CN111584840A - Carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material and preparation method and application thereof - Google Patents

Carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material and preparation method and application thereof Download PDF

Info

Publication number
CN111584840A
CN111584840A CN202010376721.8A CN202010376721A CN111584840A CN 111584840 A CN111584840 A CN 111584840A CN 202010376721 A CN202010376721 A CN 202010376721A CN 111584840 A CN111584840 A CN 111584840A
Authority
CN
China
Prior art keywords
carbon
carbon cloth
coated nickel
composite material
disulfide nanosheet
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.)
Pending
Application number
CN202010376721.8A
Other languages
Chinese (zh)
Inventor
安琴友
段美江
麦立强
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.)
Wuhan University of Technology WUT
Original Assignee
Wuhan University of Technology WUT
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 Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CN202010376721.8A priority Critical patent/CN111584840A/en
Publication of CN111584840A publication Critical patent/CN111584840A/en
Pending legal-status Critical Current

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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/11—Sulfides
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material and a preparation method thereof. The nickel disulfide nanosheet is formed by assembling 10-15 nm of nickel disulfide small particles, and the thickness of the nanosheet is 10-50 nm. The composite material shows better electrochemical performance when being used as an aluminum ion anode material: the material can be used as a potential application material of a long-life, excellent cycle stability and high-multiplying-power aluminum ion battery anode material.

Description

Carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano materials and electrochemistry, and particularly relates to a carbon cloth loaded carbon clothCarbon-coated nickel disulfide nanosheet composite (NiS)2@ PANI-CF) and a preparation method thereof, and the material can be used as a potential application material of a long-life and excellent cycle stability aluminum ion battery positive electrode material.
Background
Currently, lithium ion batteries are receiving wide attention due to their high energy density and charge-discharge cycle stability, and have been commercialized. With the increase of the mass production of lithium ion batteries, the problems of limited lithium storage capacity, expensive price and the like become increasingly prominent. The development of a novel battery with wide raw material sources, low price and good performance is imminent. With the rapid development of portable charging devices and Electric Vehicles (EVs), the development of new high-performance energy storage devices and related materials required for core components thereof is receiving more and more high attention. A battery system can be applied to actual production and life and needs to meet the following conditions: high safety; long cycle life; high energy density; a high power density; low cost and the like. As a novel multivalent ion battery system, the aluminum ion battery has the advantages of three positive charges, high volume capacity, high mass capacity, rich storage capacity and the like, and becomes a promising substitute. Radius of aluminum ion
Figure BDA0002480371740000011
Much smaller than lithium ions
Figure BDA0002480371740000012
However, due to the three charges carried by the material, a strong coulombic effect exists between the material and the anode material, so that the material is low in embedding rate, slow in migration and large in polarization, and the reversible capacity and the rate performance are low. The search for suitable cathode materials is a critical issue to be solved urgently.
Transition metal oxides, sulfides, selenides, and the like have all been studied in aluminum ion batteries. The materials have high capacity, but due to the problems of high charge density of aluminum ions, electrolyte adaptation and the like, most of the materials have structures which collapse and expand in volume due to embedding of unknown complex ions in the circulation process, the discharge platform is low, most of the materials have low discharge capacity, discharge is unstable, the capacity is rapidly attenuated in the discharge process, the reversibility is poor, and many of the materials and the ionic liquid have unknown side reactions. All of these factors result in poor electrochemical performance, hindering the development of high energy density aluminum ion batteries. Transition metal sulfide such as nickel sulfide has a higher theoretical specific capacity due to multiple valence states of nickel, and the material has a lower cost and is environmentally friendly, so that the transition metal sulfide is considered as a promising positive electrode material of an aluminum ion battery. In recent years, nickel sulfide and trinickel disulfide have been studied as aluminum ion positive electrode materials, but nickel disulfide has not been reported as an aluminum ion positive electrode material. According to the related research of the current aluminum ion battery, the active substance has larger specific surface area, and the microstructure is not damaged in the charging and discharging process, so that the electrochemical performance is greatly influenced.
