CN107565106B - Preparation method of composite nanowire of graphene quantum dot and iron-manganese solid solution - Google Patents
Preparation method of composite nanowire of graphene quantum dot and iron-manganese solid solution Download PDFInfo
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Abstract
The invention provides a preparation method of a composite nanowire of a graphene quantum dot and a ferro-manganese solid solution, which comprises the following steps: a) preparing a solvent dispersion of graphene quantum dots, wherein the average particle size of the graphene quantum dots is 2 to 5nm, and the concentration of the graphene quantum dots in the solvent dispersion is 5 to 10 mg/mL; b) reacting manganese acetate with oxalic acid to obtain manganous oxalate, adding ferrous sulfate into the manganous oxalate, further reacting to obtain a mixed precursor of the manganous oxalate and the ferrous oxalate, and washing and drying the obtained product; c) mixing and stirring the solvent dispersion of the graphene quantum dots obtained in the step a), the mixed precursor of manganous oxalate and ferrous oxalate obtained in the step b) and a stabilizer to obtain a mixed solution; d) preparing the mixed solution obtained in the step c) into nanowires by an electrostatic spinning method and drying and annealing the nanowires.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of a composite nanowire of a graphene quantum dot and a ferro-manganese solid solution.
Background
With the development of industry and society, electrical energy storage has become an increasingly important issue. Currently, Lithium Ion Batteries (LIBS) are widely used in various portable electronic devices, such as mobile phones, notebook computers, and video cameras, due to their advantages of high energy density, high rate capability, high safety, and low cost. Due to the low theoretical specific capacity of graphite-based materials (372mA hg)-1) And limited rate capability, it is a current urgent matter to develop lithium ion batteries with good performance in all aspects. In recent years, zero-dimensional graphene quantum dots have a plurality of unique properties due to quantum confinement effect, size effect, boundary effect and the like, and are expected to be applied to the fields of photoelectrons, biology, catalysis, batteries and the like. Chao et al use graphene quantum dots to coat VO2The arrays are used in high performance lithium ion or sodium ion batteries [ Chao et al, Nano Lett.2015,15,565-]. The transition metal oxide has potential application in the fields of lithium ion batteries, super capacitors and the like. The application of manganese oxide as anode material in LIBS is receiving more and more attention, and in order to control the performance of the anode material, efforts are being made to control the structure of manganese oxide. Qiu et al prepared Mn in different shapes by hydrothermal chemical method with functional polyol molecule and potassium permanganate as precursors2O3And the nano Mn is researched2O3Effect of anode material on insertion/extraction cycling process of electrochemical lithium storage. [ Qiu et al. ACS appl. Mater. interfaces 2013,5, 10975-.]. In addition, Sun et al report that graphene-reinforced manganous oxide has higher specific capacity and good cycling performance.
However, developing a new method for synthesizing new materials for lithium ion battery energy storage applications is still of great interest.
Disclosure of Invention
Based on the technical problems stated above, the invention aims to prepare the composite nanowire of the graphene quantum dot and the ferro-manganese solid solution by an electrostatic spinning method, and the composite nanowire has a good application prospect in the fields of lithium ion batteries and the like.
Specifically, the invention relates to a preparation method of a composite nanowire of a graphene quantum dot and a ferro-manganese solid solution, wherein the ferro-manganese solid solution has a chemical composition represented by the following formula: mn0.8Fe0.2And O, taking the solvent dispersion of the graphene quantum dots as an electrostatic spinning precursor solution, wherein the average diameter of the obtained composite nanowire of the graphene quantum dots and the ferro-manganese solid solution is 200-500 nm.
According to one aspect of the present invention, there is provided a method for preparing a composite nanowire of a graphene quantum dot and a ferro-manganese solid solution, the method comprising the steps of:
a) preparing a solvent dispersion of graphene quantum dots, wherein the average particle size of the graphene quantum dots is 2 to 5nm, and the concentration of the graphene quantum dots in the solvent dispersion is 5 to 10 mg/mL;
b) reacting manganese acetate with oxalic acid to obtain manganous oxalate, adding ferrous sulfate into the manganous oxalate, further reacting to obtain a mixed precursor of the manganous oxalate and the ferrous oxalate, and washing and drying the obtained product;
c) mixing and stirring the solvent dispersion of the graphene quantum dots obtained in the step a), the mixed precursor of manganous oxalate and ferrous oxalate obtained in the step b) and a stabilizer to obtain a mixed solution;
d) preparing the mixed solution obtained in the step c) into a nanowire by an electrostatic spinning method, and drying and annealing the nanowire to obtain the composite nanowire of the graphene quantum dot and the ferro-manganese solid solution.
