CN112054186A - Preparation method and application of Al-MOF negative electrode material synthesized by solvothermal method - Google Patents
Preparation method and application of Al-MOF negative electrode material synthesized by solvothermal method Download PDFInfo
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Abstract
The invention provides a preparation method and application of an Al-MOF negative electrode material synthesized by a solvothermal method. The method comprises the following steps: preparing an Al-MOF material by a solvothermal method; and preparing the Al-MOF negative electrode material for the lithium ion battery by using the Al-MOF material. The metal aluminum ions related by the invention belong to the recycling of silicon-aluminum alloy after dealloying treatment, and the method has the advantages of low cost, simple process equipment and easy large-scale industrial production.
Description
Technical Field
The invention relates to a preparation method and application of an Al-MOF negative electrode material synthesized by a solvothermal method.
Background
Metal organic framework Materials (MOFs), also known as metal coordination polymers, refer to crystalline materials formed by linking inorganic metals or metal clusters and organic ligands through coordination bonds, and have a multidimensional network porous structure with high porosity, high specific surface area and adjustable pore diameter. Compared with the conventional porous material, the metal organic framework material has the following three advantages: the texture properties such as the morphology, the specific surface area, the pore diameter and the like of the material can be effectively controlled by regulating the lengths of the metal ions and the organic ligands; the internal three-dimensional pore system is developed without dead volume; the metal ion content on the surface of the framework is high, and the availability is high. In recent years, metal organic framework derivative materials are widely applied to a plurality of fields such as adsorption, energy materials, catalytic materials, environmental atmosphere treatment and the like. Common preparation methods include hydrothermal method, solvothermal method, microwave method, electrochemical method and the like. At present, the metal organic framework material is more prone to the research on transition group metals (Fe, Co, Ni and the like), but the research on Al-MOF is still less, wherein patent CN109289800A discloses a preparation method and application of an aluminum-based MOFs @ graphene doped PAN nano composite nanofiber material, and the material can adsorb formaldehyde in air and can effectively filter PM 2.5. Patent CN110478259B discloses an application of Al-MOF material in preparing hair and scalp cleaning products. It can be found that the research of using the synthesized novel Al-MOF material for the anode material of the lithium ion battery is still blank. And the problem of recycling or reusing a large amount of metal ion byproducts after dealloying is only paid attention to solving, so that the problems of great material economic loss and environmental pollution are caused, and sustainable green development is not facilitated.
In conclusion, the invention aims at the problem of recycling metal aluminum ions after the dealloying treatment of the silicon-aluminum alloy, provides a novel porous Al-MOF structural material prepared by the combined reaction of aluminum salt and an organic ligand by a solvothermal method, and shows excellent cycle stability when the porous Al-MOF structural material is used for the first time in a lithium ion battery cathode material.
Disclosure of Invention
According to the problem of recycling or reusing a large amount of metal ion byproducts after dealloying, which is provided, attention is paid to solving, the problems of great material economic loss and environmental pollution are caused, and the technical problem of being not beneficial to sustainable green development is solved, so that the preparation method and the application of the Al-MOF negative electrode material synthesized by the solvothermal method are provided. According to the invention, a solvothermal method is mainly utilized to combine and react aluminum salt and an organic ligand to prepare a novel porous Al-MOF material, and the novel porous Al-MOF material is used for a lithium ion battery cathode material for the first time and shows excellent cycling stability.
