CN114784227A - Graphene/metal oxide composite nano material, preparation method and application thereof, electrode plate and application thereof - Google Patents

Graphene/metal oxide composite nano material, preparation method and application thereof, electrode plate and application thereof Download PDF

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CN114784227A
CN114784227A CN202210377798.6A CN202210377798A CN114784227A CN 114784227 A CN114784227 A CN 114784227A CN 202210377798 A CN202210377798 A CN 202210377798A CN 114784227 A CN114784227 A CN 114784227A
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graphene
acetate
transition metal
metal oxide
preparation
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CN114784227B (en
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张熊
刘文杰
马衍伟
李晨
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Institute of Electrical Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals

Abstract

The invention provides a graphene/metal oxide composite nano material, a preparation method and application thereof, an electrode plate and application thereof, and relates to the technical field of nano materials. The preparation method of the graphene/metal oxide composite nano material provided by the invention comprises the following steps: mixing the graphene oxide dispersion liquid with a transition metal acetate solution, and freeze-drying to obtain graphene oxide/transition metal acetate precursor powder; and carrying out heat treatment on the graphene oxide/transition metal acetate precursor powder under a protective atmosphere to obtain the graphene/metal oxide composite nanomaterial. The preparation method provided by the invention is simple and easy for large-scale production, and the obtained graphene/metal oxide composite nano material has good structural stability and excellent lithium storage performance.

Description

Graphene/metal oxide composite nano material, preparation method and application thereof, electrode plate and application thereof
Technical Field
The invention relates to the technical field of nano materials, in particular to a graphene/metal oxide composite nano material, a preparation method and application thereof, and an electrode plate and application thereof.
Background
The metal oxide (such as MnO, CoO, NiO, ZnO and the like) is used as a typical conversion type cathode material, the theoretical specific capacity is up to 500-1200 mAh/g, the voltage platform is moderate, the cost is low, and the metal oxide can be used as a high-performance cathode of a lithium ion battery and a lithium ion capacitor and has a wide application prospect. However, most metal oxides have low electronic conductivity, and the internal structure is easily rearranged during charging and discharging, so that the capacity and the cycle performance are easily attenuated, thereby preventing further commercial application. To address these problems, current traditional solutions include rational design of low dimensional structures (nanoparticles, nanowires, or nanoarrays), compounding highly conductive carbon materials (such as graphene or porous carbon materials), and introducing defects or heteroatoms in metal oxides. Most of the research focuses on obtaining metal oxide/carbon composite materials through complicated synthetic routes, thereby reducing pulverization or agglomeration of the metal oxide materials to some extent and accelerating reaction kinetics of the electrodes.
However, these methods add significant cost and difficulty to the scale-up of the preparation. In addition, the conventional method of conductive carbon layer/framework composite metal oxide is through physical contact rather than chemical interface interaction, which results in that the active material is easy to peel off during long-term circulation and the stability of the electrode material is poor.
Disclosure of Invention
The invention aims to provide a graphene/metal oxide composite nano material, a preparation method and application thereof, an electrode plate and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a graphene/metal oxide composite nano material, which comprises the following steps:
mixing the graphene oxide dispersion liquid with a transition metal acetate solution, and freeze-drying to obtain graphene oxide/transition metal acetate precursor powder;
and carrying out heat treatment on the graphene oxide/transition metal acetate precursor powder under a protective atmosphere to obtain the graphene/metal oxide composite nano material.
Preferably, the concentration of the graphene oxide in the graphene oxide dispersion liquid is 2-8 g/L.
Preferably, the transition metal acetate in the transition metal acetate solution comprises one or more of manganese acetate, cobalt acetate, nickel acetate, ferrous acetate, copper acetate and zinc acetate.
Preferably, the concentration of the transition metal ions in the transition metal acetate solution is 0.01-0.1 mol/L.
Preferably, the mixing of the graphene oxide dispersion liquid and the transition metal acetate solution is performed under a stirring condition at room temperature; the room-temperature stirring time is 2-4 h.
Preferably, the temperature of the heat treatment is 300-600 ℃, and the heat preservation time is 1-4 h.
