CN113501552A - MOFs-derived hollow polyhedrons Co3S4And preparation method and application thereof - Google Patents
MOFs-derived hollow polyhedrons Co3S4And preparation method and application thereof Download PDFInfo
- Publication number
- CN113501552A CN113501552A CN202110866496.0A CN202110866496A CN113501552A CN 113501552 A CN113501552 A CN 113501552A CN 202110866496 A CN202110866496 A CN 202110866496A CN 113501552 A CN113501552 A CN 113501552A
- Authority
- CN
- China
- Prior art keywords
- polyhedron
- hollow
- zif
- nano
- mofs
- 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
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title description 10
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 14
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical group [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000004146 energy storage Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 28
- 239000011259 mixed solution Substances 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 239000002131 composite material Substances 0.000 description 16
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 238000011068 loading method Methods 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920001021 polysulfide Polymers 0.000 description 7
- 239000005077 polysulfide Substances 0.000 description 7
- 150000008117 polysulfides Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/30—Sulfides
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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
- C01P2006/14—Pore volume
-
- 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
- C01P2006/16—Pore diameter
-
- 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
- H01M2004/026—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 discloses a MOFs-derived hollow polyhedron Co3S4Said hollow polyhedron Co3S4Is a ZIF-67 derived micro-mesoporous nano hollow polyhedron, the size of the hollow polyhedron Co3S4 is 200 nm-1000 nm, and the thickness of a shell layer is 5 nm-20 nm. The invention also discloses a hollow polyhedron Co derived from the MOFs3S4The method is implemented according to the following steps: step 1, synthesizing a ZIF-67 nano polyhedron by adopting a simple room temperature precipitation method; step 2, taking the ZIF-67 nano polyhedron obtained in the step 1 as a templateAdding thioacetamide into a cobalt source, and then reacting by adopting a solvothermal method to obtain a precursor; the molar ratio of the ZIF-67 nano polyhedron to the thioacetamide is 1: 1-5; step 3, putting the precursor obtained in the step 2 in an inert atmosphere for heat treatment to obtain hollow polyhedral Co3S4。
Description
Technical Field
The invention belongs to the technical field of sulfur lithium batteries, and particularly relates to MOFs-derived hollow polyhedral Co3S4And also relates to hollow polyhedron Co derived from MOFs3S4And hollow polyhedral Co derived from the MOFs3S4The use of (1).
Background
Metal-Organic Frameworks (MOFs) are three-dimensional network structure crystals formed by hybridization of Organic ligands and inorganic Metal centers through coordination bonds. Has high specific surface area (1000 m)2/g～10000m2/g), rich and controllable pore structure, multiple reactive sites, biocompatibility and other characteristics, and has potential application value in various fields (Chemical Society Reviews,2017,46: 3108-. Energy crisis and environmental pollution have gradually become the key problems that hinder social development and influence human life, electrochemical energy storage is receiving much attention due to its high energy efficiency and cleanness, and lithium sulfur batteries are widely researched due to the advantages of having theoretical specific capacity up to 1675mAh/g, energy density 2600Wh/kg, environmental friendliness, rich sulfur storage capacity and the like. However, the development of lithium-sulfur batteries is severely hampered by the low sulfur loading of the positive electrode material and the "shuttle effect" caused by the dissolution and migration of lithium polysulfides, which generally requires the increase in sulfur loading and the suppression of the "shuttle effect" by structure and material design.
The construction of hollow structures is one of the effective methods to increase sulfur loading and inhibit the "shuttle effect". In recent years, metal organic frameworks have been used as an ideal precursor for designing transition metal compounds of specific structures. For example: the invention patent with publication number CN111424429A discloses a metal sulfide porous frame material, a preparation method and application thereof, the method comprises the steps of firstly growing a transition metal oxide nano array on the surface of carbon cloth, taking the transition metal oxide nano array as a substrate to grow MOFs material originally, and obtaining the metal sulfide porous and hollow frame material through vulcanization; the invention patent with the publication number of CN111668503A provides a bimetallic sulfide lithium-air battery anode material and a preparation method and application thereof, which comprises the steps of firstly preparing carbon black modified carbon paper, then growing a cobalt-zinc bimetallic MOFs nanosheet array on the surface of the carbon black modified carbon paper in situ by utilizing a coprecipitation method, and finally preparing a hollow zinc-cobalt bimetallic sulfide nanosheet array by taking thioacetamide as a sulfur source through a low-temperature hydrothermal method. However, both of them require the preparation of a compound having a specific structure using a carbon cloth or a carbon paper as a substrate, and the preparation method is complicated, the process cost is high, and a high-purity transition metal compound having a specific structure cannot be obtained.
Disclosure of Invention
The first purpose of the invention is to provide a MOFs-derived hollow polyhedron Co3S4So as to solve the problem of 'shuttle effect' caused by low sulfur loading of electrode materials and dissolution and migration of lithium polysulfide of the lithium-sulfur battery.
In order to achieve the purpose, the invention adopts the technical scheme that: MOFs-derived hollow polyhedron Co3S4Said hollow polyhedron Co3S4Is a micro-mesoporous nano hollow polyhedron derived from ZIF-67.
As a preferable technical scheme of the invention, the hollow polyhedron Co3S4The size is 200 nm-1000 nm, and the thickness of the shell layer is 5 nm-20 nm.
It is a second object of the present invention to provide a MOFs-derived hollow polyhedron Co3S4For preparing the above MOFs-derived hollow polyhedron Co3S4。
In order to achieve the second object, the invention adopts the technical scheme that: hollow polyhedral Co derived from MOFs according to any of claims 1-23S4The method is implemented according to the following steps:
step 1, synthesizing a ZIF-67 nano polyhedron by adopting a simple room temperature precipitation method;
step 2, taking the ZIF-67 nano polyhedron obtained in the step 1 as a template and adding thioacetamide into the template and a cobalt source, and then reacting by adopting a solvothermal method to prepare a precursor; the molar ratio of the ZIF-67 nano polyhedron to the thioacetamide is 1: 1-5;
step 3, putting the precursor obtained in the step 2 in an inert atmosphere for heat treatment to obtain hollow polyhedral Co3S4。
As a preferred technical solution of the present invention, in the step 1, synthesizing the ZIF-67 nano polyhedron by a simple room temperature precipitation method specifically comprises: weighing 4mmol of cobalt nitrate hexahydrate and 16mmol of 2-methylimidazole, respectively dissolving in 100mL of methanol, and uniformly mixing to form a cobalt nitrate solution and a 2-methylimidazole solution; and (2) rapidly pouring the 2-methylimidazole solution into the cobalt nitrate solution under magnetic stirring, repeatedly washing the solution with absolute ethyl alcohol for three times after 30min of magnetic stirring, performing vacuum filtration, and drying the solution at 50 ℃ for 12h to obtain the ZIF-67 nano polyhedron.
As a preferred technical solution of the present invention, in the step 2, the precursor prepared by the solvothermal reaction is specifically: dispersing ZIF-67 nano polyhedron and thioacetamide in ethanol, vulcanizing in a reaction kettle at 90-150 ℃ for 2-12 h, washing with deionized water and ethanol, and finally vacuum drying at 50 ℃ for 12h to obtain the precursor.
As a preferred technical solution of the present invention, in the step 3, the heat treatment of the precursor obtained in the step 2 in an inert atmosphere specifically comprises: putting the precursor in a tube furnace, heating to 300-400 ℃ at the speed of 2-5 ℃/min under the protection of nitrogen or argon atmosphere, carrying out heat treatment for 1-6 h, and collecting the product to obtain the hollow polyhedral Co3S4。
The third object of the present invention is to provide the above hollow polyhedron Co3S4The method is applied to the field of energy storage, and the energy storage is electrochemical energy storage of the lithium-sulfur battery.
The invention has the beneficial effects that: the invention synthesizes hollow nano polyhedron Co by taking ZIF-67 nano polyhedron as a template3S4The dodecahedron of ZIF-67 was retained and hollow nanostructures were formed; hollow nano polyhedral Co3S4The hollow cubic structure provides larger specific surface area, can improve the loading amount of active substance sulfur and physically and chemically adsorb polysulfide,can effectively inhibit shuttle effect, improve polysulfide catalytic conversion, realize the synergistic promotion process of adsorption-conversion, and the hollow nano polyhedral Co3S4The material can accelerate the electron transmission rate, has higher cycling stability and rate capability when being used for the anode of the lithium-sulfur battery, can realize stable electrochemical energy storage, and is a very ideal anode carrier material; the synthesis process is simple and efficient, environment-friendly, good in repeatability and high in product purity.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a hollow polyhedron Co3S4And Co3S4A preparation flow chart of the/S composite material;
FIG. 2 is a scanning electron microscope and a transmission mirror of a ZIF-67 nano-polyhedron prepared in example 1 of the present invention;
FIG. 3 is a hollow polyhedron Co prepared in example 1 of the present invention3S4Scanning electron microscope images of;
FIG. 4 is a hollow polyhedron Co prepared in example 1 of the present invention3S4Transmission electron microscopy images of;
FIG. 5 shows ZIF-67 nano-polyhedrons and hollow polyhedrons Co prepared in example 1 of the present invention3S4X-ray diffraction spectrum of (a);
FIG. 6 is a hollow nano-polyhedron Co prepared in example 1 of the present invention3S4Synthetic Co3S4Co hydrothermally synthesized in/S composite electrode and comparative example 13S4A cycle performance diagram of the/S composite electrode;
FIG. 7 shows a hollow nano-polyhedron Co prepared in example 1 of the present invention3S4Synthetic Co3S4Multiplying power performance diagram of the/S composite electrode.
Detailed Description
The technical scheme of the invention is further explained in detail by combining the description of the attached drawings and the specific embodiment.
Example 1
The invention relates to hollow polyhedron Co derived from MOFs3S4The method is implemented according to the following steps:
step 1, weighing 4mmol of cobalt nitrate hexahydrate and 16mmol of 2-methylimidazole, respectively dissolving in 100mL of methanol, and uniformly mixing to form a cobalt nitrate solution and a 2-methylimidazole solution; rapidly pouring the 2-methylimidazole solution into the cobalt nitrate solution under magnetic stirring, repeatedly washing the solution with absolute ethyl alcohol for three times after 30min of magnetic stirring, performing vacuum filtration, and drying the solution at 50 ℃ for 12h to obtain a ZIF-67 nano polyhedron;
step 2, firstly weighing 50mg of ZIF-67 nano polyhedron, adding the ZIF-67 nano polyhedron into 12mL of ethanol, and carrying out ultrasonic treatment for 30min until the ZIF-67 nano polyhedron is completely dispersed to obtain a mixed solution A; weighing 50mg of thioacetamide and dissolving into 4mL of ethanol to obtain a mixed solution B; adding the mixed solution B into the mixed solution A and continuously stirring to obtain a mixed solution C, finally transferring the mixed solution C into a reaction kettle and vulcanizing at 90 ℃ for 2h, naturally cooling, collecting products, washing with water and ethanol for 6 times respectively, and then drying in vacuum at 50 ℃ for 12h to obtain a precursor;
and 3, putting the precursor obtained in the step 2 in an inert atmosphere for heat treatment, wherein the heat treatment specifically comprises the following steps: putting the precursor in a tube furnace, heating to 300 ℃ at the speed of 2 ℃/min under the protection of nitrogen atmosphere, carrying out heat treatment for 1h, and collecting the product to obtain the hollow polyhedral Co3S4。
Example 2
The invention relates to hollow polyhedron Co derived from MOFs3S4The method is implemented according to the following steps:
step 1, weighing 4mmol of cobalt nitrate hexahydrate and 16mmol of 2-methylimidazole, respectively dissolving in 100mL of methanol, and uniformly mixing to form a cobalt nitrate solution and a 2-methylimidazole solution; rapidly pouring the 2-methylimidazole solution into the cobalt nitrate solution under magnetic stirring, repeatedly washing the solution with absolute ethyl alcohol for three times after 30min of magnetic stirring, performing vacuum filtration, and drying the solution at 50 ℃ for 12h to obtain a ZIF-67 nano polyhedron;
step 2, firstly weighing 50mg of ZIF-67 nano polyhedron, adding the ZIF-67 nano polyhedron into 12mL of ethanol, and carrying out ultrasonic treatment for 30min until the ZIF-67 nano polyhedron is completely dispersed to obtain a mixed solution A; weighing 150mg of thioacetamide and dissolving into 4mL of ethanol to obtain a mixed solution B; adding the mixed solution B into the mixed solution A and continuously stirring to obtain a mixed solution C, and finally transferring the mixed solution C into a reaction kettle and vulcanizing at 120 ℃ for 7 hours; after natural cooling, collecting the product, washing with water and ethanol for 6 times respectively, and then vacuum-drying at 50 ℃ for 12h to obtain a precursor;
step 3, putting the precursor in a tube furnace, heating to 350 ℃ at the speed of 3 ℃/min under the protection of nitrogen or argon atmosphere, carrying out heat treatment for 3h, and collecting the product to obtain the hollow polyhedral Co3S4。
Example 3
The invention relates to hollow polyhedron Co derived from MOFs3S4The method is implemented according to the following steps:
step 1, weighing 4mmol of cobalt nitrate hexahydrate and 16mmol of 2-methylimidazole, respectively dissolving in 100mL of methanol, and uniformly mixing to form a cobalt nitrate solution and a 2-methylimidazole solution; rapidly pouring the 2-methylimidazole solution into the cobalt nitrate solution under magnetic stirring, repeatedly washing the solution with absolute ethyl alcohol for three times after 30min of magnetic stirring, performing vacuum filtration, and drying the solution at 50 ℃ for 12h to obtain a ZIF-67 nano polyhedron;
step 2, firstly weighing 50mg of ZIF-67 nano polyhedron, adding the ZIF-67 nano polyhedron into 12mL of ethanol, and carrying out ultrasonic treatment for 30min until the ZIF-67 nano polyhedron is completely dispersed to obtain a mixed solution A; weighing 250mg of thioacetamide and dissolving into 4mL of ethanol to obtain a mixed solution B; adding the mixed solution B into the mixed solution A and continuously stirring to obtain a mixed solution C, and finally transferring the mixed solution C into a reaction kettle and vulcanizing at 150 ℃ for 12 hours; after natural cooling, collecting the product, washing with water and ethanol for 6 times respectively, and then vacuum-drying at 50 ℃ for 12h to obtain a precursor;
step 3, placing the precursor in a tube furnace, heating to 400 ℃ at the speed of 5 ℃/min under the protection of nitrogen or argon atmosphere, carrying out heat treatment for 6h, and collecting the product to obtain the hollow polyhedral Co3S4。
Comparative example 1
Step 1, weighing 0.1455g of cobalt nitrate and 0.09g of thiourea, adding into 30mL of distilled water, stirring to completely dissolve the cobalt nitrate and the thiourea, transferring the solution into a 40mL of polytetrafluoroethylene reaction kettle, reacting at 120 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is finished; washing the mixture with distilled water and ethanol for three times respectively, and drying the mixture in a drying oven for 12 hours to obtain a precursor;
step 2, weighing 0.016g of precursor and 0.11128g of thiourea, respectively placing the precursor and the thiourea on two sides of a porcelain boat (the molar ratio of Co to S is 1: 10), then placing the porcelain boat into a tube furnace, keeping the heat treatment temperature at 300 ℃ (the heating rate is 5 ℃/min) under the protection of nitrogen, preserving the heat for 2h, and cooling to room temperature to obtain Co3S4And (3) obtaining the product.
For convenient analysis, weighing a certain mass of hollow polyhedron Co3S4The method is used for preparing an electrode material by compounding with elemental sulfur, is used for a lithium-sulfur battery anode, and is used for testing the electrochemical performance of the lithium-sulfur battery anode, and comprises the following specific operations: weighing 3g of hollow polyhedron Co3S4Uniformly mixing the mixture with 7g of elemental sulfur, and then carrying out heat treatment for 10 hours at 155 ℃ in a high-pressure reaction kettle to obtain Co3S4the/S composite material is mixed, coated and cut to obtain Co3S4And the/S composite electrode is assembled into a button type lithium-sulfur battery, and the electrochemical performance of the button type lithium-sulfur battery is tested.
For the hollow nano-polyhedrons Co prepared in examples 1 to 33S4Performing characterization analysis and performance test: the analysis and characterization adopts an XRD-6100X-ray diffractometer to carry out qualitative analysis on the microstructure of the sample, and the test adopts CuK alpha and continuously scans in the range of 5-80 degrees; observing the morphological characteristics of the material by adopting a German Karl Zeiss JSM 6700F type scanning electron microscope and a Japanese JEM-3010 transmission electron microscope; testing the specific surface area and pore size distribution of the material by adopting a microscopic high-Bo specific surface area tester; the electrochemical performance of the composite electrode prepared by the hollow nano polyhedral Co3S4 is tested by a Xinwei battery tester, and the cycle performance and the rate performance are tested at a voltage of 1.5V-3V.
The test results were as follows: FIG. 1 depicts a hollow polyhedron Co3S4And Co3S4The preparation method of the/S composite material comprises the steps of synthesizing a nano polyhedron ZIF-67 by using cobalt nitrate and 2-methylimidazole as raw materials, carrying out hydrothermal vulcanization by using the nano polyhedron ZIF-67 as a template and thioacetamide as a vulcanizing agent, and finally carrying out heat treatment on a vulcanized precursor to obtain a hollow nano polyhedron Co3S 4; finally, sulfur loading is carried out by a hot melting method to obtain the Co3S4/S composite electrode. FIG. 2 is a scanning electron microscope microscopic morphology analysis of the ZIF-67 nano polyhedron prepared by the method of the present invention, which can clearly see that the structure of ZIF-67 is a dodecahedron structure, the particle size is 0.5-1 μm, the surface is smooth, the size is uniform and no agglomeration exists. FIG. 3 is a hollow nano-polyhedron Co obtained by sulfurization and heat treatment according to the method of the present invention3S4Can clearly see Co in the scanning electron microscope image3S4The hollow polyhedral structure is presented, the polyhedral structure of ZIF-67 is kept, the particle size is 200-1000 nm, the thickness of the hollow shell is 5-20 nm, the distribution is uniform, no impurity is generated, the surface is smooth and flat, and the hollow nano polyhedral Co shown in figure 4 is a hollow nano polyhedral Co3S4The transmission electron micrograph further demonstrates that Co3S4Has a hollow porous structure and a shell layer thickness of 5-20 nm. FIG. 5 shows ZIF-67 nano-polyhedrons and hollow polyhedrons Co prepared by the method of the present invention3S4The XRD pattern shows that the prepared ZIF-67 nano polyhedron and hollow polyhedron are completely coincided with the standard pattern, and no other miscellaneous peak appears, so that the high-purity Co is proved to be prepared3S4A polyhedron.
Specific surface area and pore size analysis of examples 1 to 3 and comparative example 1, and the test results are shown in Table 1, it can be seen that the hollow polyhedrons Co prepared in examples 1 to 33S4All have higher specific surface area and abundant micro-mesopores, which are beneficial to containing sulfur and binding polysulfide, while the Co obtained in comparative example 13S4The specific surface area of the material is only 152m2The volume of the pores is larger, and the hollow polyhedron Co provided by the invention3S4High specific surface area and rich pore size distribution of the sulfur catalyst are beneficial to improving the sulfur content of an active substanceThe loading capacity, the hollow structure and the abundant micro-mesopores are beneficial to physically binding polysulfide, thereby inhibiting the shuttle effect and improving the electrochemical performance of the battery.
TABLE 1
Mixing hollow polyhedron Co3S4the/S composite material is prepared into an electrode, and a button cell is assembled in a glove box for testing the electrochemical performance. FIG. 6(a) is a hollow polyhedron Co provided in example 13S4Preparation of Co3S4The cycle performance curve of the/S composite electrode material shows that the hollow nano polyhedral Co3S4the/S composite electrode has better capacity retention rate (63%), coulombic efficiency close to 100%, and higher cycling stability, while the Co synthesized by the hydrothermal method in comparative example 1 (FIG. 6(b), electrode preparation and battery assembly process parameters are completely the same)3S4After 50-week circulation of the/S composite electrode, the capacity is only 130mAh/g, the capacity is attenuated quickly, and the circulation stability is poor. The comparison proves that the hollow nano polyhedron Co provided by the invention3S4the/S composite electrode has better cycling stability and electrochemical performance. FIG. 7 is a hollow polyhedron Co provided in example 13S4The rate capability of the/sulfur composite electrode is still maintained at 462mAh/g when 1C (1C: 1675mAh/g) constant current is discharged, which indicates that the hollow polyhedron Co3S4The sulfur/sulfur composite electrode has better rate capability and electrochemical performance. The invention provides a hollow polyhedron Co3S4The material is an excellent lithium-sulfur battery matrix material, is beneficial to improving the active substance loading capacity, physically and chemically adsorbing polysulfide and inhibiting shuttle effect, and provides a new idea for energy storage of the lithium-sulfur battery.
While the foregoing description shows and describes several preferred embodiments of the invention, it is to be understood, as noted above, that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. MOFs-derived hollow polyhedron Co3S4Characterized in that said hollow polyhedron Co3S4Is a micro-mesoporous nano hollow polyhedron derived from ZIF-67.
2. MOFs-derived hollow polyhedron Co according to claim 13S4The hollow polyhedron Co3S4 is characterized in that the size is 200 nm-1000 nm, and the shell thickness is 5 nm-20 nm.
3. Hollow polyhedral Co derived from MOFs according to any of claims 1-23S4The method is characterized by comprising the following steps:
step 1, synthesizing a ZIF-67 nano polyhedron by adopting a simple room temperature precipitation method;
step 2, taking the ZIF-67 nano polyhedron obtained in the step 1 as a template and adding thioacetamide into the template and a cobalt source, and then reacting by adopting a solvothermal method to prepare a precursor; the molar ratio of the ZIF-67 nano polyhedron to the thioacetamide is 1: 1-5;
step 3, putting the precursor obtained in the step 2 in an inert atmosphere for heat treatment to obtain hollow polyhedral Co3S4。
4. MOFs derived hollow polyhedrons Co according to claim 33S4The method is characterized in that in the step 1, the synthesis of the ZIF-67 nano polyhedron by adopting a simple room temperature precipitation method specifically comprises the following steps: weighing 4mmol of cobalt nitrate hexahydrate and 16mmol of 2-methylimidazole, respectively dissolving in 100mL of methanol, and uniformly mixing to form a cobalt nitrate solution and a 2-methylimidazole solution; rapidly pouring the 2-methylimidazole solution into the nitre under magnetic stirringAnd (3) magnetically stirring in the acid cobalt solution for 30min, repeatedly washing with absolute ethyl alcohol for three times, performing vacuum filtration, and drying at 50 ℃ for 12h to obtain the ZIF-67 nano polyhedron.
5. MOFs derived hollow polyhedrons Co according to claim 43S4The method is characterized in that in the step 2, the precursor prepared by adopting a solvothermal method reaction is specifically as follows: dispersing ZIF-67 nano polyhedron and thioacetamide in ethanol, vulcanizing in a reaction kettle at 90-150 ℃ for 2-12 h, washing with deionized water and ethanol, and finally vacuum drying at 50 ℃ for 12h to obtain the precursor.
6. MOFs derived hollow polyhedrons Co according to claim 53S4The method is characterized in that in the step 3, the heat treatment of the precursor obtained in the step 2 in an inert atmosphere comprises the following steps: putting the precursor in a tube furnace, heating to 300-400 ℃ at the speed of 2-5 ℃/min under the protection of nitrogen or argon atmosphere, carrying out heat treatment for 1-6 h, and collecting the product to obtain the hollow polyhedral Co3S4。
7. Hollow polyhedral Co derived from MOFs according to any of claims 1-23S4Characterized by a hollow polyhedron Co3S4The method is applied to the field of energy storage.
8. MOFs-derived hollow polyhedrons Co according to claim 73S4Wherein the stored energy is lithium-sulfur battery electrochemical stored energy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110866496.0A CN113501552A (en) | 2021-07-29 | 2021-07-29 | MOFs-derived hollow polyhedrons Co3S4And preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110866496.0A CN113501552A (en) | 2021-07-29 | 2021-07-29 | MOFs-derived hollow polyhedrons Co3S4And preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113501552A true CN113501552A (en) | 2021-10-15 |
Family
ID=78015187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110866496.0A Pending CN113501552A (en) | 2021-07-29 | 2021-07-29 | MOFs-derived hollow polyhedrons Co3S4And preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113501552A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114506876A (en) * | 2021-12-30 | 2022-05-17 | 杭州电子科技大学 | Preparation method and application of hollow open-pore nanocube cobaltosic sulfide material |
| CN114566627A (en) * | 2022-03-03 | 2022-05-31 | 北京理工大学 | Co3S4Preparation method of-CoN @ NC sodium ion electrode material |
| CN115274310A (en) * | 2022-08-10 | 2022-11-01 | 桂林电子科技大学 | Polyhedral-structure cobalt sulfide-loaded NiGa-LDH electrode material and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017143549A1 (en) * | 2016-02-25 | 2017-08-31 | 东莞市迈科科技有限公司 | Sulphur-carbon composite and preparation method therefor, electrode material and lithium-sulphur battery containing sulphur-carbon composite |
| CN109461906A (en) * | 2018-09-30 | 2019-03-12 | 昆明理工大学 | A kind of preparation method of lithium sulfur battery anode material |
| CN109473651A (en) * | 2018-11-09 | 2019-03-15 | 扬州大学 | By ZIF-67 derivative compounds metal sulfide Co in pairs8FeS8The method of/N-C polyhedron nano material |
| CN110310838A (en) * | 2019-07-03 | 2019-10-08 | 安徽师范大学 | A kind of hollow nanocages composite material and preparation method and application |
| CN110380062A (en) * | 2019-07-16 | 2019-10-25 | 运城学院 | The preparation method of the difunctional VPO catalysts of sulfur doping based on ZIF-67 and conductive graphene |
| CN110586160A (en) * | 2019-09-20 | 2019-12-20 | 济南大学 | Preparation method of cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst |
| CN111370707A (en) * | 2020-03-17 | 2020-07-03 | 东北大学秦皇岛分校 | Cobalt sulfide-based composite material and preparation method and application thereof |
| CN111924887A (en) * | 2020-07-20 | 2020-11-13 | 北京科技大学 | Preparation method of micron cobalt disulfide composite material |
| CN113161527A (en) * | 2021-04-23 | 2021-07-23 | 陕西科技大学 | Preparation method and application of MOFs-derived cobalt sulfide particle composite carbon material |
-
2021
- 2021-07-29 CN CN202110866496.0A patent/CN113501552A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017143549A1 (en) * | 2016-02-25 | 2017-08-31 | 东莞市迈科科技有限公司 | Sulphur-carbon composite and preparation method therefor, electrode material and lithium-sulphur battery containing sulphur-carbon composite |
| CN109461906A (en) * | 2018-09-30 | 2019-03-12 | 昆明理工大学 | A kind of preparation method of lithium sulfur battery anode material |
| CN109473651A (en) * | 2018-11-09 | 2019-03-15 | 扬州大学 | By ZIF-67 derivative compounds metal sulfide Co in pairs8FeS8The method of/N-C polyhedron nano material |
| CN110310838A (en) * | 2019-07-03 | 2019-10-08 | 安徽师范大学 | A kind of hollow nanocages composite material and preparation method and application |
| CN110380062A (en) * | 2019-07-16 | 2019-10-25 | 运城学院 | The preparation method of the difunctional VPO catalysts of sulfur doping based on ZIF-67 and conductive graphene |
| CN110586160A (en) * | 2019-09-20 | 2019-12-20 | 济南大学 | Preparation method of cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst |
| CN111370707A (en) * | 2020-03-17 | 2020-07-03 | 东北大学秦皇岛分校 | Cobalt sulfide-based composite material and preparation method and application thereof |
| CN111924887A (en) * | 2020-07-20 | 2020-11-13 | 北京科技大学 | Preparation method of micron cobalt disulfide composite material |
| CN113161527A (en) * | 2021-04-23 | 2021-07-23 | 陕西科技大学 | Preparation method and application of MOFs-derived cobalt sulfide particle composite carbon material |
Non-Patent Citations (2)
| Title |
|---|
| JIAN WEI ET AL.: "Porous carbon/Co3S4 hollow polyhedron as sulfur carrier to enhance cyclic stability for lithium-sulfur batteries", FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES, pages 1 - 5 * |
| 商梦莉等: "金属有机骨架 ZIF-67 材料的合成及微结构调控研究", 人工晶体学报, vol. 48, no. 12, pages 2229 - 2231 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114506876A (en) * | 2021-12-30 | 2022-05-17 | 杭州电子科技大学 | Preparation method and application of hollow open-pore nanocube cobaltosic sulfide material |
| CN114566627A (en) * | 2022-03-03 | 2022-05-31 | 北京理工大学 | Co3S4Preparation method of-CoN @ NC sodium ion electrode material |
| CN114566627B (en) * | 2022-03-03 | 2023-11-28 | 北京理工大学 | Co (cobalt) 3 S 4 Preparation method of-CoN@NC sodium ion electrode material |
| CN115274310A (en) * | 2022-08-10 | 2022-11-01 | 桂林电子科技大学 | Polyhedral-structure cobalt sulfide-loaded NiGa-LDH electrode material and preparation method and application thereof |
| CN115274310B (en) * | 2022-08-10 | 2023-06-02 | 桂林电子科技大学 | Polyhedral cobalt sulfide loaded NiGa-LDH electrode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Preparation of porous ZnO/ZnFe2O4 composite from metal organic frameworks and its applications for lithium ion batteries | |
| CN113501552A (en) | MOFs-derived hollow polyhedrons Co3S4And preparation method and application thereof | |
| CN111293300B (en) | Zinc-cobalt sulfide/carbon nano anode material and preparation method thereof | |
| Shen et al. | Metal-organic frameworks (MOFs) and their derivative as electrode materials for lithium-ion batteries | |
| CN109244427B (en) | Preparation method of carbon-coated zinc sulfide loaded graphene as potassium ion battery cathode | |
| CN113725432B (en) | ZIF-67 and preparation method of cobalt selenide/carbon electrode material derived from ZIF-67 | |
| CN109473651B (en) | Synthesis of bimetallic sulfide Co by ZIF-67 derivatization8FeS8Method for preparing/N-C polyhedral nano material | |
| Ren et al. | Flower-like bimetal Ni/Co-based metal–organic-framework materials with adjustable components toward high performance solid-state supercapacitors | |
| CN110518213A (en) | A kind of porous silicon-carbon nano tube compound material and its preparation method and application | |
| CN103855385B (en) | A kind of preparation method with the micro nano structure cobaltosic oxide of high rate capability | |
| CN112436145A (en) | Preparation method and application of MOF-74 derived carbon-coated cobalt-nickel bimetallic sulfide for sodium ion battery negative electrode | |
| CN107611425B (en) | Fusiform zinc ferrite/carbon lithium ion battery nano composite negative electrode material and preparation method and application thereof | |
| CN111403712A (en) | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery | |
| CN111785943A (en) | Preparation method and application of NPC @ C/S composite material | |
| CN111082050A (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN108336292B (en) | Electrode and preparation method thereof, carbon nano tube and application thereof | |
| CN110817881B (en) | Silicon-transition metal silicide nano composite material and preparation method and application thereof | |
| CN113292105A (en) | Carbon and nitrogen coated Fe0.4Co0.6S2Preparation method and application of @ NC hollow nano box | |
| CN112010361A (en) | Preparation method for synthesizing heteroatom-doped nickel sulfide with various shapes by using metal organic framework | |
| CN109273703B (en) | Graphene/sulfur/nickel hydroxide self-supporting composite material for lithium-sulfur battery positive electrode and preparation method thereof | |
| CN112803017B (en) | Hollow spherical bimetal chalcogenide, preparation method thereof and sodium battery cathode | |
| CN110364365B (en) | Method for preparing single-layer porous cobalt oxyhydroxide nanosheet by electrochemical oxidation method | |
| CN114349071A (en) | Synthesis method of high-nickel cobalt-rich cathode material with single crystal core-shell structure | |
| CN111573745B (en) | Preparation method of nickel-cobalt sulfide and graphene composite material rich in elemental sulfur | |
| CN109473634A (en) | Solid phase heat together synthesizes two selenizing molybdenums/N doping carbon-point method |
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 |