CN113871209A - Carbon-coated graphene-iron oxide composite electrode material and preparation method and application thereof - Google Patents
Carbon-coated graphene-iron oxide composite electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a carbon-coated graphene-iron oxide composite electrode material and a preparation method and application thereof. The preparation method comprises the steps of ultrasonically dispersing graphene oxide in a solvent, adding an iron precursor and a morphology regulator, stirring and mixing, carrying out solvent heat treatment, carrying out suction filtration 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, carrying out freeze drying, and carrying out high-temperature annealing in an inert gas to obtain the carbon-coated graphene-iron oxide composite electrode material. The preparation method has the advantages of wide raw material source, simple method, no use of strong acid and strong alkali, less environmental pollution and batch production. The lithium ion capacitor cathode prepared by the material has high specific capacity, excellent rate capability and good cycling stability.
Description
Technical Field
The invention relates to the field of manufacturing of lithium ion battery devices, in particular to a carbon-coated graphene-iron oxide composite electrode material and a preparation method and application thereof.
Background
With the rapid development of global economy, the rapid consumption of fossil fuels and the increasing increase of environmental pollution, high-efficiency, green and renewable clean energy sources are favored, and meanwhile, the construction of a novel chemical power source is widely concerned and researched. Among them, lithium ion batteries and supercapacitors are electrochemical energy storage systems with great prospect at present. 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 cycling performance. In contrast, ultracapacitors have great advantages in 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, power grid energy storage and the like, the energy storage equipment is urgently expected to have excellent performances such as high energy density, high power density and long cycle life.
Since lithium-ion capacitors (also called hybrid supercapacitors) consisting of a prelithiated battery-type negative electrode, a capacitive positive electrode and an organic electrolyte containing a lithium salt have higher power density and longer cycle life than lithium-ion batteries, and higher energy density than supercapacitors, high performance lithium-ion capacitors are considered to be one of the most promising electrochemical energy storage systems today. The preparation of the high-performance negative electrode material is important for the construction of the high-performance lithium ion capacitor. In the lithium ion capacitor electrode material, the development and application of the lithium ion capacitor are limited to a great extent by the problems of low specific capacitance of the carbon material, such as 372mAh/g of theoretical specific capacity of the traditional graphite cathode material, poor cycle performance of the conductive polymer, serious pollution and the like. The transition metal oxide (about 1000mAh/g) has a conversion reaction mechanism, shows the advantages of environmental friendliness, low cost, high theoretical specific capacity and the like, and becomes a good choice for researchers, but the poor cyclic stability and poor rate capability caused by the poor conductivity and the severe volume expansion phenomenon in the charging and discharging processes restrict the practical application of the transition metal oxide.
Therefore, how to provide a lithium ion capacitor negative electrode material with high capacity and excellent cycling stability and rate capability is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a carbon-coated graphene-iron oxide composite electrode material, a preparation method thereof and a lithium ion capacitor negative electrode aiming at the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a carbon-coated graphene-iron oxide composite electrode material, which comprises the following steps:
s1, ultrasonically dispersing graphene oxide in a solvent, adding an iron precursor and a morphology regulator, stirring and mixing, carrying out solvent heat treatment, carrying out suction filtration washing and freeze drying to obtain a graphene/iron oxide composite material;
and S2, mixing the graphene/iron oxide composite material obtained in the step S1 with a carbon source in an aqueous solution, freezing and drying the mixture, and then annealing the mixture at a high temperature in an inert gas to obtain the carbon-coated graphene-iron oxide composite electrode material.
Further, in step S1, the iron precursor includes any one or more of ferric chloride, ferrous lactate, ferric citrate, ferric glycinate, 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 a sulfate and a phosphate in a certain ratio, where 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, ammonium dihydrogen phosphate, sodium polyphosphate and ammonium polyphosphate.
Further, in step S1, the temperature of the solvothermal treatment is 160-220 ℃, and the solvothermal treatment time is 10-20 hours.
Further, the method comprises the following steps: in step S1, the mass ratio of the graphene oxide to the iron precursor to the morphology regulator is (3-6): 65: (1-2).
