CN113451570A - MOF-derived core-shell-structured lithium ion battery negative electrode material and preparation method thereof - Google Patents

MOF-derived core-shell-structured lithium ion battery negative electrode material and preparation method thereof Download PDF

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CN113451570A
CN113451570A CN202110721453.3A CN202110721453A CN113451570A CN 113451570 A CN113451570 A CN 113451570A CN 202110721453 A CN202110721453 A CN 202110721453A CN 113451570 A CN113451570 A CN 113451570A
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mof
lithium ion
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胡宪伟
李卓
张文帝
石忠宁
王兆文
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Northeastern University China
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    • 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
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    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
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    • H—ELECTRICITY
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    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of secondary battery electrode materials, and particularly relates to a lithium ion battery cathode material with an MOF derived core-shell structure and a preparation method thereof. The invention provides a MOF (metal organic framework) derived core-shell structure MoS2@Fe2O3The preparation method of the negative electrode material of the-C lithium ion battery is characterized in that an iron-based MOF derivative Fe2O3-C as a core substrate material, MoS grown in situ on the surface thereof2The nano shell forms a heterostructure, the conductivity is improved, meanwhile, the MOF precursor framework structure inherited by the core material can adjust the volume change of the electrode material in the charging and discharging processes, and meanwhile, lithium intercalation active sites are added. Hair brushThe prepared electrode material simultaneously improves MoS2The conductivity, the structural stability and the electrochemical activity of the composite material, and the overall preparation process has the advantages of low cost, simple and convenient operation, environmental friendliness and the like.

Description

MOF-derived core-shell-structured lithium ion battery negative electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of secondary battery electrode materials, and particularly relates to a lithium ion battery cathode material with an MOF derived core-shell structure and a preparation method thereof.
Background
Lithium ion batteries are widely used in the field of portable electronic devices and hybrid electric vehicles due to their advantages of high energy density, long cycle life, environmental friendliness, and the like. However, the lower theoretical specific capacity (372mAh/g) of the commercialized graphite negative electrode material severely limits the further development of the lithium ion battery in a large-scale energy storage system. Therefore, the development of a novel negative electrode material with high performance, environmental protection and low cost for the lithium ion battery is urgently needed. Wherein the MoS is two-dimensionally layered2The nano material has a graphene-like layered structure, is easy to combine with other active materials through van der waals force interaction between layers, has the advantages of high theoretical capacity and the like, and is widely applied to the field of energy storage. But MoS2The nano-sheet is easy to agglomerate in the preparation process, so that poor conductivity and limited active sites are caused, and the application of the nano-sheet in the electrochemical field is limited. The invention patent with the publication number of CN111111729A discloses a preparation method of a molybdenum disulfide-based nano composite material with a hollow laminated structure, and a product obtained by the preparation method can effectively improve the conductivity and reduce the agglomeration. The invention patent with the publication number of CN110391089A discloses a MoS2@CoS2The preparation method of the composite material is applied to the field of supercapacitors, and shows excellent electrochemical performance. However, the above-disclosed patents do not address the simultaneous improvement of MoS2The conductivity, the structural stability and the electrochemical activity of the base composite material, the corresponding preparation cost and the like. Therefore, how to perfect MoS2The above-mentioned shortcomings of the matrix composite are key factors for realizing the matrix composite as a novel lithium ion battery cathode material.
Disclosure of Invention
In order to solve the problems, the invention provides an MOF (metal organic framework) derived core-shell structure MoS2@Fe2O3-C lithium ion battery cathode materialThe preparation method of (1) is that the Fe-based MOF derivative Fe2O3-C as a core substrate material, MoS grown in situ on the surface thereof2The nano shell forms a heterostructure, the conductivity is improved, meanwhile, the MOF precursor framework structure inherited by the core material can adjust the volume change of the electrode material in the charging and discharging processes, and meanwhile, lithium intercalation active sites are added. Therefore, the lithium ion battery cathode material has high specific capacity and excellent cycling stability, and the specific preparation technical scheme is as follows:
MOS (MoMoMoF) derived core-shell structure2@Fe2O3The preparation method of the negative electrode material of the-C lithium ion battery comprises the following steps:
step 1, preparing an iron-based metal organic framework (MIL-88) precursor:
dissolving ferric salt and fumaric acid in a reaction solvent, and stirring uniformly to obtain an orange transparent mixed solution 1, wherein the reaction solvent can be deionized water or N, N-Dimethylformamide (DMF), and the ferric salt can be dissolved in the reaction solvent, such as ferric chloride, ferric nitrate, ferric sulfate and the like. Preferably, the mass ratio of the iron salt to the fumaric acid is (0.8-5): 1, the ratio of the mass sum of the ferric salt and the fumaric acid to the volume of the reaction solvent is 1 g: (12.5-40) mL.
