneously, the crystallinity of the ferric oxide particles is improved, the conductivity and the mechanical stability of the ferric oxide particles are further improved, and the problems of poor cycle stability and rate capability caused by too large volume change and particle pulverization in the repeated charge and discharge cycle process can be effectively solved.
(2) In the preparation process of the carbon-coated graphene-ferric oxide composite electrode material, the raw material source is wide, the method is simple, strong acid and strong alkali are not used, the environmental pollution is less, and batch production can be carried out.
(3) The lithium ion capacitor cathode prepared by the method has high specific capacity, excellent multiplying power performance and good cycle stability.
Drawings
Fig. 1 is a scanning electron microscope image of a carbon-coated graphene-iron oxide composite electrode material according to example 1 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings and examples.
The invention provides a preparation method of a carbon-coated graphene-ferric oxide composite electrode material, which comprises the following steps:
step S1, after graphene oxide is ultrasonically dispersed in a solvent, an iron precursor and a morphology regulator are added, and after stirring and mixing, solvothermal treatment is carried out, and after suction filtration, washing and freeze drying, a graphene/iron oxide composite material is obtained;
and S2, mixing the graphene/ferric oxide composite material obtained in the step S1 with a carbon source in an aqueous solution, and carrying out high-temperature annealing in inert gas after freeze drying to obtain the carbon-coated graphene-ferric oxide composite electrode material.
The method of the invention is to prepare a graphene/ferric oxide composite material, and then combine a carbon source with the graphene/ferric oxide composite material to prepare the carbon-coated graphene-ferric oxide composite electrode material, as shown in figure 1. The method has the advantages that the growth of the iron oxide particles on the graphene sheets can be ensured through electrostatic interaction, the iron oxide particles cannot fall off easily due to certain interaction, excellent conductivity of graphene and flexibility of the two-dimensional sheets are fully utilized, finally, the added carbon source can be uniformly coated on the surfaces of the iron oxide particles and areas, which are not occupied by the iron oxide particles, on the graphene sheets, of the graphene sheets, a carbon shell layer can be formed after high-temperature annealing, on one hand, the conductivity of the iron oxide is further improved, on the other hand, serious volume expansion of the iron oxide in a charging and discharging cycle process is contained, and when the lithium ion capacitor cathode is applied, the multiplying power performance and the cycle are obviously improved.
The morphology regulator selected by the invention obtains the nano-shuttle-shaped particles with specific morphology. After the morphology regulator is added, ferric oxide tends to form nano shuttle-shaped particles with uniform size and regular morphology, and the nano shuttle-shaped particles have richer active sites for contacting and reacting with lithium ions and electrolyte, and meanwhile, the ferric oxide shuttle-shaped particles also serve as a spacing agent to prevent spontaneous re-stacking of graphene sheets, increase the interlayer spacing and facilitate rapid electron and ion transmission between the graphene sheets. The action mechanisms of different morphology regulators for regulating morphology are different to a certain extent, the obtained specific morphology and the uniformity degree of the morphology are also different, and the morphology regulator adopted by the invention can obtain nano-shuttle-shaped ferric oxide particles with high uniformity degree.
In order to ensure that the carbon source is fully carbonized into a carbon shell layer and improve the reduction degree of the graphene, other adverse effects are not generated on other components, in the step S2, the annealing temperature can be 500-900 ℃, the annealing time can be 1-10h, and the heating rate can be 1-10 ℃/min.
In step S2, the ferric oxide/graphene composite is formed and then mixed with a carbon source in a solution, and then freeze-dried, so that the carbon source is uniformly coated on ferric oxide shuttle particles and a graphene substrate, and particle agglomeration can be effectively avoided. Finally, through high-temperature annealing treatment, the carbon source can be carbonized into a thin carbon shell layer with high conductivity coated on the ferric oxide and the graphene in situ, and simultaneously, the crystallinity of the ferric oxide particles is improved, the conductivity and the mechanical stability of the ferric oxide particles are further improved, and the problem of poor rate performance of circulation stability caused by overlarge volume change and particle pulverization in the repeated charge-discharge circulation process can be effectively solved.
The technical scheme and advantages of the present invention will be described in detail with reference to specific examples and comparative examples.
Graphene oxide: is prepared by a modified Hummers method.
Example 1
Dispersing 60mg of graphene oxide in 120mL of deionized water in an ultrasonic manner, wherein the ultrasonic power and the ultrasonic power are respectively 300W and 1h, obtaining uniformly mixed graphene oxide dispersion liquid, adding 1.296g of ferric trichloride hexahydrate, magnetically stirring for 30min, uniformly mixing, adding 0.0188g of sodium sulfate and 0.0028g of sodium dihydrogen phosphate dihydrate, continuously stirring for 30min, uniformly mixing, transferring the dispersion liquid into a hydrothermal kettle, placing in an electrothermal blowing drying box, performing 180 ℃ solvothermal treatment for 10h, performing suction filtration, washing and freeze-drying to obtain a graphene/ferric oxide composite material; the graphene/ferric oxide composite material and polyvinyl alcohol are mixed according to the mass ratio of 1:10, mixing in an aqueous solution, freeze-drying, and annealing for 2 hours at 800 ℃ in argon to obtain a carbon-coated graphene-ferric oxide composite electrode material; the carbon-coated graphene-ferric oxide composite electrode material is used as a negative electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. Wherein the mass ratio of the carbon-coated graphene-ferric oxide composite electrode material to the conductive agent to the binder is 8:1:1. And (3) after blade coating and vacuum drying at 50 ℃ for 6 hours, heating to 70 ℃ and drying for 12 hours to obtain the negative electrode of the lithium ion capacitor.
Example 2
Dispersing 120mg of graphene oxide in 120mL of deionized water in an ultrasonic manner, wherein the ultrasonic power and the ultrasonic power are respectively 300W and 1h, obtaining uniformly mixed graphene oxide dispersion liquid, adding 1.296g of ferric trichloride hexahydrate, magnetically stirring for 30min, uniformly mixing, adding 0.0376g of sodium sulfate and 0.0028g of sodium dihydrogen phosphate dihydrate, continuously stirring for 30min, uniformly mixing, transferring the dispersion liquid into a hydrothermal kettle, placing in an electrothermal blowing drying box, performing solvent heat treatment at 220 ℃ for 10h, performing suction filtration, washing and freeze-drying to obtain a graphene/ferric oxide composite material; mixing graphene/ferric oxide composite material with glucose according to a mass ratio of 1:10, mixing in an aqueous solution, freeze-drying, and annealing for 2 hours at 600 ℃ in argon to obtain a carbon-coated graphene-ferric oxide composite electrode material; the carbon-coated graphene-ferric oxide composite electrode material is used as a negative electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. Wherein the mass ratio of the carbon-coated graphene-ferric oxide composite electrode material to the conductive agent to the binder is 7:1:2. And (3) carrying out blade coating and vacuum drying at 60 ℃ for 18 hours to obtain the negative electrode of the lithium ion capacitor.
Example 3
Dispersing 90mg of graphene oxide in 120mL of mixed solvent (the volume ratio of water to ethanol is 5:1) by ultrasound, wherein the ultrasonic power and the ultrasonic power are 300W and the ultrasonic power are 1h respectively, obtaining uniformly mixed graphene oxide dispersion liquid, adding 1.296g of ferric trichloride hexahydrate, magnetically stirring for 60min, uniformly mixing, adding 0.0188g of sodium sulfate and 0.0028g of sodium dihydrogen phosphate dihydrate, continuously stirring and uniformly mixing, transferring the dispersion liquid into a hydrothermal kettle, placing in an electrothermal blowing drying box, performing 160 ℃ solvothermal treatment for 20h, performing suction filtration, washing and freeze-drying to obtain the graphene/ferric oxide composite material; the graphene/ferric oxide composite material and dopamine hydrochloride are mixed according to the mass ratio of 1:8, mixing in an aqueous solution, stirring for 0.5h, freeze-drying, and annealing for 4h at 800 ℃ in argon to obtain a carbon-coated graphene-ferric oxide composite electrode material; the carbon-coated graphene-ferric oxide composite electrode material is used as a negative electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. Wherein the mass ratio of the carbon-coated graphene-ferric oxide composite electrode material to the conductive agent to the binder is 8:1:1. Vacuum drying for 6 hours at 50 ℃ through knife coating, heating to 70 ℃ and drying for 12 hours to obtain the negative electrode of the lithium ion capacitor.
Example 4
Dispersing 60mg of graphene oxide in 120mL of mixed solvent (the volume ratio of water to glycerol is 1:2) in an ultrasonic manner, wherein the ultrasonic power and the ultrasonic power are 300W and the ultrasonic power are 1h respectively, obtaining uniformly mixed graphene oxide dispersion liquid, adding 1.296g of ferric trichloride hexahydrate, magnetically stirring for 60min to uniformly mix, adding 0.0188g of sodium sulfate and 0.0028g of sodium dihydrogen phosphate dihydrate, continuously stirring and uniformly mixing, transferring the dispersion liquid into a hydrothermal kettle, placing the hydrothermal kettle in an electrothermal blowing drying box, carrying out 220 ℃ solvent heat treatment for 10h, and carrying out suction filtration, washing and freeze drying to obtain the graphene/ferric oxide composite material; mixing graphene/ferric oxide composite material with glucose according to a mass ratio of 1:10 in aqueous solution, stirring for 0.5h, freeze-drying, and annealing at 500 ℃ in argon for 10h to obtain a carbon-coated graphene-ferric oxide composite electrode material; the carbon-coated graphene-ferric oxide composite electrode material is used as a negative electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. Wherein the mass ratio of the carbon-coated graphene-ferric oxide composite electrode material to the conductive agent to the binder is 7:1:2. And (3) carrying out blade coating and vacuum drying at 70 ℃ for 12 hours to obtain the negative electrode of the lithium ion capacitor.
Example 5
Dispersing 60mg of graphene oxide in 120mL of mixed solvent (the volume ratio of water to glycerol is 1:2) in an ultrasonic manner, wherein the ultrasonic power and the ultrasonic power are 300W and the ultrasonic power are 1h respectively, obtaining uniformly mixed graphene oxide dispersion liquid, adding 1.296g of ferric trichloride hexahydrate, magnetically stirring for 60min to uniformly mix, adding 0.0188g of sodium sulfate and 0.0028g of sodium dihydrogen phosphate dihydrate, continuously stirring and uniformly mixing, transferring the dispersion liquid into a hydrothermal kettle, placing the hydrothermal kettle in an electrothermal blowing drying box, carrying out solvent heat treatment at 160 ℃ for 12h, and carrying out suction filtration, washing and freeze drying to obtain the graphene/ferric oxide composite material; the graphene/ferric oxide composite material and polyacrylamide are mixed according to the mass ratio of 1:20, mixing in an aqueous solution, freeze-drying, and annealing for 3 hours at 700 ℃ in argon to obtain a carbon-coated graphene-ferric oxide composite electrode material; the carbon-coated graphene-ferric oxide composite electrode material is used as a negative electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. Wherein the mass ratio of the carbon-coated graphene-ferric oxide composite electrode material to the conductive agent to the binder is 7:2:1. And (3) carrying out blade coating and vacuum drying at 70 ℃ for 18 hours to obtain the negative electrode of the lithium ion capacitor.
Example 6
Dispersing 30mg of graphene oxide in 120mL of mixed solvent (the volume ratio of water to glycerol is 1:2) in an ultrasonic manner, wherein the ultrasonic power and the ultrasonic power are 300W and the ultrasonic power are 1h respectively, obtaining uniformly mixed graphene oxide dispersion liquid, adding 1.296g of ferric trichloride hexahydrate, magnetically stirring for 60min to uniformly mix, adding 0.0188g of sodium sulfate and 0.0028g of sodium dihydrogen phosphate dihydrate, continuously stirring and uniformly mixing, transferring the dispersion liquid into a hydrothermal kettle, placing the hydrothermal kettle in an electrothermal blowing drying box, carrying out 180 ℃ solvent heat treatment for 20h, carrying out suction filtration, washing and freeze-drying to obtain the graphene/ferric oxide composite material; the graphene/ferric oxide composite material and chitosan are mixed according to the mass ratio of 1:40 in aqueous solution, then freeze-drying, and annealing for 4 hours at 500 ℃ in argon to obtain a carbon-coated graphene-ferric oxide composite electrode material; the carbon-coated graphene-ferric oxide composite electrode material is used as a negative electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. Wherein the mass ratio of the carbon-coated graphene-ferric oxide composite electrode material to the conductive agent to the binder is 8:1:1. And (3) carrying out blade coating and vacuum drying at 70 ℃ for 18 hours to obtain the negative electrode of the lithium ion capacitor.
Comparative example 1
Adding 1.296g of ferric trichloride hexahydrate into 120mL of deionized water, magnetically stirring for 10min, uniformly mixing, adding 0.0188g of sodium sulfate and 0.0028g of sodium dihydrogen phosphate dihydrate, continuously stirring, uniformly mixing, transferring the dispersion into a hydrothermal kettle, placing into an electrothermal blowing drying oven, performing solvent heat treatment at 200 ℃ for 14h, performing suction filtration, washing and freeze drying to obtain ferric oxide; the method comprises the steps of taking an iron oxide anode active material as an anode active material, taking conductive carbon black as a conductive agent, taking polyvinylidene fluoride as a binder, taking N-methyl pyrrolidone as a dispersing agent to prepare slurry, and taking copper foil as a current collector. Wherein the mass ratio of the electrode active material to the conductive agent to the binder is 8:1:1. And after the negative electrode of the lithium ion capacitor is obtained after the negative electrode is dried for 12 hours after the negative electrode is subjected to blade coating and vacuum drying at 50 ℃ for 6 hours and then is heated to 70 ℃.
Comparative example 2
Dispersing 60mg of graphene oxide in 120mL of deionized water in an ultrasonic manner, wherein the ultrasonic power and the ultrasonic power are respectively 300W and 1h, obtaining uniformly mixed graphene oxide dispersion liquid, adding 1.296g of ferric trichloride hexahydrate, magnetically stirring for 10min, uniformly mixing, transferring the dispersion liquid into a hydrothermal kettle, placing the hydrothermal kettle in an electrothermal blowing drying box, performing 180 ℃ solvothermal treatment for 10h, and performing suction filtration, washing and freeze drying to obtain a graphene-ferric oxide composite material; the graphene-ferric oxide composite material is used as a negative electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. Wherein the mass ratio of the electrode active material to the conductive agent to the binder is 7:1:2. And (3) after blade coating and vacuum drying at 50 ℃ for 6 hours, heating to 70 ℃ and vacuum drying for 12 hours to obtain the negative electrode of the lithium ion capacitor.
Comparative example 3
Dispersing 60mg of graphene oxide in 120mL of deionized water in an ultrasonic manner, wherein the ultrasonic power and the ultrasonic power are respectively 300W and 1h, obtaining uniformly mixed graphene oxide dispersion liquid, adding 1.296g of ferric trichloride, magnetically stirring for 30min, uniformly mixing, adding 0.0188g of sodium sulfate and 0.0028g of sodium dihydrogen phosphate dihydrate, continuously stirring for 30min, uniformly mixing, adding polyethylene amide (the mass ratio of the ferric trichloride to the polyethylene amide is 1:10) under stirring, finally transferring the dispersion liquid into a hydrothermal kettle, placing in an electric heating blowing drying box, performing solvent heat treatment at 180 ℃ for 10h, performing suction filtration, washing, and freeze-drying to obtain a graphene-ferric oxide composite material; the graphene-ferric oxide composite material is used as a negative electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. Wherein the mass ratio of the electrode active material to the conductive agent to the binder is 8:1:1. And (3) after blade coating and vacuum drying at 50 ℃ for 6 hours, heating to 70 ℃ and vacuum drying for 12 hours to obtain the negative electrode of the lithium ion capacitor.
Comparative example 4
Dispersing 1200mg of graphene oxide in 120mL of deionized water in an ultrasonic manner, wherein the ultrasonic power and the ultrasonic power are respectively 300W and 1h, obtaining uniformly mixed graphene oxide dispersion liquid, adding 1.296g of ferric trichloride hexahydrate, magnetically stirring for 30min, uniformly mixing, adding 0.0376g of sodium sulfate and 0.0028g of sodium dihydrogen phosphate dihydrate, continuously stirring for 30min, uniformly mixing, transferring the dispersion liquid into a hydrothermal kettle, placing in an electrothermal blowing drying box, performing 180 ℃ solvothermal treatment for 10h, performing suction filtration, washing and freeze-drying, and obtaining the graphene-ferric oxide composite material; mixing graphene/ferric oxide composite material with glucose according to the mass ratio of 1-10 in an aqueous solution, drying at 90 ℃ for 24 hours, and annealing at 600 ℃ in argon for 2 hours to obtain a carbon-coated graphene-ferric oxide composite electrode material; the carbon-coated graphene-ferric oxide composite electrode material is used as a negative electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. Wherein the mass ratio of the electrode active material to the conductive agent to the binder is 7:1:2. And (5) carrying out blade coating and drying at 70 ℃ for 18 hours to obtain the finished product.
The negative electrodes of the lithium ion capacitors prepared in examples 1 to 6 and comparative examples 1 to 4 were subjected to performance test, and the results are shown in table 1:
TABLE 1 negative electrode performance Table of lithium ion capacitors
As can be seen from the results of table 1, the electrode material in the example of the present invention has a higher specific capacity and significantly better rate performance and cycle stability than the comparative example, in which only nano-shuttle iron oxide is used as the anode active material in the comparative example 1 and only graphene-iron oxide is used as the anode active material in the comparative example 2, compared to the nanocomposite material obtained by compositing iron oxide and graphene and coating the carbon layer in the example of the present invention. In addition, compared with comparative example 3, in example 1, since the carbon source, the iron source, the graphene oxide and the like are directly subjected to hydrothermal and annealing treatment after being fully mixed in comparative example, nano-shuttle-shaped iron oxide particles cannot be ensured to grow and uniformly distribute on the graphene flexible substrate in situ, volume expansion of the iron oxide in the charge and discharge cycle process cannot be effectively relieved, and the specific capacity of the corresponding lithium ion capacitor cathode is remarkably lower and the multiplying power and the cycle performance are poor. Compared with comparative example 4, in the comparative example, the graphene-ferric oxide obtained by mixing the carbon source with the water is directly dried at 90 ℃ after being mixed in the water solution, the dried sample is adhered to the wall of the beaker, the loss is easy to cause because of being difficult to take down, the particle agglomeration is easy to cause because of being dried at high temperature, the three-dimensional porous structure formed by self-assembly of the original graphene is severely contracted, and in the lithium ion capacitor, the rapid infiltration of the electrolyte is difficult to rapidly realize and more ion transmission channels cannot be provided, so that the multiplying power and the cycle performance of the corresponding lithium ion capacitor are poor.
In summary, the lithium ion capacitor negative electrode material with high specific capacity, high rate capability and good cycle stability can be obtained by compositing the iron oxide material with graphene with high conductivity, high specific area and unique two-dimensional structure and further coating the carbon layer.
The embodiments described above and features of the embodiments herein may be combined with each other without conflict.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (6)
1. A preparation method of a carbon-coated graphene-ferric oxide composite electrode material is characterized by comprising the following steps of: the method comprises the following steps:
s1, after graphene oxide is ultrasonically dispersed in a solvent, adding an iron precursor and a morphology regulator, stirring and mixing, performing solvothermal treatment, and performing suction filtration washing and freeze drying to obtain a graphene/iron oxide composite material; the iron precursor is ferric trichloride; the solvent comprises any one or more of water, absolute ethyl alcohol, isopropanol, ethylene glycol, propylene glycol and glycerol; the morphology regulator consists of sodium sulfate and sodium dihydrogen phosphate dihydrate according to a certain proportion;
the mass ratio of the graphene oxide to the iron precursor to the morphology regulator is (3-6): (1-2);
the temperature of the solvothermal treatment is 160-220 ℃, and the solvothermal treatment time is 10-20 hours;
s2, mixing the graphene/ferric oxide composite material obtained in the step S1 with a carbon source in an aqueous solution, and carrying out high-temperature annealing in inert gas after freeze drying to obtain a carbon-coated graphene-ferric oxide composite electrode material; the mass ratio of the graphene/ferric oxide composite material to the carbon source is 1: (8-40);
the carbon source comprises any one of dopamine hydrochloride, aniline, polyacrylamide, polyvinyl alcohol, chitosan and glucose;
the annealing temperature is 500-900 ℃, the annealing time is 1-10h, and the heating rate is 1-10 ℃/min.
2. The method for preparing the carbon-coated graphene-ferric oxide composite electrode material according to claim 1, wherein the method comprises the following steps: the mass ratio of the sodium sulfate to the sodium dihydrogen phosphate dihydrate is (6-13.5): 1.
3. the method for preparing the carbon-coated graphene-ferric oxide composite electrode material according to claim 2, wherein the method comprises the following steps: in the step S2, the annealing temperature is 500-600 ℃ and the annealing time is 2-10h.
4. The method for preparing the carbon-coated graphene-ferric oxide composite electrode material according to claim 2, wherein the method comprises the following steps: in the step S2, the annealing temperature is 700-800 ℃ and the annealing time is 2-4h.
5. The carbon-coated graphene-ferric oxide composite electrode material is characterized in that: obtained by the process according to any one of claims 1 to 4.
6. The negative electrode of the lithium ion capacitor is characterized in that: a carbon-coated graphene-iron oxide composite electrode material comprising the carbon-coated graphene-iron oxide composite electrode material according to claim 5, wherein the negative electrode of the lithium ion capacitor is prepared from the carbon-coated graphene-iron oxide composite electrode material, conductive carbon black and polyvinylidene fluoride according to (7-8): (1-2): the mass ratio of (1-2) is configured into slurry; and (3) coating the slurry on a copper foil, drying at 50 ℃ for 0-6h, heating to 70 ℃ and continuously drying for 12-18h to obtain the copper foil.
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