CN113725434A - Composite electrode material derived from nickel-based metal organic framework and preparation method thereof - Google Patents

Composite electrode material derived from nickel-based metal organic framework and preparation method thereof Download PDF

Info

Publication number
CN113725434A
CN113725434A CN202110902068.9A CN202110902068A CN113725434A CN 113725434 A CN113725434 A CN 113725434A CN 202110902068 A CN202110902068 A CN 202110902068A CN 113725434 A CN113725434 A CN 113725434A
Authority
CN
China
Prior art keywords
electrode material
nickel
composite electrode
metal organic
based metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110902068.9A
Other languages
Chinese (zh)
Other versions
CN113725434B (en
Inventor
严平
陈修栋
刘金杭
李振峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiujiang University
Original Assignee
Jiujiang University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiujiang University filed Critical Jiujiang University
Priority to CN202110902068.9A priority Critical patent/CN113725434B/en
Publication of CN113725434A publication Critical patent/CN113725434A/en
Application granted granted Critical
Publication of CN113725434B publication Critical patent/CN113725434B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention provides a composite electrode material derived from a nickel-based metal organic framework and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Respectively dissolving nickel chloride hexahydrate and malonic acid in N, N-dimethylformamide, and stirring to completely dissolve the nickel chloride hexahydrate and the malonic acid; (2) mixing the two solutions and placing the mixture in a drying oven for reaction; (3) Washing a product obtained by the reaction, centrifugally separating the product, and drying the product to obtain a precursor material; (4) Heating the precursor material in a tubular furnace, and then annealing to obtain a flower-shaped electrode material; (5) Uniformly mixing the flower-shaped electrode material, the conductive carbon black and the PVDF adhesive to form a mixture, adding the mixture into N, N-dimethyl pyrrolidone, and dispersing the slurry by using a high-speed internal rotation type pulping machine to obtain black colloidal slurry; (6) And uniformly coating the black colloidal slurry on the copper foil which is processed in advance, and drying in a vacuum drying oven to prepare the composite electrode material.