According to certain preferred embodiments of the present invention, wherein in step b), the weight ratio of manganese acetate, oxalic acid and ferrous sulfate is 1.94-2.18:1.27: 0.39-0.78.
According to certain preferred embodiments of the present invention, wherein in the step c), the amount of the mixed precursor of manganous oxalate and ferrous oxalate is 0.06 to 0.1g per mL of the solvent dispersion of the graphene quantum dots.
According to certain preferred embodiments of the present invention, the solvent is selected from one or more of N, N-dimethylformamide and ethanol.
According to certain preferred embodiments of the present invention, said step a) further comprises the steps of: subjecting the solvent dispersion of the graphene quantum dots to hydrothermal treatment, the hydrothermal treatment being performed in a reaction kettle, wherein the temperature of the hydrothermal treatment is 180 to 200 ℃, and the time of the hydrothermal treatment is 6 to 8 hours.
According to certain preferred embodiments of the present invention, the manganese acetate is manganese acetate tetrahydrate, the oxalic acid is oxalic acid dihydrate, and the ferrous sulfate is ferrous sulfate heptahydrate.
According to certain preferred embodiments of the present invention, step b) comprises: dissolving manganese acetate tetrahydrate in water and vigorously stirring to obtain a manganese acetate aqueous solution; adding oxalic acid dihydrate to the aqueous manganese acetate solution to obtain a white precipitate; to the white precipitate was added ferrous sulfate heptahydrate, and the resulting pale yellow precipitate was washed and dried.
According to certain preferred embodiments of the present invention, the stabilizer is selected from one or more of polyvinylpyrrolidone and polyacrylonitrile.
According to certain preferred embodiments of the present invention, wherein in step c), the stabilizer is added in an amount of 100 to 200mg per mL of the solution of the graphene quantum dots.
According to certain preferred embodiments of the present invention, in step d), the drying comprises heating at a temperature of 60-80 ℃ for 8-10 hours.
According to certain preferred embodiments of the present invention, in step d), the annealing is carried out at a temperature of 300 to 500 ℃ for 1 to 2 hours under an inert atmosphere.
According to certain preferred embodiments of the present invention, in step d), the ramp rate in the annealing is from 5 to 10 ℃/min.
According to certain preferred embodiments of the present invention, the inert atmosphere is an argon atmosphere.
According to certain preferred embodiments of the present invention, the average diameter of the prepared composite nanowire of the graphene quantum dot and the iron-manganese solid solution is 200 to 500 nm.
The invention has the beneficial effects that: the invention provides a novel method for compounding graphene quantum dots with a ferro-manganese solid solution through an electrostatic spinning method, and finally obtaining the graphene quantum dot and ferro-manganese solid solution composite nanowire through a series of processes.
Drawings
Fig. 1 shows a Transmission Electron Microscope (TEM) photograph of a graphene quantum dot prepared according to example 1 of the present invention;
fig. 2 shows a Scanning Electron Microscope (SEM) photograph of a composite nanowire of a graphene quantum dot and a ferro-manganese solid solution prepared according to example 1 of the present invention, at a magnification of 1 ten thousand times;
fig. 3 shows an X-ray diffraction pattern (XRD) of the composite nanowire of graphene quantum dots and iron-manganese solid solution prepared according to example 1 of the present invention;
fig. 4 shows battery performance of the composite nanowire of the graphene quantum dot and the iron-manganese solid solution prepared according to example 1 of the present invention, i.e., a charge and discharge curve of the prepared battery at the first turn;
fig. 5 shows impedance performance curves of the composite nanowire battery of the graphene quantum dots and the iron-manganese solid solution prepared according to example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It will be appreciated that other embodiments are contemplated and may be made without departing from the scope or spirit of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense.
