CN114937764B - 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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 title claims description 25
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 6
- 238000004073 vulcanization Methods 0.000 claims description 15
- 239000007790 solid phase Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 102000020897 Formins Human genes 0.000 claims description 9
- 108091022623 Formins Proteins 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 abstract description 50
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 49
- 230000002441 reversible effect Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 abstract description 4
- 239000010941 cobalt Substances 0.000 abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000137 annealing Methods 0.000 abstract description 3
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- 230000001681 protective effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 15
- 239000007772 electrode material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
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- 239000003792 electrolyte Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- -1 Transition metal sulfides Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
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- 239000010439 graphite Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- 229910002514 Co–Co Inorganic materials 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 238000001308 synthesis method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of a double-carbon-layer protective cobalt disulfide composite material, wherein ZIF-67 with uniform size is used as a precursor, and the ZIF-67 and melamine are mixed according to a mass ratio of 1:5, mixing, annealing under the protection of segmented argon at 350 ℃ and 700 ℃, wherein the reduced cobalt nano particles can produce a catalytic effect on melamine during carbonization, bamboo-shaped carbon nano tubes are formed around the polyhedron, and then further vulcanizing to prepare the double-carbon-layer-protection cobalt disulfide composite material. 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 protection cobalt disulfide composite material has larger specific surface area and porous structure of 0.1 Ag ‑1 The highest reversible capacity is 899 mAh g ‑1 The average coulombic efficiency was 98.4%.
Description
Technical Field
The invention relates to a cobalt disulfide composite material with double carbon layer protection, and a preparation method and application thereof, and belongs to the technical field of new materials.
Technical Field
Today's society suffers from life due to excessive use of fossil fuels, environmental pollution, and energy crisis, which requires researchers to develop alternative energy conversion and storage systems. Lithium Ion Batteries (LIBs) are used as an advanced electrochemical energy storage technology, have the characteristics of high energy density, long service life, no memory effect and the like, and are dominant in the fields of portable electronic equipment, smart grids and electric automobiles. At present, graphite is used as a negative electrode material of LIBs, and has relatively stable performance, but relatively low theoretical capacity (372 mAh g -1 ) The requirements of modern new energy electric automobiles or electronic mobile equipment on high energy density cannot be met. The proportion of electrode material in the constituent parts of the LIBs was 59% (negative electrode 18%, positive electrode 41%), so that in order to improve the performance of the LIBs, it should be started from the electrode material.
Transition metal sulfides (e.g., feS) 2 、MoS 2 、NiS 2 、CoS 2 ) It is considered as a promising graphite substitute because of its high safety and large theoretical capacity. Wherein cobalt disulfide (CoS 2 ) As a typical LIBs negative electrode material, the material has a higher theoretical capacity (874 mAh g based on four electron conversion reaction -1 ) Is considered to be a promising LIBs negative electrode material. However, the CoS is limited due to the disadvantages of large volume expansion, poor conductivity and slow ion/electron transport kinetics during charge and discharge, resulting in poor cycle life and rate capability 2 Application in energy storage.
