CN114937764A - Cobalt disulfide composite material protected by double carbon layers and preparation method and application thereof - Google Patents
Cobalt disulfide composite material protected by double carbon layers and preparation method and application thereof Download PDFInfo
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- CN114937764A CN114937764A CN202210585039.9A CN202210585039A CN114937764A CN 114937764 A CN114937764 A CN 114937764A CN 202210585039 A CN202210585039 A CN 202210585039A CN 114937764 A CN114937764 A CN 114937764A
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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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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 discloses a preparation method and application of a double-carbon-layer-protected cobalt disulfide composite material, wherein ZIF-67 with uniform size is used as a precursor, and the mass ratio of the ZIF-67 to melamine is 1: 5, mixing, annealing under the protection of argon at 350 ℃ and 700 ℃ in stages, wherein cobalt nanoparticles reduced during carbonization can generate catalytic action on melamine to form bamboo-shaped carbon nanotubes around the polyhedron, and then further vulcanizing to prepare the cobalt disulfide composite material protected by the double carbon layer. The method has the characteristics of green solvent, simple process, short reaction time, high yield and controllable product morphology, and the prepared double-carbon-layer-protected cobalt disulfide composite material has larger specific surface area and porous structure, and is in a range of 0.1A g ‑1 The highest reversible capacity is 899 mAh g ‑1 Average coulombic efficiency of98.4%。
Description
Technical Field
The invention relates to a cobalt disulfide composite material protected by a double carbon layer and a preparation method and application thereof, belonging to the technical field of new materials.
Technical Field
The current society, which is troubling people's lives due to the overuse of fossil fuels, environmental pollution and energy crisis problems, requires researchers to develop alternative energy conversion and storage systems. Lithium Ion Batteries (LIBs) are the most advanced electrochemical energy storage technology, have the characteristics of high energy density, long service life, no memory effect and the like, and occupy a leading position in the fields of portable electronic equipment, smart grids and electric vehicles. At present, graphite has relatively stable performance as a negative electrode material of LIBs, but the theoretical capacity of the graphite is relatively low (372mAh g) -1 ) And the requirement of modern new energy electric automobiles or electronic mobile equipment on high energy density cannot be met. The ratio of the electrode material in the constituent members of the LIBs is 59% (negative electrode 18%, positive electrode 41%), and therefore in order to improve the performance of the LIBs, consideration should be given to the electrode material.
Transition metal sulfides (e.g., FeS) have been used in recent years 2 、MoS 2 、NiS 2 、CoS 2 ) The graphite is considered as a promising substitute because of high safety and large theoretical capacity. Among them, cobalt disulfide (CoS) 2 ) As a typical LIBs cathode material, the four-electron conversion reaction based on the LIBs cathode material has higher theoretical capacity (874mAh g) -1 ) It is considered to be a promising anode material for LIBs. However, due to the defects of large volume expansion, poor conductivity and slow ion/electron transport kinetics in the charge and discharge process, the copper-nickel-cobalt composite material does not have good cycle life and rate capability, and CoS is limited 2 The application in energy storage.
To CoS 2 Alleviating the problems of volume expansion and poor conductivity, CoS 2 The nano particles and the carbon material are compounded to realize better lithium storage performance, such as graphene, Carbon Nanotubes (CNTs), carbon nano fibers and the like. The Metal Organic Frameworks (MOFs) can be assembled by various metal clusters/ions and organic ligands, and due to the high porosity, controllable pore size and highly ordered structure, the MOFs has a good application prospect in the field of new energy storage. The MOFs may be carbonized to obtain derivativesRaw carbon or carbon metal porous materials can be used as precursors (such as oxides, sulfides, selenides and the like) for preparing various metal matrix composite materials; in addition, as the organic ligands for synthesizing the MOFs contain heteroatoms, the carbon materials derived from the MOFs are easy to realize heteroatom doping, which is beneficial to improving the performance of the LIBs. However, after the MOFs are carbonized at high temperature, the structure can shrink or even collapse, which can make the electrode material become unstable, thereby affecting CoS 2 The electrochemical performance of (2).
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a cobalt disulfide composite material protected by a double carbon layer and a preparation method and application thereof, wherein a green synthesis method is utilized to prepare a precursor ZIF-67, and CoS is subjected to high-temperature carbonization and solid-phase vulcanization processes 2 The dual carbon layer, limited to ZIF-67 derived N-doped porous carbon and melamine converted CNTs, can enhance CoS on the one hand 2 Is Li + Providing a path for diffusion of (a); on the other hand, the stability of the structure is ensured, thereby improving the lithium storage performance of the electrode material.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a preparation method of a double-carbon-layer protected cobalt disulfide composite material is characterized in that ZIF-67 with uniform appearance and particle size of 1-2 mu m is used as a precursor, the preparation method is carried out by utilizing high-temperature carbonization and solid-phase vulcanization processes, and the specific surface area of the obtained double-carbon-layer protected cobalt disulfide composite material is 51.24m 2 g -1 The average pore diameter was 8.97 nm.
The preparation method of the cobalt disulfide composite material protected by the double carbon layer comprises the following steps:
(1) preparation of precursor ZIF-67 by standing at normal temperature
First Co (NO) 3 ) 2 ·6H 2 Dispersing O in deionized water, adding polyether F127, and dissolving completely to obtain pink transparent solution marked as solution A; dissolving 2-methylimidazole in deionized water to obtain a colorless transparent solution, and marking as solution B; pouring the solution B into the solution A for full reaction, standing at room temperature for 20-24 h, and centrifugingDrying at 60-80 ℃ for 12-24 h to obtain a ZIF-67 precursor; wherein, 2-methylimidazole and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 7.8: 1;
(2) high temperature calcination
Mixing a ZIF-67 precursor and melamine according to a mass ratio of 1: 3-7, uniformly grinding, and calcining at 350 ℃ and 700-800 ℃ in argon atmosphere in sections to obtain black powder;
(3) solid phase vulcanization
Mixing the black powder obtained in the step (2) with sublimed sulfur according to a mass ratio of 1:3, fully grinding, and carrying out solid-phase vulcanization under the protection of argon at 300 ℃ to obtain the cobalt disulfide composite material protected by the double carbon layer.
The improvement is that the mass fraction of the polyether F127 in the step (1) is 0.05-1.6 wt%, and the function of the polyether F127 is a structure directing agent.
The improvement is that in the step (2), the mass ratio of the ZIF-67 precursor to melamine is 1: 5; the first stage of calcination is 350 ℃ and the time is 1-1.5 h; the second stage of calcination is 700 ℃, and the time is 2-3 h; the temperature rise rate is 2-3 ℃ min -1 。
The improvement is that in the solid phase vulcanization process in the step (3), the temperature rise rate is 5-10 ℃ for min -1 The time is 2-3 h.
The cobalt disulfide composite material protected by the double carbon layer prepared by any one of the preparation methods.
The cobalt disulfide composite material protected by the double carbon layer is applied to a lithium ion battery cathode material.
Has the advantages that:
compared with the prior art, the preparation method and the application of the cobalt disulfide composite material protected by the double carbon layers comprise the steps of firstly preparing a ZIF-67 precursor, wherein the preparation method is green and economic, the size is uniform, the cobalt disulfide prepared by taking the ZIF-67 as the precursor is easy to control the size, and N-doped carbon obtained after MOFs carbonization has a larger specific surface and a porous structure, so that the Li can be shortened + The migration path improves the compatibility of the material and the electrolyte; CNTs distributed around the polyhedron at the same time, and is effectiveMitigating CoS 2 The volume expansion of (a) and the maintenance of structural stability of the electrode material during repeated charge and discharge.
Drawings
FIG. 1 is a diagram of CoS production according to example 1 of the present invention 2 XRD spectra of Co/NC/CNTs composite prepared by/NC/CNTs and example 5;
FIG. 2 shows CoS obtained in example 1 of the present invention 2 TG curve of/NC/CNTs composite material;
FIG. 3(a) shows CoS obtained in example 1 of the present invention 2 XPS full spectrum of/NC/CNTs composite material; FIGS. 3(b), (c), (d) and (e) are respectively CoS obtained in example 1 of the present invention 2 High resolution spectra of elements C1S, N1S, S2 p and Co 2p in the/NC/CNTs composite material;
FIG. 4 is an SEM photograph of a precursor ZIF-67 obtained in example 1 of the present invention;
FIG. 5 shows CoS obtained in example 1 of the present invention 2 TEM image of/NC/CNTs composite;
FIG. 6 depicts the CoS obtained in example 1 of the present invention 2 HRTEM image of/NC/CNTs composite;
FIG. 7 is a SEM photograph obtained in example 2 of the present invention;
FIG. 8 is an SEM photograph obtained in example 3 of the present invention;
FIG. 9 shows pure CoS obtained in example 4 of the present invention 2 SEM picture of (1);
FIG. 10(a) shows CoS obtained in example 1 of the present invention 2 N of/NC/CNTs composite material 2 Adsorption/desorption curves; (b) CoS obtained for example 1 of the invention 2 The pore diameter distribution curve of the/NC/CNTs composite material;
FIG. 11 shows CoS obtained in example 1 of the present invention 2 the/NC/CNTs composite material is used as an LIBs cathode material and is arranged at 0.1mV s -1 Cyclic voltammetry of (a);
FIG. 12 shows CoS obtained in example 1 of the present invention 2 the/NC/CNTs composite material is used as an LIBs cathode material, and the current density is 100mA g -1 A lower charge-discharge curve;
FIG. 13 shows the current density of 100mA g for LIBs cathode materials of examples 1, 4, 5 and 6 of the present invention -1 A lower charge-discharge cycle curve;
fig. 14 is a graph of rate performance at different current densities for LIBs of the negative electrode materials of examples 1, 4 and 5 of the present invention.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
Example 1 Dual carbon layer protected CoS 2 The preparation process of the composite material is as follows:
(1) putting 0.43g of cobalt nitrate hexahydrate in 30mL of deionized water, dissolving the cobalt nitrate hexahydrate, adding 0.15g of polyether F127, and marking the mixed solution as A; likewise, a mass of 0.975g of dimethylimidazole was dissolved in 30mL of deionized water and this solution was labeled B; pouring the solution A into the solution B, stirring vigorously for 30min, and standing at room temperature for 20-24 h; then washing the mixture for three times by using deionized water and absolute ethyl alcohol, and centrifuging the mixture at the rotating speed of 8500 rpm; drying in a vacuum drying oven at 60 ℃ for 12 h; cooling to room temperature to obtain a ZIF67 precursor;
(2) mixing a ZIF67 precursor obtained in the step (1) with melamine according to a mass ratio of 1: 5, fully grinding the mixture in a mortar, then putting the mixture into an alumina porcelain boat, and putting the alumina porcelain boat into a tube furnace to calcine the mixture in two stages; in the first stage, the temperature is kept at 350 ℃ for 1.5 h; in the second stage, the temperature is kept for 3 hours at 700 ℃; the calcining atmosphere is argon, and the heating rate is 2 ℃ for min -1 (ii) a And cooling to room temperature to obtain black powder Co/NC/CNTs.
(3) Mixing the Co/NC/CNTs obtained in the step (2) with sublimed sulfur in a mass ratio of 1:3, fully grinding in a mortar, then putting the mixture into an alumina porcelain boat, and putting the alumina porcelain boat into a tube furnace for calcination; the temperature is 300 ℃, the temperature is kept for 2h, and the heating rate is 10 ℃ for min -1 The calcining atmosphere is argon; after the mixture is cooled to the room temperature,the dual-carbon layer protection CoS can be obtained 2 Composite material CoS 2 /NC/CNTs。
Dual carbon layer protection CoS 2 Preparing an electrode material:
the CoS obtained in the step (3) is put into 2 The mass ratio of the/NC/CNTs composite material to polyvinylidene fluoride (binder) and acetylene black (conductive agent) is 7: 2: 1, fully grinding the mixture in a mortar for 30min, dissolving the mixture in N-methylpyrrolidone (an oily solvent), stirring for 12h to form uniform slurry, coating the slurry on a copper foil wiped by absolute ethyl alcohol by using a film coater, drying the copper foil in vacuum at 60 ℃, cutting the copper foil into electrode slices of 13mm serving as a negative electrode of an LIBs (lithium ion battery) by using a manual slicer as a counter electrode, assembling a half cell (model LIR 2032) in an argon-filled glove box (the water content and the oxygen content are both less than 0.01ppm), wherein a diaphragm adopts Celgard2600, an adopted model electrolyte is LB266, and the formula is as follows: lithium hexafluorophosphate (1 mol. L) -1 LiPF 6 ) Dissolving in a solvent with the volume ratio of 1: 1: 1 of a mixed solution of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC), 1.0% of Vinylene Carbonate (VC) is used as an additive. Standing for 24h, and then testing the lithium storage performance, wherein the testing temperature is 25 ℃, the voltage window of the cycle and rate test is 0.01-3V, and the standing time between the charging and discharging steps is set to be 2 min; wherein the loading amount of the active substance in the single sheet electrode is 0.8-1 mg.
CoS of example 1 2 Placing the/NC/CNTs sample in a clamping groove of 10 x 0.5mm of an XRD slide glass, compacting, and performing compression within an angle range of 10-80 ℃ for 5 min -1 The test result is shown in FIG. 1, and it can be seen that the vulcanized Co/NC/CNTs can be successfully converted into CoS 2 /NC/CNTs, and CoS 2 Diffraction peaks and CoS of/NC/CNTs 2 Matched with the standard diffraction pattern (JCPDS No. 41-1471). The characteristic peaks appear at positions 2 θ of 27.9 °, 32.3 °, 36.2 °, 39.7 °, 46.4 ° and 54.9 °, and the corresponding crystal planes are respectively: (111) (200), (210), (211), (220), and (311). In CoS 2 The spectrum of/NC/CNTs also shows obvious cobalt peaks, mainly because the cobalt elements are coated by carbon and cannot be heated with sulfur powder to generate gas and electricityThe electrolyte ions are formed by further reaction.
10mg of CoS obtained in example 1 was added 2 Placing the/NC/CNTs sample in a crucible, placing the crucible in a thermal weight testing instrument, wherein the temperature range is 25-800 ℃, and the heating rate is 10 ℃ for min -1 Combustion atmosphere is air, for CoS 2 the/NC/CNTs are subjected to thermogravimetric analysis test. The test results are shown in fig. 2 and are mainly used for analyzing the carbon content in the material. As can be seen from the figure, CoS 2 The mass loss of/NC/CNTs is divided into three stages, the first stage: the mass loss before 400 ℃ is mainly the evaporation of water on the surface of the material; and a second stage: the mass loss at 400-600 ℃ is 24.7%, and mainly the combustion of carbon in air; and a third stage: the mass loss after 600 ℃ is then CoS 2 Oxidation to Co 3 O 4 And (4) forming.
Cutting 1.5cm by 3cm aluminum foil, attaching 3mm by 3mm double-sided adhesive tape to the polished side of the aluminum foil, and adding CoS 2 Putting the/NC/CNTs powder sample on double-sided adhesive, folding aluminum foil, manually pressing the sample, keeping the sample under 12 MPa for 20-30 seconds, shearing the double-sided adhesive in the middle position, putting the sample on a sample tray for detection, and detecting the conditions: al Ka X-ray source, step size 5 μm. The results of the detection are shown in FIG. 3. FIG. 3(a) is the CoS prepared 2 The full spectrogram of X-ray photoelectron spectra of/NC/CNTs shows that Co, C, N, S and O elements exist in the material; the O1s peak may appear as a result of partial oxidation of the material surface exposed to air during testing. FIG. 3(b) is a high resolution spectrum of C1s, showing that the C elements are mainly C-N/C-O (27.76%), sp 3 C- C(25.93％)、sp 2 C — C (12.27%), C ═ C (34.04%), and the introduction of heteroatoms causes distortion of the carbon structure and changes in charge density due to the difference in size and electronegativity of the N atom from the C atom; fig. 3(c) is a high resolution spectrum of N1s, indicating that the N element is mainly present in the form of graphite nitrogen (63.87%), pyrrole nitrogen (32.35%), pyridine nitrogen (3.78%); FIG. 3(d) is a high resolution S2 p spectrum, in which C-S-C accounts for 9.91%; FIG. 3(e) is a high resolution spectrum of Co 2p, where the signals present at 778.3eV and 793.4 eV indicate the presence of Co-N. This indicates that the ZIF-67 carbide derived cobalt is not fully sulfided, which is comparable to the presence of a Co peak in the XRD patternThe results were the same. 779.5eV and 781.9eV correspond to Co 2p 3/2 Co-Co bonds and Co-S bonds of (A), which indicate Co 2+ Presence of (a); the signals appearing at 794.3eV and 798.4eV represent Co 2p, respectively 1/2 Co-S bond and Co-Co bond of (A) indicates the presence of Co 3+ Is present. 802.8eV is the satellite peak for Co.
FIG. 5 is an SEM image of precursor ZIF-67, the prepared ZIF-67 was relatively uniform in size and smooth in surface. The particle size range is 1-2 μm.
FIG. 6 is CoS prepared 2 The TEM image of the/NC/CNTs composite material shows that the structure of the polyhedron is still complete after vulcanization, and the melamine derives the bamboo-like carbon nano-tubes. This structure can be referred to as CoS 2 The ideal carrier not only provides enough specific surface area and porous structure for rapid charge transfer, but also plays a role in relieving volume expansion in the charge-discharge cycle process. In addition, these bamboo-like carbon nanotubes can also increase CoS 2 Is used for the electrical conductivity of (1).
FIG. 7 is the CoS prepared 2 HRTEM image of/NC/CNTs composite with a distance between two adjacent lattice fringes of 0.337nm, corresponding to CoS 2 (111) crystal plane of (iii).
Detection sample CoS 2 the/NC/CNTs are degassed for 2h at 200 ℃ to remove gas adsorbed on the surface of the sample, N 2 As a sorption gas, H 2 N formation of liquid nitrogen at 77K as carrier gas 2 Adsorbed and CoS calculated according to the BET equation 2 Specific surface area of/NC/CNTs, pore size distribution calculated by BJH method. The test results are shown in fig. 10. FIG. 10(a) is the CoS prepared 2 N of/NC/CNTs composite material 2 Adsorption/desorption diagram, wherein the curve is of type IV and has a specific surface area of 52.24m 2 g -1 (ii) a Pore volume of 0.28cm 3 g -1 Pore size concentration around 8.97nm, CoS 2 The larger specific surface area and porous structure of/NC/CNTs are beneficial to the permeation of electrolyte and Li + Insertion/removal of (a); meanwhile, the contact area of the electrode material and the electrolyte is increased, which is beneficial to improving the material capacity and the cycling stability.
Will be quietConnecting the button cell with Chenghua electrochemical workstation (CHI 760E) by cell test clamp, wherein the initial voltage is open-circuit voltage, the maximum voltage is 3.0V, the minimum voltage is 0.01V, the final voltage is 3.0V, and the scanning speed is 0.1mV s -1 CoS prepared by this test with a scanning portion set at 8 and a test temperature of 25 deg.C 2 CV diagram of/NC/CNTs composite material as LIBs anode material. The test results are shown in FIG. 11, and it can be seen from FIG. 11 that CoS was produced 2 When the/NC/CNTs composite material is used as an LIBs anode material, a reduction peak appears at 0.8V in the first circle, which indicates that an SEI film is formed between the electrode material and an electrolyte; two strong peaks at 1.3 and 1.8V, indicating Li x CoS 2 Generation and subsequent Li x CoS 2 Decomposition (formation of Co metal and Li, respectively) 2 S); the oxidation peaks are at 2.0V and 2.4V and are from Co to CoS 2 (delithiation process). The CV curves in subsequent cycles had better coincidence than in the first cycle, indicating CoS 2 the/NC/CNTs composite material has good reversibility and stability.
And (3) carrying out charge and discharge tests on the button cell subjected to standing on a Wuhan blue electricity test system (LAND-CT2001A) at the test temperature of 25 ℃ for 2min after charge and discharge, wherein the voltage range is 0.01-3V. CoS thus produced 2 the/NC/CNTs composite material is used as an LIBs cathode material, and the current density is 100mA g -1 The test result of the following charge-discharge curve is shown in FIG. 12, and it can be seen from FIG. 12 that the first discharge capacity of the material is 1449.3mAh g -1 Coulombic efficiency 58.8%; after activation, coulombic efficiency increased, indicating good reversibility.
And (3) performing cycle performance test on the button cell after standing on a Wuhan blue electricity test system (LAND-CT2001A), wherein the voltage range is 0.01-3V, the standing time is 2min after charging and discharging, and the test temperature is 25 ℃. FIG. 13 is pure CoS 2 Co/NC/CNTs and prepared CoS 2 The current density of the/NC/CNTs composite material is 100mA g -1 Comparative graph of cycle performance of the following. It can be seen that the CoS produced in 100 cycles 2 The curve of the/NC/CNTs composite material is stable, and the average coulombic efficiency is 98.4%.Shows that the electrode material has good structural stability in the circulation process and is consistent with pure CoS 2 Compared with the prior art, the volume expansion problem in the charging and discharging process can be fully relieved.
And carrying out rate performance test on the button cell after standing, wherein the voltage range is 0.01-3V, the standing time after charging and discharging is 2min, the test temperature is 25 ℃, and the number of cycles is 10 under each current density. FIG. 14 is pure CoS 2 Co/NC/CNTs and prepared CoS 2 The current density of the/NC/CNTs composite material is from 100mA g -1 To 2000mA g -1 A time rate performance plot; wherein the electrode is at 100, 200, 500, 1000 and 2000mA g -1 The specific capacities of the carbon nanotubes are 830, 728, 589, 395 and 264mAh g -1 When the current density returns to 100mA g -1 Then the reversible capacity can be restored to 815mAh g -1 Example 1 is demonstrated to have good rate capability and the rate capability is far superior to the other two materials.
Example 2
The difference from example 1 is that the mass ratio of ZIF-67 precursor to melamine was 1: 3. And preparing the electrode material by a solid-phase vulcanization process.
The morphology is shown in FIG. 7. The surface is rough and no distinct CNTs fraction around the polyhedrons can be seen.
Example 3
The difference from the embodiment 1 is that the electrode material is prepared by the solid phase vulcanization process with the mass ratio of the ZIF-67 precursor to the melamine being 1: 7.
The morphology is shown in fig. 8. Although CNTs can be seen, agglomeration occurs.
Example 4
Placing cobalt nitrate hexahydrate in a tube furnace for oxidation at 300 ℃ for 3h at a heating rate of 5 ℃ for min -1 And then mixing the obtained black powder with sulfur powder according to the mass ratio of 1:3, uniformly mixing, reacting for 2 hours at the temperature of 300 ℃ in an argon atmosphere, and heating up at the rate of 10 ℃ for min -1 . Obtaining pure CoS 2 Electrode materials were prepared in the same proportions as in example 1, and tested for electrochemical properties, test conditions and resultsThe same is described in example 1. The morphology is shown in fig. 9. The particles are larger. The cycle performance and the rate performance are shown in fig. 13 and 14. At 100mA g -1 Pure CoS at Current Density 2 The average specific discharge capacity after 100 cycles of the cycle is 336.5mAh g -1 ，2Ag -1 The reversible specific capacity of the multiplying power test is 121.9mAh g -1 Pure CoS due to the absence of protection by a carbon layer 2 The reversible specific capacity is poor.
Example 5
Mixing the prepared ZIF-67 and melamine according to the mass ratio of 1: 5, carbonizing in a tube furnace after grinding, and annealing for 1.5h at 350 ℃; annealing at 700 ℃ for 3 h; the heating rate is 2 ℃ for min -1 Thus, a Co/NC/CNTs composite material was obtained, and an electrode material was prepared in the same proportion as in example 1, and its electrochemical properties were tested. The cycle performance and rate performance are shown in fig. 13 and 14, in the same test conditions as in example 1. At 100mAg -1 Under the current density, the average specific discharge capacity after 100 cycles of Co/NC/CNTs circulation is 372.2mAh g -1 ，2Ag -1 The reversible specific capacity of the multiplying power test is 58.4mAh g -1 。
Example 6
The difference from example 1 is that ZIF-67 was mixed with melamine in a ratio of 1: 5, after fully grinding, calcining for 1.5h at 350 ℃, and then increasing the temperature to 800 ℃ for calcining for 3 h; a solid phase sulfidation process was then carried out at the same proportional temperature as in example 1. 100mAg -1 The current density was measured under the same cycle performance test conditions as in example 1, and the cycle performance test results are shown in fig. 13. After 85 circles, capacity fading occurs, the stability is not good as that of the embodiment 1, and due to the fact that the carbonization temperature is high, the material structure collapses, and the reversible capacity of multiple charging and discharging is unstable.
Polyether F127 is used as a structure directing agent, water is used as a solvent instead of methanol, a precursor ZIF-67 is prepared by a green synthesis method, Co nanoparticles obtained by high-temperature carbonization and reduction are used for generating catalytic action on melamine to form CNTs around a polyhedron, and finally, a CoS protected by a double carbon layer is prepared by a solid phase vulcanization process 2 Composite materials derived from ZIF-67The N-doped carbon skeleton has high specific surface area and porous structure, and can be Li + A diffusion-shortened path; simultaneously, the CNTs have stronger mechanical property and can fully relieve CoS 2 To maintain structural stability during repeated charge and discharge.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple changes or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (7)
1. A preparation method of a double-carbon-layer-protected cobalt disulfide composite material is characterized in that ZIF-67 with uniform appearance and particle size of 1-2 microns is used as a precursor, the preparation method is carried out by utilizing high-temperature carbonization and solid-phase vulcanization processes, and the specific surface area of the obtained double-carbon-layer-protected cobalt disulfide composite material is 51.24m 2 g -1 The average pore diameter was 8.97 nm.
2. The method for preparing the double-carbon-layer protected cobalt disulfide composite material according to claim 1, characterized by comprising the following steps:
(1) preparation of precursor ZIF-67 by standing at normal temperature
First Co (NO) 3 ) 2 ·6H 2 Dispersing O in deionized water, adding polyether F127, and dissolving completely to obtain pink transparent solution marked as solution A; dissolving 2-methylimidazole in deionized water to obtain a colorless transparent solution, and marking as solution B; pouring the solution B into the solution A for full reaction, standing at room temperature for 20-24 h, centrifuging, and drying at 60-80 ℃ for 12-24 h to obtain a ZIF-67 precursor; wherein 2-methylimidazole reacts with Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 7.8: 1;
(2) high temperature calcination
Mixing a ZIF-67 precursor and melamine according to a mass ratio of 1: 3-7, uniformly grinding, and calcining at 350 ℃ and 700-800 ℃ in argon atmosphere in sections to obtain black powder;
(3) solid phase vulcanization
Mixing the black powder obtained in the step (2) with sublimed sulfur according to a mass ratio of 1:3, fully grinding, and carrying out solid-phase vulcanization under the protection of argon at 300 ℃ to obtain the cobalt disulfide composite material protected by the double carbon layer.
3. The preparation method of the cobalt disulfide composite material protected by the double carbon layer as claimed in claim 1, wherein the mass fraction of polyether F127 in step (1) is 0.05-1.6 wt%, and the function of polyether F127 is a structure directing agent.
4. The preparation method of the cobalt disulfide nanocomposite protected by a double carbon layer as claimed in claim 1, wherein the mass ratio of the ZIF-67 precursor to melamine in step (2) is 1: 5; the first stage of calcination is 350 ℃ and the time is 1-1.5 h; the second stage of calcination is 700 ℃, and the time is 2-3 h; the temperature rise rate is 2-3 ℃ min -1 。
5. The method for preparing a cobalt disulfide composite material protected by a double carbon layer according to claim 1, wherein in the solid phase vulcanization process in the step (3), the temperature rise rate is 5-10 ℃ for min -1 The time is 2-3 h.
6. A cobalt disulfide composite protected by a double carbon layer prepared based on any one of the preparation methods as set forth in claims 1 to 5.
7. Use of a cobalt disulfide composite protected by a double carbon layer according to claim 1 or claim 6 as a negative electrode material for lithium ion batteries.
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