CN115584032A - Ultrathin bimetal organic framework/carbon composite material and preparation method and application thereof - Google Patents

Ultrathin bimetal organic framework/carbon composite material and preparation method and application thereof Download PDF

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CN115584032A
CN115584032A CN202211294792.9A CN202211294792A CN115584032A CN 115584032 A CN115584032 A CN 115584032A CN 202211294792 A CN202211294792 A CN 202211294792A CN 115584032 A CN115584032 A CN 115584032A
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邹国强
纪效波
侯红帅
肖诩桓
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Central South University
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Abstract

The invention provides an ultrathin bimetal organic frame/carbon composite material, a preparation method and application thereof, and a preparation method thereofThe method comprises the following steps: dissolving soluble salt of metal M, fe 3+ Adding the soluble salt, the organic ligand and a proper amount of carbon dots into the mixed solvent, and uniformly mixing to obtain a mixed solution; adding a second solvent into the mixed solution, and stirring at normal temperature to react to obtain a suspension; carrying out solid-liquid separation on the suspension, washing and drying to obtain the ultrathin bimetal organic framework/carbon composite material; wherein the mixed solvent is a mixed solvent of a first solvent, water and ethanol; the method can obtain the nano-sheet bimetallic organic framework/carbon composite material by simply stirring at normal temperature for reaction, the preparation process is simple, the preparation process and the product are not stacked, the obtained bimetallic organic framework/carbon composite material is in a single-layer nano-sheet shape, the thickness is 1-10nm, and the obtained bimetallic organic framework/carbon composite material is used as a cathode active material and has more excellent electrochemical performance.

Description

Ultrathin bimetal organic framework/carbon composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of negative electrode materials, in particular to an ultrathin bimetal organic frame/carbon composite material and a preparation method and application thereof.
Background
Metal organic frameworks (hereinafter MOFs) are crystalline porous materials made by linking metal nodes (e.g., metal ions and clusters) with organic ligands (e.g., carboxylic acid ligands or other negatively charged ligands). The MOFs material has the characteristics of adjustable structural function, large specific surface area, high porosity and the like, and is one of the fastest research hotspots in the fields of chemistry and materials in recent years. Because of these characteristics, MOFs have great potential for applications in many areas, such as gas storage and separation, energy storage and conversion, catalysis, sensors, and biomedicine.
In recent years, ultra-thin two-dimensional (2D) nanomaterials have attracted attention because of their advantages such as ductility, light transmittance, and electrical conductivity. The 2D MOFs nanosheet with the thickness of several nanometers has the advantages of more excellent conductivity, structural stability and the like by combining the advantages of 2D nanomaterials and MOFs. Common methods for preparing 2D MOFs are the top-down method and the bottom-up method. Although the top-down method can effectively prepare 2D MOFs nanosheets with high crystallinity, the low yield and easy stacking tendency limit their large-scale application. In contrast, the bottom-up approach shows potential practical applications by limiting the growth in the vertical direction, directly synthesizing 2D MOFs nanosheets from metal ions and organic ligands. Bottom-up synthesis methods generally include interfacial synthesis, surface-assisted synthesis, modulation synthesis, and ultrasonic synthesis. However, such conventional methods have disadvantages of complicated synthetic routes and difficulty in separation, thereby limiting mass production and application thereof.
Therefore, the development of a preparation method of MOFs nanosheets which is high in yield and can avoid stacking of the nanosheets is of great significance to the industrial application of the preparation method.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a preparation method of an ultrathin bimetal organic framework/carbon composite material, the method can obtain a nano-sheet bimetal organic framework/carbon composite material with the thickness of several nanometers by simply stirring at normal temperature for reaction, the preparation process and the product are not stacked, and a single-layer ultrathin organic framework/carbon composite material nanosheet can be obtained without separating the nanosheet by ultrasonic.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of an ultrathin bimetal organic framework/carbon composite material comprises the following steps:
s1, dissolving soluble salt of metal M and Fe 3+ Adding the soluble salt, the organic ligand and the carbon dots into the mixed solvent, and uniformly mixing to obtain a mixed solution;
s2, adding a second solvent into the mixed solution, and stirring at normal temperature to react to obtain a suspension;
s3, carrying out solid-liquid separation on the suspension, washing and drying to obtain the ultrathin bimetal organic frame/carbon composite material;
wherein the mixed solvent is a mixed solvent of a first solvent, water and ethanol; the first solvent is at least one of DMF (N, N-dimethylformamide), DMAC (N, N-dimethylacetamide) and NMP (N-methylpyrrolidone); the second solvent is at least one of ammonia water, triethylamine, ethylenediamine and n-butylamine.
