CN111313111A - Heteroatom-doped carbon/CoS based on metal organic framework derivation2Functional material and application thereof - Google Patents
Heteroatom-doped carbon/CoS based on metal organic framework derivation2Functional material 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 28
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 24
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 13
- 239000012924 metal-organic framework composite Substances 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 3
- 238000009795 derivation Methods 0.000 claims abstract description 3
- 238000004073 vulcanization Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000000047 product Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000002131 composite material Substances 0.000 claims description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 23
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 22
- 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 22
- 238000002156 mixing Methods 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 22
- 229910052573 porcelain Inorganic materials 0.000 claims description 21
- 239000002033 PVDF binder Substances 0.000 claims description 20
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000003828 vacuum filtration Methods 0.000 claims description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 5
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 5
- 238000009987 spinning Methods 0.000 claims description 5
- 229940045136 urea Drugs 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000004873 anchoring Methods 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010041 electrostatic spinning Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 229920005594 polymer fiber Polymers 0.000 claims description 2
- 150000001721 carbon Chemical class 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052744 lithium Inorganic materials 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 8
- 229920001021 polysulfide Polymers 0.000 abstract description 8
- 239000005077 polysulfide Substances 0.000 abstract description 8
- 150000008117 polysulfides Polymers 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 24
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 14
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000011888 foil Substances 0.000 description 13
- 229920002239 polyacrylonitrile Polymers 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 8
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 7
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000005086 pumping Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910001216 Li2S Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000013094 zinc-based metal-organic framework Substances 0.000 description 1
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Classifications
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- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses heteroatom doped carbon/CoS based on metal organic framework derivation2Functional materials and their use, wherein hetero atoms are doped with carbon/CoS2The functional material is porous CoS obtained by high-temperature carbonization and gas-phase vulcanization treatment of a designed and synthesized metal-organic framework composite structure2a/C functional material. Heteroatom doped carbon/CoS of the invention2The functional material has excellent chemical adsorption effect on polysulfide, namely Keesom effect of heteroatom doped carbon, and CoS2The Lewis acid base action of (1); in addition, the porous carbon structure also has physical barrier and adsorption effects, and the conductive carbon can promote reaction kinetics to activate dead sulfur and dead lithium, so that the loss of active substances is reduced, and the performance of the battery is improved.
Description
Technical Field
The invention relates to heteroatom-doped carbon/CoS based on metal organic framework derivation2Functional materials and applications thereof.
Background
The rapid progress of modern technology has led to a great increase in the dependence of people on energy. The traditional fossil energy is increasingly exhausted, and causes serious environmental pollution. Therefore, the development and utilization of novel environment-friendly energy sources are urgent. And clean energy such as wind energy, water energy, geothermal energy and the like are not uniformly distributed in time and space, and the produced power resources cannot be directly used in a grid-connected mode, so that the development of the clean energy does not achieve the expected effect. In order to fully utilize and generally popularize such clean energy, it is very important to adopt an effective electric energy storage mode. The electrochemical energy storage system has the characteristics of light weight, portability and high energy density, and is very suitable for long-term storage and instant temporary storage of energy, thereby playing an important role in an electric energy storage system.
The lithium-sulfur battery is a battery system with metal lithium as a negative electrode and elemental sulfur as a positive electrode, and the system has extremely high theoretical specific capacity and mass specific energy which respectively reach 1675mAh g-1And 2600Wh kg-1. The lithium-sulfur battery realizes the conversion of chemical energy and electric energy through the oxidation-reduction reaction between metal lithium and elemental sulfur and through the breakage/generation of S-S bonds and electron transfer. Separators are an important component in lithium sulfur batteries, and are generally composite films of polypropylene (PP), Polyethylene (PE), or both, which serve as a separation layer between a cathode and an anode in a battery to prevent short circuits. It was found that the sulfur positive electrode formed long-chain polysulfides (Li) that were readily soluble in the electrolyte during discharge2SnN is more than or equal to 4 and less than or equal to 8). Long-chain polysulfides pass through the separator under a concentration gradient and are difficult to completely migrate back to the positive electrode in subsequent reactions, resulting in loss of active species. Secondly, long-chain polysulfides react with metallic lithium to produce poorly soluble Li2S2Or Li2S and deposits on the surface of the negative electrode, hindering lithium ion conduction. Furthermore, the reaction causes corrosion of the surface of metallic lithium, is not favorable for stable formation of a Solid Electrolyte Interface (SEI) film, and deteriorates growth of lithium dendrites, increases the possibility of penetration of the lithium dendrites through a separator, and poses a threat to the safety of a battery. These problems have prevented the widespread use of lithium sulfur batteries.