Description

Composite electrode material derived from nickel-based metal organic framework and preparation method thereof
Technical Field
The invention relates to the technical field of energy storage devices and new material preparation, in particular to a composite electrode material derived from a nickel-based metal organic framework and a preparation method thereof.
Background
Currently, the energy density of commercial lead-acid batteries, alkaline zinc-manganese batteries, and other secondary batteries has not met the increasing demand of people. Meanwhile, lead-acid batteries and alkaline zinc-manganese batteries have many problems, such as poor portability, high recycling difficulty, environmental friendliness and the like. In order to solve the above problems, researchers have developed many novel energy storage devices, such as fuel cells, aluminum ion cells, lithium air cells, magnesium ion cells, lithium sulfur cells, sodium ion cells, potassium ion cells, and the like. However, they also have problems such as cycle performance and safety performance, which require further solution, and thus are far from the commercialized road. Lithium ion batteries having excellent performance have been widely used and gradually become the mainstream of secondary batteries. However, with the improvement of living standard of people, lithium ion batteries with better performance are urgently needed.
Nickel-based metal organic frame materials have been widely used in various fields such as gas separation/storage, sewage treatment, optical devices, energy storage, and the like. Currently, nickel-based metal organic framework derivative materials with regular shapes obtained by regulating and controlling reaction conditions are widely researched. Many documents have reported that the nickel-based metal organic framework derivative material with uniform and regular structure can have excellent electrochemical energy.
Currently, research on lithium ion negative electrode materials mainly focuses on developing transition metal oxides and transition metal sulfides with different morphologies, and has already been carried out with relatively good results. However, research on novel nickel-based metal organic framework materials is still relatively small, especially flower-like materials derived from the nickel-based metal organic framework materials.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:
(1) Respectively dissolving nickel chloride hexahydrate and malonic acid in N, N-dimethylformamide, and stirring to completely dissolve the nickel chloride hexahydrate and the malonic acid;
(2) Mixing the two solutions obtained in the step (1), uniformly stirring, transferring to a polytetrafluoroethylene lining reaction kettle, and placing in an oven for reaction;
(3) Washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;
(4) Placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating the porcelain boat in the air atmosphere, and then annealing the porcelain boat to obtain a flower-shaped electrode material;
(5) Uniformly mixing the flower-shaped electrode material obtained in the step (4), conductive carbon black and a PVDF adhesive to form a mixture, then adding the mixture into N, N-dimethyl pyrrolidone, and dispersing slurry by using a high-speed internal rotation type pulping machine to obtain black colloidal slurry;
(6) And (6) uniformly coating the black colloidal slurry obtained in the step (5) on a copper foil which is processed in advance, and placing the copper foil in a vacuum drying oven for drying to prepare the composite electrode material.
Wherein the mass ratio of the nickel chloride hexahydrate to the malonic acid is 2 to 3.
Preferably, the mass ratio of the nickel chloride hexahydrate to the malonic acid is 2.2.
Wherein the mass volume ratio of the nickel chloride hexahydrate to the N, N-dimethylformamide is 3-8, and the mass volume ratio of the malonic acid to the N, N-dimethylformamide is 1-5.
Preferably, the first and second electrodes are formed of a metal,
the mass volume ratio of the nickel chloride hexahydrate to the N, N-dimethylformamide is 4;
the mass-to-volume ratio of the malonic acid to the N, N-dimethylformamide is 2 g/mL,3 g/mL, 100 g/mL, 4.
Wherein the mass ratio of the flower-shaped electrode material to the conductive carbon black to the PVDF adhesive is 7 to 10.
Preferably, the mass ratio of the flower-like electrode material, the conductive carbon black and the PVDF adhesive is 8.
The mass volume ratio of a mixture formed by the flower-shaped electrode material, the conductive carbon black and the PVDF adhesive to the N, N-dimethyl pyrrolidone is 0.20 to 0.24.
Preferably, the mass to volume ratio of the mixture to the N, N-dimethylpyrrolidone is 0.21.
Wherein in the step (2), the reaction temperature is 150 to 200 ℃ and the reaction time is 10 to 15h.
Preferably, the first and second electrodes are formed of a metal,
the reaction temperature is 155 ℃,160 ℃,165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃ and 195 ℃;
the reaction time was 11h,12h,13h, and 14h.
In the step (4), the temperature is raised to 450-550 ℃ at the temperature raising rate of 2-5 ℃/min in the air atmosphere, and then annealing treatment is carried out for 1-4 h to obtain the flower-shaped electrode material.
Wherein in the step (6), the drying temperature is 50-80 ℃ and the drying time is 10-15h.
Preferably, the first and second electrodes are formed of a metal,
the drying temperature is 55 ℃,60 ℃,65 ℃,70 ℃ and 75 ℃;
the drying time was 11h,12h,13h, and 14h.
In a second aspect, the invention provides a nickel-based metal organic framework-derived composite electrode material, which is prepared according to the method provided by the first aspect of the invention.
The invention has the beneficial effects that:
the composite electrode material derived from the nickel-based metal organic framework prepared by the simple hydrothermal method has higher capacity mainly due to the stable porous structure and the special appearance, is beneficial to soaking in electrolyte and effectively relieving volume expansion and structural pulverization of the electrode material in the charging and discharging processes, and thus improves the electrochemical performance.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it should be obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an XRD spectrum of a nickel-based metal organic framework material prepared by the method provided in example 1 of the present invention;
FIGS. 2 and 3 are SEM images of a nickel-based metal organic framework-derived composite electrode material prepared by the method provided by example 1 of the invention;
FIG. 4 is a charge-discharge curve diagram of the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1 of the present invention;
FIG. 5 shows that the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1 of the present invention is 0.1A g -1 A plot of the cycle at current density;
FIG. 6 is a graph of the impedance of the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1.
Detailed Description
The following is a preferred embodiment of the present invention, and it should be noted that it would be apparent to those skilled in the art that various modifications and enhancements can be made without departing from the principles of the present invention, and such modifications and enhancements are intended to be within the scope of the present invention.
Example 1
The invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:
(1) 0.5 g of nickel chloride hexahydrate and 0.2 g of malonic acid are weighed and respectively dissolved in 10mL of N, N-dimethylformamide, and stirring is carried out for 10 min to ensure that the nickel chloride hexahydrate and the malonic acid are completely dissolved;
(2) Mixing the two solutions obtained in the step (1), stirring for 20 min, uniformly mixing, transferring to a 50mL polytetrafluoroethylene lining reaction kettle, placing in an oven, and reacting at 180 ℃ for 12 h;
(3) Washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and drying the product obtained by centrifugal separation in a vacuum drying oven to obtain a precursor material;
(4) Placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tube furnace, heating to 500 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and annealing for 2h to obtain a flower-shaped electrode material;
(5) Weighing 17.6 mg of the flower-like electrode material obtained in the step (4), 2.2 mg of conductive carbon black and 2.2 mg of PVDF adhesive, uniformly mixing to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing slurry by using a high-speed internal rotation type pulping machine for 1min each time, and repeating for 5 times to obtain black colloidal slurry;
(6) And (3) uniformly coating the black colloidal slurry obtained in the step (5) on the copper foil which is processed in advance, placing the copper foil in a vacuum drying oven, and drying the copper foil for 12 hours at the temperature of 60 ℃ to prepare the composite electrode material.
The composite electrode material prepared in example 1 was assembled into a button cell for evaluation, and LiPF (lithium ion power) using a lithium foil as a reference electrode, a polypropylene porous membrane (Celgard 2300) as a separator, and an electrolyte of 1mol/L was used 6 The cells were assembled with a mixed solution of ethylene carbonate and diethyl carbonate (w/w, 1/1) in a glove box filled with high-purity argon gas. On the LAND-CT2001C system, at 0.1A g -1 Under the current of the battery to embed lithiumAnd a lithium removal cycle at 0.1 mV s on Chenhua 760E electrochemical station -1 And the test voltage range is 1 mV-3.0V, and CV test is carried out.
Fig. 1 is an XRD spectrum of the nickel-based metal organic framework material prepared by the method provided in example 1, from which it can be seen that there are five different characteristic peaks, from which it can be seen that the nickel-based metal organic framework material has a stable crystal structure.
Fig. 2 and 3 are SEM images of the composite electrode material derived from the nickel-based metal organic framework prepared by the method provided in example 1, and it can be seen that the electrode material has a flower-like structure and a diameter of about 200-300 nm.
Fig. 4 is a charge-discharge curve diagram of the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1, and the platform of the reaction can be clearly seen from the curve in the first circle in the figure, and meanwhile, the coulombic efficiency of the nickel-based metal organic framework-derived composite electrode is 68.2%, and the main reason for the capacity loss is the formation of a solid electrolyte interface film.
FIG. 5 shows that the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1 is 0.1 Ag -1 The cycle curve under current density shows that 1205mAh g is reached after the first 10 cycles -1 From this, it can be seen that: the composite electrode material derived from the nickel-based metal organic framework is a potential high-performance electrode material.
Fig. 6 is a resistance curve diagram of the composite electrode material derived from the nickel-based metal organic framework prepared by the method provided in example 1, and it can be seen from the impedance curve diagram that the resistance of the flower-shaped electrode material is only 130 Ω after one cycle, and thus it can be seen that the composite electrode material derived from the nickel-based metal organic framework has high electrical conductivity.
Example 2
The invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:
(1) 0.4 g of nickel chloride hexahydrate and 0.2 g of malonic acid are weighed and respectively dissolved in 10mL of N, N-dimethylformamide, and stirring is carried out for 10 min to ensure that the nickel chloride hexahydrate and the malonic acid are completely dissolved;