For CoS 2 Alleviating the problems of volume expansion and poor conductivity, will be CoS 2 The composite of the nano particles and the carbon material can realize better lithium storage performance, such as graphene, carbon Nanotubes (CNTs), carbon nanofibers and the like. The Metal Organic Frameworks (MOFs) can be assembled by various metal clusters/ions and organic ligands, and have good application prospects in the field of new energy storage due to the high porosity, controllable pore diameter and highly ordered structure. The MOFs can be carbonized to obtain derivative carbon or carbon metal porous materials which can be used as precursors (such as oxides, sulfides, selenides and the like) for preparing various metal matrix composite materials; in addition, since the organic ligands for synthesizing MOFs contain heteroatoms, MOFs-derived carbon materials are susceptible to heteroatom doping, which is a great benefit in improving LIBs performance. However, after high temperature carbonization of MOFs, shrinkage or even collapse of the structure occurs, which destabilizes the electrode material and affects CoS 2 Is used for the electrochemical performance of the battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a cobalt disulfide composite material with double carbon layer protection, a preparation method and application thereof, and utilizes a green synthesis method to prepare a precursor ZIF-67, and CoS is prepared by high-temperature carbonization and solid-phase vulcanization processes 2 Limited in ZIF-67 derived N-doped porous carbon and CNTs converted from melamine, the two-carbon layer can improve CoS on one hand 2 Is of the conductivity ofLi + Is provided for a path of diffusion; 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 in the prior art, the invention adopts the following technical scheme:
a preparation method of a double-carbon-layer protection cobalt disulfide composite material takes ZIF-67 with uniform morphology and particle size of 1-2 mu m as a precursor, and is prepared by high-temperature carbonization and solid-phase vulcanization processes, and the specific surface area of the obtained double-carbon-layer protection cobalt disulfide composite material is 51.24m 2 g -1 The average pore diameter was 8.97nm.
The preparation method of the double-carbon-layer protective cobalt disulfide composite material comprises the following steps:
(1) Preparing a precursor ZIF-67 by standing at normal temperature
Co (NO) 3 ) 2 ·6H 2 Dispersing O in deionized water, then adding polyether F127, fully dissolving to obtain pink transparent solution, and marking as A solution; dissolving 2-methylimidazole in deionized water to obtain colorless transparent solution, and marking as solution B; pouring the solution B into the solution A for full reaction, standing for 20-24 hours at room temperature, centrifuging, and drying for 12-24 hours at 60-80 ℃ to obtain a ZIF-67 precursor; wherein 2-methylimidazole is combined with Co (NO 3 ) 2 ·6H 2 The molar ratio of O is 7.8:1, a step of;
(2) High temperature calcination
The ZIF-67 precursor and melamine are mixed according to the mass ratio of 1: 3-7, grinding uniformly, and calcining in sections at 350 ℃ and 700-800 ℃ under argon atmosphere to obtain black powder;
(3) Solid phase vulcanization
And (3) mixing the black powder obtained in the step (2) with sublimed sulfur according to the mass ratio of 1:3, fully grinding after mixing, and carrying out solid phase vulcanization under the protection of argon at 300 ℃ to obtain the cobalt disulfide composite material with the protection of the double carbon layers.
As an improvement, the polyether F127 in the step (1) has the mass fraction of 0.05-1.6 wt% and is used as a structure directing agent.
As an improvement, the ZIF-67 precursor and melamine in the step (2)The mass ratio of (2) is 1:5, a step of; the first stage of calcination is 350 ℃ and the time is 1 to 1.5 hours; the second stage of calcination is 700 ℃ for 2-3 hours; the temperature rising rate is 2-3 ℃ for min -1 。
As an improvement, in the solid-phase vulcanization process in the step (3), the temperature rising rate is 5-10 ℃ for min -1 The time is 2-3 h.
The cobalt disulfide composite material with the double carbon layer protection prepared by any one of the preparation methods.
The cobalt disulfide composite material protected by the double carbon layers is applied to a lithium ion battery anode material.
The beneficial effects are that:
compared with the prior art, the cobalt disulfide composite material with the double carbon layer protection and the preparation method and the application thereof are characterized in that the ZIF-67 precursor is prepared, the preparation method is green and economical, the size is uniform, the cobalt disulfide prepared by taking the ZIF-67 as the precursor is easy to control, the N-doped carbon obtained after carbonization of MOFs has larger specific surface and porous structure, and the Li can be shortened + A migration path, which improves the compatibility of the material with the electrolyte; CNTs distributed around polyhedron simultaneously for effectively relieving CoS 2 And maintain the structural stability of the electrode material during repeated charge and discharge.