Disclosure of Invention
The technical problem to be solved by the invention is provided by aiming at the prior art, and the invention aims to provide a carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material and a preparation method thereof, which have simple process and excellent performance in electrochemical tests of aluminum ion batteries.
The technical scheme adopted by the invention for solving the technical problems is as follows: the carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material is prepared from NiS with the particle size of 10-15 nanometers2The nano-sheet is 10-50 nm in thickness, and the surface of the nano-sheet is coated with a 2-3 nm carbon layer.
The preparation method of the carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material comprises the following steps:
1) dissolving nickel nitrate hexahydrate and hexamethylenetetramine in deionized water, and stirring until the nickel nitrate and the hexamethylenetetramine are completely dissolved;
2) putting carbon cloth into the solution obtained in the step 1) to perform hydrothermal reaction;
3) cleaning and drying the product obtained in the step 2) to obtain a precursor Ni (OH)2-CF；
4) Dissolving aniline and tartaric acid into deionized water, adding the precursor obtained in the step 3), and performing ultrasonic treatment in an ice-water bath;
5) adding an ammonium persulfate aqueous solution which is pre-cooled in ice water into the solution obtained in the step 4), and placing the system in an ice water bath;
6) cleaning and drying the product obtained in the step 5) to obtain the carbon cloth loaded polyaniline coated nickel precursor composite material Ni (OH)2@PANI-CF；
7) Mixing the polyaniline-coated nickel precursor composite material loaded by the carbon cloth obtained in the step 6) with sublimed sulfur and then calcining to obtain carbon-coated nickel disulfide nanosheet composite material NiS loaded by the carbon cloth2@PANI-CF。
According to the scheme, the amount of nickel nitrate hexahydrate in the step 1) is 0.9-2.3 g, and the amount of hexamethylenetetramine is 0.56-1.4 g.
According to the scheme, the hydrothermal temperature in the step 2) is 100 ℃, and the time is 8-10 hours.
According to the scheme, the amount of the aniline tartaric acid in the step 4) is as follows: aniline: tartaric acid: precursor Ni (OH)23-10 mol of-CF, 5mol and 3mol of deionized water, 150ml of deionized water, and performing ice-water bath ultrasound for 20-40 min.
According to the scheme, the concentration of the ammonium persulfate aqueous solution in the step 5) is 0.2-0.3 mol L-1The volume is 50-60 mL, and the reaction time in ice-water bath is 4-6 h.
According to the scheme, the mass ratio of the carbon cloth loaded polyaniline-coated nickel precursor composite material in the step 7) to the sulfur hydride is 1: 4; the calcination temperature is 250-300 ℃, the calcination atmosphere is nitrogen, and the calcination time is 2-3 h.
The carbon-coated nickel disulfide nanosheet composite material loaded by the carbon cloth is applied as an anode material of an aluminum ion battery.
The synthesis mechanism of the invention is as follows: based on a crystal grain nucleation-growth mechanism, in the hydrothermal synthesis process of the nickel disulfide, the introduction of the carbon cloth enables the nickel disulfide nanosheets to be uniformly loaded thereon.
The invention has the beneficial effects that: the invention utilizes the advantage of larger specific surface area of the nano sheet to prepare the nickel precursor nano loaded on the carbon cloth by a hydrothermal in-situ growth methodThe carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material is obtained by coating polyaniline on a precursor and then vulcanizing in a nitrogen closed atmosphere, and has the excellent performances of long service life, excellent cycle stability, high multiplying power and the like when an aluminum ion electrochemical performance test is carried out. When the material is used as the anode material of an aluminum ion battery, the concentration is 200mAg-1The test is carried out under the current density, and the discharge specific capacity is still as high as 112mAh g after the circulation for 150 times-1And excellent cycle performance is shown. At 300mA g-1The result of constant current discharge test under larger current density shows that the discharge specific capacity is still maintained at 70mAh g after 1500 times of circulation-1And has better long cycle performance. The multiplying power of the lithium ion battery has good capacity retention rate when tested under different current densities. Test results show that the carbon-coated nickel disulfide nanosheet composite material loaded by the carbon cloth can be used as a potential application material of a long-life, excellent cycle stability and high-rate aluminum ion battery anode material.
