CN114784227B - 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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CN114784227B
CN114784227B CN202210377798.6A CN202210377798A CN114784227B CN 114784227 B CN114784227 B CN 114784227B CN 202210377798 A CN202210377798 A CN 202210377798A CN 114784227 B CN114784227 B CN 114784227B
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graphene
acetate
transition metal
metal oxide
oxide
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CN114784227A (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 nanomaterial, a preparation method and application thereof, an electrode plate and application thereof, and relates to the technical field of nanomaterials. The preparation method of the graphene/metal oxide composite nanomaterial provided by the invention comprises the following steps: mixing graphene oxide dispersion liquid and 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 in a protective atmosphere to obtain the graphene/metal oxide composite nano material. 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, 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 negative electrode 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 has wide application prospect as a high-performance negative electrode of a lithium ion battery and a lithium ion capacitor. However, most metal oxides have low electron conductivity, and the internal structure is easily rearranged during charge and discharge, so that the capacity and the cycle performance of the metal oxides are easily attenuated, which prevents further commercial application of the metal oxides. In response to these problems, current conventional solutions include rational design of low dimensional structures (nanoparticles, nanowires, or nanoarrays), composite highly conductive carbon materials (e.g., graphene or porous carbon materials), and the introduction of defects or heteroatoms in the metal oxide. Most of the researches focus on obtaining metal oxide/carbon composite materials through complex synthetic routes, thereby reducing pulverization or agglomeration of the metal oxide materials to a certain extent and accelerating reaction kinetics of the electrode.
However, these methods greatly increase the cost and difficulty of large-scale preparation. In addition, the conventional conductive carbon layer/frame composite metal oxide method is to make the active material easily peel off during long-term circulation through physical contact rather than chemical interface interaction, resulting in poor stability of the electrode material.
Disclosure of Invention
The invention aims to provide a graphene/metal oxide composite nanomaterial, a preparation method and application thereof, and 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 nanomaterial, which comprises the following steps:
mixing graphene oxide dispersion liquid and 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 in a protective atmosphere to obtain the graphene/metal oxide composite nano material.
Preferably, the concentration of 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 graphene oxide dispersion and the transition metal acetate solution are mixed under stirring at room temperature; the stirring time at room temperature 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 the graphene/metal oxide composite nanomaterial prepared by the preparation method, which comprises graphene and metal oxide nanoparticles dispersed on the surface of the graphene; the metal oxide nanoparticles are connected with graphene through a metal-O-C chemical bond.
The invention provides 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 conductive layer comprises the graphene/metal oxide composite nanomaterial, conductive carbon black and polyvinylidene fluoride.
The invention provides application of the electrode plate in a lithium ion capacitor or a lithium ion battery.
The invention provides a preparation method of a graphene/metal oxide composite nanomaterial, which comprises the following steps: mixing graphene oxide dispersion liquid and 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 in a protective atmosphere to obtain the graphene/metal oxide composite nano material. In the invention, the graphene oxide surface has rich oxygen-containing functional groups, so that electronegativity is presented, metal ions can be adsorbed electrostatically, and the metal oxide is formed on the three-dimensional graphene surface in situ by performing heat treatment after freeze drying. Graphene can be used as a nucleation site of metal oxides, and agglomeration among the metal oxides can be prevented, so that uniformly-dispersed metal oxide nanoparticles are obtained. The invention adopts the metal acetate with proper decomposition temperature (between 200 and 400 ℃), the decomposition process is safe, and the reduction of the graphene oxide into the graphene in the heat treatment process can be ensured.
The graphene/metal oxide composite nano material prepared by the method can overcome the defect of poor intrinsic electronic conductivity of the metal oxide by strong metal-O-C chemical bonding and by utilizing the high-conductivity graphene, the problem of volume expansion of the metal oxide in the circulating process is relieved, and meanwhile, the lithium storage performance and the circulating life of the composite material can be effectively improved by combining the characteristic of high specific capacity of the metal oxide and the synergistic effect of the graphene and the metal oxide.
According to the invention, the mixing, freeze drying and subsequent heat treatment processes adopted by the method do not need to add precipitants, reducing agents and the like, do not need to introduce other impurities, do not need washing or purifying processes, can directly obtain the high-purity graphene/metal oxide composite nanomaterial, and are simple, convenient and quick in process flow, environment-friendly and beneficial to large-scale preparation.