Unless otherwise indicated, all numbers expressing feature sizes, quantities, and physical and chemical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
According to the technical scheme of the invention, the preparation method of the composite nanowire of the graphene quantum dot and the ferro-manganese solid solution is provided, and the method comprises the following steps:
a) preparing a solvent dispersion of graphene quantum dots, wherein the average particle size of the graphene quantum dots is 2 to 5nm, and the concentration of the graphene quantum dots in the solvent dispersion is 5 to 10 mg/mL;
b) reacting manganese acetate with oxalic acid to obtain manganous oxalate, adding ferrous sulfate into the manganous oxalate, further reacting to obtain a mixed precursor of the manganous oxalate and the ferrous oxalate, and washing and drying the obtained product;
c) mixing and stirring the solvent dispersion of the graphene quantum dots obtained in the step a), the mixed precursor of manganous oxalate and ferrous oxalate obtained in the step b) and a stabilizer to obtain a mixed solution;
d) preparing the mixed solution obtained in the step c) into a nanowire by an electrostatic spinning method, and drying and annealing the nanowire to obtain the composite nanowire of the graphene quantum dot and the ferro-manganese solid solution.
In step b), the weight ratio of manganese acetate, oxalic acid and ferrous sulfate is 1.94-2.18:1.27: 0.39-0.78. In step c), the amount of the mixed precursor of manganous oxalate and ferrous oxalate is 0.06 to 0.1g per mL of the solvent dispersion of graphene quantum dots.
There is no particular limitation on the graphene quantum dots employed in the method according to the present invention, which are either commercially available or can be prepared in the laboratory according to known methods. Preferably, according to an embodiment of the present invention, the graphene quantum dot solution, wherein the average particle diameter of the graphene quantum dots is 2 to 5nm, preferably 3 to 4nm, and the concentration of the graphene quantum dots in the solvent dispersion is 5 to 10mg/mL, preferably 6 to 8 mg/mL. By adopting the graphene quantum dots with the particle size range and the concentration range, the graphene quantum dots can be better compounded with the ferro-manganese solid solution.
Graphene oxide sheets (graphene oxide solution) dried from graphene oxide solution provided by Hexagon element company were used according to an embodiment of the present invention. The average size of graphene oxide in the product is 2-5 μm, which is much larger than the above required range of 2-5nm of the average particle size of the graphene oxide quantum dots, so the product is ultrasonically crushed to the desired size before use. According to an embodiment of the present invention, the graphene oxide product is sonicated for 40 minutes to 1 hour using an ultrasonic cell disruptor (SCIENTZ-IID, Ningbo New Ganoderma Biotech Co., Ltd.) with a power of 100w to 400 w.
The solvent used in the above step a) is not particularly limited as long as it can sufficiently disperse the graphene quantum dots. Preferably, the solvent is selected from one or more of N, N-dimethylformamide and ethanol.
In order to improve the crystallinity of the graphene quantum dots, step a) of the method according to the present invention further comprises the steps of: subjecting the solvent dispersion of the graphene quantum dots to hydrothermal treatment, the hydrothermal treatment being performed in a reaction kettle, wherein the temperature of the hydrothermal treatment is 180 to 200 ℃, and the time of the hydrothermal treatment is 6 to 8 hours.
Preferably, the reaction vessel has a polytetrafluoroethylene liner.
After the hydrothermal treatment in step a), the product is cooled to room temperature and filtered with suction. Preferably, the suction filtration is carried out by using a sand-core funnel and a microfiltration membrane having a pore size of 0.22. mu.m.
According to certain preferred embodiments of the present invention, the manganese acetate is manganese acetate tetrahydrate (Mn (Ac)2·4H2O), oxalic acid is oxalic acid dihydrate (C)2H2O4·2H2O) and the ferrous sulfate is ferrous sulfate heptahydrate (FeSO)4·7H2O)。
According to certain preferred embodiments of the present invention, in particular, step b) comprises: dissolving manganese acetate tetrahydrate in water and vigorously stirring to obtain a manganese acetate aqueous solution; adding oxalic acid dihydrate to the aqueous manganese acetate solution to obtain a white precipitate; to the white precipitate was added ferrous sulfate heptahydrate, and the resulting pale yellow precipitate was washed and dried. It should be noted, however, that the order of addition of the process according to the invention is not limited thereto.