In some embodiments, the first solvent is DMF; the second solvent is at least one of ammonia water, triethylamine, ethylenediamine and n-butylamine.
In some embodiments, the carbon dots are at least one of carbon quantum dots, graphene quantum dots, carbon nanodots, and carbonized polymer dots.
In some embodiments, the soluble salt of metal M is Co (NO) 3 ) 2 ·6H 2 O、CoCl 2 ·6H 2 At least one of O; said Fe 3+ The soluble salt is FeCl 3 ·6H 2 O、Fe(NO 3 ) 3 At least one of (1).
In some embodiments, the organic ligand is at least one of terephthalic acid, trimesic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid.
In some embodiments, the molar ratio of metal salt to the organic ligand is 1.5:1; metals M and Fe 3+ The molar ratio of (4-6): 1; the mass ratio of the soluble salt of the metal M to the carbon dots is (4-6): (0-2), the amount of carbon dots is more than 0.
In some embodiments, in step S1, the volume ratio of the first solvent, ethanol, and water in step S1 is 5:1:1.
in some embodiments, in step S2, the stirring rate is > 50rpm, preferably, 400 to 1000rpm.
In some embodiments, in step S2, the stirring reaction time is 12 to 14 hours.
In some embodiments, in step S3, the solid-liquid separation is performed by centrifugation, and the centrifugal speed is 8000-10000 r/min.
The invention also provides the ultrathin bimetal organic framework/carbon composite material obtained by any one of the embodiments, wherein the composite material is in a single-layer nanosheet shape, and the thickness of the composite material is 1-10nm.
The invention also provides application of the ultrathin bimetal organic framework nanosheet as a negative electrode active material of a lithium ion battery.
The invention also provides a negative electrode which comprises the ultrahigh bimetal organic framework nanosheet.
The invention also provides an electrochemical energy storage device which comprises the negative electrode.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the invention is to generate the ultrathin nanometer sheet-shaped bimetallic organic framework/carbon composite material by simple one-step reaction under normal temperature stirring, and the second solvent is added to be used as a deprotonation agent to induce effective coordination of metal ions and organic ligands, so that the generated nanometer sheet structure is more stable, and the reaction is accelerated. The generation of 2D organic framework nanosheets can be induced by partial substitution of the metal M sites by added Fe (III), and Fe 3+ H in the solvent is more easily absorbed 2 And O generates hydroxide to hinder the growth of the organic framework material in the vertical direction and promote the extension of the organic framework material in the horizontal direction, and the addition of the carbon quantum dots plays a role in columnar support on one hand and prevents the generated nanosheets from being re-stacked on the other hand, and the carbon quantum dots and Fe (III) have a synergistic effect to finally generate the ultrathin nanosheets with the thickness of 1-10nm and stable structures.
The surface of the ultrathin nano-sheet bimetallic organic framework/carbon composite material obtained by the invention can provide a large number of reaction interfaces, a large number of effective active sites are exposed, an ion transmission path is shortened, the reaction kinetics is accelerated, and the ultrathin nano-sheet bimetallic organic framework/carbon composite material has excellent electrochemical performance; in addition, the composite material has a stable structure and more excellent cycle performance based on the supporting effect of the carbon quantum dots.
In addition, the method of the invention also has the following advantages:
1. the preparation method has the advantages of simple operation flow, simple reaction conditions, no need of heating, low energy consumption and low production cost;
2. the preparation method has high yield, can recycle the organic solvent, saves the cost of raw materials, is beneficial to mass production and further realizes industrial production.
Drawings
FIG. 1 is an X-ray diffraction pattern of 5 samples obtained in examples 1 to 3 and comparative examples 1 to 2;
FIG. 2 is (a) a scanning electron micrograph and (b) an atomic force microscope micrograph of Co/Fe-BDC nanoplates made in example 1;
FIG. 3 is (a) a scanning electron microscope image and (b) an atomic force microscope image of Co/Fe-BDC-100CQDs nanosheet made in example 2;
FIG. 4 is (a) a scanning electron micrograph and (b) an atomic force microscope micrograph of Co/Fe-BDC-200CQDs nanosheet made in example 3;
FIG. 5 is (a) a scanning electron micrograph and (b) an atomic force microscope micrograph of the Co-BDC material prepared in comparative example 1;
FIG. 6 is a scanning electron micrograph of the Fe-BDC material prepared in comparative example 2;
FIG. 7 is a scanning electron micrograph of the Co/Mn-BDC material prepared in comparative example 3;
FIG. 8 is a scanning electron micrograph of the Co/Ni-BDC material prepared in comparative example 4;
FIG. 9 is a first turn constant current charge and discharge curve of 5 assembled lithium ion batteries prepared in examples 1-3 and comparative examples 1-2;
fig. 10 is a graph of cycle performance of 5 sample assembled lithium ion batteries prepared in examples 1-3 and comparative examples 1-2.
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.
Example 1
A preparation method of a Co/Fe-BDC nanosheet comprises the following specific steps:
s1, weighing 1.5mmol of Co (NO) 3 ) 2 ·6H 2 O、0.75mmol FeCl 3 ·6H 2 O and 1.5mmol of terephthalic acid were added to a solution of 10ml of H containing 50ml of DMF 2 In a beaker containing O and 10ml of EtOH mixed solvent, the stirring rate was 600rpm, stirring and dispersing uniformly to obtain a uniform mixed solution;
s2, dropwise adding 4ml of TEA into the mixed solution in the step S1, and stirring for 12 hours at normal temperature to fully react to obtain a colloidal suspension;
and S3, centrifuging the colloidal suspension obtained in the step S2 for 1 time (rotating speed is 10000 r/min) to obtain a precipitate, washing the precipitate for 1 time by using acetone, centrifuging, then washing by using EtOH and centrifuging (repeating for 3 times), finally placing the obtained precipitate in an oven, drying for 24 hours in vacuum at 100 ℃, drying the material and grinding the material to obtain the powder material Co/Fe-BDC nanosheet.
Through detection, as shown in fig. 1 and fig. 2, the obtained material has MOFs diffraction peaks and shows the morphology of an ultrathin nanosheet.
Example 2
A preparation method of Co/Fe-BDC-100CQDs nanosheets comprises the following specific steps:
s1, weighing 1.5mmol of Co (NO) 3 ) 2 ·6H 2 O、0.75mmol FeCl 3 ·6H 2 O, 1.5mmol terephthalic acid and 100mg carbon quantum dots are added to a solution containing 50ml DMF, 10ml H 2 Stirring and dispersing the mixture evenly in a beaker containing O and 10ml of EtOH mixed solvent to obtain uniform mixed solution;
s2, dropwise adding 4ml of TEA into the mixed solution in the step S1, and stirring at the stirring speed of 600rpm for 12 hours at normal temperature to fully react to obtain a colloidal suspension;
and S3, centrifuging the colloidal suspension obtained in the step S2 for 1 time (rotating speed is 10000 r/min) to obtain a precipitate, washing the precipitate for 1 time by using acetone, centrifuging, then washing by using EtOH and centrifuging (repeating for 3 times), finally placing the obtained precipitate in a drying oven, drying for 24 hours in vacuum at 100 ℃, drying the material and grinding the material to obtain the powder material Co/Fe-BDC-200CQDs nanosheet.
Through detection, as shown in fig. 1 and fig. 3, the obtained material has MOFs diffraction peaks, and the peak strength is weakened through the compounding of carbon quantum dots, and the obtained material has the appearance of an ultrathin nanosheet.
Example 3
A preparation method of a Co/Fe-BDC-200CQDs nano-sheet comprises the following specific steps:
s1, weighing 1.5mmol of Co (NO) 3 ) 2 ·6H 2 O、0.75mmol FeCl 3 ·6H 2 O, 1.5mmol terephthalic acid and 200mg carbon quantum dots are added to a solution containing 50ml DMF, 10ml H 2 Stirring and dispersing the mixture evenly in a beaker containing O and 10ml of EtOH mixed solvent to obtain uniform mixed solution;
s2, dropwise adding 4ml of TEA into the mixed solution in the step S1, and stirring at the stirring speed of 600rpm for 12 hours at normal temperature to fully react to obtain a colloidal suspension;
and S3, centrifuging the colloidal suspension obtained in the step S2 for 1 time (rotating speed is 10000 r/min) to obtain a precipitate, washing the precipitate for 1 time by using acetone, centrifuging, then washing by using EtOH and centrifuging (repeating for 3 times), finally placing the obtained precipitate in a drying oven, drying for 24 hours in vacuum at 100 ℃, drying the material and grinding the material to obtain the powder material Co/Fe-BDC-200CQDs nanosheet.
Through detection, as shown in fig. 1 and 4, the obtained material has an MOFs diffraction peak, and the peak is weakened due to the recombination of carbon quantum dots, so that the obtained material has the appearance of an ultrathin nanosheet.
Comparative example 1
A preparation method of a Co-BDC material comprises the following specific steps:
s1, weighing 2.25mmol of Co (NO) 3 ) 2 ·6H 2 O and 1.5mmol of terephthalic acid were added to a solution of 10ml of H containing 50ml of DMF 2 Stirring and dispersing the mixture evenly in a beaker of O and 10ml of EtOH mixed solvent to obtain a uniform mixed solution;
s2, dropwise adding 4ml of TEA into the clear solution in the step S1, and stirring at the stirring speed of 600rpm for 12 hours at normal temperature to fully react to obtain a colloidal suspension;
and S3, centrifuging the colloidal suspension obtained in the step S2 for 1 time (rotating speed is 10000 r/min) to obtain a precipitate, washing the precipitate for 1 time by using acetone, centrifuging, then washing by using EtOH and centrifuging (repeating for 3 times), finally placing the obtained precipitate in an oven, drying for 24 hours in vacuum at 100 ℃, drying the material and grinding the material to obtain the powder material Co-BDC material.
Through detection, as shown in fig. 1 and 5, the obtained material has MOFs diffraction peaks, presents a stacked layered morphology, and has a large stacked thickness.
Comparative example 2
A preparation method of a Fe-BDC material comprises the following specific steps:
s1, weighing 2.25mmol FeCl 3 ·6H 2 O and 1.5mmol of terephthalic acid were added to a solution of 10ml of H containing 50ml of DMF 2 Stirring and dispersing the mixture evenly in a beaker containing O and 10ml of EtOH mixed solvent to obtain uniform mixed solution;
s2, dropwise adding 4ml of TEA into the mixed solution in the step S1, and stirring for 12 hours at normal temperature to fully react to obtain a colloidal suspension;
s3, centrifuging the colloidal suspension in the step S2 for 1 time (rotating speed is 10000 r/min) to obtain a precipitate, washing the precipitate with acetone for 1 time, centrifuging, then washing with EtOH, centrifuging (repeating for 3 times), finally placing the obtained precipitate in a drying oven, vacuum-drying for 24 hours at 100 ℃, drying the material, and grinding the dried material to obtain the powder material Fe-BDC material.
Through detection, as shown in fig. 1 and fig. 6, the obtained material has MOFs diffraction peaks and shows a small particle morphology.
Comparative example 3
A preparation method of a Co/Mn-BDC material comprises the following specific steps:
s1, weighing 1.5mmol of Co (NO) 3 ) 2 ·6H 2 O、0.75mmol Mn(OAc) 2 ·4H 2 O and 1.5mmol of terephthalic acid were added to a solution of 10ml of H containing 50ml of DMF 2 Stirring and dispersing the mixture evenly in a beaker of O and 10ml of EtOH mixed solvent at the stirring speed of 600rpm to obtain uniform mixed solution;
s2, dropwise adding 4ml of TEA into the mixed solution in the step S1, and stirring for 12 hours at normal temperature to fully react to obtain a colloidal suspension;
and S3, centrifuging the colloidal suspension obtained in the step S2 for 1 time (rotating speed is 10000 r/min) to obtain a precipitate, washing the precipitate for 1 time by using acetone, centrifuging, then washing by using EtOH and centrifuging (repeating for 3 times), finally placing the obtained precipitate in an oven, drying for 24 hours in vacuum at 100 ℃, drying the material and grinding the material to obtain the powder material Co/Mn-BDC material.
Upon examination, the resulting material exhibited a stacked layered morphology, as shown in fig. 7.
Comparative example 4
A preparation method of a Co/Ni-BDC material comprises the following specific steps:
s1, weighing 1.5mmol of Co (NO) 3 ) 2 ·6H 2 O, 0.75mmol Co/Ni-BDC and 1.5mmol terephthalic acid were added to a solution containing 50ml DMF, 10ml H 2 Stirring and dispersing the mixture evenly in a beaker of O and 10ml of EtOH mixed solvent at the stirring speed of 600rpm to obtain uniform mixed solution;
s2, dropwise adding 4ml of TEA into the mixed solution in the step S1, and stirring for 12 hours at normal temperature to fully react to obtain a colloidal suspension;
s3, centrifuging the colloidal suspension in the step S2 for 1 time (rotating speed is 10000 r/min) to obtain a precipitate, washing the precipitate with acetone for 1 time, centrifuging, then washing with EtOH, centrifuging (repeating for 3 times), finally placing the obtained precipitate in a drying oven, vacuum-drying for 24 hours at 100 ℃, drying the material, and grinding the dried material to obtain the powder material Co/Ni-BDC material.
Upon examination, the resulting material exhibited a stacked layered morphology, as shown in fig. 8.
From the above, the Co-BDC in comparative example 1 tends to generate stacked lamellar morphology, and the Fe-BDC in comparative example 2 exhibits small particle morphology; while comparative examples 3 and 4 show that the introduction of Mn (II) and Ni (II) partially does not result in the generation of an ultrathin 2D nanosheet morphology, which is still a stacked morphology; whereas in example 1, the introduction of Fe (III) induced the generation of ultrathin 2D MOF nanoplates, because of the Fe (III) versus H in solvent 2 O has higher adsorption energy, while Mn (II) and Ni (II) have higher adsorption energy to H 2 The adsorption energy of O is very weak; when Fe (III) adsorbs H 2 When O forms hydroxide (just like small particles in the morphology of Fe-BDC), the hydroxide inhibits the generation of substances in the vertical direction, promotes the self-stripping dispersion of stacked layers, and finally forms the ultrathin 2D nanosheet; but the induction effect is limited, and part of sheet materials are stacked in the reaction process; compared with example 1, in examples 2-3, due to the addition of the carbon quantum dots, the generated single-layer 2D nanosheet is moreThe thin and obvious flaky dispersion is realized by the fact that the carbon quantum dots play a columnar supporting role on the generated ultrathin 2D nanosheet and prevent the nanosheet from being re-stacked, the Fe (III) induction nanosheet and the Fe (III) induction nanosheet play a synergistic role, and the finally generated 2D nanosheet is more complete and thinner, so that the thickness of the flaky material can reach 1-10nm.
The metal organic framework nanosheet materials obtained in examples 1-3 and comparative examples 1-2 were subjected to electrochemical performance testing according to the following methods:
the active substance is the metal organic framework nanosheet material or the metal organic framework/carbon composite material prepared in the examples 1-3 and the comparative examples 1-2 respectively, the binder is sodium carboxymethylcellulose (CMC), the conductive agent is acetylene black (Super P), and the metal organic framework nanosheet material, the CMC and the Super P are dissolved in a proper amount of deionized water for size mixing according to the mass ratio of 7.5; and then uniformly coating the slurry on a copper foil current collector by using a coating machine, setting the coating thickness to be 13 mu m, then placing the copper foil current collector in an oven for vacuum drying at 80 ℃ for 12h, then rolling, and cutting a negative pole piece with the diameter of 14mm by using a cutting machine.
Taking a negative pole piece as a working electrode, taking metal lithium as a counter electrode, selecting a PP diaphragm as the diaphragm, and taking 1M LiPF as electrolyte 6 (EC: DMC: EMC =1, 1vol%,5% FEC), CR2016 model button cells were assembled in an argon atmosphere glove box (water, oxygen values less than 0.1ppm each).
Each button cell was then tested and the results are shown in fig. 9 and 10.
As shown in fig. 9-10, due to the dense arrangement and stacking of the metal organic framework material, a higher active site cannot be provided, the first coulombic efficiency of the metal organic framework nanosheet obtained in comparative example 1 is 55.2%, and the reversible specific capacity after 100 cycles of 0.1A/g circulation is 896mAh/g; the initial coulombic efficiency of the metal organic framework nanosheet obtained in the comparative example 2 is 50.1%, and the reversible specific capacity after the metal organic framework nanosheet is cycled for 100 circles at 0.1A/g is 703mAh/g; the first coulombic efficiency of the metal organic framework nanosheet material obtained in the embodiment 1 can reach 65.3%, and the reversible specific capacity after the metal organic framework nanosheet material is cycled for 100 circles at 0.1A/g is 969mAh/g, because the sheet material is generated under the induction action of Fe (III), the stacking of the material is avoided to a certain extent, the effective active site is exposed, and the electrochemical performance of the negative active material is improved; the initial coulombic efficiency of the metal organic framework nanosheet obtained in the embodiment 2 is 70.9%, and the reversible specific capacity after the nanosheet is cycled for 100 circles at 0.1A/g is 1104mAh/g; the initial coulombic efficiency of the metal organic framework nanosheet obtained in the embodiment 3 is 71.4%, the reversible specific capacity after 100 cycles of 0.1A/g is 1076mAh/g, and due to the synergistic effect of the added carbon quantum dots and Fe (III), stacking of the generated flaky material is completely avoided, more effective active sites can be provided, and the electrochemical performance of the composite material is further improved.
Further, as can be seen from fig. 10, the composite materials of examples 2 and 3 have more excellent cycle stability than those of example 1 and comparative examples 1 to 2.
In conclusion, the ultrathin bimetallic organic framework/carbon composite material obtained by the invention has excellent electrochemical performance as a negative electrode active material.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure 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 specific and detailed, but not to be understood 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. The preparation method of the ultrathin bimetal organic framework/carbon composite material is characterized by comprising the following steps of:
s1, dissolving salt and Fe of metal M 3+ Adding the soluble salt, the organic ligand and the carbon dots into the mixed solvent, and uniformly mixing to obtain a mixtureA solution;
s2, adding a second solvent into the mixed solution, and stirring at normal temperature to react to obtain a suspension;
s3, carrying out solid-liquid separation on the suspension, washing and drying to obtain the ultrathin bimetal organic frame/carbon composite material;
wherein the mixed solvent is a mixed solvent of a first solvent, water and ethanol; the first solvent is at least one of DMF, DMAC and NMP; the second solvent is at least one of ammonia water, triethylamine, ethylenediamine and n-butylamine.
2. The method of claim 1, wherein the soluble salt of metal M is Co (NO) 3 ) 2 ·6H 2 O、CoCl 2 ·6H 2 At least one of O; said Fe 3+ The soluble salt is FeCl 3 ·6H 2 O、Fe(NO 3 ) 3 At least one of; the carbon dots are at least one of carbon quantum dots, graphene quantum dots, carbon nanodots and carbonized polymer dots.
3. The method of claim 1, wherein the organic ligand is at least one of terephthalic acid, trimesic acid, 2-amino terephthalic acid, 2-nitro terephthalic acid.
4. The method of preparing an ultra-thin bimetallic organic framework/carbon composite material as claimed in claim 1, wherein the molar ratio of metal M ions to the organic ligands is 1.5:1; metals M and Fe 3+ The molar ratio of (4-6): 1; the mass ratio of the soluble salt of the metal M to the carbon dots is (4-6): (0-2).
5. The method for preparing an ultra-thin bimetal organic framework/carbon composite material according to claim 1, wherein in the step S1, the volume ratio of the first solvent, ethanol and water is 5:1:1.
6. the method for preparing an ultra-thin bimetal organic framework/carbon composite material according to claim 1, wherein the stirring reaction time in the step S2 is 12-14h.
7. An ultrathin bimetallic organic framework nanosheet/carbon composite material, characterized by being prepared by the preparation method of any one of claims 1 to 6, and having a thickness of 1 to 10nm.
8. Use of the ultrathin bimetallic organic framework nanosheet/carbon composite of claim 7 as a negative active material for a lithium ion battery.
9. A negative electrode comprising the ultrathin bimetallic organic framework nanosheet/carbon composite of claim 8.
10. An electrochemical energy storage device comprising the negative electrode of claim 9.
CN202211294792.9A 2022-10-21 2022-10-21 Ultrathin bimetal organic framework/carbon composite material and preparation method and application thereof Pending CN115584032A (en)

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