CN112679966B - 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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CN112679966B
CN112679966B CN202011544416.1A CN202011544416A CN112679966B CN 112679966 B CN112679966 B CN 112679966B CN 202011544416 A CN202011544416 A CN 202011544416A CN 112679966 B CN112679966 B CN 112679966B
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mof
graphite
composite material
stirring
preparation
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CN112679966A (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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Publication of CN112679966A publication Critical patent/CN112679966A/en
Priority to PCT/CN2021/123393 priority patent/WO2022134747A1/en
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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 amino-containing organic matter 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, alternately cleaning with an organic solvent, and extracting to obtain MOF; grinding graphite into powder, mixing 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, has good structural stability, and can eliminate the volume expansion effect of a battery in the charging and discharging process caused by structural collapse of the negative electrode material due to lithium removal and lithium intercalation circulation in the charging and discharging process 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 technology, more and more technical applications rely on electronic devices for use. And the lithium battery with high capacity and convenient use is required to provide endurance for the electronic equipment. In addition, with the recent great use of electric vehicles and other electric tools by various policy-driven people, lithium batteries have become an indispensable device for social development from various industries to daily life. Currently, the negative electrode materials in lithium ion batteries are mainly carbon materials, such as graphite, soft and hard carbon, or novel electrode materials, such as silicon carbon negative electrodes or transition metal oxides. Under the development trend of gradually increasing the battery capacity requirements in the market, the lithium ion battery of the traditional negative electrode cannot meet the current situation. In this case, the preparation and application of novel materials in lithium ion batteries are hot research spots.
Metal organic framework Materials (MOFs) are crystalline framework materials with intramolecular pores formed by self-assembly of metal ions or clusters with organic ligands through coordination bonds under certain conditions. The material has large specific surface area, adjustable pore size and shape, easy modification, and proton conduction and electron conduction MOF (metal oxide semiconductor) has potential application value in the fields of fuel cells, electrocatalysis, lithium ion batteries, supercapacitors and the like. MOFs have received great attention due to their unique pore structure and the characteristic of containing transition metal elements, and electrodes have been successfully prepared using MOFs as active materials or as active material carriers, and electrodes using MOFs as precursors to form active materials or active material carriers, but MOFs as electrodes have slightly poorer electrical conductivity than other electrode materials. Secondly, the preparation process of the MOF is complex, the shape controllability of the MOF is affected, so that the MOF has poor stability, and the MOF is limited to be widely applied to electrode materials.
To date, a wide variety of MOFs have been reported for use in the negative electrode of lithium batteries. Most MOFs have the disadvantage of low capacity when used as negative electrodes for lithium batteries. Therefore, the preparation of the composite material with stable structure, large specific surface area, wider application range and greatly improved charge-discharge coulomb efficiency and circularity is very important.
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 disclosed by the invention has good structural stability, and can eliminate the volume expansion effect of the battery in the charge and discharge process caused by structural collapse of the anode material due to the cycle of lithium removal and lithium intercalation in the charge and discharge process of the lithium battery when the composite material is applied to the anode of the lithium battery, so that the capacity and other electrochemical performances are improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing a composite material containing graphite and MOF, 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 continuing stirring to obtain a suspension;
(2) Carrying out solvothermal reaction on the suspension, filtering, taking filter residues, alternately cleaning with an organic solvent, and extracting to obtain MOF;
(3) Grinding graphite into powder, mixing with alcohol, oscillating, adding the MOF, continuing oscillating, refluxing, standing, centrifuging, taking precipitate, and drying to obtain the composite material containing graphite and MOF.
Preferably, the mixed solution is obtained by mixing N, N-dimethylamide and methanol; the mass ratio of the N, N-dimethylamide to the methanol is 1: (6-9).
Preferably, the N, N-dimethylamide and the methanol are all in an anhydrous state.
Preferably, the temperature of the distillation of the N, N-dimethylamide is 50-60 ℃; the temperature of methanol distillation is 55-65 ℃.
Preferably, in step (1), the amino-containing organic matter is 2-amino-terephthalic acid; in the step (1), the mass ratio of the organic matters containing amino groups to the mixed solution is 1 (3-6).