Drawings
FIG. 1 is an X-ray diffraction pattern of graphene/MnO composite nanomaterial, mnO, and graphene prepared in example 1, comparative example 1, and comparative example 2;
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 image of the graphene/MnO composite nanomaterial prepared in example 1;
FIG. 5 is a transmission electron microscope image of the graphene/MnO composite nanomaterial prepared in example 1;
FIG. 6 is a graph of the rate performance of graphene/MnO electrode tabs, and graphene electrode tabs prepared using example 1, comparative example 1, and comparative example 2;
fig. 7 is a graph of cycle performance of graphene/MnO electrode tabs, and graphene electrode tabs 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 nanomaterial, which comprises the following steps:
mixing graphene oxide dispersion liquid and 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 in a protective atmosphere to obtain the graphene/metal oxide composite nano material.
In the present invention, all raw materials are commercially available products well known to those skilled in the art unless specified otherwise.
The graphene oxide/transition metal acetate precursor powder is obtained after the graphene oxide dispersion liquid and the transition metal acetate solution are mixed and freeze-dried. In the present invention, the concentration of graphene oxide in the graphene oxide dispersion liquid is preferably 2 to 8g/L, more preferably 4 to 6g/L. The preparation method of the graphene oxide is not particularly described, and conventional preparation methods of the graphene oxide are adopted by those skilled in the art. In a specific embodiment of the invention, graphite oxide is prepared from graphite by a modified Hummer's method. In the present invention, the preparation method of the graphene oxide dispersion liquid preferably includes: and mixing graphite oxide with water, and performing ultrasonic treatment to obtain graphene oxide dispersion liquid. In the present invention, the time of the ultrasonic treatment is preferably 90 to 120 minutes, more preferably 100 to 110 minutes; the ultrasonic treatment disperses the graphite oxide into fewer or single layers; the number of layers of the graphene oxide is preferably 1 to 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 present invention, the concentration of the transition metal ion in the transition metal acetate solution is preferably 0.01 to 0.1mol/L, more preferably 0.02 to 0.5mol/L. In the present invention, the preparation method of the transition metal acetate solution preferably includes: the transition metal acetate and water were 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 1g:0.5 to 10mmol, more preferably 1g: 2-6 mmol.
In the present invention, the graphene oxide dispersion liquid and the transition metal acetate solution are mixed preferably under stirring at room temperature; the stirring time at room temperature is preferably 2 to 4 hours, more preferably 3 hours. In the mixing process, positively charged metal ions are adsorbed on negatively charged graphene oxide and serve as nucleation sites of metal oxide nanoparticles in the subsequent heat treatment process, and metal-O-C bonds are formed in situ. The existence of the graphene substrate effectively prevents the agglomeration of nano metal oxide particles, combines high-conductivity graphene, provides more active sites for the intercalation of lithium ions, and ensures the stability of a heterostructure.
In the present invention, the temperature of the freeze-drying is preferably-30 to-55 ℃, more preferably-35 to-45 ℃; the time for the freeze-drying is preferably 20 to 30 hours, more preferably 24 hours. According to the preparation method, the graphene oxide/transition metal acetate precursor powder with a three-dimensional structure can be obtained by 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 in a protective atmosphere to obtain the graphene/metal oxide composite nanomaterial. The present invention preferably further comprises, before the heat treatment: grinding the graphene oxide/transition metal acetate precursor powder. In the present invention, the grinding is preferably performed in a mortar, and the time of the grinding is not particularly limited, and the graphene oxide/transition metal acetate precursor powder may be ground to be uniform without agglomeration.
In the present invention, the protective atmosphere is preferably a nitrogen atmosphere or an argon atmosphere.
In the present invention, the temperature of the heat treatment is preferably 300 to 600 ℃, more preferably 400 to 500 ℃; the heating rate from room temperature to the temperature of the heat treatment is preferably 3 to 7 ℃/min, more preferably 5 ℃/min; the heat-retaining time of the heat treatment is preferably 1 to 4 hours, more preferably 2 to 3 hours. In the present invention, the heat treatment is preferably performed in a tube furnace; the graphene oxide/transition metal acetate precursor powder is preferably placed in a corundum crucible to be subjected to heat treatment in a tube furnace. In the heat treatment process, graphene oxide is effectively reduced into graphene, and simultaneously adsorbed metal ions form metal oxide nano particles in situ, and are connected with the graphene through metal-O-C chemical bonds.
The invention also provides the graphene/metal oxide composite nanomaterial prepared by the preparation method, which comprises graphene and metal oxide nanoparticles dispersed on the surface of the graphene; the metal oxide nanoparticles are connected with graphene through a metal-O-C chemical bond. In the invention, the graphene is of a corrugated structure. In the present invention, the size of the metal oxide nanoparticles is preferably 100 to 700nm, more preferably 200 to 500nm. 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 70wt% of the total mass of the graphene/metal oxide composite nanomaterial, more preferably 20 to 50wt%.
According to the graphene/metal oxide composite nanomaterial prepared by the method, the graphene is crosslinked with each other to construct a three-dimensional conductive network, meanwhile, the metal oxide has a nano-size 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 application of the graphene/metal oxide composite nano material in a lithium ion capacitor or a lithium ion battery. The graphene/metal oxide composite nanomaterial provided by the invention has rich lithium storage sites, 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 conductive layer comprises the graphene/metal oxide composite nanomaterial, conductive carbon black and polyvinylidene fluoride. In the present invention, the thickness of the conductive layer is preferably 10 to 100 μm.
In the invention, the preparation method of the electrode slice preferably comprises the following steps: mixing 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 the conductive matrix to obtain the electrode plate.
In the invention, the mass ratio of the graphene/metal oxide composite nanomaterial, the conductive carbon black and 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 type solvent, and the pyrrolidone type solvent preferably includes N-methyl pyrrolidone, 2-pyrrolidone, or N-ethyl pyrrolidone. The amount of the solvent is not particularly limited in the present invention, and in the embodiment of the present invention, the mass of the graphene/metal oxide composite nanomaterial and the volume ratio of the solvent are preferably 1g:20mL.
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 the time of the stirring and mixing are not particularly limited, so that the raw materials can be uniformly mixed.
In the present invention, the conductive substrate preferably includes a copper foil or a carbon-coated copper foil.
The manner of the coating is not particularly limited, and is well known to those skilled in the artThe coating mode of (2) is just needed. 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 nanomaterial 2 More preferably 0.004-0.006 g/cm 2 。
After the coating, the invention preferably further comprises drying the coated wet film to obtain the electrode plate. In the present invention, the drying mode is preferably vacuum drying; the drying temperature is preferably 80-130 ℃, more preferably 100-120 ℃; the drying time is preferably 5 to 15 hours, more preferably 6 to 12 hours.
The invention provides application of the electrode plate in a lithium ion capacitor or a lithium ion battery.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Placing 1g of graphite oxide powder into 250mL of deionized water, and carrying out ultrasonic stirring at room temperature for 4 hours to obtain uniformly dispersed 4g/L few-layer graphene oxide dispersion liquid;
(2) Mixing the 4g/L few-layer graphene oxide dispersion liquid and 0.02 mol/L manganese acetate solution (the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution are 1g:5 mmol) under the condition of stirring at room temperature, stirring for 3 hours at room temperature, and then freeze-drying at-40 ℃ for 24 hours to obtain graphene oxide/manganese acetate precursor powder;
(3) And (3) grinding the graphene oxide/manganese acetate precursor powder uniformly in a mortar, paving the powder in a corundum crucible uniformly, placing the corundum crucible in a tube furnace, heating to 500 ℃ at a speed of 5 ℃/min under the protection of argon, performing heat treatment for 2 hours, and cooling to room temperature to obtain the graphene/MnO composite nanomaterial.
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 method has good crystallinity and high purity.
The X-ray photoelectron spectrum of the graphene/MnO composite nanomaterial prepared in this embodiment is shown in fig. 2 to 3, wherein C1 s is the photoelectron energy measured by exciting 1s orbital electrons in carbon atoms, and O1 s is the photoelectron energy measured by exciting 1s orbital electrons in oxygen atoms. As can be seen from fig. 2, after thermal reduction of graphene oxide, 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, which proves that the MnO nanoparticles are connected with the graphene through chemical bonds, so that the stability of the heterostructure material is improved.