Drawings
Fig. 1 is an X-ray diffraction spectrum (XRD) of the carbon-coated nickel disulfide nanosheet composite supported on carbon cloth in example 1 of the present invention;
fig. 2 is a Scanning Electron Microscope (SEM) image of the carbon-coated nickel disulfide nanosheet composite supported by the carbon cloth of example 1 of the present invention;
fig. 3 is a Transmission Electron Microscope (TEM) image of the carbon-coated nickel disulfide nanosheet composite supported by the carbon cloth in example 1 of the present invention;
FIG. 4 shows that the carbon cloth-supported carbon-coated nickel disulfide nanosheet composite of embodiment 1 of the present invention is 200mA g-1A battery cycle performance plot at current density;
FIG. 5 shows that the carbon cloth-supported carbon-coated nickel disulfide nanosheet composite of embodiment 1 of the present invention is at 300mA g-1A battery cycle performance plot at current density;
fig. 6 is a battery cycle rate performance diagram of the carbon-coated nickel disulfide nanosheet composite loaded with carbon cloth in example 1 of the present invention at different current densities.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1:
the preparation method of the carbon-coated nickel disulfide nanosheet composite material loaded on the carbon cloth comprises the following steps:
1) 0.9g of nickel nitrate hexahydrate and 0.56g of hexamethylenetetramine are taken, and the nickel nitrate hexahydrate and the hexamethylenetetramine are dissolved in 80ml of deionized water and stirred until the nickel nitrate and the hexamethylenetetramine are completely dissolved.
2) Putting carbon cloth into the solution obtained in the step 1), and carrying out hydrothermal reaction for 10h at 100 ℃.
3) Cleaning and drying the product obtained in the step 2) to obtain a precursor (Ni (OH)2-CF)。
4) Adding aniline: tartaric acid: step 3) calculating the precursor (Ni (OH)2-CF) is dissolved into 150ml of deionized water according to the molar ratio of 3:5:3, and the mixture is subjected to ultrasonic treatment in an ice-water bath for 30 min.
5) To the solution obtained in step 4), 0.2mol L of a solution cooled in ice water in advance was added-150ml of ammonium persulfate aqueous solution, and placing the system in an ice water bath for 6 hours.
6) Washing the product obtained in the step 5) with deionized water, and drying in a vacuum drying oven at 60 ℃ to obtain the carbon cloth loaded polyaniline coated nickel precursor composite material (Ni (OH)2@PANI-CF)；
7) Mixing the polyaniline-coated nickel precursor composite material loaded on the carbon cloth and obtained in the step 6) with sublimed sulfur (the mass ratio is 1:4), and calcining the mixture for 3 hours at the calcining temperature of 300 ℃ under the calcining atmosphere of nitrogen to obtain the carbon-coated nickel disulfide nanosheet composite material (NiS) loaded on the carbon cloth2@PANI-CF)。
Taking the carbon-coated nickel disulfide nanosheet composite loaded on the carbon cloth as an example, the structure of the composite is determined by an X-ray diffractometer. As shown in FIG. 1, the X-ray diffraction pattern (XRD) shows that the characteristic peaks of the carbon cloth and the nickel disulfide/carbon coated composite material can be well matched with those of NiS2Standard card of crystalline phase (JCPDS:01-073-0574) was matched and proved to be NiS2A major phase. As shown in figure 2 of the drawings, in which,a Field Emission Scanning Electron Microscope (FESEM) test shows that the size of the nano-sheet is 10-20 nanometers, and the nano-sheet is very uniform in shape. As shown in FIG. 3, a Transmission Electron Microscope (TEM) test can clearly show that the nanosheets are composed of nickel disulfide small particles of 10-15 nm, and the carbon layer is 2-3 nm thick.