Drawings
FIG. 1 is a diagram of a CoS prepared according to example 1 of the present invention 2 XRD spectra of the Co/NC/CNTs composite material prepared in example 5;
FIG. 2 is a CoS obtained in example 1 of the present invention 2 TG profile of NC/CNTs composites;
FIG. 3 (a) is a 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 CoS obtained in example 1 of the present invention 2 High resolution spectra of elements C1S, N1S, S2p, co2p in NC/CNTs composite material;
FIG. 4 is an SEM image of the precursor ZIF-67 of example 1 of the present invention;
FIG. 5 is a CoS obtained in example 1 of the present invention 2 TEM image of NC/CNTs composite material;
FIG. 6 is a CoS obtained in example 1 of the present invention 2 HRTEM image of NC/CNTs composite material;
FIG. 7 is an SEM image of the invention of example 2;
FIG. 8 is an SEM image of the invention of example 3;
FIG. 9 shows the pure CoS obtained in example 4 of the present invention 2 SEM images of (a);
FIG. 10 (a) is a CoS obtained in example 1 of the present invention 2 N of NC/CNTs composite material 2 Adsorption/desorption curves; FIG. 10 (b) is a CoS obtained in example 1 of the present invention 2 Pore size distribution curve of NC/CNTs composite material;
FIG. 11 is a CoS obtained in example 1 of the present invention 2 NC/CNTs composite material as LIBs negative electrode material at 0.1mV s -1 Cyclic voltammograms of (2);
FIG. 12 is a CoS obtained in example 1 of the present invention 2 The current density of the NC/CNTs composite material serving as LIBs negative electrode material is 100mA g -1 A lower charge-discharge curve;
FIG. 13 shows examples 1, 4, 5 and 6 of the present invention as LIBs negative electrode materials at a current density of 100mA g -1 A lower charge-discharge cycle curve;
fig. 14 is a graph showing the rate performance curves of examples 1, 4 and 5 of the present invention as LIBs negative electrode materials at different current densities.
Detailed Description
Unless otherwise defined, 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 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 protection CoS 2 The preparation process of the composite material specifically comprises the following steps:
(1) Putting cobalt nitrate hexahydrate with the mass of 0.43g into 30mL of deionized water, adding 0.15g of polyether F127 after the cobalt nitrate hexahydrate is dissolved, and marking the mixed solution as A; likewise, 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, vigorously stirring for 30min, and standing for 20-24 h at room temperature; washing with deionized water and absolute ethyl alcohol for three times, and centrifuging at 8500 rpm; drying in a vacuum drying oven at 60 ℃ for 12 hours; cooling to room temperature to obtain ZIF67 precursor;
(2) Mixing the ZIF67 precursor obtained in the step (1) with melamine in a mass ratio of 1:5, fully grinding in a mortar, then placing the mixture into an alumina porcelain boat, and placing the alumina porcelain boat into a tube furnace for two-stage calcination; the first stage is kept at 350 ℃ for 1.5h; the second stage is kept at 700 ℃ for 3 hours; the calcining atmosphere is argon, and the heating rate is 2 ℃ for min -1 The method comprises the steps of carrying out a first treatment on the surface of the 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 according to the mass ratio of 1: grinding fully in a mortar, then placing the mixture into an alumina porcelain boat, and placing into a tube furnace for calcination; the temperature is 300 ℃ and kept for 2 hours, and the temperature rising rate is 10 ℃ for min -1 The calcination atmosphere is argon; after cooling to room temperature, the double-carbon-layer protection CoS can be obtained 2 Composite CoS 2 /NC/CNTs。
Double carbon layer protection CoS 2 Preparation of electrode materials:
the CoS obtained in the step (3) is subjected to 2 The NC/CNTs composite material, polyvinylidene fluoride (binder) and acetylene black (conductive agent) are mixed according to the mass ratio of 7:2:1 grinding for 30min fully in a mortar, dissolving in N-methyl pyrrolidone (oily solvent), stirring for 12h to form uniform slurry, coating on a copper foil wiped by absolute ethyl alcohol by using a film coater, vacuum drying at 60 ℃, dividing into electrode slices of 13mm by using a manual slicing machine, taking lithium slices (diameter: 15.6mm and thickness: 0.45 mm) as negative electrodes of LIBs, assembling a half cell (model LIR 2032) in a glove box filled with argon (water content and oxygen content are both less than 0.01 ppm), adopting Celgard2600 as a diaphragm, adopting an electrolyte model LB266, and adopting the following formula: lithium hexafluorophosphate (1 mol. L) - 1 LiPF 6 ) The dissolution volume ratio is 1:1: ethylene Carbonate (EC) and carbonic acid of 1In the mixed solution of dimethyl ester (DMC) and diethyl carbonate (DEC), 1.0% of Vinylene Carbonate (VC) is used as an additive. After standing for 24 hours, testing lithium storage performance, wherein the test temperature is 25 ℃, the voltage window for cycle and multiplying power test is 0.01-3V, and the standing time between the charging and discharging steps is set to be 2 minutes; wherein the loading amount of the active material in the monolithic electrode is 0.8-1 mg.