A scanning electron microscope image 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 nano cabbage-like structure and is uniformly dispersed on the graphene with a rich crease structure on the surface.
A 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 size of MnO particles of the nano cabbage type structure is about 350nm, and the nano cabbage type structure is uniformly anchored on graphene.
Example 2
Substantially the same as in example 1, except that the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution in step (2) were 1g:0.5mmol.
Example 3
Substantially the same as in example 1, except that the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution in step (2) were 1g:1mmol.
Example 4
Substantially the same as in example 1, except that the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution in step (2) were 1g:2.5mmol.
Example 5
Substantially the same as in example 1, except that the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution in step (2) were 1g:7.5mmol.
Example 6
Substantially the same as in example 1, except that the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution in step (2) were 1g:10mmol.
Example 7
Substantially the same as in example 1, except that the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution in step (2) were 1g:5mmol; the heat treatment in the step (3) is 400 ℃.
Example 8
Substantially the same as in example 1, except that the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution in step (2) were 1g:5mmol; the heat treatment in the step (3) is 600 ℃.
Example 9
Substantially the same as in example 1, except that the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution in step (2) were 1g:5mmol; the heating rate of the heat treatment temperature in the step (3) is 3 ℃/min.
Example 10
Substantially the same as in example 1, except that the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution in step (2) were 1g:5mmol; the heating rate of the heat treatment temperature in the step (3) is 7 ℃/min.
Comparative example 1
Substantially the same as in example 1, except that step (1) was omitted, and the graphene oxide solution was not added in step (2), the prepared material was labeled MnO.
Comparative example 2
Substantially the same as in example 1, except that the manganese acetate solution was not added in the step (2), the prepared material was labeled as graphene.
Example 11
Substantially the same as in example 1, except that the transition metal acetate added in step (2) was cobalt acetate, a graphene/CoO composite nanomaterial was obtained.
Example 12
Substantially the same as in example 1, except that the transition metal acetate added in step (2) was nickel acetate, a graphene/NiO composite nanomaterial was obtained.
Example 13
Substantially the same as in example 1, except that the transition metal acetate added in step (2) was ferrous acetate, graphene/Fe was obtained 2 O 3 Composite nanomaterial.
Example 14
Substantially the same as in example 1, except that the transition metal acetate added in step (2) was copper acetate, graphene/CuO composite nanomaterial was obtained.
Example 15
Substantially the same as in example 1, except that the transition metal acetate added in step (2) was zinc acetate, a graphene/ZnO composite nanomaterial was obtained.
Example 16
Substantially the same as in example 1, except that the transition metal acetate added in step (2) was nickel acetate and cobalt acetate, a graphene/NiO/CoO composite nanomaterial was obtained.
Example 17
Substantially the same as in example 1, except that the transition metal acetate added in step (2) was manganese acetate and cobalt acetate, a graphene/MnO/CoO composite nanomaterial was obtained.
Example 18
Substantially the same as in example 1, except that the transition metal acetate added in the step (2) was copper acetate, zinc acetate and ferrous acetate, graphene/CuO/ZnO/Fe was obtained 2 O 3 Composite nanomaterial.
Application example
The active materials (graphene/metal oxide composite nanomaterial, mnO, and graphene) prepared in examples 1, 4, 6, comparative example 1, comparative example 2, and examples 11 to 18, conductive carbon black, polyvinylidene fluoride (PVDF), and N-methylpyrrolidone were respectively stirred and mixed, then 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 was 8:1:1, and the rate performance of the electrode sheet is shown in table 1, fig. 6, and fig. 7.