The carbon cloth-loaded carbon-coated nickel disulfide nanosheet composite material prepared by the invention is used as an active material of the anode of an aluminum ion battery. The preparation method of the electrode slice comprises the following steps of adopting carbon-coated nickel disulfide nanosheet composite (NiS) loaded by carbon cloth2@ C-CF) as an active material, and punched into disks by a punch machine for later use. Mixing the raw materials in a ratio of 1: 1.3, taking the ionic liquid obtained by the preparation of 1-ethyl-3-methylimidazole chloride and aluminum chloride as electrolyte, taking an aluminum sheet as a counter electrode, taking a glass fiber membrane as a diaphragm, and taking CR 2016 type stainless steel as a battery shell to assemble the button aluminum ion battery. As shown in FIG. 4, at 200mA g-1The test is carried out under the current density, and the discharge specific capacity is still as high as 112mAh g after the circulation for 150 times-1And excellent cycle performance is shown. FIG. 5 shows that at 300mAg-1The result of constant current discharge test under larger current density shows that the discharge specific capacity is still maintained at 70mAhg after 1500 times of circulation-1And has better long cycle performance. As shown in FIG. 6, the capacity retention rate was very good when the multiplying power was tested under different current densities. The result shows that the carbon-coated nickel disulfide nanosheet composite material loaded by the carbon cloth can be used as a potential application material of a long-life, excellent cycle stability and high-rate aluminum ion battery anode material.
Example 2:
1) 2.3g of nickel nitrate hexahydrate and 1.4g of hexamethylenetetramine are taken, dissolved in 80ml of deionized water and stirred until the nickel nitrate and the hexamethylenetetramine are completely dissolved.
2) Putting carbon cloth into the solution obtained in the step 1), and carrying out hydrothermal reaction for 10h at 100 ℃.
3) Cleaning and drying the product obtained in the step 2 to obtain a precursor (Ni (OH))2-CF)。
4) Adding aniline: tartaric acid: step 3) calculating the precursor (Ni (OH)2-CF) to 150ml in a molar ratio of 3:5:3In ionized water, performing ultrasonic treatment in ice-water bath for 30 min.
5) To the solution obtained in step 4), 0.2mol L of a solution cooled in ice water in advance was added-150ml of ammonium persulfate aqueous solution, and placing the system in an ice water bath for 6 hours.
6) Washing the product obtained in the step 5) with deionized water, and drying in a vacuum drying oven at 60 ℃ to obtain the carbon cloth loaded polyaniline coated nickel precursor composite material (Ni (OH)2@PANI-CF)；
7) Mixing the polyaniline-coated nickel precursor composite material loaded by the carbon cloth and obtained in the step 6) with sublimed sulfur (the mass ratio is 1:4), and calcining the mixture at the temperature of 300 ℃ for 3h to obtain the carbon-coated nickel disulfide nanosheet composite material (NiS) loaded by the carbon cloth2@PANI-CF)。
The product of the invention is that the thickness of the nano-sheet is 15-20 nanometers, and the nano-sheet has a large loading capacity. The carbon cloth-supported carbon-coated nickel disulfide nanosheet composite material obtained in the example was 100mA g-1The following constant-current charge and discharge test results show that the discharge specific capacity after 100 cycles is 70mAh g-1。
Example 3:
1) 0.9g of nickel nitrate hexahydrate and 0.56g of hexamethylenetetramine are taken, and the nickel nitrate hexahydrate and the hexamethylenetetramine are dissolved in 80ml of deionized water and stirred until the nickel nitrate and the hexamethylenetetramine are completely dissolved.
2) Putting carbon cloth into the solution obtained in the step 1), and carrying out hydrothermal reaction for 10h at 100 ℃.
3) Cleaning and drying the product obtained in the step 2) to obtain a precursor (Ni (OH)2-CF)。
4) Adding aniline: tartaric acid: step 3) calculating the precursor (Ni (OH)2-CF) is dissolved into 150ml of deionized water according to the molar ratio of 6:5:3, and the mixture is subjected to ultrasonic treatment in an ice-water bath for 30 min.
5) To the solution obtained in step 4), 0.2mol L of a solution cooled in ice water in advance was added-150ml of ammonium persulfate aqueous solution, and placing the system in an ice water bath for 6 hours.