The technical means adopted by the invention are as follows:
a preparation method for synthesizing an Al-MOF negative electrode material by a solvothermal method comprises the following steps:
s1, preparing an Al-MOF material;
s11, providing aluminum-silicon alloy powder prepared by a nitrogen high-pressure high-speed atomization technology as a raw material, wherein the particle size of the aluminum-silicon alloy powder is 0.1-80 mu m;
s12, mixing a certain amount of aluminum-silicon alloy powder with an inorganic acid solution, stirring with mild magnetic force, and carrying out dealloying reaction for 1-48h at 25-100 ℃;
s13, after the reaction is finished, carrying out solid-liquid separation through a suction filtration device, washing the obtained porous silicon solid particles for 3-6 times by using deionized water and absolute ethyl alcohol solution, and separately collecting the aluminum salt solution in the obtained filter flask for later use;
s14, adding the aluminum salt solution and the organic acid solution into a certain volume of solvent for mixing;
s15, adding a certain mass of high molecular surfactant polyvinylpyrrolidone into the mixed solution obtained in the step S14, and magnetically stirring for 0.2-5 hours until the mixture is uniformly mixed;
s16, putting the uniformly stirred mixed solution obtained in the step S15 into a reaction kettle, performing hydrothermal reaction, and obtaining an Al-MOF material by a hydrothermal method;
s2, preparing an Al-MOF negative electrode material;
s21, mixing and grinding the Al-MOF material obtained in the step S16, a conductive agent and a binder according to the mass ratio of 6-8:1-2:1-2, and pouring the mixture into a solvent for grinding for 0.3-2h to obtain uniform electrode slurry;
s22, coating the electrode slurry on a metal copper foil, wherein the thickness of the coating is 80-200 mu m, and placing the metal copper foil in a vacuum drying oven to be dried for 6-24h at 60-120 ℃ to obtain the Al-MOF negative electrode material for the lithium ion battery, namely the negative electrode plate of the lithium ion battery.
Further, in step S12, the inorganic acid solution is one of HCl solution, HNO3 solution, or H2SO4 solution, or a combination of more than one thereof.
Further, in step S12, the inorganic acid solution is used as the etching solution, and the mass concentration of the inorganic acid solution is 1-40%.
Further, in step S14, the solvent is one of N, N-dimethylformamide, absolute ethanol, ethylene glycol, glycerol, nitrogen-dimethyl acetamide or tetrahydrofuran, or a combination of more than one of them.
Further, in step S14, the organic acid solution is one of terephthalic acid solution, trimesic acid solution or 1, 4-naphthalene dicarboxylic acid solution, or a combination of more than one of them.
Further, in step S14, the molar ratio of the aluminum salt to the organic acid is 5:1 to 1: 5.
Further, in step S15, the mass ratio of the organic acid to the high molecular surfactant polyvinylpyrrolidone is 10:1 to 1: 10.
Further, the specific steps of step S16 are as follows:
s161, putting the uniformly stirred mixed solution obtained in the step S15 into a reaction kettle, and carrying out hydrothermal reaction at the temperature of 80-260 ℃ for 3-100 h;
s162, after the hydrothermal reaction, naturally cooling the mixed solution to obtain a white substance, then centrifugally cleaning the white substance for 2-6 times by using deionized water and an absolute ethyl alcohol solution, and carrying out vacuum drying at 80 ℃ to obtain the Al-MOF material.
Further, in step S21, the solvent is N-methylpyrrolidone or deionized water, the conductive agent is conductive carbon black, and the binder is sodium carboxymethylcellulose, polyvinylidene fluoride, or sodium alginate.
The invention also provides application of the Al-MOF negative electrode material prepared by the method in a lithium ion battery.
Compared with the prior art, the invention has the following advantages:
1. the preparation method and the application of the Al-MOF cathode material synthesized by the solvothermal method provided by the invention have the advantages that the porous Al-MOF material with uniformly distributed particle sizes is successfully prepared by the solvothermal method and is used for the cathode material of the lithium ion battery, and good cycling stability is shown.
2. The preparation method and the application of the Al-MOF cathode material synthesized by the solvothermal method provided by the invention relate to the metal aluminum ions, which belong to the recycling of silicon-aluminum alloy after dealloying treatment, and have the advantages of low cost, simple process equipment and easiness in large-scale industrial production.
In conclusion, the technical scheme of the invention can solve the problems of recovery or recycling of a large amount of metal ion byproducts after dealloying in the prior art, which causes great material economic loss and environmental pollution and is not beneficial to sustainable green development.
Based on the reasons, the invention can be widely popularized in the fields of lithium ion batteries and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an XRD pattern of Al-MOF in examples 1-4 of the present invention.
FIGS. 2 and 3 are SEM pictures of Al-MOF in example 1 of the present invention.