Wherein, the graphene/MnO-1 in Table 1 and the graphene/MnO in FIGS. 6 to 7 represent the mass of graphene oxide in example 1 and the molar ratio of manganese acetate in the manganese acetate solution were 1g:5mmol; graphene/MnO-2 represents the mass of graphene oxide in example 4 and the molar ratio of manganese acetate in the manganese acetate solution is 1g:2.5mmol; graphene/MnO-3 represents the mass of graphene oxide in example 6 and the molar ratio of manganese acetate in the manganese acetate solution is 1g:10mmol; mnO represents comparative example 1; graphene represents comparative example 2; graphene/CoO represents the mass of graphene oxide and the molar ratio of cobalt acetate in the cobalt acetate solution in example 11 as 1g:5mmol; graphene/NiO represents the mass of graphene oxide and the molar ratio of nickel acetate in the nickel acetate solution in example 12 at 1g:5mmol; graphene/Fe 2 O 3 The mass of graphene oxide and the molar ratio of ferrous acetate in the ferrous acetate solution representing example 13 were 1g:5mmol; graphene/CuO represents the mass of graphene oxide and the molar ratio of copper acetate in the copper acetate solution in example 14 as 1g:5mmol; graphene/ZnO represents the mass of graphene oxide and the molar ratio of zinc acetate in the zinc acetate solution in example 15 is 1g:5mmol; graphene/NiO/CoO represents the mass of graphene oxide and the molar ratio of nickel acetate to cobalt acetate of 1g in example 16: 3mmol:3mmol; graphene/MnO/CoO represents the mass of graphene oxide and the molar ratio of manganese acetate to cobalt acetate in example 17 as 1g:3mmol:3mmol; graphene/CuO/ZnO/Fe 2 O 3 The mass of graphene oxide and the molar ratio of copper acetate, zinc acetate and ferrous acetate in example 18 were represented as 1g: 2mmol:2mmol:2mmol.
TABLE 1 rate capability 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/Fe 2 O 3 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/Fe 2 O 3 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 were 1g:5mmol, and the specific capacity of lithium storage is 861mAh/g when the current density is 100 mA/g; when the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution are 1g:2.5mmol, and the specific capacity of lithium storage is 741mAh/g when the current density is 100 mA/g; when the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution are 1g:10mmol, and the specific capacity of the lithium storage is 829 mAh/g when the current density is 100 mA/g; the specific capacity of lithium storage of the pure MnO electrode is 638mAh/g when the current density is 100 mA/g; the lithium storage specific capacity of the pure graphene electrode is 552mAh/g at the current density of 100 mA/g. When the mass of graphene oxide and the molar ratio of manganese acetate in the manganese acetate solution are 1g:5mmol, even if the current density is increased to 10A/g, the graphene/MnO composite nanomaterial has a specific capacity of 211mAh/g, which is far higher than that of graphene/MnO composite nanomaterial, mnO and graphene electrodes prepared in other proportions. Meanwhile, when the current returns to a small current, the capacity of the graphene/MnO composite nanomaterial can return to an initial level and slightly improve, so that 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 through chemical bonds exhibits excellent cycle performance, and capacity is not attenuated after undergoing long cycles, much higher than that of graphene and MnO electrodes. The above results demonstrate that the graphene/metal oxide composite nanomaterial prepared by the method has excellent potential as a lithium storage electrode material.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1. An application of a graphene/metal oxide composite nanomaterial in a lithium ion capacitor or a lithium ion battery, wherein the preparation method of the graphene/metal oxide composite nanomaterial comprises the following steps of:
mixing graphene oxide dispersion liquid and 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 in a protective atmosphere to obtain the graphene/metal oxide composite nano material.
2. The use according to claim 1, wherein the concentration of graphene oxide in the graphene oxide dispersion is 2-8 g/L.
3. The use 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. Use according to claim 1 or 3, characterized in that the concentration of transition metal ions in the transition metal acetate solution is 0.01-0.1 mol/L.
5. The use according to claim 1, wherein the mixing of the graphene oxide dispersion and the transition metal acetate solution is performed under stirring conditions at room temperature; the stirring time at room temperature is 2-4 h.
6. The use according to claim 1, wherein the heat treatment is carried out at a temperature of 300-600 ℃ for a period of 1-4 hours.
7. The use according to claim 1, wherein the graphene/metal oxide composite nanomaterial comprises graphene and metal oxide nanoparticles dispersed on the surface of the graphene; the metal oxide nanoparticles are connected with graphene through a metal-O-C chemical bond.
8. 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 a graphene/metal oxide composite nanomaterial, conductive carbon black and polyvinylidene fluoride;
the preparation method of the graphene/metal oxide composite nanomaterial comprises the following steps:
mixing graphene oxide dispersion liquid and 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 in a protective atmosphere to obtain the graphene/metal oxide composite nano material.
9. The use of the electrode sheet of claim 8 in a lithium ion capacitor or a lithium ion battery.
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