The invention provides a graphene/metal oxide composite nano material prepared by the preparation method in the technical scheme, which comprises graphene and metal oxide nano particles dispersed on the surface of the graphene; the metal oxide nanoparticles are connected with the graphene through metal-O-C chemical bonds.
The invention provides an application of the graphene/metal oxide composite nano material in a lithium ion capacitor or a lithium ion battery.
The invention provides an electrode plate, which comprises a conductive substrate and a conductive layer coated on the surface of the conductive substrate; the conducting layer comprises the graphene/metal oxide composite nano material, conducting carbon black and polyvinylidene fluoride.
The invention provides the application of the electrode plate in the technical scheme in a lithium ion capacitor or a lithium ion battery.
The invention provides a preparation method of a graphene/metal oxide composite nano material, which comprises the following steps: mixing the graphene oxide dispersion liquid with a transition metal acetate solution, and freeze-drying to obtain graphene oxide/transition metal acetate precursor powder; and carrying out heat treatment on the graphene oxide/transition metal acetate precursor powder under a protective atmosphere to obtain the graphene/metal oxide composite nano material. In the invention, the surface of the graphene oxide has rich oxygen-containing functional groups, so that the graphene oxide is electronegative, can electrostatically adsorb metal ions, is subjected to heat treatment after freeze drying, and forms metal oxide on the surface of the three-dimensional graphene in situ. The graphene can be used as a nucleation site of the metal oxide, and can prevent the agglomeration among the metal oxides, so as to obtain the uniformly dispersed metal oxide nanoparticles. According to the invention, the metal acetate has a proper decomposition temperature (between 200 and 400 ℃), the decomposition process is safe, and the graphene oxide can be reduced into graphene in the heat treatment process.
The graphene/metal oxide composite nano material prepared by the invention is chemically bonded through strong metal-O-C, the high-conductivity graphene can make up the defect of poor intrinsic electronic conductivity of the metal oxide, the problem of volume expansion of the metal oxide in the circulating process is relieved, and meanwhile, the characteristic of high specific capacity of the metal oxide is combined, and the lithium storage performance and the circulating life of the composite material can be effectively improved through the synergistic effect of the graphene and the metal oxide.
In the mixing, freeze drying and subsequent heat treatment processes adopted by the invention, a precipitator, a reducing agent and the like are not required to be added, other impurities are not introduced, a washing or purification process is not required, the high-purity graphene/metal oxide composite nano material can be directly obtained, the process flow is simple, convenient and rapid, the environment is friendly, and the large-scale preparation is facilitated.
Drawings
FIG. 1 is an X-ray diffraction pattern of graphene/MnO composite nanomaterial prepared in example 1, comparative example 1 and comparative example 2, MnO and graphene;
FIG. 2 is an X-ray photoelectron spectrum (C1 s) of the graphene/MnO composite nanomaterial prepared in example 1;
FIG. 3 is an X-ray photoelectron spectrum (O1 s) of the graphene/MnO composite nanomaterial prepared in example 1;
FIG. 4 is a scanning electron microscope photograph of the graphene/MnO composite nanomaterial prepared in example 1;
FIG. 5 is a TEM image of the graphene/MnO composite nanomaterial prepared in example 1;
fig. 6 is a graph of rate performance of graphene/MnO electrode sheets, and graphene electrode sheets prepared using example 1, comparative example 1, and comparative example 2;
fig. 7 is a graph of cycle performance for graphene/MnO electrode sheets, and graphene electrode sheets prepared using example 1, comparative example 1, and comparative example 2.
