CN112679966A - Preparation method and application of composite material containing graphite and MOF - Google Patents

Preparation method and application of composite material containing graphite and MOF Download PDF

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CN112679966A
CN112679966A CN202011544416.1A CN202011544416A CN112679966A CN 112679966 A CN112679966 A CN 112679966A CN 202011544416 A CN202011544416 A CN 202011544416A CN 112679966 A CN112679966 A CN 112679966A
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mof
graphite
composite material
stirring
preparation
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CN112679966B (en
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余海军
彭挺
谢英豪
朱红梅
刘述敏
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the field of battery materials, and discloses a preparation method and application of a composite material containing graphite and MOF, wherein the preparation method comprises the following steps: adding an organic matter containing amino into the mixed solution, stirring, adding a titanium-containing coupling agent, and continuously stirring to obtain a suspension; carrying out solvothermal reaction on the suspension, filtering, taking filter residues, sequentially and alternately cleaning with an organic solvent, and extracting to obtain MOF; grinding graphite into powder, mixing the powder with alcohol, oscillating, adding MOF, continuing oscillating, refluxing, standing, centrifuging, taking precipitate, and drying to obtain the composite material containing graphite and MOF. The prepared graphite and MOF-containing composite material is used as a basic framework of a negative electrode material, the material has good structural stability, and can eliminate the volume expansion effect of a battery in the charge and discharge process caused by the structural collapse of the negative electrode material due to the cycle of lithium removal and lithium insertion in the charge and discharge process of the lithium battery when applied to the negative electrode of the lithium battery, thereby improving the capacity.

Description

Preparation method and application of composite material containing graphite and MOF
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a preparation method and application of a composite material containing graphite and MOF.
Background
With the progress of internet science and technology, more and more technical applications are used by depending on electronic equipment. The use of the electronic equipment requires a lithium battery with high capacity and convenient use to provide endurance. In addition, with the recent trend of various policies driving the use of electric vehicles and other electric tools in large quantities, lithium batteries have become an indispensable device for social development from various industries to daily life. Currently, the negative electrode material in lithium ion batteries is mainly carbon, such as graphite, soft and hard carbon, or a novel electrode material, such as a silicon carbon negative electrode or a transition metal oxide. Under the development trend of gradually increasing the requirement of the market on the capacity of the battery, the traditional lithium ion battery with the negative electrode cannot meet the current situation. Under the circumstances, the preparation of novel materials and the application of the novel materials in lithium ion batteries become research hotspots.
Metal organic framework Materials (MOFs) are crystalline framework materials with intramolecular pores formed by self-assembly of metal ions or clusters and organic ligands through coordination bonds under certain conditions. The material has large specific surface area, adjustable pore size and shape and easy modification, and the proton-conducting and electron-conducting MOF has potential application value in the fields of fuel cells, electrocatalysis, lithium ion batteries, supercapacitors and the like. MOF has been widely paid attention to its unique pore structure and characteristics of containing transition metal elements, and has been used to successfully prepare electrodes using MOF as an active material or as an active material carrier, and also to prepare electrodes using MOF as a precursor to form an active material or an active material carrier, but MOF as an electrode has slightly poor conductivity compared to other electrode materials. Secondly, the preparation process of the MOF is complex, the morphology controllability of the MOF is influenced, the stability of the MOF is poor, and the wide application of the MOF in electrode materials is limited.
To date, a variety of MOFs have been reported for use in negative electrodes of lithium batteries. However, most MOFs have the disadvantage of low capacity when used as negative electrodes for lithium batteries. Therefore, the method has very important significance in finding a composite material which has a stable structure, a large specific surface area, a wider application range and greatly improved charging and discharging coulombic efficiency and cyclicity.
Disclosure of Invention
The invention aims to provide a preparation method and application of a composite material containing graphite and MOF. The composite material prepared by the preparation method has good structural stability, and can eliminate the volume expansion effect of a battery in the charge and discharge process caused by the structural collapse of a negative electrode material due to the cycle of lithium removal and lithium insertion in the charge and discharge process of the lithium battery when being applied to the negative electrode of the lithium battery, thereby improving the capacity and other electrochemical properties.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of preparing a graphite and MOF containing composite material comprising the steps of:
(1) adding an amino-containing organic matter into the mixed solution, stirring, increasing the stirring speed, adding a titanium-containing coupling agent, and continuously stirring to obtain a suspension;
(2) carrying out solvothermal reaction on the suspension, filtering, taking filter residues, sequentially and alternately cleaning with an organic solvent, and extracting to obtain MOF;
(3) grinding graphite into powder, mixing the powder with alcohol, oscillating, adding the MOF, continuing oscillating, refluxing, standing, centrifuging, taking the precipitate, and drying to obtain the composite material containing graphite and MOF.