CoS of example 1 2 Placing NC/CNTs sample in XRD glass slide 10 x 0.5mm clamping groove, compacting, and at angle of 10-80 deg. for 5 deg. min -1 The scanning speed of (C) is tested, the detection result is shown in figure 1, and from the figure, it can be seen that Co/NC/CNTs can be smoothly converted into CoS after vulcanization 2 NC/CNTs, and CoS 2 Diffraction peaks of NC/CNTs and CoS 2 Is matched to the standard diffraction pattern (JCPSDSNo. 41-1471). The positions 2θ=27.9°, 32.3 °, 36.2 °, 39.7 °, 46.4 °, 54.9 ° and the corresponding crystal planes are respectively: (111) (200), (210), (211), (220), (311). In CoS 2 The obvious cobalt peaks also appear in the spectra of NC/CNTs, mainly because these cobalt elements are coated with carbon and cannot react further with the gas and electrolyte ions generated after heating the sulfur powder.
10mg of CoS obtained in example 1 2 Placing NC/CNTs sample in crucible, placing in thermogravimetric tester, heating to 25-800deg.C at a temperature rising speed of 10deg.C for min -1 The combustion atmosphere is air, for CoS 2 The NC/CNTs were subjected to thermogravimetric analysis. 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 phases, the first phase: the mass loss before 400 ℃ is mainly evaporation of water on the surface of the material; and a second stage: the mass loss at 400-600 ℃ is 24.7%, mainly the combustion of carbon in air; and a third stage: the mass loss after 600℃is CoS 2 Oxidation to Co 3 O 4 Formed by the method.
Cutting aluminum foil of 1.5cm x 3cm, attaching double faced adhesive tape of 3mm x 3mm on polished surface side of aluminum foil, and performing CoS 2 Placing NC/CNTs powder sample on double-sided adhesive tape, folding aluminum foil, manually pressing sample,and maintaining for 20-30 seconds under 12MPa, shearing double faced adhesive tape at the middle position, placing a sample plate for detection, and detecting conditions: al Ka X-ray source, step size 5 μm. The detection results are shown in FIG. 3. FIG. 3 (a) is a CoS prepared 2 A full spectrum of X-ray photoelectron spectroscopy of NC/CNTs, which shows that Co, C, N, S, O elements are contained in the material; the occurrence of the O1s peak may be caused by partial oxidation of the surface of the material when tested, which is exposed to air. FIG. 3 (b) is a high resolution C1s spectrum showing that the element C is mainly C-N/C-O (27.76%), sp 3 C-C(25.93％)、sp 2 C—c (12.27%), c=c (34.04%), since the size and electronegativity of the N atom are different from those of the C atom, the introduction of the hetero atom causes distortion of the carbon structure and variation of charge density; FIG. 3 (c) is a high resolution N1s spectrum showing that N element exists mainly in the form of graphite nitrogen (63.87%), pyrrole nitrogen (32.35%), pyridine nitrogen (3.78%); FIG. 3 (d) is a high resolution S2p map, wherein the proportion of C-S-C is 9.91%; FIG. 3 (e) is a Co2p high resolution map, with signals appearing at 778.3eV and 793.4eV indicating the presence of Co-N. This indicates that the ZIF-67 carbonization-derived cobalt was not fully sulfided, as was the case with the presence of Co peaks in the XRD pattern. 779.5eV and 781.9eV correspond to Co2p, respectively 3/2 Co-Co bonds and Co-S bonds of (C), which illustrate Co 2+ Is present; the signals appearing at 794.3eV and 798.4eV represent Co2p, respectively 1/2 Co-S bonds and Co-Co bonds of (C) indicate Co 3+ Is present. 802.8eV is the satellite peak of Co.
FIG. 5 is an SEM image of the precursor ZIF-67, which produced ZIF-67 of relatively uniform size and smooth surface. The particle size is 1-2 μm.
FIG. 6 is a prepared CoS 2 According to a TEM image of the NC/CNTs composite material, the structure of the polyhedron after vulcanization is still complete, and the melamine is derived to form bamboo-like carbon nanotubes. This structure can be referred to as CoS 2 Not only provides sufficient specific surface area and porous structure for rapid charge transfer, but also can serve to mitigate volume expansion during charge and discharge cycles. In addition, the bamboo-like carbon nanotubes can also improve CoS 2 Is a conductive material.
FIG. 7 is a diagram of the processBackup CoS 2 HRTEM image of NC/CNTs composite material, distance between two adjacent lattice stripes is 0.337nm, corresponding to CoS 2 (111) crystal plane of (a).
Detecting sample CoS 2 Degassing NC/CNTs at 200deg.C for 2 hr, removing gas adsorbed on sample surface, and removing N 2 Is used as adsorption gas, H 2 N formed by liquid nitrogen at 77K as carrier gas 2 Is adsorbed and CoS is calculated according to BET equation 2 The specific surface area of NC/CNTs, and the pore size distribution was calculated by BJH method. The test results are shown in fig. 10. FIG. 10 (a) is a CoS prepared 2 N of NC/CNTs composite material 2 Adsorption/desorption curve graph, wherein the curve type belongs to IV type, and the specific surface area is 52.24m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the Pore volume of 0.28cm 3 g -1 The pore diameter is concentrated near 8.97nm, coS 2 The NC/CNTs has larger specific surface area and porous structure, which is beneficial to the permeation of electrolyte and Li + Is inserted/removed; at the same time, the contact area between the electrode material and the electrolyte is increased, which is helpful for improving the capacity and the cycling stability of the material.
Connecting the button cell with a cell test clamp with Chen Hua electrochemical workstation (CHI 760E), with an initial voltage of open circuit voltage, highest voltage of 3.0V, lowest voltage of 0.01V, end voltage of 3.0V, and scan speed of 0.1mV s -1 The scan section was set to 8 and the test temperature was 25℃to test the prepared CoS 2 CV diagram of NC/CNTs composite material as LIBs negative electrode material. The test results are shown in FIG. 11, and it can be seen from FIG. 11 that the CoS is prepared 2 When the NC/CNTs composite material is used as LIBs cathode 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 electrolyte; two strong peaks at 1.3 and 1.8V indicate Li x CoS 2 Is formed and subsequent Li x CoS 2 Decomposition of (formation of Co metal and Li respectively) 2 S) a process of S); oxidation peaks at 2.0V and 2.4V are converted from Co to CoS 2 (delithiation process). The CV curves have better coincidence in subsequent cycles than the first circle, indicating CoS 2 The NC/CNTs composite material has good reversibility and stability.
The button cell after standing was subjected to charge and discharge test in a voltage range of 0.01-3V in a Wohan blue electric test system (LAND-CT 2001A) for a standing time of 2min after charge and discharge, and a test temperature of 25 ℃. Prepared CoS 2 The current density of the NC/CNTs composite material serving as LIBs negative electrode material is 100mA g -1 The test result of the 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 was 58.8%; after activation, the coulombic efficiency increased, indicating good reversibility.
The button cell after standing was subjected to cycle performance test on the Wohan blue electric test system (LAND-CT 2001A) with a voltage range of 0.01-3V, and a standing time of 2min after charging and discharging at a test temperature of 25 ℃. FIG. 13 is a pure CoS 2 Co/NC/CNTs and CoS prepared therefrom 2 NC/CNTs composite material at current density of 100mA g -1 The following cycle performance is compared with the graph. It can be seen that within 100 cycles, the CoS is prepared 2 The NC/CNTs composite material has a stable curve and an average coulombic efficiency of 98.4%. The electrode material has good structural stability in the circulating process and is matched with pure CoS 2 Compared with the method, the method can fully relieve the problem of volume expansion in the charge and discharge process.
And (3) performing multiplying power performance test on the button battery subjected to 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 under each current density is 10. FIG. 14 is a pure CoS 2 Co/NC/CNTs and CoS prepared therefrom 2 NC/CNTs composite material with current density of 100mA g -1 To 2000mA g -1 A time rate performance graph; wherein the electrodes are at 100, 200, 500, 1000 and 2000mA g -1 Specific capacities 830, 728, 589, 395 and 264mAh g, respectively -1 When the current density returns to 100mA g -1 When the reversible capacity is restored to 815mAh g -1 Example 1 proved to have good rate capability and rate capability 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 is 1:3. The electrode material is prepared by a solid phase vulcanization process.
The morphology is shown in figure 7. The surface is rough and no significant CNTs are visible around the polyhedron.
Example 3
The difference from example 1 is that the mass ratio of ZIF-67 precursor to melamine is 1:7, and the electrode material is prepared by the solid phase vulcanization process.
The morphology is shown in figure 8. Although CNTs can be seen, agglomeration occurs.
Example 4
Placing cobalt nitrate hexahydrate in a tube furnace for oxidation at 300 ℃ for 3 hours at a heating rate of 5 ℃ for min -1 Then, the obtained black powder and sulfur powder are mixed according to the mass ratio of 1:3, uniformly mixing, reacting for 2 hours under the argon atmosphere at 300 ℃, wherein the heating rate is 10 ℃ for min -1 . Obtaining pure CoS 2 Electrode materials were prepared in the same proportions as in example 1, tested for electrochemical performance, and the test conditions were the same as described in example 1. The morphology is shown in figure 9. The particles are larger. The cycle performance and the rate performance are shown in fig. 13 and 14. At 100mAg -1 Pure CoS at current density 2 The average specific discharge capacity after 100 circles is 336.5mAh g -1 ，2Ag -1 The reversible specific capacity of the product is 121.9mAh g -1 Pure CoS due to no protection of the carbon layer 2 The reversible specific capacity is poor.
Example 5
The prepared ZIF-67 and melamine are mixed according to the mass ratio of 1:5, carbonizing in a tube furnace after grinding, and annealing at 350 ℃ for 1.5h; annealing at 700 ℃ for 3h; heating rate of 2 ℃ min -1 The Co/NC/CNTs composite material was obtained, and an electrode material was prepared in the same ratio as in example 1, and its electrochemical properties were tested. The test conditions were the same as in example 1, and the cycle performance and rate performance are shown in fig. 13 and 14. At 100mAg -1 Under the current density, the average specific discharge capacity of Co/NC/CNTs after 100 circles of circulation is 372.2mAh g -1 ，2Ag -1 The reversible specific capacity of the product is 58.4mAh g under the multiplying power test -1 。
Example 6
The difference from example 1 is that ZIF-67 is reacted with melamine in a ratio of 1:5, after grinding fully, calcining for 1.5 hours at 350 ℃, and then, increasing the temperature to 800 ℃ and calcining for 3 hours; the solid phase vulcanization process was then carried out at the same ratio of temperatures as in example 1. 100mA g -1 The cyclic performance test was performed under the same conditions as in example 1 at the current density, and the cyclic performance test results are shown in fig. 13. Capacity fading occurs after 85 circles, stability is inferior to that of example 1, and due to higher carbonization temperature, collapse occurs in the material structure, and reversible capacity is unstable after multiple charge and discharge.