And transferring the mixed solution 1 into a reaction kettle for heating reaction (hydrothermal reaction or solvent thermal reaction according to different types of reaction solvents), then cooling to room temperature, performing centrifugal separation, washing and drying the separated solid, wherein the washing can be repeated washing by using absolute ethyl alcohol, and the drying can be vacuum drying. And washing and drying to obtain rod-shaped, diamond-shaped or spindle-shaped MIL-88 nano particles, namely the iron-based metal organic framework precursor material.
Step 2, preparing MOF derivative material Fe2O3-C：
The MIL-88 nano particles are calcined, for example, the MIL-88 nano particles can be calcined in a tube furnace by being placed in a porcelain boat, and the furnace is cooled to room temperature, so that the Fe of the MOF (metal organic framework) derivative material which is coated with carbon and inherits the framework structure of the precursor is obtained2O3-C。
Step 3, preparing MOF-MoS2@Fe2O3-C nanocomposite:
mixing Fe2O3Preparing Fe by ultrasonically dispersing-C in deionized water2O3-C dispersion, Fe2O3The ratio of mass-C to volume of deionized water is preferably (0.1 to 0.3) g: (40-80) mL, and dissolving molybdenum salt and thiourea in Fe under stirring2O3Forming a mixed solution 2 in the-C dispersion liquid, wherein the molybdenum salt can be ammonium molybdate or sodium molybdate and the like, and the mass ratio of the molybdenum salt to the thiourea is (0.5-0.75): 1, Fe2O3The mass ratio of-C to (molybdenum salt + thiourea) is (1-3) to (7-9).
Continuously stirring for a certain time, transferring the mixed solution 2 into a reaction kettle for hydrothermal reaction, cooling to room temperature, performing centrifugal separation, washing and drying the separated solid to obtain MoS2Nanosheet-coated Fe2O3Core-shell structure MOF-MoS of the-C core2@Fe2O3-C nanocomposite, MOF-MoS2@Fe2O3-C nano composite material, namely the MOF derived core-shell structure lithium ion battery negative electrode material. The washing can be repeated by ultrapure water or absolute ethyl alcohol respectively, and the drying can be vacuum drying.
In the step 1, the stirring speed is 600-800 r/min, and the stirring time is 30-50 min.
In the step 1, the temperature of the heating reaction (hydrothermal reaction or solvothermal reaction) is 130-150 ℃, and the reaction time is 3-5 h.
In the step 2, the calcining temperature is 400-500 ℃, the heating rate is controlled at 3-5 ℃/min, the heat preservation time is 2-4 h, and inert protective gas is adopted for protection during calcining, wherein the inert protective gas is argon or nitrogen.
In the step 3, the ultrasonic dispersion time is 10-30 min, the stirring speed is 600-800 r/min, the stirring time is 10-30 min, the hydrothermal reaction temperature is 180-210 ℃, and the reaction time is 20-24 h.
In the step 1 and the step 3, the centrifugal separation speed is 3000-5000 r/min, the centrifugal time is 2-4 min, the separated solid is dried in vacuum, the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
The MOS with the MOF derivative core-shell structure is prepared by the method2@Fe2O3Compared with the prior art, the negative electrode material of the-C lithium ion battery has the beneficial effects that:
firstly, Fe-MOF derivative material Fe prepared by the invention2O3the-C inherits the unique frame structure of the precursor and is simultaneously used as the inner core of the composite material, and can be used as a lithium ion storage device to improve the charge-discharge specific capacity of the battery.
Secondly, in the calcining process, organic ligands in iron-based metal organic framework (Fe-MOF) precursors are cracked to form isolated amorphous carbon layers to coat the derived Fe2O3The surface can effectively protect MoS2Structural integrity during charging and discharging, and the simultaneous formation of an activated carbon layer can improve MoS2The conductivity of the electrolyte improves the performance of the battery. The method for generating the activated carbon in situ is more advanced and simpler than other carbon doping technologies.
III, adopting Fe derived from MOFs2O3-C as core material, surface coated with MoS2The nano sheet is taken as a shell, so that MoS can be effectively improved2The agglomeration problem is solved, the conductivity is improved, and meanwhile, the heterogeneous core-shell structure not only can increase the active sites for lithium intercalation, but also can construct a stable organism structure.
Fourthly, the invention forms MoS by epitaxial in-situ growth on the derivatives on the surface of the MOFs2The shell is constructed by the nano-sheets, so that the specific surface area of the composite material is greatly increased, reversible deintercalation sites of lithium ions are increased while the electrolyte is fully infiltrated, and the electrochemical performance of the electrode material is improved.
And fifthly, the overall preparation process has the advantages of low cost, simplicity and convenience in operation, environmental friendliness and the like, and has good realizability.
Drawings
FIG. 1 shows different structures-MIL-88 materials prepared in the examples: wherein (a) spindle-MIL-88, (b) diamond-MIL-88, (c) rod-MIL-88;
FIG. 2 is a MOF-derived material Fe2O3-C、MoS2@Fe2O3SEM photograph of-C: wherein (a) simple MoS2、(b)Fe2O3-C、(c)MoS2@Fe2O3-C；
FIG. 3 is the MoS prepared in example 12@Fe2O3-C composite charge and discharge performance diagram at current density of 100 mA/g: the figure is respectively the charging and discharging curves of the 1 st, 2 nd, 3 rd, 4 th and 5 th circles;
FIG. 4 shows MoS prepared in example 12@Fe2O3-graph of the rate performance of the C composite at different current densities (50, 100, 200, 500, 1000 mA/g).
Detailed Description
The present invention will be described in detail with reference to the following embodiments and accompanying fig. 1-4, but the scope of the present invention is not limited to the following embodiments.
Example 1
MOS (MoMoMoF) derived core-shell structure2@Fe2O3The preparation method of the negative electrode material of the-C lithium ion battery comprises the following steps:
step 1, preparing a spindle-shaped iron-based MOF precursor (spindle-MIL-88):
respectively weighing 1.6g of ferric chloride and 0.42g of fumaric acid, dissolving the ferric chloride and the fumaric acid in 25mLN, N-Dimethylformamide (DMF), uniformly stirring at 600rpm for 30min to obtain orange transparent liquid, transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out solvothermal reaction at 130 ℃, carrying out heat preservation for 4h, cooling to room temperature, carrying out centrifugal separation at the rotation speed of 5000r/min for 3min, repeatedly washing with absolute ethyl alcohol for 3 times, and finally drying at 70 ℃ for 12h under the vacuum condition to obtain the spindle-shaped s-MIL-88 (spindle-MIL-88) nanoparticles with the average particle size of 700 nm.
Step 2, preparing MOF derivative material Fe2O3-C：
MIL-88 nanoparticles were placed in a porcelain boat and then transferred to a tube furnace under argonCalcining for 4h at 400 ℃ in a gas atmosphere, heating at a rate of 5 ℃/min, and finally cooling to room temperature along with the furnace to obtain a carbon-coated MOF derivative material Fe inheriting a precursor framework structure2O3-C。
Step 3, preparing MOF-MoS2@Fe2O3-C nanocomposite:
0.1g of Fe2O3Ultrasonic dispersing for 10min in 60mL deionized water, then weighing 0.3g ammonium molybdate and 0.4g thiourea respectively, dissolving in Fe under stirring at 800r/min2O3Stirring the deionized water dispersion liquid of the component-C for 30min, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at the temperature of 200 ℃, keeping the temperature for 20h, cooling to room temperature, carrying out centrifugal separation on the solution obtained by the reaction, washing for 3 times by using ultrapure water and absolute ethyl alcohol, and finally drying for 12h at the temperature of 70 ℃ under the vacuum condition to obtain the product with MoS2Nano-sheet coated core-shell structured MOF-MoS2@Fe2O3-a C nanocomposite;
the MOF-MoS obtained in this example2@Fe2O3And pressing the-C composite material into an electrode plate of the lithium ion battery, assembling the electrode plate into a CR2032 button battery by taking metal lithium as a counter electrode and EC/EMC (ethylene carbonate/ethyl methyl carbonate) solution of 1M lithium hexafluorophosphate as electrolyte, and performing charge and discharge tests on the battery. FIG. 1a is an SEM photograph of s-MIL-88, showing a spindle-like structure with a particle size of 600 nm. FIG. 2a is a simple MoS2SEM photograph of (1) shows simple MoS2There is a severe agglomeration phenomenon. FIG. 2b is s-MIL-88 derived Fe2O3SEM photograph of C, which inherits the spindle-like framework structure of the precursor. FIG. 2c is MOF-MoS2@Fe2O3SEM photograph of the composite material, it can be seen from the figure that the composite material presents the nano flower-shaped microspheres with the particle size of about 800nm, the product is uniformly dispersed, and no obvious agglomeration phenomenon exists. FIG. 3 is a MOF-MoS2@Fe2O3the-C has charge and discharge performance as the negative electrode material of the lithium ion battery, and the first discharge specific capacity can reach 1290 mAh/g. FIG. 4 is a MOF-MoS2@Fe2O3-C composite at different current densitiesLower cycle performance curve, from which we can see MOF-MoS2@Fe2O3The discharge specific capacity of the-C composite material can still be kept at 700mAh/g under the condition of high current density of 1000mA/g, and the excellent rate capability of the composite material is reflected. The battery performance test result shows that the heterogeneous core-shell structure not only can increase the active sites for lithium intercalation and improve the battery capacity, but also can construct a stable matrix structure to show excellent cycle performance.
Example 2
MOS (MoMoMoF) derived core-shell structure2@Fe2O3The preparation method of the negative electrode material of the-C lithium ion battery comprises the following steps:
step 1, preparing a spindle-shaped iron-based MOF precursor (spindle-MIL-88):
respectively weighing 1.6g of ferric chloride and 0.42g of fumaric acid, dissolving the ferric chloride and the fumaric acid in 25mL of N, N-Dimethylformamide (DMF), uniformly stirring at 600rpm for 30min to obtain an orange transparent liquid, transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out solvothermal reaction at 130 ℃, carrying out heat preservation for 4h, cooling to room temperature, carrying out centrifugal separation at the rotation speed of 5000r/min for 5min, repeatedly washing with absolute ethyl alcohol for 3 times, and finally drying at 70 ℃ for 12h under a vacuum condition to obtain spindle-shaped s-MIL-88 nanoparticles with the average particle size of 700 nm.