Further, in 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-iron oxide composite electrode material prepared by the preparation method.
The invention also provides a lithium ion capacitor cathode which comprises the carbon-coated graphene-iron oxide composite electrode material, wherein the carbon-coated graphene-iron oxide composite electrode material, conductive carbon black and polyvinylidene fluoride are mixed according to the following ratio of (7-8): (1-2): the mass ratio of (1-2) is prepared into slurry; 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-iron oxide composite electrode material provided by the invention, graphene oxide is ultrasonically dispersed in a solvent, an iron precursor and a morphology regulating agent are added under magnetic stirring to obtain a uniformly mixed dispersion liquid with a preset concentration, and as graphene oxide is negatively charged due to oxygen-containing functional groups and the like, positively charged iron ions are tightly attached to a graphene oxide sheet layer due to electrostatic interaction; then the dispersion liquid is moved to a hydrothermal kettle for solvent heat treatment, the iron oxide crystal on the graphene oxide sheet layer is nucleated and grows up, and after the morphology regulating agent is added, the iron oxide tends to form nano spindle-shaped particles with uniform size and regular morphology, and has richer active sites which are contacted and reacted with lithium ions and electrolyte, meanwhile, graphene oxide can be reduced to a certain degree in the solvothermal process and forms a three-dimensional conductive network due to pi-pi conjugation self-assembly, thereby improving the conductivity of the iron oxide and relieving the volume expansion of the iron oxide particles as a flexible substrate in the process of multiple charge-discharge cycles, meanwhile, the ferric oxide spindle-shaped particles also serve as a spacing agent to prevent spontaneous re-stacking of graphene sheet layers, so that the interlayer spacing is increased, and rapid electron and ion transmission between the graphene sheet layers is facilitated. And then the carbon source is mixed with the carbon source in the solution and then is frozen and dried, so that the carbon source is uniformly wrapped on the iron oxide fusiform particles and the graphene substrate, and the particle aggregation phenomenon can be effectively avoided. And finally, through high-temperature annealing treatment, the carbon source can be carbonized in situ into a high-conductivity thin carbon shell layer coated on the iron oxide and the graphene, the crystallinity of iron oxide particles is improved, the conductivity and the mechanical stability of the iron 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 process of multiple charging and discharging cycles can be effectively solved.
(2) In the preparation process of the carbon-coated graphene-iron 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 the carbon-coated graphene-iron oxide composite electrode material can be produced in batches.
(3) The lithium ion capacitor cathode prepared by the invention has high specific capacity, excellent rate capability and good cycling stability.
Drawings
Fig. 1 is a scanning electron microscope image of the carbon-coated graphene-iron oxide composite electrode material of embodiment 1 of the present invention.
Detailed Description
In order to make 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-iron oxide composite electrode material, which comprises the following steps:
step S1, ultrasonically dispersing graphene oxide in a solvent, adding an iron precursor and a morphology regulator, stirring and mixing, carrying out solvent heat treatment, carrying out suction filtration washing and freeze drying to obtain a graphene/iron oxide composite material;
and step S2, mixing the graphene/iron oxide composite material obtained in the step S1 with a carbon source in an aqueous solution, freezing and drying the mixture, and then annealing the mixture at a high temperature in an inert gas to obtain the carbon-coated graphene-iron oxide composite electrode material.
The method comprises the steps of firstly preparing the graphene/iron oxide composite material, and then combining a carbon source with the graphene/iron oxide composite material to prepare the carbon-coated graphene-iron oxide composite electrode material, as shown in figure 1. Can guarantee that the iron oxide granule grows on the graphite alkene lamella through electrostatic interaction, and owing to there is certain interact, the iron oxide granule can not drop easily, make full use of graphite alkene excellent electric conductivity and the flexibility of two-dimensional lamella, the carbon source that adds at last can even cladding be in the iron oxide granule surface and the graphite alkene lamella on the region that the iron oxide granule occupied, can form the carbon shell layer after the high temperature annealing, on the one hand further improve the electric conductivity of iron oxide, on the one hand hold the serious volume expansion of iron oxide in charge-discharge cycle process, when using as the lithium ion capacitor negative pole, its multiplying power performance and circulation obtain obvious improvement.
The shape regulating agent selected by the invention obtains the special shape-nano fusiform particles. After the morphology regulating agent is added, the iron oxide tends to form nano spindle-shaped particles with uniform size and regular morphology, and the nano spindle-shaped particles have richer active sites which are in contact with and react with lithium ions and electrolytes, and meanwhile, the iron oxide spindle-shaped particles are also used as a spacing agent to prevent spontaneous re-stacking of graphene lamellar layers, so that the interlayer spacing is increased, and rapid electron and ion transmission between the graphene lamellar layers is facilitated. The different morphology regulators have certain difference in the mechanism of regulating the morphology, the obtained specific morphology and the uniformity degree of the morphology are different, and the adopted morphology regulator can obtain the spindle-shaped nano iron oxide particles with high uniformity degree.
In order to ensure that the carbon source is fully carbonized into a carbon shell layer, the reduction degree of the graphene is improved, and other adverse effects on other components are not generated, in 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 iron oxide/graphene composite is formed and then mixed with a carbon source in a solution, followed by freeze drying, so that the carbon source is uniformly coated on the iron oxide fusiform particles and the graphene substrate, and the particle aggregation phenomenon can be effectively avoided. And finally, through high-temperature annealing treatment, the carbon source can be carbonized in situ into a high-conductivity thin carbon shell layer coated on the iron oxide and the graphene, the crystallinity of iron oxide particles is improved, the conductivity and the mechanical stability of the iron oxide particles are further improved, and the problem of poor cycling stability and multiplying power performance caused by too large volume change and particle pulverization in the process of multiple charging and discharging cycles can be effectively solved.
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
Ultrasonically dispersing 60mg of graphene oxide in 120mL of deionized water, wherein the ultrasonic power and the ultrasonic time 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 the hydrothermal kettle into an electrothermal blowing drying box, carrying out 180 ℃ solvent heat treatment for 10h, and carrying out suction filtration, washing and freeze drying to obtain the graphene/iron oxide composite material; mixing a graphene/ferric oxide composite material and polyvinyl alcohol according to a mass ratio of 1:10, mixing the mixture in an aqueous solution, freeze-drying the mixture, and annealing the mixture for 2 hours at 800 ℃ in argon gas to obtain a carbon-coated graphene-iron oxide composite electrode material; the carbon-coated graphene-iron oxide composite electrode material is used as a negative active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. The mass ratio of the carbon-coated graphene-iron oxide composite electrode material to the conductive agent to the binder is 8:1: 1. Scraping and coating, vacuum drying at 50 ℃ for 6h, heating to 70 ℃ and drying for 12h to obtain the lithium ion capacitor cathode.
Example 2
Ultrasonically dispersing 120mg of graphene oxide in 120mL of deionized water, wherein the ultrasonic power and the ultrasonic time 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 the hydrothermal kettle into an electrothermal blowing drying oven, carrying out solvent heat treatment at 220 ℃ for 10h, and carrying out suction filtration, washing and freeze drying to obtain the graphene/iron oxide composite material; mixing a graphene/ferric oxide composite material and glucose according to a mass ratio of 1:10, mixing the mixture in an aqueous solution, freeze-drying the mixture, and annealing the mixture for 2 hours at the temperature of 600 ℃ in argon gas to obtain a carbon-coated graphene-iron oxide composite electrode material; the carbon-coated graphene-iron oxide composite electrode material is used as a negative active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. The mass ratio of the carbon-coated graphene-iron oxide composite electrode material to the conductive agent to the binder is 7:1: 2. And blade coating and vacuum drying at 60 ℃ for 18h to obtain the lithium ion capacitor cathode.