6) Washing the product obtained in the step 5) with deionized water, and drying in a vacuum drying oven at 60 ℃ to obtain the carbon cloth loaded polyaniline-coated nickel precursor composite materialMaterial (Ni (OH)2@PANI-CF)；
7) Mixing the polyaniline-coated nickel precursor composite material loaded by the carbon cloth and obtained in the step 6) with sublimed sulfur (the mass ratio is 1:4), and calcining the mixture at the temperature of 300 ℃ for 3h to obtain the carbon-coated nickel disulfide nanosheet composite material (NiS) loaded by the carbon cloth2@PANI-CF)。
The product of the invention is of a nanosheet structure, and the thickness of the nanosheet structure is 20-25 nanometers. Taking the carbon cloth-supported carbon-coated nickel disulfide nanosheet composite obtained in the example as an example, 100mA g-1The result of the constant-current charge and discharge test shows that the discharge specific capacity is 60mAh g after 100 cycles-1。
Example 4:
1) 0.9g of nickel nitrate hexahydrate and 0.56g of hexamethylenetetramine are taken, and the nickel nitrate hexahydrate and the hexamethylenetetramine are dissolved in 80ml of deionized water and stirred until the nickel nitrate and the hexamethylenetetramine are completely dissolved.
2) Putting carbon cloth into the solution obtained in the step 1), and carrying out hydrothermal reaction for 10h at 100 ℃.
3) Cleaning and drying the product obtained in the step 2) to obtain a precursor (Ni (OH)2-CF)。
4) Adding aniline: tartaric acid: step 3) calculating the precursor (Ni (OH)2-CF) is dissolved into 150ml of deionized water according to the molar ratio of 8:5:3, and the mixture is subjected to ultrasonic treatment in an ice-water bath for 30 min.
5) To the solution obtained in step 4), 0.2mol L of a solution cooled in ice water in advance was added-150ml of ammonium persulfate aqueous solution, and placing the system in an ice water bath for 6 hours.
6) Washing the product obtained in the step 5) with deionized water, and drying in a vacuum drying oven at 60 ℃ to obtain the carbon cloth loaded polyaniline coated nickel precursor composite material (Ni (OH)2@PANI-CF)；
7) Mixing the polyaniline-coated nickel precursor composite material loaded by the carbon cloth and obtained in the step 6) with sublimed sulfur (the mass ratio is 1:4), and calcining the mixture at the temperature of 300 ℃ for 3h to obtain the carbon-coated nickel disulfide nanosheet composite material (NiS) loaded by the carbon cloth2@PANI-CF)。
The product of the invention is of a nanosheet structureThe thickness is 30-40 nm. Taking the carbon cloth-supported carbon-coated nickel disulfide nanosheet composite obtained in the example as an example, 100mA g-1The result of the constant-current charge and discharge test shows that the discharge specific capacity is 65mAh g after 100 cycles-1。
Example 5:
1) 0.9g of nickel nitrate hexahydrate and 0.56g of hexamethylenetetramine are taken, and the nickel nitrate hexahydrate and the hexamethylenetetramine are dissolved in 80ml of deionized water and stirred until the nickel nitrate and the hexamethylenetetramine are completely dissolved.
2) Putting carbon cloth into the solution obtained in the step 1), and carrying out hydrothermal reaction for 10h at 100 ℃.
3) Cleaning and drying the product obtained in the step 2) to obtain a precursor (Ni (OH)2-CF)。
4) Adding aniline: tartaric acid: step 3) calculating the precursor (Ni (OH)2-CF) is dissolved into 150ml of deionized water according to the molar ratio of 10:5:3, and the mixture is subjected to ultrasonic treatment in an ice-water bath for 30 min.
5) To the solution obtained in step 4), 0.2mol L of a solution cooled in ice water in advance was added-150ml of ammonium persulfate aqueous solution, and placing the system in an ice water bath for 6 hours.