Step 2, preparing MOF derivative material Fe2O3-C：
Placing MIL-88 nano-particles into a porcelain boat, transferring the porcelain boat into a tube furnace, calcining the porcelain boat for 4h at the temperature of 400 ℃ under the argon atmosphere, heating at the rate of 5 ℃/min, and finally cooling the porcelain boat to room temperature along with the furnace to obtain the MOF derivative material Fe coated with carbon and inheriting the framework structure of the precursor2O3-C。
Step 3, preparing MOF-MoS2@Fe2O3-C nanocomposite:
0.2g of Fe2O3Ultrasonic dispersing for 10min in 60mL deionized water, then weighing 0.3g ammonium molybdate and 0.4g thiourea respectively, dissolving in Fe under stirring at 800r/min2O3-C in a dispersion of deionized water,stirring for 30min, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 200 ℃, keeping the temperature for 20h, cooling to room temperature, carrying out centrifugal separation on the solution obtained by the reaction, washing for 3 times by using ultrapure water and absolute ethyl alcohol, and finally drying for 12h at 70 ℃ under a vacuum condition to obtain the product with MoS2Nano-sheet coated core-shell structured MOF-MoS2@Fe2O3-a C nanocomposite;
the MOF-MoS obtained in this example2@Fe2O3And pressing the-C composite material into an electrode plate of the lithium ion battery, assembling the electrode plate into a CR2032 button battery by taking metal lithium as a counter electrode and EC/EMC solution of 1M lithium hexafluorophosphate as electrolyte, and performing charge and discharge tests on the battery. At 100mA g-1The first discharge capacity is 1147mAh/g under the current density test; under the condition of high current density of 1000mA/g, the specific discharge capacity can still be kept at 600 mAh/g.
Example 3
MOS (MoMoMoF) derived core-shell structure2@Fe2O3The preparation method of the negative electrode material of the-C lithium ion battery comprises the following steps:
step 1, preparing a spindle-shaped iron-based MOF precursor (spindle-MIL-88):
respectively weighing 1.6g of ferric chloride and 0.42g of fumaric acid, dissolving the ferric chloride and the fumaric acid in 25mL of N, N-Dimethylformamide (DMF), uniformly stirring at 600rpm for 30min to obtain an orange transparent liquid, transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out solvothermal reaction at 130 ℃, carrying out heat preservation for 4h, cooling to room temperature, carrying out centrifugal separation at the rotation speed of 5000r/min for 3min, repeatedly washing with absolute ethyl alcohol for 3 times, and finally drying at 70 ℃ for 12h under a vacuum condition to obtain spindle-shaped s-MIL-88 nanoparticles with the average particle size of 700 nm.
Step 2, preparing MOF derivative material Fe2O3-C：
Placing MIL-88 nano-particles into a porcelain boat, transferring the porcelain boat into a tube furnace, calcining the porcelain boat for 4 hours at the temperature of 400 ℃ under the argon atmosphere, heating at the rate of 5 ℃/min, and finally cooling the porcelain boat to room temperature along with the furnace to obtain the MOF derivative with carbon coating and inheriting the precursor framework structureMaterial Fe2O3-C。
Step 3, preparing MOF-MoS2@Fe2O3-C nanocomposite:
0.3g of Fe2O3Ultrasonic dispersing for 10min in 60mL deionized water, then weighing 0.3g ammonium molybdate and 0.4g thiourea respectively, dissolving in Fe under stirring at 800r/min2O3Stirring the deionized water dispersion liquid of the component-C for 30min, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at the temperature of 200 ℃, keeping the temperature for 20h, cooling to room temperature, carrying out centrifugal separation on the solution obtained by the reaction, washing for 3 times by using ultrapure water and absolute ethyl alcohol, and finally drying for 12h at the temperature of 70 ℃ under the vacuum condition to obtain the product with MoS2Nano-sheet coated core-shell structured MOF-MoS2@Fe2O3-a C nanocomposite;
the MOF-MoS obtained in this example2@Fe2O3And pressing the-C composite material into an electrode plate of the lithium ion battery, assembling the electrode plate into a CR2032 button battery by taking metal lithium as a counter electrode and EC/EMC solution of 1M lithium hexafluorophosphate as electrolyte, and performing charge and discharge tests on the battery. At 100mA g-1The first discharge capacity is 1025mAh/g under the current density test; under the condition of high current density of 1000mA/g, the specific discharge capacity can still be kept at 570 mAh/g.
Example 4
MOS (MoMoMoF) derived core-shell structure2@Fe2O3The preparation method of the negative electrode material of the-C lithium ion battery comprises the following steps:
step 1, preparing an iron-based MOF precursor (diamond-MIL-88) with a diamond structure:
respectively weighing 2.0g of ferric chloride and 0.5g of fumaric acid, dissolving the ferric chloride and the fumaric acid in 100mL of deionized water, uniformly stirring the mixture for 30min at 800rpm to obtain orange transparent liquid, transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 150 ℃, keeping the temperature for 5h, cooling the mixture to room temperature, carrying out centrifugal separation for 5min at the rotating speed of 3000r/min, repeatedly washing the mixture for 3 times by using absolute ethyl alcohol, and finally drying the mixture for 8h at 80 ℃ under a vacuum condition to obtain the d-MIL-88 (rhombus-MIL-88) nano particles with the rhombus structure, wherein the average particle size of the d-MIL-88 nano particles is 700 nm.
Step 2, preparing MOF derivative material Fe2O3-C：
Placing MIL-88 nano-particles into a porcelain boat, transferring the porcelain boat into a tube furnace, calcining the porcelain boat for 2h at 500 ℃ under the argon atmosphere, heating at a rate of 3 ℃/min, and finally cooling the porcelain boat to room temperature along with the furnace to obtain a carbon-coated MOF derivative material Fe inheriting the framework structure of the precursor2O3-C。
Step 3, preparing MOF-MoS2@Fe2O3-C nanocomposite:
0.1g of Fe2O3Ultrasonic dispersing for 30min in 80mL deionized water, then weighing 0.3g ammonium molybdate and 0.6g thiourea respectively, dissolving in Fe under stirring at 800r/min2O3Stirring the deionized water dispersion liquid of the component-C for 20min, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃, keeping the temperature for 24h, cooling to room temperature, carrying out centrifugal separation on the solution obtained by the reaction, washing for 3 times by using ultrapure water and absolute ethyl alcohol, and finally drying for 10h at 80 ℃ under a vacuum condition to obtain the product with MoS2Nano-sheet coated core-shell structured MOF-MoS2@Fe2O3-a C nanocomposite;
the MOF-MoS obtained in this example2@Fe2O3And pressing the-C composite material into an electrode plate of the lithium ion battery, assembling the electrode plate into a CR2032 button battery by taking metal lithium as a counter electrode and EC/EMC solution of 1M lithium hexafluorophosphate as electrolyte, and performing charge and discharge tests on the battery. FIG. 1b is an SEM photograph of d-MIL-88 showing diamond structures. At 100mA g-1Under the current density test, the first discharge capacity is 1132 mAh/g; under the condition of high current density of 1000mA/g, the specific discharge capacity can still be kept at 670 mAh/g.
Example 5
MOS (MoMoMoF) derived core-shell structure2@Fe2O3The preparation method of the negative electrode material of the-C lithium ion battery comprises the following steps:
step 1, preparing an iron-based MOF precursor (diamond-MIL-88) with a diamond structure:
respectively weighing 2.0g of ferric chloride and 0.5g of fumaric acid, dissolving the ferric chloride and the fumaric acid in 100mL of deionized water, uniformly stirring the mixture for 30min at 800rpm to obtain orange transparent liquid, transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 150 ℃, keeping the temperature for 5h, cooling the mixture to room temperature, carrying out centrifugal separation for 5min at the rotating speed of 3000r/min, repeatedly washing the mixture for 3 times by using absolute ethyl alcohol, and finally drying the mixture for 8h at 80 ℃ under a vacuum condition to obtain the d-MIL-88 nano particles with the diamond structure and the average particle size of 700 nm.
Step 2, preparing MOF derivative material Fe2O3-C：
Placing MIL-88 nano-particles into a porcelain boat, transferring the porcelain boat into a tube furnace, calcining the porcelain boat for 2h at 500 ℃ under the argon atmosphere, heating at a rate of 3 ℃/min, and finally cooling the porcelain boat to room temperature along with the furnace to obtain a carbon-coated MOF derivative material Fe inheriting the framework structure of the precursor2O3-C。
Step 3, preparing MOF-MoS2@Fe2O3-C nanocomposite:
0.2g of Fe2O3Ultrasonic dispersing for 30min in 80mL deionized water, then weighing 0.3g ammonium molybdate and 0.6g thiourea respectively, dissolving in Fe under stirring at 800r/min2O3Stirring the deionized water dispersion liquid of the component-C for 20min, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃, keeping the temperature for 24h, cooling to room temperature, carrying out centrifugal separation on the solution obtained by the reaction, washing for 3 times by using ultrapure water and absolute ethyl alcohol, and finally drying for 10h at 80 ℃ under a vacuum condition to obtain the product with MoS2Nano-sheet coated core-shell structured MOF-MoS2@Fe2O3-a C nanocomposite;
the MOF-MoS obtained in this example2@Fe2O3And pressing the-C composite material into an electrode plate of the lithium ion battery, assembling the electrode plate into a CR2032 button battery by taking metal lithium as a counter electrode and EC/EMC solution of 1M lithium hexafluorophosphate as electrolyte, and performing charge and discharge tests on the battery. At 100mA g-1The first discharge capacity was 1107 mAh/g; under the condition of high current density of 1000mA/g, the specific discharge capacity can still be kept at 630 mAh/g.
Example 6
MOS (MoMoMoF) derived core-shell structure2@Fe2O3The preparation method of the negative electrode material of the-C lithium ion battery comprises the following steps:
step 1, preparing an iron-based MOF precursor (diamond-MIL-88) with a diamond structure:
respectively weighing 2.0g of ferric chloride and 0.5g of fumaric acid, dissolving the ferric chloride and the fumaric acid in 100mL of deionized water, uniformly stirring the mixture for 30min at 800rpm to obtain orange transparent liquid, transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 150 ℃, keeping the temperature for 5h, cooling the mixture to room temperature, carrying out centrifugal separation for 5min at the rotating speed of 3000r/min, repeatedly washing the mixture for 3 times by using absolute ethyl alcohol, and finally drying the mixture for 8h at 80 ℃ under a vacuum condition to obtain the d-MIL-88 nano particles with the diamond structure and the average particle size of 700 nm.
Step 2, preparing MOF derivative material Fe2O3-C：
Placing MIL-88 nano-particles into a porcelain boat, transferring the porcelain boat into a tube furnace, calcining the porcelain boat for 2h at 500 ℃ under the argon atmosphere, heating at a rate of 3 ℃/min, and finally cooling the porcelain boat to room temperature along with the furnace to obtain a carbon-coated MOF derivative material Fe inheriting the framework structure of the precursor2O3-C。
Step 3, preparing MOF-MoS2@Fe2O3-C nanocomposite:
0.3g of Fe2O3Ultrasonic dispersing for 30min in 80mL deionized water, then weighing 0.3g ammonium molybdate and 0.6g thiourea respectively, dissolving in Fe under stirring at 800r/min2O3Stirring the deionized water dispersion liquid of the component-C for 20min, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃, keeping the temperature for 24h, cooling to room temperature, carrying out centrifugal separation on the solution obtained by the reaction, washing for 3 times by using ultrapure water and absolute ethyl alcohol, and finally drying for 10h at 80 ℃ under a vacuum condition to obtain the product with MoS2Nano-sheet coated core-shell structured MOF-MoS2@Fe2O3-a C nanocomposite;
the MOF-MoS obtained in this example2@Fe2O3And pressing the-C composite material into an electrode plate of the lithium ion battery, assembling the electrode plate into a CR2032 button battery by taking metal lithium as a counter electrode and EC/EMC solution of 1M lithium hexafluorophosphate as electrolyte, and performing charge and discharge tests on the battery. At 100mA g-1The first discharge capacity is 1090mAh/g under the current density test; under the condition of high current density of 1000mA/g, the specific discharge capacity can still be kept at 580 mAh/g.
Example 7
MOS (MoMoMoF) derived core-shell structure2@Fe2O3The preparation method of the negative electrode material of the-C lithium ion battery comprises the following steps:
step 1, preparing a rod-shaped iron-based MOF precursor (rod-shaped-MIL-88):
respectively weighing 3.0g of ferric nitrate and 2.0g of fumaric acid, dissolving in 100mL of deionized water, uniformly stirring at 800rpm for 50min to obtain orange transparent liquid, transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 130 ℃, keeping the temperature for 3h, cooling to room temperature, carrying out centrifugal separation at the rotation speed of 5000r/min for 3min, repeatedly washing with absolute ethyl alcohol for 3 times, and finally drying at 60 ℃ for 10h under a vacuum condition to obtain rod-shaped r-MIL-88 (rod-shaped-MIL-88) nanoparticles with the average particle size of 700 nm.
Step 2, preparing MOF derivative material Fe2O3-C：
Putting MIL-88 nano-particles into a porcelain boat, then transferring the porcelain boat into a tube furnace to calcine for 4h at 450 ℃ under the argon atmosphere, wherein the heating rate is 5 ℃/min, and finally cooling the porcelain boat to room temperature along with the furnace to obtain the MOF derivative material Fe coated with carbon and inheriting the framework structure of the precursor2O3-C。
Step 3, preparing MOF-MoS2@Fe2O3-C nanocomposite:
0.1g of Fe2O3Ultrasonic dispersing for 10min in 40mL deionized water, then weighing 0.3g ammonium molybdate and 0.6g thiourea respectively, stirring together at 800r/minDissolved in Fe2O3Stirring the deionized water dispersion liquid of the-C for 10min, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 210 ℃, keeping the temperature for 20h, cooling to room temperature, carrying out centrifugal separation on the solution obtained by the reaction, washing for 3 times by using ultrapure water and absolute ethyl alcohol, and finally drying for 10h at 70 ℃ under a vacuum condition to obtain the product with MoS2Nano-sheet coated core-shell structured MOF-MoS2@Fe2O3-a C nanocomposite;
the MOF-MoS obtained in this example2@Fe2O3And pressing the-C composite material into an electrode plate of the lithium ion battery, assembling the electrode plate into a CR2032 button battery by taking metal lithium as a counter electrode and EC/EMC solution of 1M lithium hexafluorophosphate as electrolyte, and performing charge and discharge tests on the battery. FIG. 1c is an SEM photograph of r-MIL-88 showing a rod-like structure. At 100mA g-1Under the current density test, the first discharge capacity is 1132 mAh/g; under the condition of high current density of 1000mA/g, the specific discharge capacity can still be kept at 670 mAh/g.