(2) Mixing the two solutions obtained in the step (1), stirring for 20 min, uniformly mixing, transferring to a 50mL polytetrafluoroethylene-lined reaction kettle, placing in an oven, and reacting for 14h at 160 ℃;
(3) Washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and drying the product obtained by centrifugal separation in a vacuum drying oven to obtain a precursor material;
(4) Placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating to 480 ℃ at a heating rate of 4 ℃/min in an air atmosphere, and then annealing for 3 hours to obtain a flower-shaped electrode material;
(5) Weighing 16.0 mg of the flower-shaped electrode material obtained in the step (4), 2.0 mg of conductive carbon black and 2.0 mg of PVDF adhesive, uniformly mixing to form a mixture, then adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing slurry by using a high-speed internal rotation type pulping machine, 1min for each time, and repeating for 6 times to obtain black colloidal slurry;
(6) And (6) uniformly coating the black colloidal slurry obtained in the step (5) on a copper foil which is treated in advance, placing the copper foil in a vacuum drying oven, and drying for 14 hours at the temperature of 55 ℃ to prepare the composite electrode material.
Example 3
The invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:
(1) Weighing 0.6 g of nickel chloride hexahydrate and 0.2 g of malonic acid, respectively dissolving in 10mL of N, N-dimethylformamide, and stirring for 10 min to completely dissolve the nickel chloride hexahydrate and the malonic acid;
(2) Mixing the two solutions obtained in the step (1), stirring for 20 min, uniformly mixing, transferring to a 50mL polytetrafluoroethylene lining reaction kettle, placing in an oven, and reacting for 10 h at 200 ℃;
(3) Washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;
(4) Placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tube furnace, heating to 520 ℃ at a heating rate of 3 ℃/min in an air atmosphere, and then annealing for 1.5 h to obtain a flower-shaped electrode material;
(5) Weighing 17.5 mg of the flower-like electrode material obtained in the step (4), 2.5 mg of conductive carbon black and 2.5 mg of PVDF adhesive, uniformly mixing to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing slurry by using a high-speed internal rotation type pulping machine for 1min each time, and repeating for 5 times to obtain black colloidal slurry;
(6) And (6) uniformly coating the black colloidal slurry obtained in the step (5) on a copper foil which is treated in advance, placing the copper foil in a vacuum drying oven, and drying the copper foil for 15 hours at the temperature of 50 ℃ to prepare the composite electrode material.
Example 4
The invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:
(1) 0.5 g of nickel chloride hexahydrate and 0.2 g of malonic acid are weighed and respectively dissolved in 10mL of N, N-dimethylformamide, and stirring is carried out for 10 min to ensure that the nickel chloride hexahydrate and the malonic acid are completely dissolved;
(2) Mixing the two solutions obtained in the step (1), stirring for 20 min, uniformly mixing, transferring to a 50mL polytetrafluoroethylene lining reaction kettle, placing in an oven, and reacting for 13h at 170 ℃;
(3) Washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;
(4) Placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating the porcelain boat to 450 ℃ at a heating rate of 5 ℃/min in the air atmosphere, and then annealing for 4 hours to obtain a flower-shaped electrode material;
(5) Weighing 20.0 mg of the flower-shaped electrode material obtained in the step (4), 2.0 mg of conductive carbon black and 2.0 mg of PVDF adhesive, uniformly mixing to form a mixture, then adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing slurry by using a high-speed internal rotation type pulping machine, 1min for each time, and repeating for 6 times to obtain black colloidal slurry;
(6) And (4) uniformly coating the black colloidal slurry obtained in the step (5) on the copper foil which is processed in advance, placing the copper foil in a vacuum drying oven, and drying for 11 hours at the temperature of 75 ℃ to prepare the composite electrode material.
Example 5
The invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:
(1) 0.6 g of nickel chloride hexahydrate and 0.2 g of malonic acid are weighed and respectively dissolved in 10mL of N, N-dimethylformamide, and stirring is carried out for 10 min to ensure that the nickel chloride hexahydrate and the malonic acid are completely dissolved;
(2) Mixing the two solutions obtained in the step (1), stirring for 20 min, uniformly mixing, transferring to a 50mL polytetrafluoroethylene lining reaction kettle, placing in an oven, and reacting for 15h at 150 ℃;
(3) Washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;
(4) Placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating the porcelain boat to 550 ℃ at a heating rate of 3 ℃/min in an air atmosphere, and then annealing for 1h to obtain a flower-shaped electrode material;
(5) Weighing 20.0 mg of the flower-shaped electrode material obtained in the step (4), 2.0 mg of conductive carbon black and 2.0 mg of PVDF adhesive, uniformly mixing to form a mixture, then adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing slurry by using a high-speed internal rotation type pulping machine, 1min for each time, and repeating for 5 times to obtain black colloidal slurry;
(6) And (6) uniformly coating the black colloidal slurry obtained in the step (5) on a copper foil which is treated in advance, placing the copper foil in a vacuum drying oven, and drying for 12 hours at the temperature of 65 ℃ to prepare the composite electrode material.
The above examples only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the present invention. It should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the spirit of the present invention, and these changes and modifications are all within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (9)