Example 3
Ultrasonically dispersing 90mg of graphene oxide in 120mL of mixed solvent (the volume ratio of water to ethanol is 5:1) deionized water, wherein the ultrasonic power and the ultrasonic time are respectively 300W and 1h to obtain 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 the hydrothermal kettle in an electrothermal blowing drying oven, carrying out solvent heat treatment at 160 ℃ for 20h, carrying out suction filtration, washing and freeze drying to obtain a graphene/iron oxide composite material; mixing a graphene/iron oxide composite material and dopamine hydrochloride according to a mass ratio of 1: 8, mixing the mixture in the aqueous solution, stirring the mixture for 0.5h, then freeze-drying the mixture, and annealing the mixture for 4h at 800 ℃ in argon to obtain a carbon-coated graphene-iron oxide composite electrode material; the carbon-coated graphene-iron oxide composite electrode material is used as a negative active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. The mass ratio of the carbon-coated graphene-iron oxide composite electrode material to the conductive agent to the binder is 8:1: 1. And (3) carrying out blade coating, vacuum drying at 50 ℃ for 6h, heating to 70 ℃ and drying for 12h to obtain the lithium ion capacitor cathode.
Example 4
Ultrasonically dispersing 60mg of graphene oxide in 120mL of mixed solvent (the volume ratio of water to glycerol is 1: 2), wherein the ultrasonic power and the ultrasonic time are respectively 300W and 1h, 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 the hydrothermal kettle in an electrothermal blowing drying oven, carrying out solvent heat treatment at 220 ℃ for 10h, carrying out suction filtration, washing and freeze drying to obtain the graphene/iron oxide composite material; mixing a graphene/ferric oxide composite material and glucose according to a mass ratio of 1:10, mixing the mixture in an aqueous solution, stirring the mixture for 0.5h, then freeze-drying the mixture, and annealing the mixture for 10h at 500 ℃ in argon to obtain a carbon-coated graphene-iron oxide composite electrode material; the carbon-coated graphene-iron oxide composite electrode material is used as a negative active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. The mass ratio of the carbon-coated graphene-iron oxide composite electrode material to the conductive agent to the binder is 7:1: 2. And blade coating and vacuum drying at 70 ℃ for 12h to obtain the lithium ion capacitor cathode.
Example 5
Ultrasonically dispersing 60mg of graphene oxide in 120mL of mixed solvent (the volume ratio of water to glycerol is 1: 2), wherein the ultrasonic power and the ultrasonic time are respectively 300W and 1h, 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 the hydrothermal kettle in an electrothermal blowing drying oven, carrying out solvent heat treatment at 160 ℃ for 12h, carrying out suction filtration, washing and freeze drying, and obtaining the graphene/iron oxide composite material; mixing a graphene/ferric oxide composite material and polyacrylamide according to a mass ratio of 1: 20, mixing in an aqueous solution, freeze-drying, and annealing at 700 ℃ for 3h in argon to obtain a carbon-coated graphene-iron oxide composite electrode material; the carbon-coated graphene-iron oxide composite electrode material is used as a negative active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. The mass ratio of the carbon-coated graphene-iron oxide composite electrode material to the conductive agent to the binder is 7:2: 1. And blade coating and vacuum drying at 70 ℃ for 18h to obtain the lithium ion capacitor cathode.
Example 6
Ultrasonically dispersing 30mg of graphene oxide in 120mL of mixed solvent (the volume ratio of water to glycerol is 1: 2), wherein the ultrasonic power and the ultrasonic time are respectively 300W and 1h, 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 the hydrothermal kettle in an electrothermal blowing drying oven, carrying out solvent heat treatment at 180 ℃ for 20h, carrying out suction filtration, washing and freeze drying, and obtaining the graphene/iron oxide composite material; mixing the graphene/ferric oxide composite material and chitosan according to a mass ratio of 1: 40, mixing the mixture in an aqueous solution, freeze-drying the mixture, and annealing the mixture for 4 hours at 500 ℃ in argon to obtain a carbon-coated graphene-iron oxide composite electrode material; the carbon-coated graphene-iron oxide composite electrode material is used as a negative active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil is used as a current collector. The mass ratio of the carbon-coated graphene-iron oxide composite electrode material to the conductive agent to the binder is 8:1: 1. And blade coating and vacuum drying at 70 ℃ for 18h to obtain the lithium ion capacitor cathode.
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 and uniformly mixing, transferring the dispersion into a hydrothermal kettle, placing the hydrothermal kettle into an electrothermal blowing drying oven, carrying out solvent heat treatment at 200 ℃ for 14h, and carrying out suction filtration, washing and freeze drying to obtain iron oxide; the method comprises the steps of preparing slurry by taking an iron oxide negative active material as a negative active material, taking conductive carbon black as a conductive agent, taking polyvinylidene fluoride as a binder and taking N-methylpyrrolidone as a dispersing agent, 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. Scraping and coating, vacuum drying at 50 ℃ for 6h, heating to 70 ℃ and drying for 12h to obtain the lithium ion capacitor cathode.
Comparative example 2
Ultrasonically dispersing 60mg of graphene oxide in 120mL of deionized water, wherein the ultrasonic power and the ultrasonic time 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 electric heating forced air drying oven, carrying out solvent heat treatment at 180 ℃ for 10h, and carrying out suction filtration, washing and freeze drying to obtain the graphene-iron oxide composite material; the preparation method comprises the steps of preparing slurry by taking a graphene-iron oxide composite material as a negative active material, taking conductive carbon black as a conductive agent, taking polyvinylidene fluoride as a binder, taking N-methyl pyrrolidone as a dispersing agent, 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 7:1: 2. Scraping and coating, vacuum drying at 50 ℃ for 6h, heating to 70 ℃ and vacuum drying for 12h to obtain the lithium ion capacitor cathode.
Comparative example 3
Ultrasonically dispersing 60mg of graphene oxide in 120mL of deionized water, wherein the ultrasonic power and the ultrasonic time are respectively 300W and 1h to obtain 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 polyvinyl amide under stirring (the mass ratio of the ferric trichloride to the polyvinyl amide is 1:10), finally transferring the dispersion liquid into a hydrothermal kettle, placing the hydrothermal kettle in an electric heating forced air drying oven, carrying out 180 ℃ solvent heat treatment for 10h, carrying out suction filtration, washing and freeze drying to obtain a graphene-iron oxide composite material; the preparation method comprises the steps of preparing slurry by taking a graphene-iron oxide composite material as a negative active material, taking conductive carbon black as a conductive agent, taking polyvinylidene fluoride as a binder, taking N-methyl pyrrolidone as a dispersing agent, 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. Scraping and coating, vacuum drying at 50 ℃ for 6h, heating to 70 ℃ and vacuum drying for 12h to obtain the lithium ion capacitor cathode.
Comparative example 4
Ultrasonically dispersing 1200mg of graphene oxide in 120mL of deionized water, wherein the ultrasonic power and the ultrasonic time 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 the hydrothermal kettle into an electrothermal blowing drying oven, carrying out 180 ℃ solvent heat treatment for 10h, carrying out suction filtration, washing and freeze drying, and obtaining the graphene-iron oxide composite material; mixing the graphene/ferric oxide composite material and glucose in an aqueous solution according to a mass ratio of 1-10, 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-iron oxide composite electrode material is used as a negative active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone 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. Obtained by blade coating and drying for 18h at 70 ℃.
The lithium ion capacitor negative electrodes prepared in examples 1 to 6 and comparative examples 1 to 4 were subjected to performance tests, and the results are shown in table 1:
TABLE 1 lithium ion capacitor negative electrode Performance Table
As can be seen from the results in table 1, when only the nano spindle-shaped iron oxide is used as the negative active material in comparative example 1 and only the graphene-iron oxide is used as the negative active material in comparative example 2, compared with the nano composite material obtained by compositing the iron oxide and the graphene and coating the carbon layer in the embodiment of the present invention as the negative active material of the lithium ion capacitor, the electrode material in the embodiment of the present invention has a higher specific capacity, and the rate capability and the cycle stability are both significantly better than those in the comparative example. In addition, in example 1, compared with comparative example 3, in the comparative example, since the carbon source, the iron source, the graphene oxide and the like are all mixed and then directly subjected to hydrothermal annealing treatment, in-situ growth and uniform distribution of the nano spindle-shaped iron oxide particles on the graphene flexible substrate cannot be guaranteed, volume expansion of the iron oxide in the charge-discharge cycle process cannot be effectively relieved, and the corresponding lithium ion capacitor negative electrode has significantly lower specific capacity and poorer rate and cycle performance. Compared with the comparative example 4, in the comparative example, a carbon source and graphene-iron oxide obtained after hydrothermal treatment are mixed in an aqueous solution and then directly dried at 90 ℃, a dried sample is attached to the wall of a beaker and is difficult to remove, so that loss is easily caused, particle agglomeration is easily caused by high-temperature drying, a three-dimensional porous structure formed by self-assembly of the original graphene is seriously shrunk, in a lithium ion capacitor, rapid infiltration of an electrolyte is difficult to rapidly realize, more ion transmission channels cannot be provided, and the multiplying power and the cycle performance of the corresponding lithium ion capacitor are poor.