6) Washing the product obtained in the step 5) with deionized water, and drying in a vacuum drying oven at 60 ℃ to obtain the carbon cloth loaded polyaniline coated nickel precursor composite material (Ni (OH)2@PANI-CF)；
7) Mixing the polyaniline-coated nickel precursor composite material loaded by the carbon cloth and obtained in the step 6) with sublimed sulfur (the mass ratio is 1:4), and calcining the mixture at the temperature of 300 ℃ for 3h to obtain the carbon-coated nickel disulfide nanosheet composite material (NiS) loaded by the carbon cloth2@PANI-CF)。
The product of the invention is of a nanosheet structure, and the thickness of the nanosheet structure is 40-45 nanometers. The carbon cloth-supported carbon-coated nickel disulfide nanosheet composite material obtained in the example was 100mA g-1The test result of constant current charging and discharging shows that the specific discharge capacity after 100 cycles is 80mAh g-1。
Comparative example 6:
1) 0.9g of nickel nitrate hexahydrate and 0.56g of hexamethylenetetramine are taken, and the nickel nitrate hexahydrate and the hexamethylenetetramine are dissolved in 80ml of deionized water and stirred until the nickel nitrate and the hexamethylenetetramine are completely dissolved.
2) Putting carbon cloth into the solution obtained in the step 1), and carrying out hydrothermal reaction for 10h at 100 ℃.
3) Cleaning and drying the product obtained in the step 2) to obtain a precursor (Ni (OH)2-CF)。
4) The precursor (Ni (OH) obtained in the step 3)2mixing-CF) and sublimed sulfur (mass ratio is 1:4), calcining at 300 ℃ for 3h to obtain the carbon cloth loaded nickel disulfide nanosheet composite material (NiS)2-CF)。
The product of the invention is of a nanosheet structure, and the thickness of the nanosheet structure is 10-15 nanometers. The carbon cloth-loaded nickel disulfide nanosheet composite material obtained in the example is 100mA g-1The result of the constant-current charge and discharge test shows that the discharge specific capacity is 65mAh g after 100 cycles-1。

Claims (8)

1. The carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material is prepared from NiS with the particle size of 10-15 nanometers2The nano-sheet is coated with a carbon layer of 2-3 nanometers on the surface, and the thickness of the nano-sheet is 10-50 nanometers.
2. The method for preparing the carbon cloth-supported carbon-coated nickel disulfide nanosheet composite material of claim 1, comprising the steps of:
1) dissolving nickel nitrate hexahydrate and hexamethylenetetramine in deionized water, and stirring until the nickel nitrate and the hexamethylenetetramine are completely dissolved;
2) putting carbon cloth into the solution obtained in the step 1) to perform hydrothermal reaction;
3) cleaning and drying the product obtained in the step 2) to obtain a precursor Ni (OH)2-CF；
4) Dissolving aniline and tartaric acid into deionized water, adding the precursor obtained in the step 3), and performing ultrasonic treatment in an ice-water bath;
5) adding an ammonium persulfate aqueous solution which is pre-cooled in ice water into the solution obtained in the step 4), and placing the system in an ice water bath;
6) cleaning the product obtained in the step 5),drying to obtain the carbon cloth loaded polyaniline coated nickel precursor composite material Ni (OH)2@PANI-CF；
7) Mixing the polyaniline-coated nickel precursor composite material loaded by the carbon cloth obtained in the step 6) with sublimed sulfur and then calcining to obtain carbon-coated nickel disulfide nanosheet composite material NiS loaded by the carbon cloth2@PANI-CF。
3. The carbon cloth-supported carbon-coated nickel disulfide nanosheet composite of claim 2, wherein the amount of nickel nitrate hexahydrate in step 1) is 0.9 to 2.3g, and the amount of hexamethylenetetramine is 0.56 to 1.4 g.
4. The carbon cloth-supported carbon-coated nickel disulfide nanosheet composite material of claim 2, wherein the hydrothermal temperature of step 2) is 100 ℃ for 8-10 hours.
5. The carbon cloth-supported carbon-coated nickel disulfide nanosheet composite of claim 2, wherein the amount of aniline tartaric acid of step 4) is: aniline: tartaric acid: precursor Ni (OH)23-10 mol of-CF, 5mol and 3mol of deionized water, 150ml of deionized water, and performing ice-water bath ultrasound for 20-40 min.
6. The carbon cloth-supported carbon-coated nickel disulfide nanosheet composite of claim 2, wherein the concentration of the aqueous solution of ammonium persulfate in step 5) is 0.2 to 0.3mol L-1The volume is 50-60 mL, and the reaction time in ice-water bath is 4-6 h.
7. The carbon cloth-supported carbon-coated nickel disulfide nanosheet composite of claim 2, wherein the mass ratio of the carbon cloth-supported polyaniline-coated nickel precursor composite of step 7) to the sulfur trioxide is 1: 4; the calcination temperature is 250-300 ℃, the calcination atmosphere is nitrogen, and the calcination time is 2-3 h.
8. The use of the carbon cloth-supported carbon-coated nickel disulfide nanosheet composite of claim 1 as an aluminum ion battery cathode material.
CN202010376721.8A 2020-05-07 2020-05-07 Carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material and preparation method and application thereof Pending CN111584840A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010376721.8A CN111584840A (en) 2020-05-07 2020-05-07 Carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010376721.8A CN111584840A (en) 2020-05-07 2020-05-07 Carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN111584840A true CN111584840A (en) 2020-08-25

Family

ID=72112051

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010376721.8A Pending CN111584840A (en) 2020-05-07 2020-05-07 Carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111584840A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112018361A (en) * 2020-08-31 2020-12-01 华中科技大学 Carbon cloth loaded carbon coated cobalt selenide nanosheet battery cathode material and preparation thereof
CN113036097A (en) * 2021-02-04 2021-06-25 淮阴工学院 Sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and preparation method thereof
CN113223869A (en) * 2021-04-15 2021-08-06 山东科技大学 Three-dimensional porous nanoflower-like NiS2Preparation and application of/carbon cloth composite material
CN113694952A (en) * 2021-08-24 2021-11-26 青岛科技大学 Sulfur-containing vacancy NiS quantum dot/S, N and O co-doped carbon electrode material and preparation method thereof
CN114956212A (en) * 2021-02-24 2022-08-30 陕西则明未来科技有限公司 Carbon-coated alpha-Ni (OH) 2 Preparation and application of nanosheet composite material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105633371A (en) * 2016-01-05 2016-06-01 北京金吕能源科技有限公司 Aluminum-ion secondary battery employing nickel-sulfur compound as positive electrode and preparation technology of aluminum-ion secondary battery
CN108666540A (en) * 2018-04-02 2018-10-16 中南大学 A kind of carbon coating curing nickel material and preparation method thereof and as anode material of lithium-ion battery application
CN108832097A (en) * 2018-06-13 2018-11-16 东华大学 A kind of curing nickel carbon nano-composite material and its preparation method and application
CN110538663A (en) * 2019-09-03 2019-12-06 国电新能源技术研究院有限公司 Preparation method of porous NiS2 nanosheet and NiS2 material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105633371A (en) * 2016-01-05 2016-06-01 北京金吕能源科技有限公司 Aluminum-ion secondary battery employing nickel-sulfur compound as positive electrode and preparation technology of aluminum-ion secondary battery
CN108666540A (en) * 2018-04-02 2018-10-16 中南大学 A kind of carbon coating curing nickel material and preparation method thereof and as anode material of lithium-ion battery application
CN108832097A (en) * 2018-06-13 2018-11-16 东华大学 A kind of curing nickel carbon nano-composite material and its preparation method and application
CN110538663A (en) * 2019-09-03 2019-12-06 国电新能源技术研究院有限公司 Preparation method of porous NiS2 nanosheet and NiS2 material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHUN TANG等: ""NiS2 nanosheets array grown on carbon cloth as an efficient 3D hydrogen evolution cathode"", 《ELECTROCHIMICA ACTA》 *
QIUYU MA等: ""Identifying the electrocatalytic sites of nickel disulfide in alkaline hydrogen evolution reaction"", 《NANO ENERGY》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112018361A (en) * 2020-08-31 2020-12-01 华中科技大学 Carbon cloth loaded carbon coated cobalt selenide nanosheet battery cathode material and preparation thereof
CN112018361B (en) * 2020-08-31 2021-10-15 华中科技大学 Carbon cloth loaded carbon coated cobalt selenide nanosheet battery cathode material and preparation thereof
CN113036097A (en) * 2021-02-04 2021-06-25 淮阴工学院 Sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and preparation method thereof
CN113036097B (en) * 2021-02-04 2022-05-17 淮阴工学院 Sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and preparation method thereof
CN114956212A (en) * 2021-02-24 2022-08-30 陕西则明未来科技有限公司 Carbon-coated alpha-Ni (OH) 2 Preparation and application of nanosheet composite material
CN113223869A (en) * 2021-04-15 2021-08-06 山东科技大学 Three-dimensional porous nanoflower-like NiS2Preparation and application of/carbon cloth composite material
CN113694952A (en) * 2021-08-24 2021-11-26 青岛科技大学 Sulfur-containing vacancy NiS quantum dot/S, N and O co-doped carbon electrode material and preparation method thereof
CN113694952B (en) * 2021-08-24 2023-09-01 乌海瑞森新能源材料有限公司 Sulfur-vacancy-containing NiS quantum dot/S, N, O co-doped carbon electrode material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN111584840A (en) Carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material and preparation method and application thereof
CN109167056B (en) Tungsten ion doped high-nickel layered oxide lithium battery positive electrode material and preparation method thereof
CN106229498B (en) Cathode material suitable for water-based metal ion battery and preparation method thereof
CN103904321B (en) The high-temperature solid phase preparation method of lithium ion battery negative material LiMn2O4
CN111082026A (en) Ternary cathode material coated with lithium tungstate and preparation method thereof
CN107069001B (en) Honeycomb zinc sulfide/carbon composite negative electrode material and preparation method thereof
CN108172808B (en) Modification method of cerium-tin composite oxide coated lithium-rich manganese-based positive electrode material
CN110416530B (en) Flower-like manganese dioxide/carbon composite material and preparation method and application thereof
WO2021088354A1 (en) Core-shell nickel ferrite and preparation method therefor, nickel ferrite@c material, preparation method therefor, and use thereof
WO2019075910A1 (en) Lithium-enriched layered oxide material having phase structure gradiently changing in proportion and preparation method therefor
CN112018344B (en) Carbon-coated nickel sulfide electrode material and preparation method and application thereof
CN109860536B (en) Lithium-rich manganese-based material and preparation method and application thereof
CN103078099A (en) Anode material for lithium ion cell and preparation method thereof
CN112599765A (en) Sodium/potassium-doped high-performance lithium-manganese-nickel-based positive electrode material and preparation method thereof
CN113314715A (en) Nickel sulfide composite material and preparation method and application thereof
CN111490241A (en) Lithium phosphate in-situ coated lithium-rich manganese-based positive electrode material and preparation method thereof
CN109279663B (en) Borate sodium-ion battery negative electrode material and preparation and application thereof
CN102544473A (en) Lithium ion battery anode material layered lithium manganese oxide and manufacturing method thereof
CN108598463B (en) Preparation method of nano flaky lithium-rich manganese-based positive electrode material
CN110137472B (en) Preparation method of composite positive electrode material
WO2023060992A1 (en) Method for synthesizing high-safety positive electrode material by recycling positive electrode leftover materials, and application
CN110931750A (en) Copper-doped cobalt oxide porous nanosheet composite material and energy storage application
CN110931726A (en) Lithium titanate negative electrode composite material, preparation method thereof and lithium ion battery
CN107799762B (en) Preparation method of nickel-cobalt-manganese ternary positive electrode material for improving first discharge efficiency of lithium ion battery
CN114824204A (en) Preparation method of carbon-coated cobalt-nickel binary transition metal sulfide negative electrode material

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200825