FIG. 4 is a graph of the cycling performance of Al-MOF in example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise. Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. Any specific values in all examples shown and discussed herein are to be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
As shown in the figure, the invention provides a preparation method for synthesizing an Al-MOF negative electrode material by a solvothermal method, which comprises the following steps:
firstly, synthesizing an Al-MOF material by a solvothermal method:
(a) aluminum-silicon alloy powder is used as a raw material, and the size of the particles is 0.1-80 mu m. Mixing a certain amount of aluminum-silicon alloy powder with an inorganic acid solution, and stirring under mild magnetic force to perform dealloying reaction, wherein the mass concentration of a corrosion solution is 1-40%, the reaction temperature is 25-100 ℃, and the reaction time is 1-48 h. Finally, solid-liquid separation is realized by using a suction filtration device, wherein the porous silicon solid particles are washed for 3-6 times by using deionized water and absolute ethyl alcohol solution, and the obtained aluminum salt solution in the filter flask is separately collected for later use.
In the step (a), the inorganic acid solution is selected from the group consisting of: HCl solution, HNO3 solution, H2SO4 solution, or a combination thereof.
(b) Adding the aluminum salt solution and organic acid into a certain volume of solvent for mixing, wherein the molar ratio of the aluminum salt to the organic acid is 5: 1-1: 5; adding a certain mass of high molecular surfactant polyvinylpyrrolidone (PVP) into the mixed solution, and magnetically stirring for 0.2-5h until the mixture is uniformly mixed, wherein the mass ratio of the organic acid to the PVP is 10: 1-1: 10;
in step (b), the solvent is selected from the group consisting of: n, N-Dimethylformamide (DMF), absolute ethanol, ethylene glycol, glycerol, azodicarbonamide, tetrahydrofuran, or combinations thereof.
The organic acid solution is selected from the group consisting of: terephthalic acid solution, trimesic acid solution, 1, 4-naphthalenedicarboxylic acid solution, or combinations thereof.
(c) And (2) putting the uniformly stirred mixed solution into a reaction kettle, carrying out hydrothermal reaction at the temperature of 80-260 ℃ for 3-100 h, naturally cooling the mixed solution after the hydrothermal reaction to obtain a white substance, centrifugally cleaning the white substance for 2-6 times by using deionized water and an absolute ethanol solution, and carrying out vacuum drying at the temperature of 80 ℃ to obtain the Al-MOF material.
Secondly, preparing a lithium ion battery cathode material:
(d) mixing and grinding the Al-MOF material obtained by the solvothermal method, a conductive agent and a binder according to the mass ratio of 6-8:1-2:1-2, and pouring the mixture into a solvent for grinding for 0.3-2h to obtain uniform electrode slurry;
(e) and coating the electrode slurry on a metal copper foil, wherein the thickness of the coating is 80-200 mu m, and placing the coating in a vacuum drying oven at 60-120 ℃ for drying for 6-24h to obtain the Al-MOF negative electrode material for the lithium ion battery, namely the negative electrode plate of the lithium ion battery.
In the step (d), the solvent is N-methyl pyrrolidone or deionized water, the conductive agent is conductive carbon black, and the binder is sodium carboxymethylcellulose, polyvinylidene fluoride or sodium alginate.
Example 1
Taking aluminum-silicon alloy as a raw material, wherein the size of the D50 particle size is about 6 mu m; carrying out dealloying chemical reaction on the micron alloy powder and 2mol/L HCl solution, stirring the mixture for 10 hours in a mild way, wherein the reaction temperature is 50 ℃, and finally obtaining porous silicon solid particles and an aluminum trichloride solution through a suction filtration device; adding the aluminum trichloride solution (5ml), terephthalic acid (0.61g) and PVP (1.83g) obtained after dealloying into a mixed solution of 60ml of DMF and 10ml of deionized water, and magnetically stirring for 0.5h until the solutions are uniformly mixed; and (3) putting the uniformly stirred mixed solution into a 100ml reaction kettle, carrying out hydrothermal reaction at the temperature of 150 ℃ for 6h, naturally cooling the mixed solution after the hydrothermal reaction to obtain a white substance, centrifugally cleaning the white substance for 3 times by using deionized water and absolute ethyl alcohol, and carrying out vacuum drying at the temperature of 80 ℃ for 12 hours to obtain the Al-MOF material. Mixing and grinding the obtained Al-MOF material, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1 for 0.5h to obtain uniform electrode slurry; and coating the electrode slurry on a metal copper collector, wherein the thickness of the coating is 100 microns, and placing the coating in a vacuum drying oven at 80 ℃ for drying for 12 hours to obtain the Al-MOF negative electrode material for the lithium ion battery, namely the lithium ion battery negative electrode material. In this example, the battery test results show; the first discharge specific capacity reaches 202.2mAh/g, the charge specific capacity reaches 186.1mAh/g, and the discharge and charge specific capacities respectively reach 172.4mAh/g and 171.8mAh/g after 100-time circulation under the current density of 100 mA/g.