Disclosure of Invention
In view of the above problems, the present invention provides a method for preparing heteroatom-doped carbon/CoS with different structures by structural design based on metal-organic framework as precursor and subsequent derivatization2Functional material (CoS)2and/C) and the application thereof in the modification of the lithium-sulfur battery diaphragm. Heteroatom doped carbon/CoS of the invention2The functional material has excellent chemical adsorption effect on polysulfide, namely Keesom effect of heteroatom doped carbon, and CoS2The Lewis acid base action of (1); in addition, the porous carbon structure also has physical barrier and adsorption effects, and the conductive carbon can promote reaction kinetics to activate dead sulfur and dead lithium, so that the loss of active substances is reduced, and the performance of the battery is improved.
The invention is based on heteroatom doped carbon/CoS derived from metal organic framework2The functional material is prepared by designing a composite structure of a synthetic metal organic framework, and then carrying out high-temperature carbonization and gas-phase vulcanization treatment to obtain the porous CoS2a/C functional material.
The metal organic framework composite structure comprises a ZIF8/ZIF67 composite structure, an LDH/ZIF67 composite structure, a Polymer/ZIF67 composite structure and the like.
The invention is based on heteroatom doped carbon/CoS derived from metal organic framework2The functional material is prepared by the method comprising the following steps:
step 1: preparation of metal-organic framework composite structure
1a, taking ZIF8 (zinc-based metal organic framework) as a precursor, and coating a layer of ZIF67 (cobalt-based metal organic framework) on the surface of the precursor to obtain a ZIF8/ZIF67 composite structure;
1b, taking double hydroxide (LDH) as a precursor, and anchoring and growing ZIF67 on the surface of the precursor by utilizing the unsaturated coordination state of metal ions on the surface of the precursor to obtain an LDH/ZIF67 composite structure;
1c, coating cobalt salt inside the Polymer fiber by using an electrostatic spinning technology, and then growing ZIF67 in situ through the reaction of cobalt ions and an organic ligand to obtain a Polymer/ZIF67 composite structure.
Step 2: CoS2Structure of/CPreparation of
Placing the metal organic framework composite structure obtained in the step 1 into a crucible, then placing the crucible into a tube furnace, heating to 700-900 ℃, preserving heat for 2-6h, and naturally cooling to obtain a carbonized product; weighing proper amount of carbonized product and sublimed sulfur in two porcelain boats respectively, placing the porcelain boats in a tube furnace at a distance of 1cm, heating to 400-2A structure of/C.
The metal organic framework composite structure comprises a ZIF8/ZIF67 composite structure, an LDH/ZIF67 composite structure, a Polymer/ZIF67 composite structure and the like. The product is derived from ZIF8/ZIF67 and named as CoS2The structure of/C-1, which is derived from LDH/ZIF67, is named CoS2The structure of/C-2, derived from Polymer/ZIF67, was designated CoS2/C-3。
In the step 2, the mass ratio of the sublimed sulfur to the carbonized product is 1-10: 1, the heating rate is 2-10 ℃/min.
Further, step 1a comprises the steps of:
1 a-1: respectively dissolving a proper amount of zinc nitrate hexahydrate and dimethylimidazole in 100mL of methanol solution to prepare solution A and solution B; slowly dripping the solution B into the solution A, keeping stirring and reacting for 10-36h, and vacuum-drying the reaction product at 50-80 ℃ for 6-12h to obtain ZIF 8; wherein the mass ratio of the dimethyl imidazole to the zinc nitrate hexahydrate is 1-5: 1.
1 a-2: dispersing a certain amount of ZIF8 in 100mL of methanol, adding a proper amount of cobalt nitrate hexahydrate and dimethyl imidazole, stirring and reacting for 10-36h at room temperature, and vacuum drying a reaction product for 6-12h at 50-80 ℃ to obtain a ZIF8/ZIF67 composite structure; wherein the mass ratio of the dimethyl imidazole to the cobalt nitrate hexahydrate is 1-5: 1; the mass ratio of ZIF8 to cobalt nitrate hexahydrate is 1: 7 to 20.
Further, step 1b comprises the steps of:
1 b-1: dissolving cobalt chloride hexahydrate, aluminum chloride hexahydrate and urea in deionized water, heating to 70-100 ℃, keeping stirring for reacting for 12-48h, centrifuging, collecting a product, and performing vacuum drying at 50-80 ℃ for 6-12h to obtain LDH; wherein the mass ratio of cobalt chloride hexahydrate, aluminum chloride hexahydrate and urea is 2-6: 1: 1.5 to 4.5.
1 b-2: dispersing a certain amount of LDH in methanol, adding a proper amount of cobalt nitrate hexahydrate and dimethylimidazole, keeping stirring at room temperature for reaction for 0.5-4h, and drying a reaction product at 60-80 ℃ for 8-24h to obtain an LDH/ZIF67 composite structure; wherein the mass ratio of the dimethyl imidazole to the cobalt nitrate hexahydrate is 1-6: 1, the mass ratio of LDH to cobalt nitrate hexahydrate is 1: 6 to 18.
Further, step 1c comprises the steps of:
1 c-1: dissolving a certain amount of polymer and cobalt nitrate hexahydrate in DMF, uniformly stirring at room temperature, putting the mixture into a 10ml syringe, fixing the syringe on an injection pump, carrying out pressure spinning to obtain a polymer/cobalt salt membrane, and putting the membrane in a vacuum oven at 50-80 ℃ for 6-12 hours;
the polymer comprises polyacrylonitrile, polyurethane or polyvinylidene fluoride and the like, and the mass ratio of the polymer to the cobalt nitrate hexahydrate is 1: 1 to 4.
The voltage and flow rate applied during pressure spinning are respectively 13-20kV and 0.02-0.5mm min-1(ii) a The distance between the injector nozzle and the collector is 10-18 cm.
1 c-2: immersing the obtained Polymer/cobalt salt membrane into a methanol solution of dimethyl imidazole, standing and reacting for 10-24h to obtain a Polymer/ZIF67 composite structure; the concentration of the dimethyl ether imidazole methanol solution is 2-10 g/L.
The invention is based on heteroatom doped carbon/CoS derived from metal organic framework2Use of functional materials doped with carbon/CoS with said heteroatoms2Functional material (CoS for short)2and/C) modifying the diaphragm material of the lithium-sulfur battery to improve the battery performance.
Further, CoS is prepared2and/C and a binder (polyvinylidene fluoride and PVDF) are mixed and loaded on the surface of the lithium-sulfur battery diaphragm. The method specifically comprises the following steps:
adding CoS2Mixing with binder at certain ratio in N-methylpyrrolidone (NMP) solution, ball milling, and vacuum filteringAnd (3) pumping the lithium-sulfur battery diaphragm, and drying in vacuum to obtain the modified diaphragm.
The membrane material is preferably a commercial Celgard 2325 membrane (the composition of which is polypropylene/polyethylene/polypropylene, sandwich structure, abbreviated PP/PE/PP).
Wherein the mass ratio of CoS2C: PVDF (1-10): 1, mass ratio NMP: CoS220-80 parts of/C: 1, the ball milling speed is 200-600 r/min, and the binder is PVDF.
The above heteroatom doped carbon/CoS2Structure (CoS)2The raw materials involved in the modification of the lithium-sulfur battery separator are all commercially available.
Compared with the prior art, the invention has the beneficial effects that:
1) prepared CoS2the/C structure has a porous structure, provides enough space for accommodating electrolyte and hindering polysulfide diffusion, and is beneficial to performance improvement. Heteroatom doping and active CoS2Has chemical adsorption effect on polysulfide. The presence of conductive carbon promotes reaction kinetics;
2) the diaphragm preparation method is simple and convenient to operate. Prepared CoS2the/C @ Celgard can effectively inhibit the shuttling effect of polysulfide, avoid the loss of active substances, and improve the cycle and rate performance of the battery.
Drawings
FIG. 1: CoS2SEM image of/C-1 @ Celgard. As can be seen in FIG. 1, the CoS2the/C-1 modified layer uniformly covered the surface of the commercial separator.
FIG. 2: using CoS2Cycling performance of/C-1 @ Celgard separator cell. As can be seen from FIG. 2, CoS is used2After 100 cycles of the/C-1 @ Celgard diaphragm cell at a current density of 0.5C, about 560mAhg of the cell still remains-1Specific discharge capacity of (2).
FIG. 3: CoS2SEM image of/C-2 @ Celgard. As can be seen in FIG. 3, the CoS2the/C-2 modified layer uniformly covered the surface of the commercial separator.
FIG. 4: using CoS2Cycling performance of/C-2 @ Celgard separator cell. From the figure4 it can be seen that CoS is used2After 100 cycles of the/C-2 @ Celgard diaphragm cell at a current density of 0.5C, about 670mAhg of the cell still remains-1Specific discharge capacity of (2).
FIG. 5: CoS2SEM image of/C-3 @ Celgard. As can be seen in FIG. 5, CoS2the/C-3 modified layer uniformly covered the surface of the commercial separator.
FIG. 6: using CoS2Cycling performance of/C-3 @ Celgard separator cell. As can be seen from FIG. 6, CoS is used2After 100 cycles of the/C-3 @ Celgard diaphragm cell at a current density of 0.5C, about 563mAhg still remained-1Specific discharge capacity of (2).
FIG. 7: SEM images of commercial Celgard membranes. As can be seen in fig. 7, many small pores are present in the surface of the commercial membrane.
FIG. 8: cycling performance of a commercial Celgard separator cell was used. As can be seen in fig. 8, after 100 cycles at 0.5C using the Celgard separator cell, there was only about 270mAhg-1Specific discharge capacity of (2).
Detailed Description
Example 1:
1. preparation of ZIF8/ZIF67 composite structures
Taking the mass ratio of 1: respectively dissolving zinc nitrate hexahydrate and dimethylimidazole of 1 in 100ml of methanol solution to form solution A and solution B, slowly dropwise adding the solution B into the solution A, keeping stirring for reacting for 24 hours, and then performing vacuum drying at 60 ℃ for 12 hours to obtain ZIF 8; dispersing a certain amount of ZIF8 in 100ml of methanol, and adding a mixture of ZIF8 and methanol in a mass ratio of 1: 1 is cobalt nitrate hexahydrate and dimethyl imidazole, and the mass ratio of ZIF8 to cobalt nitrate hexahydrate is 1: and 7, keeping stirring at room temperature for reaction for 24 hours, and then performing vacuum drying at 60 ℃ for 12 hours to obtain a ZIF8/ZIF67 composite structure.
2. Preparation of CoS2Structure of/C-1
Putting the product ZIF8/ZIF67 in a crucible, then putting the crucible in a tube furnace, heating to 700 ℃, keeping the temperature for 4h, and naturally cooling to obtain a carbonized product, wherein the heating rate is 4 ℃/min; weighing the components in a mass ratio of 1: 5, respectively placing the carbonized product and the sublimed sulfur in two porcelain boats, placing the porcelain boats in a tube furnace at a distance of 1cm, heating to 400 ℃, keeping the temperature for 2 hours, and naturally cooling to obtain the product, wherein the heating rate is 2 ℃/min.
3. Preparation of CoS2Modified diaphragm of/C-1 @ Celgard
Taking the mass ratio of 4: 1 CoS2Solution of/C-1 and PVDF in NMP of a defined mass ratio (mass ratio NMP: CoS)2NSCNHF ═ 20: 1) ball-milling and mixing at medium and low speed for 0.5h, wherein the rotation speed of the ball mill is 400 r/min, pumping the mixed solution on a Celgard 2325 diaphragm through a vacuum filtration device, and drying at 80 ℃ for 12h to obtain the modified diaphragm CoS2C-1@ Celgard. SEM images of the commercial separator and the results of the element distribution thereof are shown in fig. 1.
4. Assembled lithium-sulfur battery
Mixing elemental sulfur, SuperP and a binder PVDF in a mass ratio of 6: 3: 1, uniformly mixing, using NMP as a dispersing agent to prepare uniform black slurry, coating the slurry on an aluminum foil, and then putting the aluminum foil into a vacuum oven at 60 ℃ for drying for 12 hours to obtain the positive pole piece. Using a lithium plate as a negative electrode, and using the CoS obtained in the step 32And the button cell is assembled in a glove box under argon atmosphere by using a/C-1 @ Celgard as a diaphragm and a mixed solution of lithium bistrifluoromethanesulfonylimide (LiTFSI), 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) as an electrolyte. Button cells were tested by the wuhan blue testing system. Using CoS2The cycle for a lithium sulfur battery with/C-1 @ Celgard separator is given in FIG. 2.
Example 2:
1. preparation of ZIF8/ZIF67 structures
Taking the mass ratio of 1: respectively dissolving zinc nitrate hexahydrate and dimethylimidazole of 1 in 100ml of methanol solution to form solution A and solution B, slowly dropwise adding the solution B into the solution A, keeping stirring for reacting for 24 hours, and then performing vacuum drying at 60 ℃ for 12 hours to obtain ZIF 8; dispersing a certain amount of ZIF8 in 100ml of methanol, and adding a mixture of ZIF8 and methanol in a mass ratio of 1: 1 is cobalt nitrate hexahydrate and dimethyl imidazole, and the mass ratio of ZIF8 to cobalt nitrate hexahydrate is 1: 10, the reaction was kept stirred at room temperature for 24 hours, and then dried under vacuum at 60 ℃ for 12 hours to obtain ZIF8/ZIF 67.
2. Preparation of CoS2Structure of/C-1
Putting the product ZIF8/ZIF67 in a crucible, then putting the crucible in a tube furnace, heating to 900 ℃, preserving heat for 2 hours, and naturally cooling to obtain a carbonized product; weighing the components in a mass ratio of 1: 10, respectively placing the carbonized product and the sublimed sulfur in two porcelain boats, placing the porcelain boats in a tube furnace at a distance of 1cm, heating to 400 ℃, keeping the temperature for 4 hours, and naturally cooling to obtain the product, wherein the heating rate is 4 ℃/min.
3. Preparation of CoS2Modified diaphragm of/C-1 @ Celgard
Taking the mass ratio of 4: 1 CoS2Solution of/C-1 and PVDF in NMP of a defined mass ratio (mass ratio NMP: CoS)220/C-1: 1) performing ball milling and mixing for 1 hour at medium and low speed, wherein the rotating speed of the ball mill is 200 revolutions per minute; pumping the mixed solution on a Celgard 2325 diaphragm through a vacuum filtration device, and drying at 60 ℃ for 12h to obtain a modified diaphragm CoS2/C-1@Celgard。
4. Assembled lithium-sulfur battery
Mixing elemental sulfur, SuperP and a binder PVDF in a mass ratio of 6: 3: 1, uniformly mixing, using NMP as a dispersing agent to prepare uniform black slurry, coating the slurry on an aluminum foil, and then putting the aluminum foil into a vacuum oven at 60 ℃ for drying for 12 hours to obtain the positive pole piece. Using a lithium plate as a negative electrode, and using the CoS obtained in the step 32The electrolyte is a mixed solution of lithium bistrifluoromethanesulfonylimide (LiTFSI), 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME). Button cell assembly was performed in a glove box under argon atmosphere. Button cells were tested by the wuhan blue testing system.
Example 3:
1. preparation of LDH/ZIF67
Taking the mass ratio of 2: 1: 1.5, dissolving cobalt chloride hexahydrate, aluminum chloride hexahydrate and urea in 500mL of deionized water, heating to 90 ℃, keeping stirring for reaction for 12 hours, centrifugally collecting a product, and performing vacuum drying for 6 hours at 80 ℃ to obtain LDH; dispersing a certain amount of LDH (LDH: cobalt nitrate hexahydrate-1: 6) in 100mL of methanol, adding a mixture of LDH and cobalt nitrate hexahydrate in a mass ratio of 2: 1, reacting the cobalt nitrate hexahydrate and the dimethyl imidazole for 0.5 to 4 hours under stirring at room temperature, and drying the reaction product for 8 hours at the temperature of 80 ℃ to obtain the LDH/ZIF 67.
2、CoS2Preparation of/C-2
Putting the product LDH/ZIF67 obtained in the step (1) into a porcelain boat, then putting the porcelain boat into a tube furnace, carrying out programmed heating to 900 ℃, carrying out heat preservation for 2h at the heating rate of 5 ℃/min, and naturally cooling to obtain a carbonized product; weighing the components in a mass ratio of 6: 1, respectively putting the sublimed sulfur and the carbonized product in two porcelain boats, putting the porcelain boats in a tube furnace, heating to 400 ℃, keeping the temperature for 2 hours, wherein the heating rate is 2 ℃/min, and naturally cooling to obtain CoS2/C-2。
3、CoS2Preparation of/C-2 @ Celgard modified diaphragm
Taking the mass ratio of 9: 1 CoS2NMP (mass ratio of NMP to NSPCF @ CoS) in a certain mass ratio of/C-2 and PVDF215: 1) and carrying out ball milling and mixing for 1 hour at a medium and low speed, wherein the rotating speed of the ball mill is 200 revolutions per minute. Loading the mixed solution on a Celgard 2325 diaphragm through a vacuum filtration device, and drying at 60 ℃ for 8h to obtain a modified diaphragm CoS2C-2@ Celgard. FIG. 3 shows a commercial separator and CoS2SEM image of/C-2 @ Celgard modified membrane.
4. Assembled lithium-sulfur battery
Mixing elemental sulfur, SuperP and a binder PVDF in a mass ratio of 6: 3: 1, uniformly mixing, using NMP as a dispersing agent to prepare uniform black slurry, coating the uniform black slurry on an aluminum foil by using a film drawing device, and then drying the aluminum foil in a vacuum oven at 60 ℃ for 12 hours to obtain a positive pole piece; using lithium plate as cathode and CoS obtained in the third step2And the button cell assembly is carried out in a glove box under an argon atmosphere by taking a/C-2 @ Celgard as a diaphragm and a mixed solution of lithium bistrifluoromethanesulfonylimide (LiTFSI), 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) as an electrolyte. Button cells were tested by the wuhan blue testing system. Using CoS2The cycle for a lithium sulfur battery with a/C-2 @ Celgard separator is given in FIG. 4.
Example 4:
1. preparation of LDH/ZIF67
Taking the mass ratio of 4: 1: 3.5, dissolving cobalt chloride hexahydrate, aluminum chloride hexahydrate and urea in 500mL of deionized water, heating to 95 ℃, keeping stirring for reaction for 12 hours, centrifugally collecting a product, and performing vacuum drying for 6 hours at 80 ℃ to obtain LDH; a certain amount of CoAlLDH (LDH: cobalt nitrate hexahydrate of 1: 10 by mass) was dispersed in 100mL of methanol, and a solution of CoAlLDH (LDH: cobalt nitrate hexahydrate of 4: 1, reacting the cobalt nitrate hexahydrate and the dimethyl imidazole for 2 hours under stirring at room temperature, and drying the reaction product for 8 hours at 80 ℃ to obtain the LDH/ZIF 67.
2、CoS2Preparation of/C-2
Putting the product LDH/ZIF67 obtained in the step (1) into a porcelain boat, then putting the porcelain boat into a tube furnace, carrying out programmed heating to 800 ℃, carrying out heat preservation for 3h at the heating rate of 4 ℃/min, and naturally cooling to obtain a carbonized product; weighing 10 parts of: 1, respectively putting the sublimed sulfur and the carbonized product in two porcelain boats, putting the porcelain boats in a tube furnace, heating to 600 ℃, keeping the temperature for 3 hours, wherein the heating rate is 3 ℃/min, and naturally cooling to obtain CoS2/C-2。
3、CoS2Preparation of/C-2 @ Celgard modified diaphragm
Taking the mass ratio of 7: 1 CoS2(ii) a combination of/C-2 and PVDF in a constant mass of NMP (mass ratio NMP: CoS)225/C-2: 1) and carrying out ball milling and mixing for 1.5h at a medium-low speed, wherein the rotating speed of the ball mill is 250 r/min. Loading the mixed solution on a Celgard 2325 diaphragm through a vacuum filtration device, and drying at 60 ℃ for 8h to obtain a modified diaphragm CoS2/C-2@Celgard。
4. Assembled lithium-sulfur battery
Mixing elemental sulfur, SuperP and a binder PVDF in a mass ratio of 6: 3: 1, uniformly mixing, using NMP as a dispersing agent to prepare uniform black slurry, coating the uniform black slurry on an aluminum foil by using a film drawing device, and then drying the aluminum foil in a vacuum oven at 60 ℃ for 12 hours to obtain a positive pole piece; using lithium plate as cathode and CoS obtained in the third step2The electrolyte is a mixed solution of lithium bistrifluoromethanesulfonylimide (LiTFSI), 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME). Button cell assembly was performed in a glove box under argon atmosphere. Button cells were tested by the wuhan blue testing system.
Example 5:
1. preparation of PAN/ZIF67
Polyacrylonitrile (PAN) and cobalt nitrate hexahydrate (mass ratio 1: 1) were dissolved in 10mL of DMF. After stirring well at room temperature, the mixture was put into a 10ml syringe, fixed on a syringe pump, and applied with electricityThe pressure and the flow are respectively 15kV and 0.2mm min-1Spinning with the distance between the injector nozzle and the collector being 16cm to obtain a polymer/cobalt salt film, and placing the polymer/cobalt salt film in a vacuum oven at 80 ℃ for 6 hours; and (3) immersing the obtained polymer/cobalt salt membrane into a methanol solution of dimethyl imidazole with the concentration of 2g/L, and standing for reaction for 10 hours to obtain a PAN/ZIF67 composite structure.
2、CoS2Preparation of/C-3
And (3) placing the product PAN/ZIF67 in a crucible, then placing in a tube furnace, heating to 700 ℃, preserving heat for 2h, and naturally cooling to obtain a carbonized product. Weighing the components in a mass ratio of 1: 5, respectively placing the carbonized product and the sublimed sulfur in two porcelain boats, placing the porcelain boats in a tube furnace, keeping the distance between the porcelain boats at 1cm, heating to 400 ℃, and keeping the temperature for 4 hours, wherein the heating rate is 3 ℃/min. Naturally cooling to obtain the product.
3. Preparation of CoS2Modified diaphragm of/C-3 @ Celgard
Taking the mass ratio of 4: 1 CoS2Solution of/C-3 and PVDF in NMP of a certain mass (mass ratio NMP: CoS)220/C-3: 1) performing ball milling and mixing for 1 hour at medium and low speed, wherein the rotating speed of the ball mill is 200 revolutions per minute; pumping the mixed solution on a Celgard 2325 diaphragm through a vacuum filtration device, and drying at 60 ℃ for 12h to obtain a modified diaphragm CoS2C-3@ Celgard. The topography of the diaphragm is shown in figure 5.
4. Assembled lithium-sulfur battery
Mixing elemental sulfur, SuperP and a binder PVDF in a mass ratio of 6: 3: 1, uniformly mixing, using NMP as a dispersing agent to prepare uniform black slurry, coating the slurry on an aluminum foil, and then putting the aluminum foil into a vacuum oven at 60 ℃ for drying for 12 hours to obtain the positive pole piece. Using a lithium plate as a negative electrode, and using the CoS obtained in the step 32The electrolyte is a mixed solution of lithium bistrifluoromethanesulfonylimide (LiTFSI), 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME). Button cell assembly was performed in a glove box under argon atmosphere. Button cells were tested by the wuhan blue testing system. Assembly CoS2The cycle performance of the lithium sulfur battery with the/C-3 @ Celgard separator is given in FIG. 6.
Example 6:
1. preparation of PAN/ZIF67
Dissolving Polyacrylonitrile (PAN) and cobalt nitrate hexahydrate (mass ratio of 1: 2) in 10mL of DMF, stirring at room temperature, placing the mixture into a 10mL syringe, fixing on an injection pump, and applying voltage and flow rate of 18kV and 0.1mm min respectively-1Spinning with the distance between the injector nozzle and the collector of 17cm to obtain a polymer/cobalt salt film, and placing the polymer/cobalt salt film in a vacuum oven at 80 ℃ for 6 hours; and (3) immersing the obtained polymer/cobalt salt membrane into a methanol solution of dimethyl imidazole with the concentration of 5g/L, standing and reacting for 12 hours to obtain a PAN/ZIF67 composite structure.
2、CoS2Preparation of/C-3
Putting the product PAN/ZIF67 into a crucible, then putting the crucible into a tube furnace, heating to 800 ℃, preserving heat for 3 hours, naturally cooling to obtain a carbonized product; weighing the components in a mass ratio of 1: and (8) respectively placing the carbonized product and the sublimed sulfur in two porcelain boats, placing the porcelain boats in a tube furnace at a distance of 1cm, heating to 400 ℃, keeping the temperature for 4 hours, and naturally cooling to obtain the product, wherein the heating rate is 2 ℃/min.
3. Preparation of CoS2Modified diaphragm of/C-3 @ Celgard
Taking the mass ratio of 7: 1 CoS2Solution of/C-3 and PVDF in NMP of a certain mass (mass ratio NMP: CoS)225/C-3: 1) performing ball milling and mixing for 1.5h at medium and low speed, wherein the rotating speed of the ball mill is 250 revolutions per minute; pumping the mixed solution on a Celgard 2325 diaphragm through a vacuum filtration device, and drying at 60 ℃ for 12h to obtain a modified diaphragm CoS2/C-3@Celgard。
4. Assembled lithium-sulfur battery
Mixing elemental sulfur, SuperP and a binder PVDF in a mass ratio of 6: 3: 1, uniformly mixing, using NMP as a dispersing agent to prepare uniform black slurry, coating the slurry on an aluminum foil, and then putting the aluminum foil into a vacuum oven at 60 ℃ for drying for 12 hours to obtain the positive pole piece. Using a lithium plate as a negative electrode, and using the CoS obtained in the step 32The electrolyte is a mixed solution of lithium bistrifluoromethanesulfonylimide (LiTFSI), 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME). Button cell in glove box under argon atmosphereAnd (6) assembling. Button cells were tested by the wuhan blue testing system.
Comparative example:
mixing elemental sulfur, SuperP and a binder PVDF in a mass ratio of 7: 2: 1, uniformly mixing, using NMP as a dispersing agent to prepare uniform black slurry, and coating the slurry on an aluminum foil. And then putting the anode plate into a vacuum oven at 60 ℃ for drying for 12 hours to obtain the anode plate. A lithium plate is taken as a negative electrode, a commercial Celgard diaphragm is taken as a diaphragm, and a mixed solution of lithium bistrifluoromethanesulfonylimide (LiTFSI), 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) is taken as an electrolyte. Button cell assembly was performed in a glove box under argon atmosphere. Button cells were tested by the wuhan blue testing system. SEM images of commercial Celgard membranes are shown in fig. 7. The cycle for a lithium sulfur battery using a commercial Celgard separator is given in fig. 8.
Claims (10)
1. Heteroatom-doped carbon/CoS based on metal organic framework derivation2Functional material, characterized in that:
the heteroatom doped carbon/CoS2The functional material is porous CoS obtained by high-temperature carbonization and gas-phase vulcanization treatment of a designed and synthesized metal-organic framework composite structure2a/C functional material;
the metal organic framework composite structure comprises a ZIF8/ZIF67 composite structure, an LDH/ZIF67 composite structure or a Polymer/ZIF67 composite structure.
2. The heteroatom-doped carbon/CoS according to claim 12The functional material is characterized by being prepared by a method comprising the following steps:
step 1: preparation of metal-organic framework composite structure
1a, coating a layer of ZIF67 on the surface of a precursor ZIF8 to obtain a ZIF8/ZIF67 composite structure;
1b, taking double hydroxide LDH as a precursor, and anchoring and growing ZIF67 on the surface of the double hydroxide LDH by utilizing the unsaturated coordination state of metal ions on the surface of the double hydroxide LDH to obtain an LDH/ZIF67 composite structure;
1c, coating cobalt salt inside the Polymer fiber by using an electrostatic spinning technology, and then growing ZIF67 in situ through the reaction of cobalt ions and an organic ligand to obtain a Polymer/ZIF67 composite structure;
step 2: CoS2Preparation of the structure/C
Placing the metal organic framework composite structure obtained in the step 1 into a crucible, then placing the crucible into a tube furnace, heating to 700-900 ℃, preserving heat for 2-6h, and naturally cooling to obtain a carbonized product; weighing proper amount of carbonized product and sublimed sulfur in two porcelain boats respectively, placing the porcelain boats in a tube furnace at a distance of 1cm, heating to 400-2A structure of/C.
3. The heteroatom-doped carbon/CoS according to claim 22Functional material, characterized in that step 1a comprises the steps of:
1 a-1: respectively dissolving a proper amount of zinc nitrate hexahydrate and dimethylimidazole in a methanol solution to prepare a solution A and a solution B; slowly dripping the solution B into the solution A, keeping stirring and reacting for 10-36h, and vacuum-drying the reaction product at 50-80 ℃ for 6-12h to obtain ZIF 8;
1 a-2: dispersing a certain amount of ZIF8 in methanol, adding a proper amount of cobalt nitrate hexahydrate and dimethyl imidazole, stirring and reacting for 10-36h at room temperature, and vacuum drying the reaction product for 6-12h at 50-80 ℃ to obtain a ZIF8/ZIF67 composite structure.
4. The heteroatom-doped carbon/CoS according to claim 22Functional material, characterized in that step 1b comprises the steps of:
1 b-1: dissolving cobalt chloride hexahydrate, aluminum chloride hexahydrate and urea in deionized water, heating to 70-100 ℃, keeping stirring for reacting for 12-48h, centrifuging, collecting a product, and performing vacuum drying at 50-80 ℃ for 6-12h to obtain LDH;
1 b-2: dispersing a certain amount of LDH in methanol, adding a proper amount of cobalt nitrate hexahydrate and dimethylimidazole, keeping stirring at room temperature for reaction for 0.5-4h, and drying a reaction product at 60-80 ℃ for 8-24h to obtain an LDH/ZIF67 composite structure.
5. The heteroatom-doped carbon/CoS according to claim 22Functional material, characterized in that step 1c comprises the steps of:
1 c-1: dissolving a certain amount of polymer and cobalt nitrate hexahydrate in DMF, uniformly stirring at room temperature, putting the mixture into a 10ml syringe, fixing the syringe on an injection pump, carrying out pressure spinning to obtain a polymer/cobalt salt membrane, and putting the membrane in a vacuum oven at 50-80 ℃ for 6-12 hours;
1 c-2: and immersing the obtained Polymer/cobalt salt membrane into a methanol solution of dimethyl imidazole, standing and reacting for 10-24h to obtain a Polymer/ZIF67 composite structure.
6. The heteroatom-doped carbon/CoS according to claim 22Functional material, characterized in that:
in the step 2, the mass ratio of the sublimed sulfur to the carbonized product is 1-10: 1, the heating rate is 2-10 ℃/min.
7. Any of the heteroatom-doped carbon/CoS derivatives of claims 1-6 derived from metal organic frameworks2The application of the functional material is characterized in that:
doping the carbon/CoS with said hetero atom2The functional material modifies the diaphragm material of the lithium-sulfur battery so as to improve the battery performance.
8. Use according to claim 7, characterized in that:
adding CoS2And mixing the/C and the binder and loading the mixture on the surface of the lithium-sulfur battery separator.
9. Use according to claim 7 or 8, characterized in that it comprises the following steps:
adding CoS2and/C and the binder are ball-milled and uniformly mixed in an N-methyl pyrrolidone solution according to a certain proportion, the mixed solution is pumped and dried on the lithium-sulfur battery diaphragm through a vacuum filtration device, and the modified diaphragm is obtained after vacuum drying.
10. Use according to claim 9, characterized in that:
mass ratio CoS2C: PVDF (1-10): 1, mass ratio NMP: CoS220-80 parts of/C: 1, and the binder is PVDF.
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Application publication date: 20200619 |