Preferably, the mixed solution is obtained by mixing N, N-dimethyl amide and methanol; the mass ratio of the N, N-dimethyl amide to the methanol is 1: (6-9).
Preferably, the N, N-dimethyl amide and the methanol are both in an anhydrous state.
Preferably, the distillation temperature of the N, N-dimethyl amide is 50-60 ℃; the temperature of methanol distillation is 55-65 ℃.
Preferably, in step (1), the amino group-containing organic substance is 2-amino-terephthalic acid; in the step (1), the mass ratio of the amino-containing organic matter to the mixed solution is 1 (3-6).
Preferably, in the step (1), the stirring temperature is 15-35 ℃, the stirring speed is 500-800 r/min, and the stirring time is 10-30 min.
Preferably, in the step (1), the stirring speed is increased to 1000-1500 r/min, and the continuous stirring time is 10-30 min.
Preferably, in step (1), the titanium-containing coupling agent is tetrabutyl titanate.
Preferably, in the step (1), the mass ratio of the mixed solution to the titanium-containing coupling agent is 1 (15-35).
More preferably, in the step (1), the mass ratio of the mixed solution to the titanium-containing coupling agent is 1 (20-30).
Preferably, in step (2), the organic solvent is N, N-dimethylamide and methanol.
Preferably, in the step (2), the sequentially and alternately washing with the organic solvent is sequentially and alternately washing with N, N-dimethyl amide and methanol for 3-5 times.
Preferably, in the step (2), the temperature of the solvothermal reaction is 130-150 ℃, and the time of the solvothermal reaction is 24-72 hours.
Preferably, in the step (2), the extraction is performed by using a Soxhlet extractor.
Preferably, in the step (3), the grinding of the graphite into powder is to grind the graphite to 100-200 meshes.
Preferably, in step (3), the alcohol is anhydrous methanol.
Preferably, in the step (3), the mass ratio of the graphite to the alcohol is 1 (10-20).
More preferably, in the step (3), the mass ratio of the graphite to the alcohol is 1 (15-20).
Preferably, in the step (3), the mass ratio of the MOF to the alcohol is 1 (10-20).
More preferably, in the step (3), the mass ratio of the MOF to the alcohol is 1 (15-20).
Preferably, in the step (3), the oscillation is ultrasonic oscillation, the time of the ultrasonic oscillation is 20-40 min, and the time of the continuous oscillation is 20-40 min.
Preferably, in the step (3), the reflux temperature is 60-70 ℃, and the reflux time is 12-18 hours; the standing time is 12-18 hours.
A composite material containing graphite and MOF, which is prepared by the preparation method; the specific capacity of the graphite-coated MOF material is 460-495mAh/g, the porosity is 32-37%, and the specific surface area is 2.7-3.5m2/g。
A negative electrode sheet comprising the graphite and MOF-containing composite material.
The invention also provides a preparation method of the negative plate, which comprises the following steps:
mixing the composite material containing the graphite and the MOF with acetylene black, and then carrying out ball milling to obtain a mixture; mixing the mixture, PVDF and N-methyl pyrrolidone to prepare slurry; coating and drying the slurry to prepare the negative plate.
Preferably, the weight ratio of the composite material containing graphite and MOF to acetylene black is 1 (0.1-0.3).
Preferably, the rotation speed of the ball milling is 3000-6000 r/min, and the time of the ball milling is 10-20 min.
Preferably, the mass ratio of the mixture to the PVDF and the N-methyl pyrrolidone is 1: (0.1-0.15) and (0.1-0.5).
The invention also provides a battery, which comprises the negative plate.