Example 2
Taking aluminum-silicon alloy as a raw material, wherein the size of the D50 particle size is about 6 mu m; carrying out dealloying chemical reaction on the micron alloy powder and 2mol/L HCl solution, stirring the mixture for 10 hours in a mild way, wherein the reaction temperature is 50 ℃, and finally obtaining porous silicon solid particles and an aluminum trichloride solution through a suction filtration device; adding the aluminum trichloride solution (5ml), terephthalic acid (0.61g) and PVP (1.83g) obtained after dealloying into a mixed solution of 60ml of DMF and 10ml of deionized water, and magnetically stirring for 0.5h until the solutions are uniformly mixed; and (3) putting the uniformly stirred mixed solution into a 100ml reaction kettle, carrying out hydrothermal reaction at the temperature of 150 ℃ for 9h, naturally cooling the mixed solution after the hydrothermal reaction to obtain a white substance, centrifugally cleaning the white substance for 3 times by using deionized water and absolute ethyl alcohol, and carrying out vacuum drying at the temperature of 80 ℃ for 12 hours to obtain the Al-MOF material. Mixing and grinding the obtained Al-MOF material, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1 for 0.5h to obtain uniform electrode slurry; and coating the electrode slurry on a metal copper collector, wherein the thickness of the coating is 100 microns, and placing the coating in a vacuum drying oven at 80 ℃ for drying for 12 hours to obtain the Al-MOF negative electrode material for the lithium ion battery, namely the lithium ion battery negative electrode material. In this example, the battery test results show; the first discharge specific capacity reaches 169.7mAh/g, the charge specific capacity reaches 160.8mAh/g, the discharge and charge specific capacities respectively reach 143.7mAh/g and 143.6mAh/g after 100 times of circulation under the current density of 100mA/g, and the excellent circulation stability is shown.
Example 3
Taking aluminum-silicon alloy as a raw material, wherein the size of the D50 particle size is about 6 mu m; carrying out dealloying chemical reaction on the micron alloy powder and 2mol/L HCl solution, stirring the mixture for 10 hours in a mild way, wherein the reaction temperature is 50 ℃, and finally obtaining porous silicon solid particles and an aluminum trichloride solution through a suction filtration device; adding the aluminum trichloride solution (5ml), terephthalic acid (0.61g) and PVP (1.83g) obtained after dealloying into a mixed solution of 60ml of DMF and 10ml of deionized water, and magnetically stirring for 0.5h until the solutions are uniformly mixed; and (3) putting the uniformly stirred mixed solution into a 100ml reaction kettle, carrying out hydrothermal reaction at the temperature of 150 ℃ for 15h, naturally cooling the mixed solution after the hydrothermal reaction to obtain a white substance, centrifugally cleaning the white substance for 3 times by using deionized water and absolute ethyl alcohol, and carrying out vacuum drying at the temperature of 80 ℃ for 12 hours to obtain the Al-MOF material. Mixing and grinding the obtained Al-MOF material, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1 for 0.5h to obtain uniform electrode slurry; and coating the electrode slurry on a metal copper collector, wherein the thickness of the coating is 100 microns, and placing the coating in a vacuum drying oven at 80 ℃ for drying for 12 hours to obtain the Al-MOF negative electrode material for the lithium ion battery, namely the lithium ion battery negative electrode material. In this example, the battery test results show; the first discharge specific capacity reaches 159.9mAh/g, the charge specific capacity reaches 139.7mAh/g, and the discharge and charge specific capacities respectively reach 102.7mAh/g and 100.2mAh/g after 100-time circulation under the current density of 100 mA/g.