Detailed Description
The invention provides a preparation method of a graphene/metal oxide composite nano material, which comprises the following steps:
mixing the graphene oxide dispersion liquid with a transition metal acetate solution, and freeze-drying to obtain graphene oxide/transition metal acetate precursor powder;
and carrying out heat treatment on the graphene oxide/transition metal acetate precursor powder under a protective atmosphere to obtain the graphene/metal oxide composite nano material.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
According to the preparation method, the graphene oxide dispersion liquid and the transition metal acetate solution are mixed, and freeze-dried to obtain graphene oxide/transition metal acetate precursor powder. In the invention, the concentration of the graphene oxide in the graphene oxide dispersion liquid is preferably 2-8 g/L, and more preferably 4-6 g/L. The preparation method of the graphene oxide is not particularly described, and a conventional preparation method of the graphene oxide can be adopted by a person skilled in the art. In the specific embodiment of the invention, the modified Hummer's method is adopted to prepare the graphite oxide by taking graphite as a raw material. In the present invention, the method for preparing the graphene oxide dispersion preferably includes: and mixing graphite oxide with water, and performing ultrasonic treatment to obtain a graphene oxide dispersion liquid. In the invention, the time of ultrasonic treatment is preferably 90-120 min, and more preferably 100-110 min; the ultrasonic treatment disperses the graphite oxide into few layers or a single layer; the number of layers of the graphene oxide is preferably 1-10.
In the present invention, the transition metal acetate in the transition metal acetate solution preferably includes one or more of manganese acetate, cobalt acetate, nickel acetate, ferrous acetate, copper acetate, and zinc acetate. In the invention, the concentration of the transition metal ions in the transition metal acetate solution is preferably 0.01-0.1 mol/L, and more preferably 0.02-0.5 mol/L. In the present invention, the preparation method of the transition metal acetate solution preferably includes: the transition metal acetate and water are mixed and stirred until completely dissolved.
In the present invention, the water is preferably deionized water.
In the present invention, the mass of graphene oxide in the graphene oxide dispersion liquid and the molar ratio of transition metal ions in the transition metal acetate solution are preferably 1 g: 0.5 to 10mmol, more preferably 1 g: 2-6 mmol.
In the present invention, the mixing of the graphene oxide dispersion and the transition metal acetate solution is preferably performed under a stirring condition at room temperature; the room-temperature stirring time is preferably 2-4 h, and more preferably 3 h. In the mixing process, metal ions with positive charges are adsorbed on graphene oxide with negative charges and serve as nucleation sites of metal oxide nanoparticles in the subsequent heat treatment process, and metal-O-C bonds are formed in situ. Due to the existence of the graphene substrate, the agglomeration of nano metal oxide particles is effectively prevented, more active sites are provided for the insertion of lithium ions by combining the high-conductivity graphene, and the stability of a heterostructure is also ensured.
In the present invention, the temperature of the freeze-drying is preferably-30 to-55 ℃, more preferably-35 to-45 ℃; the freeze drying time is preferably 20-30 h, and more preferably 24 h. According to the invention, the graphene oxide/transition metal acetate precursor powder with a three-dimensional structure can be obtained by adopting freeze drying.
After graphene oxide/transition metal acetate precursor powder is obtained, the graphene oxide/transition metal acetate precursor powder is subjected to heat treatment under a protective atmosphere to obtain the graphene/metal oxide composite nanomaterial. Before the heat treatment, the present invention preferably further comprises: and grinding the graphene oxide/transition metal acetate precursor powder. In the present invention, the grinding is preferably performed in a mortar, and the time for the grinding is not particularly limited in the present invention, and the graphene oxide/transition metal acetate precursor powder may be ground to be uniform without agglomeration of large blocks.
In the present invention, the protective atmosphere is preferably a nitrogen atmosphere or an argon atmosphere.
In the invention, the temperature of the heat treatment is preferably 300-600 ℃, and more preferably 400-500 ℃; the heating rate from room temperature to the heat treatment temperature is preferably 3-7 ℃/min, and more preferably 5 ℃/min; the heat treatment is preferably carried out for 1-4 h, and more preferably for 2-3 h. In the present invention, the heat treatment is preferably performed in a tube furnace; according to the invention, the graphene oxide/transition metal acetate precursor powder is preferably placed in a corundum crucible and subjected to heat treatment in a tubular furnace. In the heat treatment process, the graphene oxide is effectively reduced into graphene, and the adsorbed metal ions form metal oxide nanoparticles in situ and are connected with the graphene through a metal-O-C chemical bond.