The invention has the advantages that:
1. the prepared composite material containing graphite and MOF (graphite coated MOF) is used as a basic framework of a negative electrode material, the material has good structural stability, and the material can eliminate the volume expansion effect (the volume expansion can cause the material structure collapse and the electrochemical performance is weakened) of a battery in the charge and discharge process caused by the structural collapse of the negative electrode material due to the cycle of lithium removal and lithium insertion in the charge and discharge process of the lithium battery when being applied to the negative electrode of the lithium battery, so that the capacity and other electrochemical performances are improved.
2. The composite material designed by the invention has excellent charge-discharge capacity and conductivity superior to those of a graphite material, and also has excellent structural stability of an MOF material.
3. The invention is achieved by introducing NH into MOF materials2 -The electronic density of the material is enhanced, so that the conductivity of the material is increased to a certain extent, and more importantly, lithium insertion sites are provided, so that the charge and discharge capacity of the material is remarkably increased; the first discharge specific capacity can reach 492.3mAh/g, and the capacity retention rate is 96.6 percent.
Drawings
FIG. 1 is an XRD pattern of a graphite and MOF containing composite material prepared in example 1;
figure 2 is a TEM image of a graphite and MOF containing composite prepared in example 1.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below with reference to the examples to further illustrate the features and advantages of the invention, and any changes or modifications that do not depart from the gist of the invention will be understood by those skilled in the art to which the invention pertains, the scope of which is defined by the scope of the appended claims.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
The preparation method of the composite material containing graphite and MOF comprises the following steps:
(1) distilling anhydrous N, N-dimethyl amide and anhydrous methanol at 50 ℃ and 55 ℃ respectively, and then distilling the anhydrous N, N-dimethyl amide and the anhydrous methanol obtained by distillation according to the weight ratio of 1:6, mixing in proportion to obtain a mixed solution;
(2) adding 2-amino-terephthalic acid according to the mass volume ratio of 1:3, stirring at 15 ℃ for 10min at the rotating speed of 500r/min, increasing the rotating speed to 1000r/min, adding tetrabutyl titanate according to the volume ratio of 1:15, and continuously stirring for 10min to obtain a suspension;
(3) transferring the obtained suspension into a dry hydrothermal kettle, carrying out solvothermal reaction for 24h at 130 ℃, filtering a product of the solvothermal reaction, sequentially and alternately cleaning the product for 3 times by using anhydrous N, N-dimethyl amide and anhydrous methanol, and extracting the product by using a Soxhlet extractor to obtain a white solid MOF material;
(4) grinding graphite into powder (sieving by a 100-mesh sieve), mixing the powder with anhydrous methanol according to the mass-to-volume ratio of 1:10, carrying out ultrasonic treatment for 20min, adding a white solid MOF material according to the mass-to-volume ratio of 1:10, continuing ultrasonic oscillation for 20min, refluxing at 60 ℃ for 12 h, standing for 12 h, centrifuging, and drying to obtain the composite material (graphite coated MOF) containing graphite and MOF.
The preparation method of the negative electrode plate of the embodiment comprises the following steps: mixing a composite material containing graphite and MOF with acetylene black in a weight ratio of 1:0.1, ball-milling at a rotating speed of 3000r/min for 10min, preparing slurry from the obtained mixture powder, PVDF and N-methyl pyrrolidone in a ratio of 1:0.1:0.1, coating and drying to prepare the negative plate.
Example 2
The preparation method of the composite material containing graphite and MOF comprises the following steps:
(1) distilling anhydrous N, N-dimethyl amide and anhydrous methanol at 50 ℃ and 60 ℃ respectively, and then distilling the anhydrous N, N-dimethyl amide and the anhydrous methanol obtained by distillation according to the weight ratio of 1: 7, mixing in proportion to obtain a mixed solution;
(2) adding 2-amino-terephthalic acid according to the mass volume ratio of 1:5, stirring at the rotating speed of 700r/min for 20min at the temperature of 20 ℃, increasing the rotating speed to 1200r/min, adding tetrabutyl titanate according to the volume ratio of 1:25, and continuously stirring for 20min to obtain a suspension;
(3) transferring the obtained suspension into a dry hydrothermal kettle, carrying out solvothermal reaction for 48h at 140 ℃, filtering a product of the solvothermal reaction, sequentially and alternately cleaning the product for 3 times by using anhydrous N, N-dimethyl amide and anhydrous methanol, and extracting the product by using a Soxhlet extractor to obtain a white solid MOF material;
(4) grinding graphite into powder (sieving by a 150-mesh sieve), mixing the powder with anhydrous methanol according to the mass-to-volume ratio of 1:15, carrying out ultrasonic treatment for 30min, adding a white solid MOF material according to the mass-to-volume ratio of 1:15, continuing ultrasonic oscillation for 30min, refluxing at 65 ℃ for 15 h, standing for 15 h, centrifuging, and drying to obtain the composite material (graphite coated MOF) containing graphite and MOF.