In order to disperse the graphene quantum dots in the solvent uniformly, the step a) further comprises the following steps: adding a stabilizer to the solvent dispersion of the graphene quantum dots. The kind of the stabilizer is not particularly limited, however, the stabilizer is preferably selected from one or more of polyvinylpyrrolidone and polyacrylonitrile. Preferably, in step c), the amount of the stabilizer added is 100 to 200mg per mL of the solution of the graphene quantum dots.
According to certain preferred embodiments of the present invention, in step d), the drying comprises heating at a temperature of 60-80 ℃ for 8-10 hours.
According to certain preferred embodiments of the present invention, in step d), the annealing is carried out at a temperature of 300 to 500 ℃ for 1 to 2 hours under an inert atmosphere. Preferably, in step d), the ramp rate in the annealing is 5 to 10 ℃/min. Further, the inert atmosphere is preferably an argon atmosphere.
According to certain preferred embodiments of the present invention, the average diameter of the prepared composite nanowire of the graphene quantum dot and the iron-manganese solid solution is 200 to 500nm, preferably 300 to 500 nm.
According to the technical scheme of the invention, the mixed solution obtained in the step c) is prepared into the nanowire by adopting an electrostatic spinning method, and the nanowire is dried and annealed to obtain the composite nanowire of the graphene quantum dot and the iron-manganese solid solution. Preferably, the volume of the needle tube used in electrospinning is 5mL to 10mL, and the needle size is 16 to 24G. Preferably, in the electrospinning, a positive electrode of a high voltage direct current power supply having a voltage of 10 to 16kV is connected to the needle, and a negative electrode of a high voltage direct current power supply having a voltage of-1 kV is connected to a receiving plate. Preferably, the distance between the needle and the receiving plate is 15 to 20 cm.
The present invention will be described in more detail with reference to examples. It should be noted that the description and examples are intended to facilitate the understanding of the invention, and are not intended to limit the invention. The scope of the invention is to be determined by the claims appended hereto.
Examples
In the present invention, unless otherwise indicated, all reagents used were commercially available products and were used without further purification treatment. Further, "%" mentioned is "% by weight", and "parts" mentioned is "parts by weight".
Example 1
Preparing the composite nanowire of the graphene quantum dot and the ferro-manganese solid solution by the following steps:
(1) preparation of solvent dispersion of graphene quantum dots:
1.62g of graphite oxide flakes were dissolved in 60ml of DMF and disrupted by ultrasonication using an ultrasonic cell disrupter (SCIENTZ-IID, Ningbo New Ganoderma Biotech Co., Ltd.) with a power of 100W for 1 hour. The solution prepared above was transferred to a reaction kettle having a polytetrafluoroethylene liner with a volume of 100mL, and the reaction kettle was placed in an oven and subjected to hydrothermal treatment at a temperature of 200 ℃ for 6 hours. After the hydrothermal treatment, the reaction kettle was cooled to room temperature and removed from the oven. The solution was suction filtered using a sand-core funnel and a microfiltration membrane with a pore size of 0.22 μm. And filtering to obtain a filtrate, namely the solvent dispersion of the graphene quantum dots. The concentration of the graphene quantum dots in the prepared solution dispersion is 5-10 mg/mL. The average particle size of the prepared graphene quantum dots is about 2-5nm as can be seen by Transmission Electron Microscope (TEM) measurement.
(2) Preparation of a mixed precursor of manganous oxalate doped with ferrous oxalate (i.e., a mixed precursor of manganous oxalate and ferrous oxalate):
1.9376g of Mn (Ac)2·4H2O was dissolved in 50ml of boiled water and stirred vigorously. Slowly add 1.27g C during vigorous stirring of the above solution2H2O4·2H2O to give a white precipitate, to which 0.7785g of FeSO were added4·7H2And O, obtaining light yellow precipitate, centrifugally washing the light yellow precipitate, and drying at 70 ℃ for 6 hours to obtain a mixed precursor of the ferrous oxalate and the manganous oxalate.