1. A preparation method of a composite electrode material derived from a nickel-based metal organic framework is characterized by comprising the following steps:
(1) Respectively dissolving nickel chloride hexahydrate and malonic acid in N, N-dimethylformamide, and stirring to completely dissolve the nickel chloride hexahydrate and the malonic acid;
(2) Mixing the two solutions obtained in the step (1), uniformly stirring, transferring to a polytetrafluoroethylene lining reaction kettle, and placing in an oven for reaction;
(3) Washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;
(4) Placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating the porcelain boat in the air atmosphere, and then annealing the porcelain boat to obtain a flower-shaped electrode material;
(5) Uniformly mixing the flower-shaped electrode material obtained in the step (4), conductive carbon black and a PVDF adhesive to form a mixture, adding the mixture into N, N-dimethyl pyrrolidone, and dispersing slurry by using a high-speed internal rotation type pulping machine to obtain black colloidal slurry;
(6) And (5) uniformly coating the black colloidal slurry obtained in the step (5) on the copper foil which is processed in advance, and placing the copper foil in a vacuum drying oven for drying to prepare the composite electrode material.
2. The method for preparing the composite electrode material derived from the nickel-based metal organic framework, according to claim 1, is characterized in that: the mass ratio of the nickel chloride hexahydrate to the malonic acid is (2) - (3).
3. The method for preparing the composite electrode material derived from the nickel-based metal organic framework, according to claim 1, is characterized in that: the mass volume ratio of the nickel chloride hexahydrate to the N, N-dimethylformamide is 3-8.
4. The method for preparing the composite electrode material derived from the nickel-based metal organic framework, according to claim 1, is characterized in that: the mass ratio of the flower-shaped electrode material to the conductive carbon black to the PVDF adhesive is (7) - (10).
5. The method for preparing the composite electrode material derived from the nickel-based metal organic framework, according to claim 1, is characterized in that: the mass volume ratio of a mixture formed by the flower-shaped electrode material, the conductive carbon black and the PVDF adhesive to the N, N-dimethyl pyrrolidone is 0.20 to 0.24.
6. The preparation method of the composite electrode material derived from the nickel-based metal organic framework, which is characterized by comprising the following steps of: in the step (2), the reaction temperature is 150 to 200 ℃, and the reaction time is 10 to 15h.
7. The preparation method of the composite electrode material derived from the nickel-based metal organic framework, which is characterized by comprising the following steps of: in the step (4), the temperature is raised to 450 to 550 ℃ at a heating rate of 2 to 5 ℃/min in the air atmosphere, and then annealing treatment is carried out for 1 to 4h to obtain the flower-shaped electrode material.
8. The method for preparing the composite electrode material derived from the nickel-based metal organic framework according to any one of claims 1 to 5, wherein the method comprises the following steps: in the step (6), the drying temperature is 50 to 80 ℃, and the drying time is 10 to 15h.
9. A composite electrode material derived from a nickel-based metal organic framework is characterized in that: the composite electrode material is prepared by the method provided by any one of claims 1-8.
CN202110902068.9A 2021-08-06 2021-08-06 Nickel-based metal organic frame derived composite electrode and preparation method thereof Active CN113725434B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110902068.9A CN113725434B (en) 2021-08-06 2021-08-06 Nickel-based metal organic frame derived composite electrode and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110902068.9A CN113725434B (en) 2021-08-06 2021-08-06 Nickel-based metal organic frame derived composite electrode and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113725434A true CN113725434A (en) 2021-11-30
CN113725434B CN113725434B (en) 2023-05-16