The preparation method of the negative electrode plate of the embodiment comprises the following steps: mixing a composite material (graphite coated MOF) containing graphite and MOF with acetylene black in a weight ratio of 1:0.2, ball-milling at a rotating speed of 4500r/min for 15min, and mixing the obtained mixture powder in a ratio of 1: 0.12:0.3, PVDF and N-methyl pyrrolidone to prepare slurry, and coating and drying the slurry to prepare the negative plate.
Example 3
The preparation method of the composite material containing graphite and MOF comprises the following steps:
(1) distilling anhydrous N, N-dimethyl amide and anhydrous methanol at the temperature of 60 ℃ and 65 ℃ respectively, and then distilling the anhydrous N, N-dimethyl amide and the anhydrous methanol obtained by distillation according to the weight ratio of 1: mixing in proportion of 9 to obtain a mixed solution;
(2) adding 2-amino-terephthalic acid according to the mass volume ratio of 1:6, stirring at the rotating speed of 800r/min for 30min at the temperature of 35 ℃, increasing the rotating speed to 1500r/min, adding tetrabutyl titanate according to the volume ratio of 1:35, and continuously stirring for 30min to obtain a suspension;
(3) transferring the obtained suspension into a dry hydrothermal kettle, carrying out a solvothermal reaction for 72h at the temperature of 150 ℃, filtering a product of the solvothermal reaction, sequentially and alternately cleaning the product for 3 times by using anhydrous N, N-dimethyl amide and anhydrous methanol, and extracting the product by using a Soxhlet extractor to obtain a white solid MOF material;
(4) grinding commercial graphite into powder (sieving with a 200-mesh sieve), mixing with anhydrous methanol according to the mass-to-volume ratio of 1:20, carrying out ultrasonic treatment for 40min, adding a white solid MOF material according to the mass-to-volume ratio of 1:20, continuing ultrasonic oscillation for 40min, refluxing at 70 ℃ for 18 h, standing for 18 h, centrifuging, and drying to obtain the composite material (graphite coated MOF) containing graphite and MOF.
The preparation method of the negative electrode plate of the embodiment comprises the following steps: mixing a composite material containing graphite and MOF with acetylene black in a weight ratio of 1:0.3, ball-milling at a rotating speed of 6000r/min for 20min, and mixing the obtained mixture powder in a ratio of 1: 0.15:0.5, PVDF and N-methyl pyrrolidone to prepare slurry, and coating and drying the slurry to prepare the negative plate.
Comparative example 1
A preparation method of a titanium-based MOF lithium ion battery negative electrode material comprises the following steps: dispersing 2, 5-dihydroxy terephthalic acid in isopropanol solution, dropwise adding the solution into acetonitrile solution containing tetraisopropoxytitanium, and stirring at room temperature to obtain orange brown slurry for 30 min; transferring into a Teflon high-pressure reaction kettle, heating to 120 ℃, keeping the temperature for 24 hours to obtain dark red crystals, performing suction filtration in air atmosphere, washing with DMF (N, N-dimethylformamide) and ethanol for three times respectively, and performing vacuum drying to obtain the electrode material.
Comparative example 2
A method of preparing a graphite-and MOF-containing material, comprising the steps of: grinding commercial graphite into powder, mixing the powder with anhydrous methanol according to the mass-to-volume ratio of 1:20, carrying out ultrasonic treatment for 40min, adding the MOF material obtained in the comparative example 1 according to the mass-to-volume ratio of 1:20, continuing to carry out ultrasonic vibration for 40min, refluxing at 70 ℃ for 18 h, standing for 18 h, centrifuging, and drying to obtain the graphite-coated MOF material.