The invention also provides the graphene/metal oxide composite nano material prepared by the preparation method in the technical scheme, which comprises graphene and metal oxide nano particles dispersed on the surface of the graphene; the metal oxide nanoparticles are connected with the graphene through metal-O-C chemical bonds. In the present invention, the graphene has a corrugated structure. In the invention, the size of the metal oxide nanoparticles is preferably 100-700 nm, and more preferably 200-500 nm. In the present invention, the metal oxide nanoparticles have a nano cabbage-type structure. In the present invention, the mass of the metal oxide nanoparticles is preferably 10 to 70 wt%, and more preferably 20 to 50 wt% of the total mass of the graphene/metal oxide composite nanomaterial.
According to the graphene/metal oxide composite nanomaterial prepared by the invention, the graphene is mutually crosslinked to construct a three-dimensional conductive network, and meanwhile, the metal oxide has a nano-sized structure and is connected with the graphene through chemical bonds to form a heterostructure, so that the graphene/metal oxide composite nanomaterial has excellent structural stability and lithium storage performance.
The invention provides an application of the graphene/metal oxide composite nano material in a lithium ion capacitor or a lithium ion battery. The graphene/metal oxide composite nano material provided by the invention has abundant lithium storage sites, a stable structure and rapid lithium ion transmission capability.
The invention provides an electrode plate, which comprises a conductive substrate and a conductive layer coated on the surface of the conductive substrate; the conducting layer comprises the graphene/metal oxide composite nano material, conducting carbon black and polyvinylidene fluoride. In the present invention, the thickness of the conductive layer is preferably 10 to 100 μm.
In the present invention, the method for preparing the electrode sheet preferably comprises the following steps: mixing a graphene/metal oxide composite nano material, conductive carbon black, polyvinylidene fluoride and a solvent to obtain slurry; and coating the slurry on the surface of a conductive substrate to obtain the electrode plate.
In the invention, the mass ratio of the graphene/metal oxide composite nano material to the conductive carbon black to the polyvinylidene fluoride (PVDF) is preferably (7-9): (0.5-1.5): (0.5 to 1.5), more preferably (7.5 to 8.5): (0.8-1.2): (0.8 to 1.2), most preferably 8:1: 1.
in the present invention, the solvent is preferably a pyrrolidone-based solvent, and the pyrrolidone-based solvent preferably includes N-methylpyrrolidone, 2-pyrrolidone, or N-ethylpyrrolidone. The amount of the solvent used is not particularly limited, and in the embodiment of the present invention, the ratio of the mass of the graphene/metal oxide composite nanomaterial to the volume of the solvent is preferably 1 g: 20 mL.
In the invention, the graphene/metal oxide composite nanomaterial, the conductive carbon black, the polyvinylidene fluoride and the solvent are preferably mixed by stirring, and the speed and time of stirring and mixing are not particularly limited, so that the raw materials can be uniformly mixed.
In the present invention, the conductive substrate preferably comprises a copper foil or a carbon-coated copper foil.
The coating method of the present invention is not particularly limited, and a coating method known to those skilled in the art may be used. In the present invention, the coating amount of the slurry is preferably 0.001 to 0.01g/cm based on the amount of the graphene/metal oxide composite nanomaterial2More preferably 0.004 to 0.006g/cm2。
After the coating, the invention preferably further comprises drying the coated wet film to obtain the electrode plate. In the present invention, the drying is preferably performed by vacuum drying; the drying temperature is preferably 80-130 ℃, and more preferably 100-120 ℃; the drying time is preferably 5-15 h, and more preferably 6-12 h.
The invention provides the application of the electrode plate in the technical scheme in a lithium ion capacitor or a lithium ion battery.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Placing 1g of graphite oxide powder in 250mL of deionized water, and ultrasonically stirring for 4h at room temperature to obtain a uniformly dispersed 4g/L few-layer graphene oxide dispersion liquid;
(2) under the condition of stirring at room temperature, mixing the 4g/L few-layer graphene oxide dispersion liquid with 0.02 mol/L manganese acetate solution (the molar ratio of the mass of graphene oxide to manganese acetate in the manganese acetate solution is 1 g: 5mmol), stirring at room temperature for 3h, and then freeze-drying at-40 ℃ for 24h to obtain graphene oxide/manganese acetate precursor powder;
(3) and uniformly grinding the graphene oxide/manganese acetate precursor powder in a mortar, uniformly paving the powder in a corundum crucible, placing the corundum crucible in a tubular furnace, heating to 500 ℃ at a speed of 5 ℃/min under the protection of argon, carrying out heat treatment for 2h, and cooling to room temperature to obtain the graphene/MnO composite nano material.
The X-ray diffraction spectrum of the graphene/MnO composite nanomaterial prepared in this example is shown in fig. 1. As can be seen from FIG. 1, the graphene/MnO composite nanomaterial prepared by the present invention has characteristics of good crystallinity and high purity.
An X-ray photoelectron energy spectrum of the graphene/MnO composite nanomaterial prepared in this embodiment is shown in fig. 2 to 3, where C1 s is energy of a measured photoelectron excited by a 1s orbital electron in a carbon atom, and O1 s is energy of a measured photoelectron excited by a 1s orbital electron in an oxygen atom. As can be seen from fig. 2, after the graphene oxide is thermally reduced, the C — O bond is greatly weakened and converted into graphene. As can be seen from FIG. 3, after the graphene/MnO composite nanomaterial is reduced at high temperature, Mn-O-C bonds appear, and the MnO nanoparticles and the graphene are connected by chemical bonds, so that the stability of the heterostructure material is improved.
The scanning electron micrograph of the graphene/MnO composite nanomaterial prepared in this example is shown in FIG. 4. As can be seen from fig. 4, the MnO material has a structure similar to that of a nano cabbage, and is uniformly dispersed on graphene having a surface with a rich wrinkle structure.
The transmission electron microscope image of the graphene/MnO composite nanomaterial prepared in this example is shown in FIG. 5. As can be seen from fig. 5, the MnO particle size of the nano cabbage-type structure is around 350nm, evenly anchored on the graphene.
Example 2
The same as example 1 except that the mass of graphene oxide in step (2) and the molar ratio of manganese acetate in the manganese acetate solution were 1 g: 0.5 mmol.
Example 3
The same as example 1 except that the mass of graphene oxide in step (2) and the molar ratio of manganese acetate in the manganese acetate solution were 1 g: 1mmol of the total amount of the reaction solution.
Example 4
The same as example 1 except that the mass of graphene oxide in step (2) and the molar ratio of manganese acetate in the manganese acetate solution were 1 g: 2.5 mmol.
Example 5
The method is basically the same as example 1, except that the mass of graphene oxide in the step (2) and the molar ratio of manganese acetate in the manganese acetate solution are 1 g: 7.5 mmol.
Example 6
The method is basically the same as example 1, except that the mass of graphene oxide in the step (2) and the molar ratio of manganese acetate in the manganese acetate solution are 1 g: 10 mmol.
Example 7
The method is basically the same as example 1, except that the mass of graphene oxide in the step (2) and the molar ratio of manganese acetate in the manganese acetate solution are 1 g: 5mmol of the total weight of the solution; the heat treatment in step (3) was 400 ℃.
Example 8
The method is basically the same as example 1, except that the mass of graphene oxide in the step (2) and the molar ratio of manganese acetate in the manganese acetate solution are 1 g: 5mmol of the total weight of the solution; the heat treatment in step (3) was 600 ℃.
Example 9
The same as example 1 except that the mass of graphene oxide in step (2) and the molar ratio of manganese acetate in the manganese acetate solution were 1 g: 5mmol of the active carbon; the rate of temperature rise to the heat treatment temperature in step (3) is 3 ℃/min.
Example 10
The same as example 1 except that the mass of graphene oxide in step (2) and the molar ratio of manganese acetate in the manganese acetate solution were 1 g: 5mmol of the active carbon; the heating rate of the temperature rise to the heat treatment temperature in the step (3) is 7 ℃/min.
Comparative example 1
The same as example 1 except that the step (1) was omitted, the graphene oxide solution was not added in the step (2), and the prepared material was labeled MnO.
Comparative example 2
The same as example 1 except that the manganese acetate solution was not added in step (2), and the material thus prepared was labeled as graphene.
Example 11
Substantially the same as example 1, except that the transition metal acetate added in step (2) was cobalt acetate, resulting in a graphene/CoO composite nanomaterial.
Example 12
The method is basically the same as example 1, except that the transition metal acetate added in the step (2) is nickel acetate, and a graphene/NiO composite nano material is obtained.
Example 13
Substantially the same as example 1, except that the transition metal acetate added in step (2) is ferrous acetate to give graphene/Fe2O3A composite nanomaterial.
Example 14
Substantially the same as example 1 except that the transition metal acetate added in step (2) was copper acetate, resulting in a graphene/CuO composite nanomaterial.
Example 15
Substantially the same as example 1 except that the transition metal acetate added in step (2) was zinc acetate, resulting in a graphene/ZnO composite nanomaterial.
Example 16
Basically the same as example 1, except that the transition metal acetates added in step (2) were nickel acetate and cobalt acetate, resulting in a graphene/NiO/CoO composite nanomaterial.
Example 17
Substantially the same as example 1 except that the transition metal acetate added in step (2) was manganese acetate and cobalt acetate, resulting in a graphene/MnO/CoO composite nanomaterial.
Example 18
Substantially the same as example 1, except that the transition metal acetate added in step (2) was copper acetate, zinc acetate and ferrous acetate to give graphene/CuO/ZnO/Fe2O3A composite nanomaterial.
Application example
The active materials (graphene/metal oxide composite nanomaterial, MnO and graphene), conductive carbon black, polyvinylidene fluoride (PVDF) and N-methyl pyrrolidone prepared in examples 1, 4 and 6, comparative example 1 and 2 and examples 11 to 18 were respectively stirred, mixed, coated on a copper foil, and vacuum-dried to obtain an electrode sheet, wherein the mass ratio of the active material, the conductive carbon black and the PVDF is 8:1:1, and the rate performance graphs of the electrode sheet are shown in table 1, fig. 6 and fig. 7.
Wherein, graphene/MnO-1 in table 1 and graphene/MnO in fig. 6 to 7 both represent the mass of graphene oxide and the molar ratio of manganese acetate in manganese acetate solution of 1g in example 1: 5mmol of the active carbon; graphene/MnO-2 represents the mass of graphene oxide in example 4 and the molar ratio of manganese acetate in manganese acetate solution of 1 g: 2.5 mmol; graphene/MnO-3 represents the mass of graphene oxide in example 6 and the molar ratio of manganese acetate in manganese acetate solution of 1 g: 10mmol of the total weight of the solution; MnO stands for comparative example 1; graphene represents comparative example 2; graphene/CoO represents that the molar ratio of the mass of graphene oxide to cobalt acetate in the cobalt acetate solution in example 11 was 1 g: 5mmol of the total weight of the solution; graphene/NiO represents the mass of graphene oxide in example 12 and the molar ratio of nickel acetate in nickel acetate solution as 1 g: 5mmol of the total weight of the solution; graphene/Fe2O3The molar ratio of the mass of graphene oxide to the ferrous acetate in the ferrous acetate solution in example 13 is represented by 1 g: 5mmol of the active carbon; graphene/CuO represents the mass of graphene oxide and copper acetate in example 14The molar ratio of copper acetate in the solution is 1 g: 5mmol of the total weight of the solution; graphene/ZnO represents the mass of graphene oxide in example 15 and the molar ratio of zinc acetate in the zinc acetate solution is 1 g: 5mmol of the active carbon; graphene/NiO/CoO represents the mass of graphene oxide and the molar ratio of nickel acetate to cobalt acetate in example 16 as 1 g: 3 mmol: 3mmol of the total weight of the solution; graphene/MnO/CoO represents the mass of graphene oxide and the molar ratio of manganese acetate to cobalt acetate of 1g in example 17: 3 mmol: 3mmol of the active carbon; graphene/CuO/ZnO/Fe2O3The mass of graphene oxide and the molar ratio of copper acetate, zinc acetate and ferrous acetate in example 18 were represented as 1 g: 2 mmol: 2 mmol: 2mmol of the resulting solution.
TABLE 1 Rate Properties of electrode sheets prepared in examples 1, 4, 6, 11-18
Examples Lithium storage capacity (0.1A/g)
Example 1 graphene/MnO-1 861mAh/g
Example 4 graphene/MnO-2 741mAh/g
Example 6 graphene/MnO-3 829mAh/g
Comparative example 1MnO 638mAh/g
Comparative example 2 graphene 552mAh/g
Example 11 graphene/CoO 835mAh/g
Example 12 graphene/NiO 891mAh/g
Example 13 graphene/Fe2O3 811mAh/g
Example 14 graphene/CuO 785mAh/g
Example 15 graphene/ZnO 621mAh/g
Example 16 graphene/NiO/CoO 850mAh/g
Example 17 graphene/MnO/CoO 861mAh/g
Example 18 graphene/CuO/ZnO/Fe2O3 825mAh/g
As can be seen from fig. 6 and table 1, when the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution are 1 g: 5mmol, and the specific capacity of the lithium storage is 861mAh/g when the current density is 100 mA/g; when the mass of the graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution are 1 g: 2.5mmol, and the specific capacity of lithium storage is 741mAh/g when the current density is 100 mA/g; when the mass of the graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution are 1 g: 10mmol, and the specific capacity of the lithium storage at the current density of 100mA/g is 829 mAh/g; the lithium storage specific capacity of the pure MnO electrode at the current density of 100mA/g is 638 mAh/g; the lithium storage specific capacity of the pure graphene electrode is 552mAh/g when the current density is 100 mA/g. When the mass of the graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution are 1 g: 5mmol, even if the current density is increased to 10A/g, the specific capacity of 211mAh/g is still higher than that of graphene/MnO composite nano materials, MnO and graphene electrodes prepared by other proportions. Meanwhile, when the current returns to a small current, the capacity of the graphene/MnO composite nano material can return to the initial level and is slightly improved, and the stability of the material structure is proved. Fig. 7 is a cycle stability test of the prepared graphene/MnO composite nanomaterial, MnO and graphene electrode sheet, and it can be seen that the graphene/MnO composite nanomaterial connected by chemical bonds shows excellent cycle performance, and the capacity does not fade after long cycles, which is much higher than that of graphene and MnO electrodes. The above results show that the graphene/metal oxide composite nanomaterial prepared by the invention has excellent potential as a lithium storage electrode material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a graphene/metal oxide composite nano material comprises the following steps:
mixing the graphene oxide dispersion liquid with a transition metal acetate solution, and freeze-drying to obtain graphene oxide/transition metal acetate precursor powder;
and carrying out heat treatment on the graphene oxide/transition metal acetate precursor powder under a protective atmosphere to obtain the graphene/metal oxide composite nanomaterial.
2. The preparation method according to claim 1, wherein the concentration of graphene oxide in the graphene oxide dispersion liquid is 2-8 g/L.
3. The method of claim 1, wherein the transition metal acetate in the transition metal acetate solution comprises one or more of manganese acetate, cobalt acetate, nickel acetate, ferrous acetate, copper acetate, and zinc acetate.
4. The method according to claim 1 or 3, wherein the concentration of the transition metal ion in the transition metal acetate solution is 0.01 to 0.1 mol/L.
5. The preparation method according to claim 1, wherein the mixing of the graphene oxide dispersion liquid and the transition metal acetate solution is performed under stirring at room temperature; and stirring at room temperature for 2-4 h.
6. The preparation method according to claim 1, wherein the heat treatment temperature is 300-600 ℃ and the holding time is 1-4 h.
7. The graphene/metal oxide composite nano-material prepared by the preparation method of any one of claims 1 to 6 comprises graphene and metal oxide nano-particles dispersed on the surface of the graphene; the metal oxide nanoparticles are connected with the graphene through a metal-O-C chemical bond.
8. The use of the graphene/metal oxide composite nanomaterial of claim 7 in a lithium ion capacitor or a lithium ion battery.
9. The electrode plate is characterized by comprising a conductive substrate and a conductive layer coated on the surface of the conductive substrate; the conductive layer comprises the graphene/metal oxide composite nanomaterial of claim 7, conductive carbon black, and polyvinylidene fluoride.
10. Use of the electrode sheet according to claim 9 in a lithium ion capacitor or a lithium ion battery.
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