CN113948669A - Metal oxide-graphene quantum dot composite material and preparation method and application thereof - Google Patents
Metal oxide-graphene quantum dot composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a metal oxide-graphene quantum dot composite material and a preparation method and application thereof, wherein the preparation method of the composite material comprises the following steps: adding the synthesized graphene quantum dots into water to form a dispersion solution, then adding a soluble metal salt and an oxidant, and carrying out hydrothermal reaction after the soluble metal salt is dissolved to obtain the metal oxide-graphene quantum dot composite material. The invention utilizes graphene quantum dots as a modifier to modify metal oxide to form MOx-GQDs composites, on the one hand improving the intrinsic low of metal oxidesOn the other hand, the electron conductivity suppresses the dissolution of the material of the metal oxide during the charge and discharge of the aqueous polyvalent metal ion battery, and exhibits excellent cycle stability. In addition, the preparation method is simple, and a universal and efficient method is provided for optimizing the material structure.
Description
Technical Field
The invention relates to the technical field of metal oxide-graphene quantum dot composite materials, in particular to a metal oxide-graphene quantum dot composite material and a preparation method and application thereof.
Background
With the increasing consumption of fossil fuels, the concentration of toxic gases in the atmosphere, such as nitrogen oxides and sulfur oxides, which are associated with global warming, has also increased. Renewable energy sources such as wind and solar are the most promising energy sources to reduce fossil fuel usage and have unlimited advantages. While these resources are unlimited, they are intermittent and not always available. To utilize these unlimited sources of energy, it is necessary to store energy when available, where battery systems play an important role. Rechargeable aqueous multivalent ion batteries (zinc ion batteries, magnesium ion batteries, aluminum ion batteries, and the like) are considered as the most promising candidate products for power grid energy storage, and can replace the currently used lead-acid batteries using toxic lead compounds and lithium ion batteries with limited resources. The low price, safety, non-toxicity and abundant metal reserves make it very attractive. Wherein the theoretical weight capacity and the volume capacity of the metal zinc are 820 mAmph/g and 5855 mAmph/cubic centimeter respectively. Albeit zinc ion
And lithium ion
The radius of (a) is similar, but the larger atomic mass and the higher charge density hinder transport kinetics and solid-state solubility in the electrode, and therefore, an electrode material suitable for lithium ion insertion/extraction may not be suitable for an aqueous zinc ion battery. Therefore, selecting a suitable cathode material is one of the major challenges facing zinc ions at present. To date, manganese-based oxides, vanadium-based oxides, prussian blue analogs, organic substances, and the like have been reported as high-performance zinc ion battery positive electrode materials.
The manganese-based material has high safety, abundant resources,Environmental protection, non-toxicity, low cost and the like, and is widely used in a plurality of battery applications. Manganese dioxide with high working voltage and theoretical capacity of 308mAh g-1Has become one of the main positive electrode materials of aqueous manganese-based Zinc Ion Batteries (ZIBs). In general, MnO shared by corners/edges6Various arrangements of octahedra result in different polymorphs of manganese dioxide, a manganese-based oxide material, as a superior positive electrode for ZIBs. They generally have stable cycle performance, higher Zn2+Insertion potential and higher reversible capacity. However, Mn2+Rapid capacity fade by dissolution is prevalent in manganese-based oxide positive electrode materials. Another problem is the lack of effective tools to study the reaction mechanism of manganese-based oxide anodes, which are complex and immature. Among them, the most fatal disadvantage is the slower reaction kinetics due to Zn2+Strong electrostatic interaction between the ions and the host material. Therefore, new methods of designing new nanostructures are needed to provide better structural integrity and fast and short Zn2+And (4) transferring the channel. The currently widely adopted modification strategy is as follows: 1) interlayer intercalation: metal ions or molecules/polymers are introduced between layers, the interlayer environment of the layered material is adjusted, the spacing is increased, the structural stability is improved, and the transmission dynamics is improved; 2) doping: the structure of the cathode material is introduced with the hetero metal ions or hetero non-metal atoms, and the electronic structure and the surface property of the cathode material are adjusted, so that the reaction kinetics and the electrochemical performance of the cathode material are improved; 3) defect engineering: providing more active sites, improving ion/electron transport kinetics, and enhancing structural stability; 4) surface coating and composite materials: the strategy of constructing a uniform and stable protective layer on the surface of the electrode material is used as a conductive network to improve the conductivity, promote the electron transmission of the interface, effectively relieve the self-accumulation or aggregation of active substances, serve as a physical interface and reduce MnOxThe direct contact with the electrolyte inhibits the dissolution of Mn; 5) and (3) morphology regulation and control: the reasonable design of the regular nano structure is expected to endow the cathode material with high specific surface area, abundant active sites, shorter ion/electron transmission path and fast reaction kinetics.
However, the design of manganese oxide is still in the research stage at present, the optimization result is not ideal enough, and the following problems mainly exist: 1) simple carbon compounding cannot fundamentally improve the conductivity, the ion intercalation can be influenced by comprehensive coating, the carbon content is difficult to control, and the conventional carbon compounding is easy to generate overhigh carbon content and reduce the capacity; 2) defect engineering, doping, interlayer intercalation and morphology design sometimes face various complicated design steps and crystal structure changes, and the charge-discharge reaction mechanism becomes complicated.
Disclosure of Invention
Based on the above, in order to solve the above technical problems in the prior art, an object of the present invention is to provide a method for simply and efficiently preparing metal oxide-graphene quantum dots (MO)x-GQDs) composite material, the method utilizes low-cost metal salt as raw material and graphene quantum dots as modification additive to carry out in-situ modification, on one hand, the inherent low electron conductivity of metal oxide is improved, and the charge transfer dynamics in the charge and discharge process of the water system polyvalent metal ion battery is promoted; on the other hand, the dissolution of the metal oxide in the charge and discharge process of the water-system polyvalent metal ion battery is inhibited, so that the composite material shows excellent cycle stability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a metal oxide-graphene quantum dot composite material comprises the following steps:
s1, dissolving the graphene quantum dots in deionized water to form graphene quantum dot dispersion liquid;
s2, adding soluble metal salt, an oxidant and a buffer solution into the dispersion solution, and carrying out hydrothermal reaction after the soluble metal salt is dissolved to obtain a metal oxide-graphene quantum dot composite material;
wherein the metal soluble salt is soluble salt of any one of manganese, vanadium and cobalt.
Further, the method also comprises the steps of washing and drying the metal oxide-graphene quantum dot composite material. The method specifically comprises the following steps: and (3) respectively and repeatedly washing the product obtained after the hydrothermal reaction with deionized water and ethanol for at least 3 times, and then carrying out vacuum drying for 6-12h at the temperature of 60-100 ℃ to obtain the metal oxide-graphene quantum dot composite material.
In some embodiments, the hydrothermal reaction is carried out at a hydrothermal temperature of 120-160 ℃ for 12-16 h.
In some embodiments, the mass ratio of the graphene quantum dots to the metal oxide is 0-0.2: 1.
in some embodiments, the buffer is potassium acetate and acetic acid in a 1: 1, mixing the mixture.
In some embodiments, the soluble metal salt is at least one of a sulfate, chloride, nitrate, acetate, etc. of a metal, in particular any of the metals manganese, vanadium, cobalt, more particularly, as: manganese sulfate, manganese chloride, manganese acetate, manganese nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate, vanadium chloride, vanadium nitrate, and the like.
In some embodiments, the oxidizing agent is potassium chlorate, potassium permanganate, or the like.
In some embodiments, the method of preparation comprises the steps of:
s1, dissolving the GQDs in deionized water, and stirring to form a uniform GQDs dispersion liquid;
s2, adding an oxidant, a soluble metal salt and a weak base substance in a buffer solution into the GQDs dispersion solution, stirring until the mixture is completely dissolved to obtain a mixed solution, then dropwise adding the weak base substance in the buffer solution into the mixed solution, stirring, heating to 120-160 ℃, and carrying out heat preservation reaction for 12-16 hours to obtain a metal oxide-graphene quantum dot composite material;
wherein the mass ratio of the GQDs to the soluble metal salt is 0-0.2: 1.
the second object of the present invention is to provide a metal oxide-graphene quantum dot composite material prepared by the preparation method according to any one of the above embodiments.
The invention also aims to provide a positive pole piece, which comprises the metal oxide-graphene quantum dot composite material.
The fourth object of the present invention is to provide an aqueous polyvalent metal ion battery comprising the positive electrode sheet described above, wherein the aqueous polyvalent metal ion battery comprises one of a zinc ion battery, a magnesium ion battery and an aluminum ion battery.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the graphene quantum dots are used as a modifier, and the low-cost metal salt is used as a raw material to prepare the metal oxide-graphene quantum dot composite material, so that the in-situ modification effect is realized, and the metal oxide-graphene quantum dot composite material with high length-diameter ratio is obtained. The preparation method can effectively improve the electronic conductivity of the composite material, and is simple. The invention provides a universal and efficient method for optimizing the material structure.
The preparation method of the metal oxide-graphene quantum dot composite material provided by the invention comprises the steps of dispersing graphene quantum dots in water, adding soluble metal salt, an oxidant and a buffer solution, and then carrying out hydrothermal reaction. In the hydrothermal reaction process, metal ions are oxidized by an oxidant to form metal oxides, graphene quantum dots dispersed in an aqueous solution can induce the growth of the metal ions to prevent particle aggregation, and a buffer solution has the function of keeping the pH of the solution stable to avoid influencing the appearance of a product due to unstable pH of the solution caused by the existence or oxidation of the metal ions. The composite material prepared by the invention improves the problem of low electronic conductivity inherent in metal oxides. In addition, the high-length-diameter-ratio composite material prepared by the invention has the advantages that the graphene quantum dots are tightly compounded on the nano-wires, when the graphene quantum dots are used for a positive electrode material of a water system bimetal ion battery, the contact area of the positive electrode material and an electrolyte can be increased, the transmission dynamics of the battery is improved, the dissolution of the electrode material can be inhibited, the circulation stability of the material is improved, and compared with other reported metal oxide-based electrode materials, the performance is obviously improved.
Drawings
FIG. 1 shows MnO in example 1 of the present invention2SE for-10 GQDs compositesAn M diagram;
FIG. 2 shows MnO in example 2 of the present invention2SEM picture of 20GQDs composite material;
FIG. 3 shows MnO in example 3 of the present invention2SEM picture of 40GQDs composite material;
FIG. 4 shows pure MnO in comparative example 1 of the present invention2SEM picture of (1);
FIG. 5 shows MnO obtained in example 1 of the present invention2-10GQDs composites and MnO as obtained in example 22-20GQDs composite, MnO made in example 32-40GQDs composite and pure MnO prepared in comparative example 12X-ray diffraction patterns of (a);
FIG. 6 shows MnO obtained in example 1 of the present invention2-10GQDs composites and MnO as obtained in example 22-20GQDs composite, MnO made in example 32-40GQDs composite and pure MnO prepared in comparative example 12The sample is used as the positive electrode material of the zinc ion battery to prepare the button cell of the positive electrode piece at 100mA g-1A 100-cycle mass-to-capacity curve under current density;
FIG. 7 shows MnO obtained in example 1 of the present invention2-10GQDs composites and MnO as obtained in example 22-20GQDs composite, MnO made in example 32-40GQDs composite and pure MnO prepared in comparative example 12The sample is used as the positive electrode material of the zinc ion battery to prepare the button cell of the positive electrode piece at 100mA g-1-1000mAg-1Rate capability at current density.
FIG. 8 shows MnO obtained in example 3 of the present invention2-40GQDs composite and pure MnO prepared in comparative example 12The sample is used as the positive electrode material of the zinc ion battery to prepare the impedance performance of the button cell of the positive electrode piece.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the embodiments of the present invention, the equipment and instruments used are commercially available or prepared by the prior art.
Preparation of graphene quantum dots
The Graphene Quantum Dots (GQDs) are obtained by a chemical oxidation method, and the specific preparation method comprises the following steps:
firstly, 1g of 325-mesh graphite flake is added into concentrated H2SO4/HNO3(60mL, V/V, 3:1), and then magnetically stirring for 10 minutes to obtain a dispersion; sonicating the dispersion for one hour; then, transferring the obtained mixture into a 100mL stainless steel autoclave with a polytetrafluoroethylene lining, then putting the sealed autoclave into an oven, heating to 120 ℃, and carrying out heat preservation reaction for 24 hours; after completion of the reaction, it was cooled, and when the autoclave was cooled to room temperature, the resulting mixture was further treated with Na2CO3And NaOH to pH 7; and then removing large-particle graphite by suction filtration, dialyzing to remove small-molecular salt, and finally freeze-drying to obtain the final CQDs powder with the diameter of 2-4 nm.
The graphene quantum dots used in the following examples are all the graphene quantum dots prepared by the above method.
Example 1
MnO2-10GQDs composite preparation comprising the steps of:
s1, dissolving 10mg of GQDs in 60mL of deionized water, and magnetically stirring to form a uniform GQDs dispersion liquid;
s2, mixing 7mmol of potassium chlorate (KClO)3) 4mmol of manganese sulfate (II) (MnSO)4·H2O) and 7mmol of potassium acetate (CH)3COOK) is added into the GQDs dispersion liquid, and the mixture is magnetically stirred until the mixture is dissolved, so that a mixed solution is obtained; then 3.2mL of acetic acid (CH)3COOH) is added into the mixed solution drop by drop and stirred for 30 minutes to obtain uniform mixed solution, the uniform mixed solution is transferred into a 100mL stainless steel autoclave lined with polytetrafluoroethylene, the temperature is heated to 160 ℃, and the heat preservation reaction is carried out for 12 hours; after the reaction is finished, cooling to room temperature, filtering to obtain precipitate, washing with distilled water and ethanol for several times, and drying at 55 ℃ for 24 hours to obtain MnO2-10GQDs composites. Detected, MnO2The morphology of the-10 GQDs composite material is shown in figure 1; the X-ray diffraction pattern is shown in FIG. 5.
MnO prepared by the above method2The-10 GQDs composite material is used as an active substance of a zinc ion secondary battery to prepare a positive pole piece. The concrete mode is as follows: MnO to be prepared2-10GQDs composites with acetylene black (conductive agent), polyvinylidene fluoride (PVDF, binder) according to 70: 20: 10, adding a proper amount of N-methyl pyrrolidone (NMP, solvent) to prepare slurry, then coating the slurry on a stainless steel mesh with the diameter of 14mm which is cut from a current collector by a manual coating method, and drying the slurry in vacuum at 120 ℃ for 10 hours after the NMP is volatilized.
Metal zinc as the negative pole and 2.0M ZnSO4+0.2M MnSO4The aqueous solution is used as electrolyte, GF/D type glass fiber filter paper is used as a diaphragm, and the LIR2016 type button cell is assembled. Electrochemical performance tests were then performed and the results are shown in figures 6-7. As shown in fig. 6 and 7, at 0.1A g-1Keeping 178.5mAh g after 100 cycles under the current density-1The capacity of (a); at 0.05, 0.1, 0.2, 0.5, 1.0A g-1The reversible specific capacities are 267.6, 228.5, 161.8, 90.4 and 34.4mAh g respectively under the current density of (A)-1. After the charging and discharging of different current densities are finished, when the current density returns to 0.05A g again-1The reversible specific capacity is recovered to 227.4mAh g-1。
Example 2
MnO2-20GQDs composite preparation comprising the steps of:
s1, dissolving 20mg of GQDs in 60mL of deionized water, and magnetically stirring to form a uniform GQDs dispersion liquid;
s2, mixing 7mmol of potassium chlorate (KClO)3) 4mmol of manganese sulfate (II) (MnSO)4·H2O) and 7mmol of potassium acetate (CH)3COOK) is added into the GQDs dispersion liquid, and the mixture is magnetically stirred until the mixture is dissolved, so that a mixed solution is obtained; then 3.2mL of acetic acid (CH)3COOH) is added into the mixed solution drop by drop and stirred for 30 minutes to obtain uniform mixed solution; transferring the uniform mixed solution into a 100mL stainless steel autoclave lined with polytetrafluoroethylene, heating to 160 ℃, and carrying out heat preservation reaction for 12 hours; after the reaction is finished, cooling to room temperature, filtering to obtain precipitate, washing with distilled water and ethanol for a plurality of times, and drying at 55 ℃ for 24 hours to obtain MnO2-20GQDs composites. Detected, MnO2The morphology of the-20 GQDs composite material is shown in FIG. 2; the X-ray diffraction pattern is shown in FIG. 5.
MnO to be made2The-20 GQDs composite material is used as an active substance to prepare a positive pole piece, and then the positive pole piece is applied to a zinc ion battery to prepare an LIR2016 type button cell for electrochemical performance test, wherein the specific method is the same as that in the embodiment 1.
The results of the test are shown in FIGS. 6-7, at 0.1A g-1Under the current density, 182.3mAh g is kept after 100 cycles-1The capacity of (a); at 0.05, 0.1, 0.2, 0.5, 1.0A g-1The reversible specific capacities are respectively 258.2, 202.7, 140.3, 61.9 and 28.6mAh g under the current density of (A)-1. After the charging and discharging of different current densities are finished, when the current density returns to 0.05A g again-1The reversible specific capacity is recovered to 258.1mAh g-1。
Example 3
MnO2-40GQDs composite material preparation, comprising the steps of:
s1, dissolving 40mg of GQDs in 60mL of deionized water, and magnetically stirring to form a uniform GQDs dispersion liquid;
s2, mixing 7mmol of potassium chlorate (KClO)3) 4mmol of manganese sulfate (II) (MnSO)4·H2O) and 7mmol of potassium acetate (CH)3COOK) is added into the GQDs dispersion liquid, and the mixture is magnetically stirred until the mixture is dissolved, so that a mixed solution is obtained; then 3.2mL of acetic acid (CH)3COOH) was added dropwise to the above mixed solution and stirred for 30 minutes to obtain a uniform mixed solution, and the uniform mixed solution was transferred toMoving the mixture into a 100mL stainless steel autoclave lined with polytetrafluoroethylene, heating the mixture to 160 ℃, and carrying out heat preservation reaction for 12 hours; after the reaction is finished, cooling to room temperature, filtering to obtain precipitate, washing with distilled water and ethanol for a plurality of times, and drying at 55 ℃ for 24 hours to obtain brown spongy solid, namely MnO2-40GQDs composites. Detected, MnO2The morphology of the-40 GQDs composite material is shown in FIG. 3; the X-ray diffraction pattern is shown in FIG. 5.
MnO to be made2The-40 GQDs composite material is used as an active substance to prepare a positive pole piece, and then the positive pole piece is applied to a zinc ion battery to prepare an LIR2016 type button cell for electrochemical performance test, wherein the specific method is the same as that in the embodiment 1.
The results of the test are shown in FIGS. 6-7, at 0.1A g-1Keeping 195.6mAh g after 100 cycles under the current density-1The capacity of (a); at 0.05, 0.1, 0.2, 0.5, 1.0A g-1The reversible specific capacities are 363.5, 310.7, 221.8, 125 and 42.8mAh g respectively under the current density of (A)-1. After the charging and discharging of different current densities are finished, when the current density returns to 0.05A g again-1The reversible specific capacity is recovered to 284.1mAh g-1。
The impedance performance of the composite material prepared in the example and the material prepared in the comparative example 1 as the positive electrode material of the zinc ion battery is shown in fig. 8.
Comparative example 1
MnO2The preparation method comprises the following steps:
adding 7mmol of potassium chlorate (KClO)3) 4mmol of manganese sulfate (II) (MnSO)4·H2O) and 7mmol of potassium acetate (CH)3COOK) was added to 60mL of deionized water, magnetically stirred until dissolved to give a mixed solution, and then 3.2mL of acetic acid (CH) was added3COOH) is added into the mixed solution drop by drop and stirred for 30 minutes to obtain uniform mixed solution; transferring the uniform mixed solution into a 100mL stainless steel autoclave lined with polytetrafluoroethylene, heating to 160 ℃, and carrying out heat preservation reaction for 12 hours; cooling to room temperature after the reaction is finished, filtering to obtain precipitate, washing with distilled water and ethanol for a plurality of times, and drying at 55 ℃ for 24 hours to obtain brown spongy solid MnO2A material. Detected, MnO2The morphology of the material is shown in fig. 4; the X-ray diffraction pattern is shown in FIG. 5.
MnO to be made2The material is used as an active substance to prepare a positive pole piece, and then the positive pole piece is applied to a zinc ion battery to prepare an LIR2016 type button battery for electrochemical performance test, wherein the specific method is the same as that in the embodiment 1.
The results of the test are shown in FIGS. 6-7, at 0.1A g-1Under the current density, 50.8mAh g is kept after 100 cycles-1The capacity of (a); at 0.05, 0.1, 0.2, 0.5, 1.0A g-1The reversible specific capacities are 192.0, 182.0, 138.7, 70.6 and 26.9mAh g respectively under the current density of (A)-1. After the charging and discharging of different current densities are finished, when the current density returns to 0.05A g again-1When the specific capacity is recovered to 169.9mAh g-1。
In summary, the method of the invention can form a stable metal oxide-graphene quantum dot composite material by using low-cost metal salt as a raw material and introducing graphene quantum dots as a modifier to regulate and modify metal oxide, and can effectively improve the electrochemical performance of the composite material2The innovation in the material is high.
It should be noted that the method of the present invention is also applicable to the preparation of other valence oxide-graphene quantum dot composite materials of manganese metal and cobalt and vanadium metal, including but not limited to Mn3O4-GQDs composite material, V2O5-GQDs composites, Co2O3GQDs composites and the like, which are prepared by substantially the same method as in the above examples, do not exclude the appropriate reaction conditions including adjustment of oxidizing agents, temperatures, reaction times in order to obtain composites of optimal structure.
Besides being applied to a zinc ion battery, the metal oxide-graphene quantum dot composite material can also be used as an active material of a positive pole piece of a magnesium ion battery and an aluminum ion battery, and tests show that the metal oxide-graphene quantum dot composite material is applied to the magnesium ion battery and the aluminum ion battery, and the cycle stability and the rate performance curve of the battery are similar to those of fig. 6 and 7. The composite material of the invention can be used as a positive active material, and can also improve the rate capability and the cycling stability of a magnesium ion battery and an aluminum ion battery.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a metal oxide-graphene quantum dot composite material is characterized by comprising the following steps:
s1, dissolving the graphene quantum dots in deionized water to form graphene quantum dot dispersion liquid;
s2, adding soluble metal salt, an oxidant and a buffer solution into the dispersion solution, and carrying out hydrothermal reaction after the soluble metal salt is dissolved to obtain a metal oxide-graphene quantum dot composite material;
wherein the metal soluble salt is soluble salt of any one of manganese, vanadium and cobalt.
2. The preparation method of the metal oxide-graphene quantum dot composite material according to claim 1, wherein the temperature of the hydrothermal reaction is 120-160 ℃, and the reaction time is 12-16 h.
3. The preparation method of the metal oxide-graphene quantum dot composite material according to claim 1, wherein the mass ratio of the graphene quantum dot to the metal soluble salt is 0-0.2: 1.
4. the method for preparing the metal oxide-graphene quantum dot composite material according to claim 1, wherein the buffer solution is potassium acetate and acetic acid in a molar ratio of 1: 1, mixing the mixture.
5. The method for preparing the metal oxide-graphene quantum dot composite material according to claim 1, wherein the metal soluble salt is at least one of chloride, sulfate, nitrate and acetate of metal.
6. The metal oxide-graphene quantum dot composite material of claim 1, wherein the oxidant is potassium chlorate or potassium permanganate.
7. The method for preparing the metal oxide-graphene quantum dot composite material according to any one of claims 1 to 6, comprising the steps of:
s1, dissolving the GQDs in deionized water, and stirring to form a uniform GQDs dispersion liquid;
s2, adding an oxidant, a soluble metal salt and a weak base substance in a buffer solution into the GQDs dispersion solution, stirring until the mixture is completely dissolved to obtain a mixed solution, then dropwise adding the weak base substance in the buffer solution into the mixed solution, stirring, heating to 120-160 ℃, and carrying out heat preservation reaction for 12-16 hours to obtain a metal oxide-graphene quantum dot composite material;
wherein the mass ratio of the GQDs to the soluble metal salt is 0-0.2: 1.
8. a metal oxide-graphene quantum dot composite material prepared by the preparation method of any one of claims 1 to 7.
9. A positive electrode plate, characterized by comprising the metal oxide-graphene quantum dot composite material according to claim 8.
10. An aqueous bi-metal ion battery comprising the positive electrode sheet according to claim 9; the water system bimetal ion battery is a zinc ion battery, a magnesium ion battery or an aluminum ion battery.
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| CN114613980B (en) * | 2022-03-30 | 2024-05-03 | 中南大学 | Zinc ion battery composite negative electrode and preparation method and application thereof |
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