And (3) performance detection:
negative electrode materials of the composite material containing graphite and MOF prepared in the above examples 1-3 and negative electrode materials prepared in the comparative examples 1-2 were respectively prepared into negative electrode sheets, lithium sheets were used as positive electrodes to assemble button cells, and the results of the first discharge test at 1C rate are shown in tables 1 and 2. As can be seen from Table 1, at a rate of 1C, the specific first discharge capacity of the negative electrode material of the composite material containing graphite and MOF is higher than that of the MOF materials of comparative examples 1 and 2, the specific first discharge capacity of example 2 is 492.3mAh/g, the specific first discharge capacity of comparative example 1 is only 333.1mAh/g, and the specific first discharge capacity of comparative example 2 is only 367.2 mAh/g. As can be seen from table 2, at the 1C rate, the cycle life of the negative electrode material of the composite material containing graphite and MOF of the present invention is longer than that of the comparative MOF material, and after 1600 cycles of 1C, the capacity retention rate of example 2 is 96.6%, while the capacity retention rates of comparative examples 1-2 are only 92.8% and 90.2%, respectively.
TABLE 1 button cell Performance of graphite and MOF containing composites
Figure BDA0002855331900000061
TABLE 2 full cell cycling performance of graphite and MOF containing composites
Figure BDA0002855331900000071
Figure 1 is an XRD pattern of a composite material comprising graphite and MOF, in which characteristic peaks of the composite material are reflected. FIG. 2 is a TEM image of a composite material comprising graphite and MOF as a bulk morphology.
While the above detailed description of the method of making a graphite and MOF containing composite material and its use according to the present invention has been provided, and while the principles and embodiments of the present invention have been described herein using specific examples, the above examples are provided only to facilitate an understanding of the method and its core ideas, including the best mode, of the present invention and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combination of the methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. A preparation method of a composite material containing graphite and MOF is characterized by comprising the following steps:
(1) adding an amino-containing organic matter into the mixed solution, stirring, increasing the stirring speed, adding a titanium-containing coupling agent, and continuously stirring to obtain a suspension;
(2) carrying out solvothermal reaction on the suspension, filtering, taking filter residues, sequentially and alternately cleaning with an organic solvent, and extracting to obtain MOF;
(3) grinding graphite into powder, mixing the powder with alcohol, oscillating, adding the MOF, continuing oscillating, refluxing, standing, centrifuging, taking the precipitate, and drying to obtain the composite material containing graphite and MOF.
2. The method according to claim 1, wherein in the step (1), the mixed solution is obtained by mixing N, N-dimethylamide and methanol; the mass ratio of the N, N-dimethyl amide to the methanol is 1: (6-9).
3. The production method according to claim 1, wherein in the step (1), the amino group-containing organic substance is 2-amino-terephthalic acid; in the step (1), the mass ratio of the amino-containing organic matter to the mixed solution is 1 (3-6).
4. The preparation method according to claim 1, wherein in the step (1), the stirring temperature is 15-35 ℃, the stirring speed is 500-800 r/min, and the stirring time is 10-30 min; in the step (1), the stirring speed is increased to 1000-1500 r/min, and the continuous stirring time is 10-30 min.
5. The method according to claim 1, wherein in the step (1), the titanium-containing coupling agent is tetrabutyl titanate; in the step (1), the mass ratio of the mixed solution to the titanium-containing coupling agent is 1 (15-35).
6. The method according to claim 1, wherein in the step (2), the organic solvent is N, N-dimethylformamide and methanol.
7. The production method according to claim 1, wherein in the step (3), the alcohol is anhydrous methanol; the mass ratio of the graphite to the alcohol is 1 (10-20); in the step (3), the mass ratio of the MOF to the alcohol is 1 (10-20).
8. The preparation method according to claim 1, wherein in the step (2), the temperature of the solvothermal reaction is 130-150 ℃, and the time of the solvothermal reaction is 24-72 hours; in the step (3), the reflux temperature is 60-70 ℃, and the reflux time is 12-18 hours; the standing time is 12-18 hours.
9. A graphite and MOF-containing composite material produced by the production method according to any one of claims 1 to 8; the specific capacity of the composite material containing the graphite and the MOF is 460-495mAh/g, the porosity is 32-37 percent, and the specific surface area is 2.7-3.5m2/g。
10. A negative electrode sheet comprising the graphite and MOF-containing composite material of claim 9.
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