Example 4
Taking aluminum-silicon alloy as a raw material, wherein the size of the D50 particle size is about 6 mu m; carrying out dealloying chemical reaction on the micron alloy powder and 2mol/L HCl solution, stirring the mixture for 10 hours in a mild way, wherein the reaction temperature is 50 ℃, and finally obtaining porous silicon solid particles and an aluminum trichloride solution through a suction filtration device; adding the aluminum trichloride solution (5ml), terephthalic acid (0.61g) and PVP (1.83g) obtained after dealloying into a mixed solution of 60ml of DMF and 10ml of deionized water, and magnetically stirring for 0.5h until the solutions are uniformly mixed; and (3) putting the uniformly stirred mixed solution into a 100ml reaction kettle, carrying out hydrothermal reaction at the temperature of 150 ℃ for 20h, naturally cooling the mixed solution after the hydrothermal reaction to obtain a white substance, centrifugally cleaning the white substance for 3 times by using deionized water and absolute ethyl alcohol, and carrying out vacuum drying at the temperature of 80 ℃ for 12 hours to obtain the Al-MOF material. Mixing and grinding the obtained Al-MOF material, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1 for 0.5h to obtain uniform electrode slurry; and coating the electrode slurry on a metal copper collector, wherein the thickness of the coating is 100 microns, and placing the coating in a vacuum drying oven at 80 ℃ for drying for 12 hours to obtain the Al-MOF negative electrode material for the lithium ion battery, namely the lithium ion battery negative electrode material. In this example, the battery test results show; the first discharge specific capacity reaches 123.9mAh/g, the charge specific capacity reaches 97.1mAh/g, and the discharge and charge specific capacities respectively reach 82.8mAh/g and 82.6mAh/g after 100-time circulation under the current density of 100 mA/g.
As shown in FIG. 1, which is an XRD (X-ray diffraction) pattern of Al-MOF in examples 1-4 of the present invention, it can be seen from FIG. 1 that distinct structural characteristic peaks appear at 2 θ angles of 8.16-8.25, 9.28-9.40, 16.12-16.24, 18.12-18.80, and 21.00-21.08, which are substantially coincident with the positions of the main peaks. The synthesis peaks at the heat of solution at 9, 15 and 20h were substantially identical, and the 6 hour local characteristic peak was not shown, indicating that the synthesis time was short, resulting in incomplete MOF synthesis.
As shown in fig. 2 and 3, which are SEM (scanning electron microscope) images of Al — MOF in example 1 of the present invention, it can be seen from fig. 2 and 3 that the solvent heat generated the olivary-type pore structure with a size of about 300nm at 6h, the particle clustering phenomenon was not obvious, and the particle distribution was relatively uniform.
As shown in fig. 4, which is a cycle performance diagram of Al-MOF in example 1 of the present invention, it can be seen from fig. 4 that the first discharge specific capacity of the Al-MOF structure reaches 202.2mAh/g and the charge specific capacity reaches 186.1mAh/g at 0.1A/g, and after 100 cycles at a current density of 100mA/g, the discharge and charge specific capacities respectively reach 172.4mAh/g and 171.8mAh/g, showing better cycle stability.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method for synthesizing an Al-MOF negative electrode material by a solvothermal method is characterized by comprising the following steps:
s1, preparing an Al-MOF material;
s11, providing aluminum-silicon alloy powder prepared by a nitrogen high-pressure high-speed atomization technology as a raw material, wherein the particle size of the aluminum-silicon alloy powder is 0.1-80 mu m;
s12, mixing a certain amount of aluminum-silicon alloy powder with an inorganic acid solution, stirring with mild magnetic force, and carrying out dealloying reaction for 1-48h at 25-100 ℃;
s13, after the reaction is finished, carrying out solid-liquid separation through a suction filtration device, washing the obtained porous silicon solid particles for 3-6 times by using deionized water and absolute ethyl alcohol solution, and separately collecting the aluminum salt solution in the obtained filter flask for later use;
s14, adding the aluminum salt solution and the organic acid solution into a certain volume of solvent for mixing;
s15, adding a certain mass of high molecular surfactant polyvinylpyrrolidone into the mixed solution obtained in the step S14, and magnetically stirring for 0.2-5 hours until the mixture is uniformly mixed;
s16, putting the uniformly stirred mixed solution obtained in the step S15 into a reaction kettle, performing hydrothermal reaction, and obtaining an Al-MOF material by a hydrothermal method;
s2, preparing an Al-MOF negative electrode material;
s21, mixing and grinding the Al-MOF material obtained in the step S16, a conductive agent and a binder according to the mass ratio of 6-8:1-2:1-2, and pouring the mixture into a solvent for grinding for 0.3-2h to obtain uniform electrode slurry;
s22, coating the electrode slurry on a metal copper foil, wherein the thickness of the coating is 80-200 mu m, and placing the metal copper foil in a vacuum drying oven to be dried for 6-24h at 60-120 ℃ to obtain the Al-MOF negative electrode material for the lithium ion battery, namely the negative electrode plate of the lithium ion battery.
2. The preparation method of the Al-MOF anode material through solvothermal synthesis according to claim 1, wherein in the step S12, the inorganic acid solution is one of an HCl solution, an HNO3 solution and an H2SO4 solution, or a combination of more than one of the above solutions.
3. The preparation method of the Al-MOF anode material synthesized by the solvothermal method according to claim 1 or 2, wherein in the step S12, the inorganic acid solution is used as a corrosion solution, and the mass concentration of the inorganic acid solution is 1-40%.
4. The preparation method of the Al-MOF anode material through solvothermal synthesis according to claim 1, wherein in the step S14, the solvent is one of N, N-dimethylformamide, absolute ethyl alcohol, ethylene glycol, glycerol, nitrogen-dimethyl acetamide or tetrahydrofuran, or a combination of more than one of N, N-dimethyl formamide, absolute ethyl alcohol, ethylene glycol, glycerol, nitrogen-dimethyl acetamide and tetrahydrofuran.
5. The preparation method of the Al-MOF anode material through solvothermal synthesis according to claim 1 or 4, wherein in the step S14, the organic acid solution is one of a terephthalic acid solution, a trimesic acid solution and a 1, 4-naphthalene dicarboxylic acid solution, or a combination of more than one of the terephthalic acid solution, the trimesic acid solution and the 1, 4-naphthalene dicarboxylic acid solution.
6. The preparation method of the Al-MOF anode material synthesized by the solvothermal method according to claim 5, wherein in the step S14, the molar ratio of the aluminum salt to the organic acid is 5: 1-1: 5.
7. The preparation method of the Al-MOF anode material synthesized by the solvothermal method according to claim 1, wherein in the step S15, the mass ratio of the organic acid to the high-molecular surfactant polyvinylpyrrolidone is 10: 1-1: 10.
8. The preparation method of the Al-MOF anode material synthesized by the solvothermal method according to claim 1, wherein the specific steps of the step S16 are as follows:
s161, putting the uniformly stirred mixed solution obtained in the step S15 into a reaction kettle, and carrying out hydrothermal reaction at the temperature of 80-260 ℃ for 3-100 h;
s162, after the hydrothermal reaction, naturally cooling the mixed solution to obtain a white substance, then centrifugally cleaning the white substance for 2-6 times by using deionized water and an absolute ethyl alcohol solution, and carrying out vacuum drying at 80 ℃ to obtain the Al-MOF material.
9. The preparation method of the Al-MOF anode material synthesized by the solvothermal method according to claim 1, wherein in the step S21, the solvent is N-methylpyrrolidone or deionized water, the conductive agent is conductive carbon black, and the binder is sodium carboxymethylcellulose, polyvinylidene fluoride or sodium alginate.
10. The Al-MOF anode material prepared by the method of any one of claims 1 to 9 is applied to a lithium ion battery.
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