Preferably, in the step (1), the stirring temperature is 15-35 ℃, the stirring rotating speed is 500-800 r/min, and the stirring time is 10-30min.
Preferably, in the step (1), the stirring speed is increased to 1000-1500 r/min, and the stirring is continued for 10-30min.
Preferably, in the 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 cleaning is performed alternately with the organic solvent 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 h.
Preferably, in step (2), the extraction is performed using a Soxhlet extractor.
Preferably, in step (3), the grinding of the graphite into powder is grinding the graphite to 100-200 mesh.
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 step (3), the mass ratio of MOF to alcohol is 1 (15-20).
Preferably, in the step (3), the vibration is ultrasonic vibration, the time of the ultrasonic vibration is 20-40 min, and the time of the continuous vibration is 20-40 min.
Preferably, in the step (3), the temperature of the reflux is 60-70 ℃ and the time of the reflux is 12-18 hours; the standing time is 12-18 hours.
A composite material containing graphite and MOF 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 2.7-3.5m 2 /g。
A negative electrode sheet comprising the graphite and MOF-containing composite material described above.
The invention also provides a preparation method of the negative plate, which comprises the following steps:
mixing the composite material containing graphite and MOF with acetylene black, and performing 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 rotating 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, PVDF and N-methylpyrrolidone 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. according to the invention, 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 volume expansion effect (the volume expansion can cause the structural collapse of the material and the electrochemical performance is weakened) of the battery in the charging and discharging process caused by the structural collapse of the negative electrode material due to the cycle of lithium removal and lithium intercalation in the charging and discharging process of the lithium battery can be eliminated when the material is 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 graphite materials, and has excellent structural stability of MOF materials.
3. The invention is realized by introducing NH into MOF material 2 - Not only the electron density of the material is enhanced, resulting in a certain increase of the conductivity of the material, but also the lithium intercalation sites are provided, so that the charge and discharge capacity of the material is remarkably increased; the specific capacity of the first discharge can reach 492.3mAh/g, and the capacity retention rate is 96.6%.
Drawings
FIG. 1 is an XRD pattern of a composite containing graphite and MOF prepared in example 1;
fig. 2 is a TEM image of the graphite and MOF containing composite material prepared in example 1.
Detailed Description
For a thorough understanding of the present invention, the following description of the preferred embodiments of the present invention will be provided in conjunction with examples to further illustrate the features and advantages of the present invention, and it will be understood by those skilled in the art that the scope of the present invention is defined by the appended claims.
The specific conditions are not noted in the examples of the present invention, and are carried out according to conventional conditions or conditions suggested by the manufacturer. The raw materials, reagents, etc. used, which are not noted to the manufacturer, are conventional products commercially available.
Example 1
The preparation method of the composite material containing graphite and MOF comprises the following steps:
(1) Distilling anhydrous N, N-dimethylamide and anhydrous methanol at 50 ℃ and 55 ℃ respectively, and then mixing the distilled anhydrous N, N-dimethylamide and anhydrous methanol according to a ratio of 1: mixing in proportion to obtain a mixed solution;
(2) Adding 2-amino-terephthalic acid in a mass volume ratio of 1:3, stirring at 15 ℃ for 10min at a rotating speed of 500r/min, then increasing the rotating speed to 1000r/min, adding tetrabutyl titanate in a 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 24 hours at 130 ℃, filtering a product of the solvothermal reaction, sequentially and alternately cleaning for 3 times by using anhydrous N, N-dimethylamide and anhydrous methanol, and extracting by using a Soxhlet extractor to obtain a white solid MOF material;
(4) Grinding graphite into powder (sieving with a 100-mesh sieve), mixing the powder with anhydrous methanol according to a mass-to-volume ratio of 1:10, adding a white solid MOF material according to a mass-to-volume ratio of 1:10 after ultrasonic treatment for 20min, continuing ultrasonic vibration for 20min, refluxing at 60 ℃ for 12 hours, standing for 12 hours, centrifuging, and drying to obtain the composite material (graphite-coated MOF) containing graphite and MOF.
The preparation method of the negative plate of the embodiment comprises the following steps: mixing the graphite-MOF-containing composite material with acetylene black in a weight ratio of 1:0.1, ball milling for 10min at a rotating speed of 3000r/min, preparing slurry from the obtained mixture powder, PVDF and N-methylpyrrolidone in a ratio of 1:0.1:0.1, coating and drying to prepare the negative electrode plate.
Example 2
The preparation method of the composite material containing graphite and MOF comprises the following steps:
(1) Distilling anhydrous N, N-dimethylamide and anhydrous methanol at 50 ℃ and 60 ℃ respectively, and then mixing the distilled anhydrous N, N-dimethylamide and anhydrous methanol according to a ratio of 1:7, mixing in proportion to obtain a mixed solution;
(2) Adding 2-amino-terephthalic acid in a mass volume ratio of 1:5, stirring at a rotating speed of 700r/min for 20min at 20 ℃, then increasing the rotating speed to 1200r/min, adding tetrabutyl titanate in a volume ratio of 1:25, and continuously stirring for 20min to obtain a suspension;
(3) Transferring the obtained suspension into a dry hydrothermal kettle, performing solvothermal reaction for 48 hours at 140 ℃, filtering a product of the solvothermal reaction, sequentially and alternately cleaning for 3 times by using anhydrous N, N-dimethylamide and anhydrous methanol, and extracting by using a Soxhlet extractor to obtain a white solid MOF material;
(4) Grinding graphite into powder (sieving with a 150-mesh sieve), mixing the powder with anhydrous methanol according to a mass-to-volume ratio of 1:15, adding a white solid MOF material according to a mass-to-volume ratio of 1:15 after ultrasonic treatment for 30min, continuing ultrasonic vibration for 30min, refluxing at 65 ℃ for 15 hours, standing for 15 hours, centrifuging, and drying to obtain the composite material (graphite-coated MOF) containing graphite and MOF.
The preparation method of the negative plate of the embodiment comprises the following steps: mixing a composite material containing graphite and MOF (graphite coated MOF) with acetylene black according to a weight ratio of 1:0.2, ball milling for 15min at a rotating speed of 4500r/min, and mixing the obtained mixture powder according to a ratio of 1:0.12:0.3, PVDF and N-methyl pyrrolidone to prepare slurry, and coating and drying 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-dimethylamide and anhydrous methanol at 60 ℃ and 65 ℃ respectively, and then mixing the distilled anhydrous N, N-dimethylamide and anhydrous methanol according to a ratio of 1:9, mixing in proportion to obtain a mixed solution;
(2) Adding 2-amino-terephthalic acid in a mass volume ratio of 1:6, stirring at a rotating speed of 800r/min for 30min at 35 ℃, then increasing the rotating speed to 1500r/min, adding tetrabutyl titanate in a 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 solvothermal reaction for 72 hours at 150 ℃, filtering a product of the solvothermal reaction, sequentially and alternately cleaning for 3 times by using anhydrous N, N-dimethylamide and anhydrous methanol, and extracting 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 the powder with anhydrous methanol according to a mass-to-volume ratio of 1:20, adding a white solid MOF material according to a mass-to-volume ratio of 1:20 after ultrasonic treatment for 40min, continuing ultrasonic vibration for 40min, refluxing at 70 ℃ for 18 hours, standing for 18 hours, centrifuging, and drying to obtain a composite material containing graphite and MOF (graphite-coated MOF).
The preparation method of the negative plate of the embodiment comprises the following steps: mixing the composite material containing graphite and MOF with acetylene black according to the weight ratio of 1:0.3, ball milling for 20min at the rotating speed of 6000r/min, and mixing the obtained mixture powder according to the ratio of 1:0.15:0.5, PVDF and N-methyl pyrrolidone to prepare slurry, and coating and drying to prepare the negative plate.
Comparative example 1
The preparation method of the titanium-based MOF lithium ion battery anode material comprises the following steps: dispersing 2, 5-dihydroxyterephthalic acid in isopropanol solution, dripping the solution into acetonitrile solution containing titanium tetraisopropoxide, and stirring the mixture at room temperature to obtain orange brown slurry for 30min; transferring into a Teflon high-pressure reaction kettle, heating to 120 ℃ and keeping the temperature for 24 hours to form dark red crystals, carrying out suction filtration in an air atmosphere, washing with DMF (N, N-dimethylformamide) and ethanol for three times respectively, and carrying out vacuum drying to obtain the electrode material.
Comparative example 2
A method for preparing a graphite and MOF-containing material, comprising the steps of: grinding commercial graphite into powder, mixing the commercial graphite with anhydrous methanol according to a mass-to-volume ratio of 1:20, adding the MOF material obtained in the comparative example 1 according to a mass-to-volume ratio of 1:20 after ultrasonic treatment for 40min, continuing ultrasonic vibration for 40min, refluxing at 70 ℃ for 18 hours, standing for 18 hours, centrifuging, and drying to obtain the graphite-coated MOF material.
And (3) performance detection:
the negative electrode materials of the composite materials containing graphite and MOF prepared in examples 1 to 3 and the negative electrode materials prepared in comparative examples 1 to 2 were prepared, respectively, to prepare negative electrode sheets, and lithium sheets were used as positive electrodes, assembled into button cells, and subjected to a first discharge test at a 1C rate, and the results are shown in tables 1 and 2. As can be seen from Table 1, the negative electrode material of the composite material containing graphite and MOF of the present invention has a higher specific first discharge capacity than the MOF materials of comparative examples 1 and 2 at a 1C rate, the specific first discharge capacity of example 2 was 492.3mAh/g, the specific first discharge capacity of comparative example 1 was 333.1mAh/g, and the specific first discharge capacity of comparative example 2 was 367.2mAh/g. As can be seen from Table 2, the cycle life of the negative electrode material of the composite material of the present invention, which was prepared by preparing graphite and MOF, was higher than that of the MOF material of the comparative example at a 1C rate, the capacity retention rate of example 2 was 96.6% after 1600 cycles at 1C, and the capacity retention rates of comparative examples 1-2 were only 92.8% and 90.2%, respectively.
TABLE 1 button cell performance of composite materials containing graphite and MOF
TABLE 2 full cell cycle performance of composite materials containing graphite and MOF
FIG. 1 is an XRD pattern of a composite containing graphite and MOF, wherein characteristic peaks of the composite are reflected. Fig. 2 is a TEM image of a composite material containing graphite and MOF, in bulk morphology.
The foregoing has outlined the detailed description of the method for preparing a composite material comprising graphite and MOF and the use thereof, wherein specific examples are provided herein to illustrate the principles and embodiments of the present invention and are intended to facilitate an understanding of the method of the present invention and its core ideas, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems, and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection 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 language of the claims.

Claims (6)

1. A method for preparing a composite material containing graphite and MOF, 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 continuing stirring to obtain a suspension;
(2) Carrying out solvothermal reaction on the suspension, filtering, taking filter residues, alternately cleaning with an organic solvent, and extracting to obtain MOF;
(3) Grinding graphite into powder, mixing with alcohol, oscillating, adding the MOF, continuing oscillating, refluxing, standing, centrifuging, taking precipitate, and drying to obtain the composite material containing graphite and MOF;
in the step (1), the mixed solution is obtained by mixing N, N-dimethylamide and methanol; the mass ratio of the N, N-dimethylamide to the methanol is 1: (6-9), wherein the amino-containing organic matter is 2-amino-terephthalic acid, the mass ratio of the amino-containing organic matter to the mixed solution is 1 (3-6), the titanium-containing coupling agent is tetrabutyl titanate, and the mass ratio of the mixed solution to the titanium-containing coupling agent is 1 (15-35); in the step (2), the organic solvent is N, N-dimethylamide and methanol.
2. The preparation method according to claim 1, wherein in the step (1), the stirring temperature is 15-35 ℃, the stirring rotation 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 stirring time is continuously 10-30min.
3. The 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).
4. The preparation method according to claim 1, wherein in the step (2), the solvothermal reaction temperature is 130-150 ℃ and the solvothermal reaction time is 24-72 hours; in the step (3), the temperature of the backflow is 60-70 ℃ and the backflow time is 12-18 hours; and standing for 12-18 hours.
5. A composite material comprising graphite and MOF, characterized in that it is produced by the production method according to any one of claims 1 to 4; the specific capacity of the composite material containing graphite and MOF is 460-495mAh/g, the porosity is 32-37%, and the specific surface area is 2.7-3.5m 2 /g。
6. A negative electrode sheet comprising the graphite and MOF-containing composite material of claim 5.
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