(3) Preparing the composite nanowire of the graphene quantum dot and the iron-manganese solid solution:
5ml of the solvent dispersion of the graphene quantum dots prepared in step (1) was taken and 1g of polyvinylpyrrolidone (PVP) was added thereto, and stirred for 10 hours. To the resulting mixture was added 0.35g of the mixed precursor of iron oxalate and manganous oxalate prepared in step (2) and stirred for 15 minutes. Wherein the mixing amount of the ferrous oxalate and the manganous oxalate mixed precursor is 0.07g per mL of the solvent dispersion of the graphene oxide quantum dots.
The nano-wire is prepared by adopting an electrostatic spinning method. The prepared solution is absorbed into a 5ml needle tube, the needle is 21G, the needle is connected with a positive electrode, a receiving plate is connected with a negative electrode, the voltage of the positive electrode is 15kV, the voltage of the negative electrode is-1 kV, the distance is 18cm, and the propelling speed is 0.75 mg/ml. And drying the film obtained by electrostatic spinning in air at 80 ℃, annealing in an argon atmosphere at 500 ℃ for 1h at a heating rate of 5 ℃/min, cooling, taking out, and testing the obtained composite nanowire of the graphene quantum dot and the ferro-manganese solid solution.
Fig. 1 shows a Transmission Electron Microscope (TEM) photograph of the graphene quantum dot prepared according to example 1 of the present invention. Fig. 2 shows an SEM image of the composite nanowire of the graphene quantum dot and the iron-manganese solid solution. Fig. 3 shows XRD spectra of the composite nanowire of graphene oxide quantum dots and iron-manganese solid solution, consistent with the desired results.
In addition, the electrical properties of the composite nanowire of the graphene quantum dot and the iron-manganese solid solution prepared in the (3) step of the above example 1 were tested.
Specifically, the lithium storage performance and the impedance performance of the composite nanowire of the graphene quantum dot and the iron-manganese solid solution are tested as follows:
in order to test the lithium storage performance of the composite nanowire, the first is to prepare an electrode: grinding and mixing the obtained carbon material, polyvinylidene fluoride (PVDF) and acetylene black for half an hour according to the mass ratio of 7:2:1, then adding the powder into a proper amount of NMP in batches, and grinding to obtain mixed slurry. The resulting slurry was uniformly applied to the matte side of a copper foil with a thickness of 200 μm using a four-sided simple coater. The copper foil coated with the slurry was then transferred to a vacuum oven and dried at 80 ℃ for 10 hours. And (4) after drying, punching the electrode plate into an electrode plate with the diameter of 12mm, wherein the loading capacity of active substances on the electrode plate is equal to the total weight of the electrode plate minus the mass of the uncoated copper foil with the same size.
The second step is that the button assembles the battery: in the glove box filled with argon gas, the batteries were assembled in the order of placing the negative electrode case → the stainless steel sheet → the lithium sheet → the electrolyte → the separator → the electrolyte → the electrode sheet → the stainless steel sheet → the spring washer → the positive electrode case. Wherein microporous polypropylene is used as a lithium battery diaphragm, and 1M LiPF6A solution of DMC 1:1(v/v) dissolved in EC was used as an electrolyte, and the amount of the electrolyte added twice was approximately 20 μ L.
The third step is battery test: testing the cycle performance of the battery by using a battery tester (Wuhan blue electricity CT 2001A) to obtain a first circle of charge-discharge curve; the cell impedance was tested using an electrochemical workstation (Shanghai Hua CHI 660E) with an initial voltage of 0.01V. All electrochemical tests were carried out in a voltage interval of 3V-0.005V.
The first-turn charge and discharge curve shown in fig. 4 illustrates that the composite nanowire of the graphene quantum dot and the iron-manganese solid solution prepared according to the technical scheme of the invention can be well used for battery applications. The impedance performance curve shown in fig. 5 shows that the battery prepared from the composite nanowire has low resistance and can provide guarantee for good cycle performance of the battery.
From the results of the above examples, it can be seen that the technical scheme according to the present invention provides a composite nanowire prepared by combining graphene quantum dots and a ferro-manganese solid solution through an electrospinning method.
The embodiments of the present invention are described only for the preferred embodiments of the present invention, and not for the purpose of limiting the spirit and scope of the present invention, and various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention, and the technical contents of the present invention as claimed are all described in the claims.
Claims (12)
1. A preparation method of a composite nanowire of a graphene quantum dot and a ferro-manganese solid solution comprises the following steps:
a) preparing a solvent dispersion of graphene quantum dots, wherein the average particle size of the graphene quantum dots is 2 to 5nm, and the concentration of the graphene quantum dots in the solvent dispersion is 5 to 10 mg/mL;
b) reacting manganese acetate with oxalic acid to obtain manganous oxalate, adding ferrous sulfate into the manganous oxalate, further reacting to obtain a mixed precursor of the manganous oxalate and the ferrous oxalate, and washing and drying the obtained product;
c) mixing and stirring the solvent dispersion of the graphene quantum dots obtained in the step a), the mixed precursor of manganous oxalate and ferrous oxalate obtained in the step b) and a stabilizer to obtain a mixed solution;
d) preparing the mixed solution obtained in the step c) into a nanowire by an electrostatic spinning method, drying and annealing the nanowire to obtain the composite nanowire of the graphene quantum dot and the ferro-manganese solid solution,
wherein the stabilizer is polyvinylpyrrolidone, and in step c), the amount of the stabilizer added is 100 to 200mg per mL of the solvent dispersion of the graphene quantum dots.
2. The method for preparing a composite nanowire of graphene quantum dots and a solid solution of iron and manganese according to claim 1, wherein in step b), the weight ratio of manganese acetate, oxalic acid and ferrous sulfate is 1.94-2.18:1.27: 0.39-0.78.
3. The method for preparing a composite nanowire of graphene quantum dots and a ferro-manganese solid solution according to claim 1, wherein in step c), the amount of the mixed precursor of manganous oxalate and ferrous oxalate is 0.06 to 0.1g per mL of the solvent dispersion of the graphene quantum dots.
4. The method for preparing the composite nanowire of the graphene quantum dot and the iron-manganese solid solution according to claim 1, wherein the solvent is selected from one or more of N, N-dimethylformamide and ethanol.
5. The method for preparing the composite nanowire of graphene quantum dots and a ferro-manganese solid solution according to claim 1, wherein the step a) further comprises the steps of: subjecting the solvent dispersion of the graphene quantum dots to hydrothermal treatment, the hydrothermal treatment being performed in a reaction kettle, wherein the temperature of the hydrothermal treatment is 180 to 200 ℃, and the time of the hydrothermal treatment is 6 to 8 hours.
6. The method of claim 1, wherein the manganese acetate is manganese acetate tetrahydrate, the oxalic acid is oxalic acid dihydrate, and the ferrous sulfate is ferrous sulfate heptahydrate.
7. The method for preparing the composite nanowire of the graphene quantum dot and the ferro-manganese solid solution according to claim 1, wherein the step b) comprises: dissolving manganese acetate tetrahydrate in water and vigorously stirring to obtain a manganese acetate aqueous solution; adding oxalic acid dihydrate to the aqueous manganese acetate solution to obtain a white precipitate; to the white precipitate was added ferrous sulfate heptahydrate, and the resulting pale yellow precipitate was washed and dried.
8. The method for preparing a composite nanowire of graphene quantum dots and a ferro-manganese solid solution according to claim 1, wherein in step d), the drying comprises heating at a temperature of 60-80 ℃ for 8-10 hours.
9. The method for preparing a composite nanowire of graphene quantum dots and a ferro-manganese solid solution according to claim 1, wherein in step d), the annealing is performed at a temperature of 300 to 500 ℃ for 1 to 2 hours under an inert atmosphere.
10. The method for preparing a composite nanowire of graphene quantum dots and a ferro-manganese solid solution according to claim 9, wherein in step d), the temperature increase rate in the annealing is 5 to 10 ℃/min.
11. The method for preparing a composite nanowire of graphene quantum dots and a ferro-manganese solid solution according to claim 9, wherein the inert atmosphere is an argon atmosphere.
12. The method for preparing a composite nanowire of a graphene quantum dot and a ferro-manganese solid solution according to claim 1, wherein the average diameter of the prepared composite nanowire of the graphene quantum dot and the ferro-manganese solid solution is 200 to 500 nm.
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