The invention takes polyether F127 as a structure guiding agent, takes water as a solvent instead of methanol, prepares a precursor ZIF-67 by a green synthesis method, simultaneously utilizes Co nano particles obtained by high-temperature carbonization and reduction to catalyze melamine to form CNTs around a polyhedron, and finally prepares the CoS protected by a double carbon layer through a solid-phase vulcanization process 2 The composite material, N-doped carbon skeleton derived from ZIF-67 has higher specific surface area and porous structure, and can be Li + Diffusion shortens the path; at the same time, CNTs have strong mechanical property and can fully relieve CoS 2 And thus maintain structural stability during repeated charge and discharge.
In the foregoing, the protection scope of the present invention is not limited to the preferred embodiments of the present invention, 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 disclosed in the present invention fall within the protection scope of the present invention.
Claims (4)
1. A preparation method of a double-carbon-layer-protected cobalt disulfide composite material is characterized in that ZIF-67 with uniform morphology and 1-2 mu m particle size is used as a precursor, and the preparation is carried out by utilizing high-temperature carbonization and solid-phase vulcanization processes, so that the specific surface area of the obtained double-carbon-layer-protected cobalt disulfide composite material is 51.24m 2 g -1 An average pore diameter of 8.97nm; the method comprises the following steps:
(1) Preparing a precursor ZIF-67 by standing at normal temperature
Co (NO) 3 ) 2 ·6H 2 Dispersing O in deionized water, then adding polyether F127, fully dissolving to obtain pink transparent solution, and marking as A solution; dissolving 2-methylimidazole in deionized water to obtain colorless transparent solution, and marking as solution B; pouring the solution B into the solution A for full reaction, standing for 20-24 hours at room temperature, centrifuging, and drying for 12-24 hours at 60-80 ℃ to obtain a ZIF-67 precursor; wherein 2-methylimidazole is combined with Co (NO 3 ) 2 ·6H 2 The molar ratio of O is 7.8:1, the mass fraction of the polyether F127 is 0.05-1.6wt% and the polyether F127 acts as a structure guiding agent;
(2) High temperature calcination
The ZIF-67 precursor and melamine are mixed according to the mass ratio of 1: 3-7, grinding uniformly, and calcining in sections at 350 ℃ and 700 ℃ under argon atmosphere to obtain black powder;
(3) Solid phase vulcanization
And (3) mixing the black powder obtained in the step (2) with sublimed sulfur according to the mass ratio of 1:3, fully grinding the mixture after mixing, and performing solid-phase vulcanization under the protection of argon at 300 ℃ to obtain the cobalt disulfide composite material with the protection of the double carbon layers, wherein in the solid-phase vulcanization process, the heating rate is 5-10 ℃ for min -1 The time is 2-3 h.
2. The method for preparing a cobalt disulfide composite material protected by a double carbon layer according to claim 1, wherein in the step (2), the mass ratio of the ZIF-67 precursor to melamine is 1:5, a step of; the first stage of calcination is 350 ℃ and the time is 1 to 1.5 hours; the second stage of calcination is 700 ℃ for 2-3 hours; the temperature rising rate is 2-3 ℃ for min -1 。
3. A dual carbon layer protected cobalt disulfide composite prepared based on any of the preparation methods of claims 1-2.
4. The application of the cobalt disulfide composite material based on the double carbon layer protection prepared by the preparation method of claim 1 in the lithium ion battery cathode material.
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