Example 8
MOS (MoMoMoF) derived core-shell structure2@Fe2O3The preparation method of the negative electrode material of the-C lithium ion battery comprises the following steps:
step 1, preparing a rod-shaped iron-based MOF precursor (rod-shaped-MIL-88):
respectively weighing 3.0g of ferric nitrate and 2.0g of fumaric acid, dissolving in 100mL of deionized water, uniformly stirring at 800rpm for 50min to obtain orange transparent liquid, transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 130 ℃, keeping the temperature for 3h, cooling to room temperature, carrying out centrifugal separation at the rotation speed of 5000r/min for 3min, repeatedly washing with absolute ethyl alcohol for 3 times, and finally drying at 60 ℃ for 10h under a vacuum condition to obtain rod-shaped r-MIL-88 nano particles with the average particle size of 700 nm.
Step 2, preparing MOF derivative material Fe2O3-C：
Putting the MIL-88 nano-particles into a porcelain boat, then transferring the porcelain boat into a tube furnace, calcining the porcelain boat for 4 hours at 450 ℃ under the argon atmosphere, and raising the temperature at a rateAt the temperature of 5 ℃/min, finally cooling to room temperature along with the furnace to obtain the MOF derivative material Fe coated with carbon and inheriting the precursor framework structure2O3-C。
Step 3, preparing MOF-MoS2@Fe2O3-C nanocomposite:
0.2g of Fe2O3Ultrasonic dispersing for 10min in 40mL deionized water, then weighing 0.3g ammonium molybdate and 0.6g thiourea respectively, dissolving in Fe under stirring at 800r/min2O3Stirring the deionized water dispersion liquid of the-C for 10min, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 210 ℃, keeping the temperature for 20h, cooling to room temperature, carrying out centrifugal separation on the solution obtained by the reaction, washing for 3 times by using ultrapure water and absolute ethyl alcohol, and finally drying for 10h at 70 ℃ under a vacuum condition to obtain the product with MoS2Nano-sheet coated core-shell structured MOF-MoS2@Fe2O3-a C nanocomposite;
the MOF-MoS obtained in this example2@Fe2O3And pressing the-C composite material into an electrode plate of the lithium ion battery, assembling the electrode plate into a CR2032 button battery by taking metal lithium as a counter electrode and EC/EMC solution of 1M lithium hexafluorophosphate as electrolyte, and performing charge and discharge tests on the battery. At 100mAg-1The first discharge capacity is 1107mAh/g under the current density test; under the condition of high current density of 1000mA/g, the specific discharge capacity can still be kept at 630 mAh/g.
Example 9
MOS (MoMoMoF) derived core-shell structure2@Fe2O3The preparation method of the negative electrode material of the-C lithium ion battery comprises the following steps:
step 1, preparing a rod-shaped iron-based MOF precursor (rod-shaped-MIL-88):
respectively weighing 3.0g of ferric nitrate and 2.0g of fumaric acid, dissolving in 100mL of deionized water, uniformly stirring at 800rpm for 50min to obtain orange transparent liquid, transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 130 ℃, keeping the temperature for 3h, cooling to room temperature, carrying out centrifugal separation at the rotation speed of 5000r/min for 3min, repeatedly washing with absolute ethyl alcohol for 3 times, and finally drying at 60 ℃ for 10h under a vacuum condition to obtain rod-shaped r-MIL-88 nano particles with the average particle size of 700 nm.
Step 2, preparing MOF derivative material Fe2O3-C：
Putting MIL-88 nano-particles into a porcelain boat, then transferring the porcelain boat into a tube furnace to calcine for 4h at 450 ℃ under the argon atmosphere, wherein the heating rate is 5 ℃/min, and finally cooling the porcelain boat to room temperature along with the furnace to obtain the MOF derivative material Fe coated with carbon and inheriting the framework structure of the precursor2O3-C。
Step 3, preparing MOF-MoS2@Fe2O3-C nanocomposite:
0.3g of Fe2O3Ultrasonic dispersing for 10min in 40mL deionized water, then weighing 0.3g ammonium molybdate and 0.6g thiourea respectively, dissolving in Fe under stirring at 800r/min2O3Stirring the deionized water dispersion liquid of the-C for 10min, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 210 ℃, keeping the temperature for 20h, cooling to room temperature, carrying out centrifugal separation on the solution obtained by the reaction, washing for 3 times by using ultrapure water and absolute ethyl alcohol, and finally drying for 10h at 70 ℃ under a vacuum condition to obtain the product with MoS2Nano-sheet coated core-shell structured MOF-MoS2@Fe2O3-a C nanocomposite;
the MOF-MoS obtained in this example2@Fe2O3And pressing the-C composite material into an electrode plate of the lithium ion battery, assembling the electrode plate into a CR2032 button battery by taking metal lithium as a counter electrode and EC/EMC solution of 1M lithium hexafluorophosphate as electrolyte, and performing charge and discharge tests on the battery. At 100mA g-1The first discharge capacity is 1090mAh/g under the current density test; under the condition of high current density of 1000mA/g, the specific discharge capacity can still be kept at 580 mAh/g.

Claims (10)

1. A preparation method of a lithium ion battery cathode material with an MOF derived core-shell structure is characterized by comprising the following steps:
step 1, preparing an iron-based metal organic framework precursor:
dissolving ferric salt and fumaric acid in a reaction solvent, uniformly stirring to obtain an orange transparent mixed solution 1, transferring the mixed solution 1 into a reaction kettle for heating reaction, then cooling to room temperature, performing centrifugal separation, washing and drying the separated solid to obtain MIL-88 nano particles, namely the iron-based metal organic framework precursor material;
step 2, preparing MOF derivative material Fe2O3-C：
Calcining MIL-88 nano particles, and cooling to room temperature along with the furnace to obtain Fe serving as an MOF derivative material2O3-C；
Step 3, preparing MOF-MoS2@Fe2O3-C nanocomposite:
mixing Fe2O3Preparing Fe by ultrasonically dispersing-C in deionized water2O3-C dispersion, dissolving molybdenum salt and thiourea in Fe under stirring2O3Forming a mixed solution 2 in the-C dispersion liquid, stirring for a certain time, transferring the mixed solution 2 into a reaction kettle for hydrothermal reaction, cooling to room temperature, performing centrifugal separation, washing and drying the separated solid to obtain the MOF-MoS2@Fe2O3-C nanocomposite, MOF-MoS2@Fe2O3-C nano composite material, namely the MOF derived core-shell structure lithium ion battery negative electrode material.
2. The preparation method of the MOF-derived core-shell-structure lithium ion battery negative electrode material according to claim 1, wherein the mass ratio of the iron salt to the fumaric acid in the step 1 is (0.8-5): 1, the ratio of the sum of the masses of the iron salt and the fumaric acid to the volume of the reaction solvent is 1 g: (12.5-40) mL.
3. The preparation method of the MOF-derived core-shell structure lithium ion battery negative electrode material according to claim 1, wherein in the step 1, a reaction solvent is deionized water or N, N-dimethylformamide.
4. The preparation method of the MOF-derived core-shell-structure lithium ion battery negative electrode material according to claim 1, characterized in that in the step 1, the stirring speed is 600-800 r/min, the stirring time is 30-50 min, the reaction temperature of the heating reaction is 130-150 ℃, and the reaction time is 3-5 h.
5. The preparation method of the MOF-derived core-shell-structure lithium ion battery negative electrode material according to claim 1, characterized in that in the step 2, the calcining temperature is 400-500 ℃, the heating rate is controlled at 3-5 ℃/min, the heat preservation time is 2-4 h, and argon or nitrogen is used as inert protective gas during calcining.
6. The preparation method of the MOF-derived core-shell structure lithium ion battery negative electrode material according to claim 1, wherein Fe in the step 32O3The mass ratio of the-C to the volume of the deionized water is (0.1-0.3) g (40-80) mL.
7. The preparation method of the MOF-derived core-shell-structure lithium ion battery negative electrode material according to claim 1, wherein in the step 3, the mass ratio of the molybdenum salt to the thiourea is (0.5-0.75): 1, the molybdenum salt is ammonium molybdate or sodium molybdate, Fe2O3The mass ratio of the mass of-C to the sum of the mass of the molybdenum salt and the thiourea is (1-3) to (7-9).
8. The preparation method of the MOF-derived core-shell-structure lithium ion battery negative electrode material according to claim 1, wherein in the step 3, the ultrasonic dispersion time is 10-30 min, the stirring speed is 600-800 r/min, the stirring time is 10-30 min, the hydrothermal reaction temperature is 180-210 ℃, and the reaction time is 20-24 h.
9. The preparation method of the MOF-derived core-shell-structure lithium ion battery negative electrode material according to claim 1, characterized in that in the steps 1 and 3, the rotation speed of centrifugal separation is 3000-5000 r/min, the centrifugal time is 2-4 min, the drying is vacuum drying, the vacuum drying temperature is 60-80 ℃, and the drying time is 8-12 h.
10. A lithium ion battery cathode material with an MOF derived core-shell structure is characterized by being prepared by the preparation method of the lithium ion battery cathode material with the MOF derived core-shell structure as claimed in any one of claims 1-9.
CN202110721453.3A 2021-06-28 2021-06-28 MOF-derived core-shell-structured lithium ion battery negative electrode material and preparation method thereof Pending CN113451570A (en)

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