CN113800503A - Porous graphene-loaded iron oxide composite negative electrode material and preparation method and application thereof - Google Patents
Porous graphene-loaded iron oxide composite negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a porous graphene loaded iron oxide composite negative electrode material and a preparation method and application thereof. Ultrasonically dispersing graphene oxide and carbon nano tubes in a solvent, adding a certain mass of iron precursor into a dispersion liquid, directly spraying the uniformly dispersed mixed liquid into a liquid nitrogen bath, quickly freezing the formed liquid drops into powder, freeze-drying, and performing microwave irradiation to obtain the porous graphene loaded iron oxide composite negative electrode material. The lithium ion capacitor negative electrode of the present invention uses the material as a negative electrode material. The nanometer iron oxide particle cladding is inside in order to solve the poor and volume expansion's of iron oxide conductivity problem inside the graphite alkene, and nanometer iron oxide particle still prevents the graphite alkene to pile up simultaneously, and the pore structure on the graphite alkene can accelerate the transportation of ion. The method of rapid spray freezing and microwave rapid reaction has the characteristics of short time consumption, low energy consumption and mass preparation, and overcomes various defects in the prior preparation process.
Description
Technical Field
The invention relates to the field of manufacturing of lithium ion battery devices, in particular to a porous graphene loaded iron oxide composite negative electrode material and a preparation method and application thereof.
Background
In the past research, most of the preparation methods of the iron oxide electrode material are hydrothermal or high-temperature heat treatment, the two methods are mature after years of development, but the problems of tedious process, long time consumption and high energy consumption always exist in the technology, and the problems of poor conductivity and huge volume expansion exist in the energy storage process of the iron oxide electrode material. Based on the problems, the porous graphene composite electrode material uniformly loaded with ferroferric oxide is obtained through a rapid spray freeze drying and microwave radiation graphene/iron precursor composite oxidation method and a rapid reaction. Rapid spray freeze drying to make high theoretical specific capacity ferroferric oxide (924mAh g)-1) Uniformly distributed on the holey graphene sheets. In addition, in the reaction, the preparation process is simple and convenient, the reaction time is only dozens of seconds, and the energy consumed in the microwave process is far less than that of a hydrothermal or heat treatment method. In the microwave reaction process, a large number of pore structures can be formed on the graphene sheet, which is beneficial to ion transportation. And after the reaction, the iron oxide particles are coated between the graphene layers, so that the problems of poor conductivity and huge volume expansion of the iron oxide can be effectively solved, and meanwhile, the iron oxide can also prevent the graphene from being stacked, so that the overall performance is enhanced. At present, iron oxide electrode materials are mostly used for lithium ion battery systems and super capacitor systems, and emerging lithium ion capacitors integrating the advantages of the two systems show great application potential.
By reasonably designing a preparation process, the composite electrode material of graphene and iron oxide is hopefully prepared to be applied to the negative electrode of a lithium ion capacitor so as to realize the function of the composite electrode material in the field of energy storage.
Disclosure of Invention
The invention aims to provide a porous graphene-loaded iron oxide composite negative 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 porous graphene loaded iron oxide composite negative electrode material, which comprises the following steps:
step S1, ultrasonically dispersing graphene oxide and carbon nano tubes in a solvent according to a certain mass ratio to prepare a dispersion liquid;
step S2, adding a certain mass of iron precursor into the dispersion liquid obtained in the step S1, stirring and mixing uniformly, directly spraying the obtained mixed liquid into a liquid nitrogen bath, and freeze-drying after the liquid drops are rapidly frozen into powder to obtain a precursor;
and S3, placing the precursor obtained in the step S2 in a crucible, and moving the crucible into a microwave oven to perform microwave irradiation according to preset power and preset time to obtain the porous graphene loaded iron oxide composite negative electrode material.
Further, in step S1, the mass ratio of the graphene oxide to the carbon nanotubes is 4: 0.25 to 1, and the concentration of the dispersion liquid is 0.1 to 10 mg/mL.
Further, in step S1, the ultrasonic power is 200W-1000W, and the ultrasonic time is 1 min-60 min.
Further, in step S1, the solvent includes any one or more of water, absolute ethanol, ethylene glycol, propylene glycol, and glycerol.
Further, in step S2, the iron precursor includes any one or more of ferric chloride, ferric nitrate, ferrous lactate, ferric citrate, ferric glycinate, and ferric sulfate.
Further, in step S2, the mass ratio of the iron precursor to the graphene oxide is (5-1): 1; the stirring time is 5-120 min, and the stirring speed is 100-3000 rpm.
Further, in step S2, the flow rate of the gas for spraying is 100 to 5000mL/min, and the diameter of the liquid droplet is 100 to 1000 μm.
Further, in step S3, the power of the microwave irradiation is 200-700W, and the time is 5-120S.
The invention also provides a porous graphene loaded iron oxide composite negative electrode material prepared by the preparation method.
The invention also provides a lithium ion capacitor negative electrode which comprises the porous graphene loaded iron oxide composite negative electrode material, wherein the porous graphene loaded iron oxide composite negative electrode material, conductive carbon black and polyvinylidene fluoride are prepared according to the following steps of (7-8): (1-2): grinding and mixing the components in the mass ratio of (1-2) in N-methyl pyrrolidone to prepare slurry; coating the slurry on a copper foil, and drying at 60 ℃ for 10-20h to obtain the copper-clad laminate.
The technical scheme provided by the invention has the beneficial effects that:
(1) the porous graphene loaded iron oxide composite negative electrode material provided by the invention is prepared by ultrasonically mixing graphene oxide and carbon nanotubes in a solvent according to a certain mass ratio, adding an iron precursor after uniformly mixing, and stirring to obtain a dispersion liquid with a preset concentration and uniform mixing. Finally spraying the dispersion liquid into liquid nitrogen in a spraying mode, and then freezing and drying. And (3) placing the solid matter after freeze drying in a crucible, and transferring the crucible into a microwave oven for microwave irradiation to obtain the composite negative electrode material. The method for spray liquid nitrogen freeze drying can greatly avoid uneven dispersion between the iron precursor and the graphene oxide/carbon nano tube in the freeze drying process, on one hand, the overall conductivity of the electrode material can be increased, and on the other hand, the carbon nano tube can relieve the stacking of graphene oxide sheet layers. After microwave irradiation, the obtained graphene has a large number of pore structures on the surface and iron oxide particles uniformly loaded on the surface. The pore structure can provide a shorter transmission path for ion transmission; and the graphene coated uniformly dispersed iron oxide can inhibit the volume expansion of the iron oxide in the charge-discharge cycle process and improve the conductivity of the iron oxide. In addition, the iron oxide can also play a role in interlayer barrier, further alleviating graphene stacking. According to the preparation method, the nano iron oxide particles are coated in the graphene, so that the problems of poor conductivity of the iron oxide and volume expansion in the charge-discharge cycle process are solved, meanwhile, the nano iron oxide particles can also block the stacking of the graphene, and the pore structure on the graphene can accelerate the transportation of ions. In addition, a way for quickly obtaining the porous graphene uniformly-loaded lithium iron oxide ion capacitor electrode material is provided by a method of quick spray freezing and quick microwave reaction, the method has the characteristics of short time consumption and low energy consumption in the preparation process and can be used for large-scale preparation, and various defects in the existing preparation process are overcome.
(2) The preparation method of the porous graphene loaded iron oxide composite negative electrode material is simple and practical, is designed by a targeted experiment from practical problems, solves the problems of difficulty in current preparation and energy storage mechanisms, is simple and practical, is low in cost, and is expected to realize batch production.
(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 photograph of example 4 of the present invention;
FIG. 2 is a transmission electron microscope photograph of example 4 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 porous graphene loaded iron oxide composite negative electrode material, which comprises the following steps:
step S1, ultrasonically dispersing graphene oxide and carbon nano tubes in a solvent according to a certain mass ratio to prepare a dispersion liquid;
step S2, adding a certain mass of iron precursor into the dispersion liquid obtained in the step S1, stirring and mixing uniformly, directly spraying the obtained mixed liquid into a liquid nitrogen bath, and after the liquid drops are rapidly frozen into powder, carrying out freeze drying to obtain a precursor of the porous graphene loaded iron oxide composite negative electrode material;
and step S3, placing the precursor solid matter of the porous graphene loaded iron oxide composite negative electrode material obtained in the step S2 in a crucible, and moving the crucible into a microwave oven to perform microwave irradiation according to preset power and preset time to obtain the porous graphene loaded iron oxide composite negative electrode material.
The method selects the carbon nano tube with excellent conductivity, improves the poorer conductivity of the ferric oxide on one hand, and can be inserted between graphene sheet layers as a one-dimensional nano material with a certain length on the other hand, so that the stacking of the graphene oxide sheet layers is avoided, a three-dimensional network structure is formed, the infiltration of electrolyte and the transmission of ions are accelerated, and the electrochemical performance is improved.
The spray liquid nitrogen freeze drying method adopted by the method can greatly avoid uneven dispersion between the iron precursor and the carbon nanotube-graphene matrix in the freeze drying process, on one hand, the overall conductivity of the electrode material can be increased, and on the other hand, the carbon nanotube can also relieve the stacking among graphene oxide sheet layers. Due to the fact that the graphene sheet layers are stacked again when the graphene sheet layers are dried at high temperature, and due to the fact that metal salts are separated out when the graphene sheet layers are frozen by an ordinary refrigerator, the metal salts are seriously unevenly distributed on the carbon nanotube-graphene substrate. Therefore, the method of rapid spray freezing and freeze drying is selected to ensure that the metal salt is uniformly distributed on the carbon nanotube-graphene substrate, so that the high conductivity of the carbon nanotube-graphene substrate is fully utilized, a buffering space is effectively provided for the ferric oxide in the circulation process, and the volume expansion of the ferric oxide is relieved. In the case of brine, there is an ice-salt eutectic point during solidification, and the corresponding concentration is called the eutectic concentration, which is equivalent to the freezing of the entire brine solution into a block of ice-salt crystals. When the brine concentration exceeds the eutectic concentration, if the brine concentration is not changed, salt crystals, rather than ice, will precipitate from the solution when the temperature drops below the freezing point corresponding to that concentration. If a common refrigerator freezing mode is adopted, the solid surface obtained after complete freezing is obviously precipitated by metal salt on a brown black graphene ice block, uniform loading of ferroferric oxide on graphene after microwave irradiation cannot be realized, and the corresponding lithium ion capacitor has low negative electrode specific capacity and poor rate capability.
And after microwave radiation, the obtained graphene surface can be obviously found to have a large number of pore structures and indicate uniformly loaded iron oxide particles. The pore structure can provide a shorter transmission path for ion transmission; and the graphene coated uniformly dispersed iron oxide can inhibit the volume expansion of the iron oxide in the charge-discharge cycle process and improve the conductivity of the iron oxide. In addition, the iron oxide can also play a role in interlayer barrier, further alleviating graphene stacking.
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 500mg of graphene oxide and 31.25mg of carbon nano tubes in 500mL of deionized water, wherein the ultrasonic power and the ultrasonic time are respectively 200W and 60min, and obtaining uniformly mixed dispersion liquid of the graphene oxide and the carbon nano tubes; adding 500mg of ferric chloride into the dispersion liquid, stirring for 5min at 100rpm, uniformly mixing, directly spraying the uniformly dispersed mixed liquid into a liquid nitrogen bath at the gas flow rate of 100mL/min, quickly freezing 100-micron droplets into powder, and freeze-drying to obtain a precursor of the porous graphene loaded iron oxide composite negative electrode material; and (3) placing the frozen and dried solid substance in a crucible, and transferring the crucible into a microwave oven to perform microwave irradiation for 5s at 200W to obtain the porous graphene loaded iron oxide composite negative electrode material.
Example 2
Ultrasonically dispersing 400mg of graphene oxide and 100mg of carbon nano tube in 40mL of deionized water, wherein the ultrasonic power and the ultrasonic time are respectively 1000W and 1min, so as to obtain uniformly mixed dispersion liquid of the graphene oxide and the carbon nano tube, and obtain uniformly mixed dispersion liquid of the graphene oxide and the carbon nano tube; adding 400mg of ferric chloride into the dispersion liquid, stirring for 5min at 100rpm, uniformly mixing, directly spraying the uniformly dispersed mixed liquid into a liquid nitrogen bath at a gas flow rate of 5000mL/min, quickly freezing 1000-micron droplets into powder, and freeze-drying to obtain a precursor of the porous graphene/iron oxide composite negative electrode material; and placing the frozen and dried solid substance in a crucible, and moving the crucible into a microwave oven to perform microwave irradiation for 120s at 700W to obtain the porous graphene loaded iron oxide composite negative electrode material.
Example 3
Ultrasonically dispersing 400mg of graphene oxide and 25.0mg of carbon nano tube in 200mL of deionized water, wherein the ultrasonic power and the ultrasonic time are respectively 600W and 10min, and obtaining uniformly mixed dispersion liquid of the graphene oxide and the carbon nano tube; adding 2000mg of ferric chloride into the dispersion liquid, stirring for 10min at 1500rpm, after uniform mixing, directly spraying the uniformly dispersed mixed liquid into a liquid nitrogen bath at a gas flow rate of 2500mL/min, quickly freezing 100-micron droplets into powder, and then freeze-drying to obtain a precursor of the porous graphene/ferric oxide composite negative electrode material; and (3) placing the frozen and dried solid substance in a crucible, and moving the crucible into a microwave oven to perform microwave irradiation for 60s at 700W to obtain the porous graphene loaded iron oxide composite negative electrode material.
Example 4
Ultrasonically dispersing 600mg of graphene oxide and 37.5mg of carbon nano tube in 600mL of deionized water, wherein the ultrasonic power and the ultrasonic time are respectively 600W and 10min, and obtaining uniformly mixed dispersion liquid of the graphene oxide and the carbon nano tube; adding 1800mg of ferric chloride into the dispersion liquid, stirring for 10min at 1500rpm, after uniform mixing, directly spraying the uniformly dispersed mixed liquid into a liquid nitrogen bath at a gas flow rate of 2500mL/min, quickly freezing 300-micron droplets into powder, and then freeze-drying to obtain a precursor of the porous graphene/ferric oxide composite negative electrode material; and (3) placing the frozen and dried solid substance in a crucible, and moving the crucible into a microwave oven to perform microwave irradiation for 60s at 700W to obtain the porous graphene loaded iron oxide composite negative electrode material.
Example 5
Ultrasonically dispersing 2000mg of graphene oxide and 50.0mg of carbon nano tube in 200mL of deionized water, wherein the ultrasonic power and the ultrasonic time are respectively 600W and 10min, and obtaining a uniformly mixed dispersion liquid of the graphene oxide and the carbon nano tube; adding 4000mg of ferric chloride into the dispersion liquid, stirring for 120min at 3000rpm, after uniform mixing, directly spraying the uniformly dispersed mixed liquid into a liquid nitrogen bath at a gas flow rate of 5000mL/min, quickly freezing 1000-micron droplets into powder, and then freeze-drying to obtain a precursor of the porous graphene/iron oxide composite negative electrode material; and (3) placing the frozen and dried solid substance in a crucible, and moving the crucible into a microwave oven to perform microwave irradiation for 60s at 700W to obtain the porous graphene loaded iron oxide composite negative electrode material.
Comparative example 1
Ultrasonically dispersing 600mg of graphene oxide in 600mL of deionized water, wherein the ultrasonic power and the ultrasonic time are respectively 600W and 10min, and obtaining a uniformly mixed graphene oxide dispersion liquid; adding 1800mg of ferric chloride into the dispersion liquid, stirring for 15min at 1500rpm, uniformly mixing, directly spraying the uniformly dispersed mixed liquid into a liquid nitrogen bath at the gas flow rate of 2500mL/min, quickly freezing 300-micron droplets into powder, and freeze-drying to obtain a precursor of the porous graphene/ferric oxide composite negative electrode material; and (3) placing the frozen and dried solid substance in a crucible, and moving the crucible into a microwave oven to perform microwave irradiation for 60s at 700W to obtain the porous graphene loaded iron oxide composite negative electrode material.
Comparative example 2
Dispersing 600mg of graphene oxide and 37.5mg of carbon nano tube in 600mL of deionized water by pulse ultrasonic dispersion, wherein the ultrasonic power and the ultrasonic time are respectively 600W and 10min, and obtaining a dispersion liquid of the graphene oxide and the carbon nano tube which are uniformly mixed; stirring the dispersion liquid at 1500rpm for 15min, directly spraying the uniformly dispersed mixed liquid into a liquid nitrogen bath at a gas flow rate of 2500mL/min, quickly freezing liquid drops of 300 mu m into powder, and freeze-drying to obtain a precursor of the composite negative electrode material; and (3) placing the frozen and dried solid substance in a crucible, and moving the crucible into a microwave oven to perform microwave irradiation for 60s at 700W to obtain the porous graphene composite negative electrode material.
Comparative example 3
Ultrasonically dispersing 600mg of graphene oxide and 37.5mg of carbon nano tube in 600mL of deionized water, wherein the ultrasonic power and the ultrasonic time are respectively 600W and 10min, and obtaining a uniformly mixed graphene oxide dispersion liquid; adding 1800mg of ferric chloride into the dispersion liquid, stirring for 120min at 1500rpm, uniformly mixing, directly placing the uniformly dispersed mixed liquid into a common refrigerator, completely freezing, then transferring into a freeze dryer for freeze drying, placing the freeze-dried solid substance into a crucible, transferring into a microwave oven, and performing microwave irradiation for 60s at 700W to obtain the graphene loaded ferric oxide composite negative electrode material.
The lithium ion capacitor negative electrode materials prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to performance tests, and the results are shown in table 1:
TABLE 10.1A/g and 4A/g electrochemical Performance test results
As can be seen from the above examples and comparative example 1, the amount of different iron precursors has a great influence on the capacity of the final electrode material as a positive electrode and a negative electrode. The iron precursor and the carbon nano tube with proper dosage can improve the overall conductivity of the material, and can play a role in blocking between layers of graphene, thereby effectively improving the capacity and rate capability of the negative electrode. And, by comparing example 4 with comparative example 2, after microwave reduction, as shown in fig. 1 and 2: the iron oxide granule cladding can effectually alleviate the iron oxide poor conductivity and the huge problem of volume expansion between graphite alkene layer, and the iron oxide also can prevent that graphite alkene from piling up simultaneously, reinforcing wholeness ability. Compared with the traditional hydrothermal treatment or high-temperature heat treatment method, the method can greatly save the time spent in the preparation process and reduce the preparation energy consumption. Compared with the comparative example 3, in the comparative example, because a common refrigerator freezing mode is adopted, the solid surface obtained by freezing is obviously precipitated by metal salt on a brown black graphene ice block, uniform loading of ferroferric oxide on graphene after microwave is not realized, and the corresponding lithium ion capacitor has low specific capacity of the negative electrode and poor rate capability.
The invention also provides a lithium ion capacitor cathode, and the porous graphene loaded iron oxide composite cathode material is used as a cathode material of a lithium ion capacitor electrode.
In conclusion, the nano iron oxide particles are coated in the graphene, so that the problems of poor conductivity and volume expansion of the iron oxide are solved, the nano iron oxide particles can prevent the graphene from being stacked, and the pore structure on the graphene can accelerate the transportation of ions. In addition, a way for quickly obtaining the porous graphene uniformly-loaded lithium iron oxide ion capacitor electrode material is provided by a method of quick spray freezing and quick microwave reaction, the method has the characteristics of short time consumption and low energy consumption in the preparation process and can be used for large-scale preparation, and various defects in the existing preparation process are overcome.
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 porous graphene loaded iron oxide composite negative electrode material is characterized by comprising the following steps: the method comprises the following steps:
s1, ultrasonically dispersing graphene oxide and carbon nano tubes in a solvent according to a certain mass ratio to prepare a dispersion liquid;
s2, adding a certain mass of iron precursor into the dispersion liquid obtained in the step S1, stirring and mixing uniformly, directly spraying the obtained mixed liquid into a liquid nitrogen bath, and freeze-drying after the liquid drops are rapidly frozen into powder to obtain a precursor;
and S3, placing the precursor obtained in the step S2 in a crucible, moving the crucible into a microwave oven, and performing microwave irradiation according to preset power and preset time to obtain the porous graphene loaded iron oxide composite negative electrode material.
2. The preparation method of the porous graphene-supported iron oxide composite anode material according to claim 1, characterized by comprising the following steps: in step S1, the mass ratio of the graphene oxide to the carbon nanotubes is 4: 0.25-1, and the concentration of the dispersion liquid is 0.1-10 mg/mL.
3. The preparation method of the porous graphene-supported iron oxide composite anode material according to claim 2, characterized by comprising the following steps: in step S1, the ultrasonic power is 200W-1000W, and the ultrasonic time is 1 min-60 min.
4. The preparation method of the porous graphene-supported iron oxide composite anode material according to claim 3, wherein the preparation method comprises the following steps: in step S1, the solvent includes any one or more of water, absolute ethanol, ethylene glycol, propylene glycol, and glycerol.
5. The preparation method of the porous graphene-supported iron oxide composite anode material according to claim 4, wherein the preparation method comprises the following steps: in step S2, the iron precursor includes any one or more of ferric chloride, ferric nitrate, ferrous lactate, ferric citrate, ferric glycinate, and ferric sulfate.
6. The preparation method of the porous graphene-supported iron oxide composite anode material according to claim 5, wherein the preparation method comprises the following steps: in step S2, the mass ratio of the iron precursor to the graphene oxide is (5-1): 1; the stirring time is 5-120 min, and the stirring speed is 100-3000 rpm.
7. The preparation method of the porous graphene-supported iron oxide composite anode material according to claim 6, wherein the preparation method comprises the following steps: in step S2, the flow rate of the sprayed gas is 100-5000 ml/min, and the diameter of the liquid drops is 100-1000 μm.
8. The preparation method of the porous graphene-supported iron oxide composite anode material according to claim 7, wherein the preparation method comprises the following steps: in step S3, the power of the microwave irradiation is 200-700W, and the time is 5-120S.
9. The porous graphene loaded iron oxide composite negative 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 porous graphene-supported iron oxide composite negative electrode material according to claim 9, wherein the lithium ion capacitor negative electrode is prepared from the porous graphene-supported iron oxide composite negative electrode material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of (7-8): (1-2): grinding and mixing the components in the mass ratio of (1-2) in N-methyl pyrrolidone to prepare slurry; coating the slurry on a copper foil, and drying at 60 ℃ for 10-20h to obtain the copper-clad laminate.
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