In conclusion, the lithium ion capacitor cathode material with high specific capacity, high rate capability and good cycling stability can be obtained by compounding the iron oxide material with the graphene with high conductivity, high specific area and unique two-dimensional structure and further coating the graphene with the carbon layer.
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a carbon-coated graphene-iron oxide composite electrode material is characterized by comprising the following steps: the method comprises the following steps:
s1, ultrasonically dispersing graphene oxide in a solvent, adding an iron precursor and a morphology regulator, stirring and mixing, carrying out solvent heat treatment, carrying out suction filtration washing and freeze drying to obtain a graphene/iron oxide composite material;
and S2, mixing the graphene/iron oxide composite material obtained in the step S1 with a carbon source in an aqueous solution, freezing and drying the mixture, and then annealing the mixture at a high temperature in an inert gas to obtain the carbon-coated graphene-iron oxide composite electrode material.
2. The method for preparing a carbon-coated graphene-iron oxide composite electrode material according to claim 1, wherein the method comprises the following steps: in step S1, the iron precursor includes any one or more of ferric chloride, ferrous lactate, ferric citrate, ferric glycinate, ferric sulfate, and ferric nitrate.
3. The method for preparing a carbon-coated graphene-iron oxide composite electrode material according to claim 2, wherein the method comprises the following steps: in step S1, the solvent includes any one or more of water, absolute ethanol, isopropanol, ethylene glycol, propylene glycol, and glycerol.
4. The method for preparing the carbon-coated graphene-iron oxide composite electrode material according to claim 3, wherein the method comprises the following steps: in step S1, the morphology regulator is composed of sulfate and phosphate in a certain ratio, where 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, ammonium dihydrogen phosphate, sodium polyphosphate and ammonium polyphosphate.
5. The method for preparing the carbon-coated graphene-iron oxide composite electrode material according to claim 4, wherein the method comprises the following steps: in the step S1, the temperature of the solvent heat treatment is 160-220 ℃, and the time of the solvent heat treatment is 10-20 h.
6. The method for preparing the carbon-coated graphene-iron oxide composite electrode material according to claim 5, wherein the method comprises the following steps: in the step S1, the mass ratio of the graphene oxide to the iron precursor to the morphology regulator is (3-6) to 65: (1-2).
7. The method for preparing the carbon-coated graphene-iron oxide composite electrode material according to claim 6, wherein the method comprises the following steps: in step S2, the carbon source includes any one or more of dopamine hydrochloride, aniline, polyacrylamide, polyvinyl alcohol, chitosan, and glucose.
8. The method for preparing a carbon-coated graphene-iron oxide composite electrode material according to claim 7, wherein the method comprises the following steps: in step S2, the annealing temperature is 500-900 ℃, the annealing time is 1-10h, and the heating rate is 1-10 ℃/min.
9. A carbon-coated graphene-iron oxide composite electrode material is characterized in that: obtained by the production method according to any one of claims 1 to 8.
10. A lithium ion capacitor negative electrode, characterized in that: the carbon-coated graphene-iron oxide composite electrode material according to claim 9, 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 the following formula (7-8): (1-2): the mass ratio of (1-2) is prepared into slurry; 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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