Family

ID=78675060

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110902068.9A Active CN113725434B (en) 2021-08-06 2021-08-06 Nickel-based metal organic frame derived composite electrode and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113725434B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012028989A1 (en) * 2010-09-01 2012-03-08 Basf Se Process for producing carbon-comprising composite
CN102962037A (en) * 2012-11-01 2013-03-13 中国科学院大连化学物理研究所 Metal-organic framework material for methane adsorption separation and preparation method thereof
CN103086867A (en) * 2011-10-27 2013-05-08 中国科学院大连化学物理研究所 Nickel base micropore material and preparation method thereof
CN111204822A (en) * 2020-01-08 2020-05-29 九江学院 Preparation method of NiO-ZnO/S lithium-sulfur battery positive electrode material with flower-like structure
CN112893858A (en) * 2019-11-19 2021-06-04 中国科学院大连化学物理研究所 Preparation method of nickel-carbon-based material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012028989A1 (en) * 2010-09-01 2012-03-08 Basf Se Process for producing carbon-comprising composite
CN103086867A (en) * 2011-10-27 2013-05-08 中国科学院大连化学物理研究所 Nickel base micropore material and preparation method thereof
CN102962037A (en) * 2012-11-01 2013-03-13 中国科学院大连化学物理研究所 Metal-organic framework material for methane adsorption separation and preparation method thereof
CN112893858A (en) * 2019-11-19 2021-06-04 中国科学院大连化学物理研究所 Preparation method of nickel-carbon-based material
CN111204822A (en) * 2020-01-08 2020-05-29 九江学院 Preparation method of NiO-ZnO/S lithium-sulfur battery positive electrode material with flower-like structure

Also Published As

Publication number Publication date
CN113725434B (en) 2023-05-16

Similar Documents

Publication Publication Date Title
CN113346054B (en) Preparation method and application of MXene-carbon nanocage-sulfur composite material
CN106099062A (en) Silicon based composite material Si@C@TiO is covered in double-contracting2and preparation method thereof
CN106920989B (en) A kind of copper selenium compound is the sodium-ion battery of negative electrode material
CN104362296A (en) Novel sulfenyl material electrode and preparation method and application thereof
CN112397704B (en) High specific energy power lithium ion battery
CN111646459A (en) Preparation method and application of boron-doped graphene material
CN114702614A (en) Cathode material for improving cycling stability of vulcanized polyacrylonitrile battery and preparation method thereof
CN113937261B (en) Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery positive electrode plate
CN111261873A (en) N-MnO2Preparation and application of/S composite material
CN111204822A (en) Preparation method of NiO-ZnO/S lithium-sulfur battery positive electrode material with flower-like structure
CN110534816A (en) Fibrous flexible rechargeable zinc-manganese battery based on multi-valence manganese oxide
CN113772718A (en) SnS-SnS2@ GO heterostructure composite material and preparation method and application thereof
CN108899473B (en) High-performance flexible lithium secondary battery positive electrode and preparation method thereof
CN111146007A (en) Zinc ion hybrid supercapacitor and preparation method thereof
CN115050944B (en) Composite material with three-dimensional nano flower structure and preparation method and application thereof
CN115084471B (en) Layered halide double perovskite lithium ion battery anode material and preparation method thereof
CN114678499B (en) Single-layer transition metal sulfide/graphene composite material and preparation method and application thereof
CN115101731A (en) Negative electrode material, preparation method thereof, negative electrode plate and secondary battery
CN112331812B (en) MoO (MoO) 2 Preparation method of nanorod anode material
CN111816853B (en) CuS-Cu7.2S4Nanocomposite, lithium battery and preparation method
CN113725434B (en) Nickel-based metal organic frame derived composite electrode and preparation method thereof
CN109119607B (en) Polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material and preparation method thereof
KR101485483B1 (en) Manufacturing method of Cathode material for Mg rechargeable batteries, and Cathode material for Mg rechargeable batteries made by the same
CN113299895B (en) Controllable synthesis and energy storage application of cake-shaped sulfur-based compound composite material
CN114242982B (en) Graphene-coated two-dimensional metal compound electrode material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant