CN115466365A - Fluorine-containing covalent organic framework nano-film, preparation method and application thereof, and lithium metal battery - Google Patents
Fluorine-containing covalent organic framework nano-film, preparation method and application thereof, and lithium metal battery Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 106
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 100
- 239000011737 fluorine Substances 0.000 title claims abstract description 100
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 85
- 239000002120 nanofilm Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 56
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 72
- -1 2,4, 6-trichloro-1, 3, 5-benzenetricarboxylic aldehyde Chemical class 0.000 claims description 59
- 239000004743 Polypropylene Substances 0.000 claims description 45
- 229920001155 polypropylene Polymers 0.000 claims description 45
- 239000012528 membrane Substances 0.000 claims description 35
- 239000003792 electrolyte Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 5
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 5
- 229960001553 phloroglucinol Drugs 0.000 claims description 5
- FVFYRXJKYAVFSB-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-diamine Chemical compound NC1=C(F)C(F)=C(N)C(F)=C1F FVFYRXJKYAVFSB-UHFFFAOYSA-N 0.000 claims description 4
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 2-(trifluoromethyl)benzene-1,4-diamine Chemical compound NC1=CC=C(N)C(C(F)(F)F)=C1 ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 0.000 claims description 3
- ZCJZVMNBJKPQEV-UHFFFAOYSA-N 4-[3,5-bis(4-formylphenyl)phenyl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC(C=2C=CC(C=O)=CC=2)=CC(C=2C=CC(C=O)=CC=2)=C1 ZCJZVMNBJKPQEV-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 3
- YOXHQRNDWBRUOL-UHFFFAOYSA-N 4-(4-formyl-n-(4-formylphenyl)anilino)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1N(C=1C=CC(C=O)=CC=1)C1=CC=C(C=O)C=C1 YOXHQRNDWBRUOL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 2
- 229920000557 Nafion® Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 241000287420 Pyrus x nivalis Species 0.000 claims description 2
- 125000002785 azepinyl group Chemical group 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000010287 polarization Effects 0.000 abstract description 11
- 230000006911 nucleation Effects 0.000 abstract description 8
- 238000010899 nucleation Methods 0.000 abstract description 8
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract 1
- 230000005501 phase interface Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 76
- 239000002585 base Substances 0.000 description 42
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 24
- 238000013112 stability test Methods 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 19
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 description 19
- 238000002425 crystallisation Methods 0.000 description 17
- 230000008025 crystallization Effects 0.000 description 17
- 230000008021 deposition Effects 0.000 description 15
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 12
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 12
- 230000001351 cycling effect Effects 0.000 description 11
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012462 polypropylene substrate Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000004807 desolvation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical group FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- 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
- 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
- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
-
- 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 belongs to the technical field of lithium metal batteries, and discloses a fluorine-containing covalent organic framework nano-film, a preparation method and application thereof, and a lithium metal battery. The method comprises the following steps: and uniformly mixing the monomer 1 solution, the monomer 2 solution, the solvent and the acetic acid catalyst, standing, and preparing the fluorine-containing covalent organic framework nano-film after the gas-liquid phase interface reaction is complete. The fluorine-containing covalent organic framework nano-film prepared by the invention is firstly transferred to the diaphragm through the medium and then is transferred to the surface of the lithium metal negative electrode in situ through the pressure in the battery assembling process, so that the formation of a lithium dendrite nucleation site is inhibited, the lithium ion mobility is improved, the polarization voltage of the battery is effectively reduced, the cycle stability and the safety performance of the lithium metal battery are obviously improved, and the fluorine-containing covalent organic framework nano-film has wide application prospect in the field of the lithium metal battery.
Description
Technical Field
The invention belongs to the technical field of lithium metal batteries, and particularly relates to a fluorine-containing covalent organic framework nano-film, a preparation method and application thereof, and a lithium metal battery.
Background
Since twenty-first century, with the continuous progress of industrial level and the rapid development of social economy, energy has been receiving wide attention as the most basic power source. The new energy battery technology is one of the most effective technologies for realizing the high-efficiency storage and conversion of energy. Among them, in the next generation of energy storage technology, lithium Metal Batteries (LMBs) have shown great development potential due to their own structural features. A typical lithium metal battery consists of a lithium metal negative electrode, an organic solvent electrolyte, and a novel positive electrode (a sulfur positive electrode, an air positive electrode, and an insertion-type positive electrode). The lithium metal electrode has ultrahigh theoretical specific capacity (3860 mAhg) -1 ) And the lowest redox potential (-3.04 Vvs standard hydrogen electrode), which is considered to be the "holy cup" in the field of negative electrode materials. However, the uneven lithium ion transport and slow transport kinetics at the lithium metal electrode side tend to induce a large number of lithium deposition sites, which in turn form dendrites and dead lithium, increase side reactions between the lithium metal and the electrolyte, thereby reducing the coulombic efficiency and the battery capacity of the battery, and even causing internal short circuits of the batteryThermal runaway of the battery or explosion.
Covalent Organic Framework (COFs) materials have the advantages of adjustable pore size and structure, low specific surface area, easy functionalization and the like, and have remarkable advantages in the aspect of realizing lithium metal electrode interface regulation. At present, the COFs exist in the shapes of powder and film. However, the selection of powder COFs materials as an artificial solid electrolyte interface film (SEI) to inhibit the growth of lithium dendrites has the problems of low ionic conductivity and poor interface contact between the electrolyte and the electrode. The lithium ion transfer capacity of the electrolyte and the interfacial compatibility between the electrode and the electrolyte have a great influence on the electrochemical performance of LMBs.
Therefore, the fluorine-containing covalent organic framework nano-film material for functionally regulating and controlling the lithium metal interface is prepared by developing a method which is simple in implementation process and easy to operate, so that the lithium metal cathode is protected, and the interface stability of the lithium metal battery is improved. Therefore, a preparation method and application of a novel fluorine-containing covalent organic framework nano-film and a lithium metal battery are needed to be provided.
Disclosure of Invention
The invention aims to provide a fluorine-containing covalent organic framework nano-film, a preparation method and application thereof and a lithium metal battery aiming at the problems of poor cycle performance and low coulombic efficiency of a negative electrode material in the conventional lithium metal battery. The fluorine-containing covalent organic framework nano-film prepared by the invention is firstly transferred to a diaphragm through a medium, and then is transferred to the surface of a lithium metal negative electrode in situ through the pressure in the battery assembling process, so that the formation of a lithium dendrite nucleation site is inhibited, the lithium ion mobility is improved, the polarization voltage of the battery is effectively reduced, the cycle stability and the safety performance of the lithium metal battery are obviously improved, and the fluorine-containing covalent organic framework nano-film has a wide application prospect in the field of the lithium metal battery.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a fluorine-containing covalent organic framework nanomembrane, the method comprising: and uniformly mixing the monomer 1 solution, the monomer 2 solution, the solvent and the acetic acid catalyst, and standing to prepare the fluorine-containing covalent organic framework nano-film.
According to the present invention, preferably, the method comprises: firstly, standing and mixing the monomer 1 solution and the solvent for 50-100min to obtain a mixed solution, then uniformly mixing the monomer 2 solution, the acetic acid catalyst and the mixed solution, and standing to obtain the fluorine-containing covalent organic framework nano-film.
Compared with the conventional COFs, the F atom in the C-F bond has extremely high electronegativity, can provide extremely strong lithium affinity, and effectively enhances Li in electrolyte + The desolvation capacity of the lithium ion battery can be improved, the migration kinetics of the lithium ion can be improved, the polarization potential of the battery can be effectively reduced, and the occurrence of side reactions can be reduced. And F-COFNs material can generate synergistic effect with fluorine-containing electrolyte (such as lithium bistrifluoromethylsulfonate imide, liTFSI), and electrostatic repulsion can effectively block fluorine-containing TFSI - Further improve the lithium ion conductivity, and form single Li at the lithium cathode interface + The interface double electron layer increases the ion transmission kinetics and obviously reduces the deposition potential of lithium ions.
According to the present invention, preferably, the molar ratio of the monomer 1 solution to the monomer 2 solution is: 1:1-4.
According to the present invention, it is preferable that the concentration of the acetic acid catalyst is 0.01 to 0.05mol/L.
According to the invention, preferably, the equipment for carrying out the standing treatment is a constant-temperature incubator or a constant-temperature drying room, the temperature is 10-80 ℃, and the time is 2-10 days.
According to the present invention, preferably, the method for preparing the monomer 1 solution comprises: mixing the monomer 1 with hydrochloric acid and carrying out ultrasonic treatment to obtain a monomer 1 solution with the concentration of 1-6mmol/L.
According to the present invention, preferably, the method for preparing the monomer 2 solution comprises: and mixing the monomer 2 with hydrochloric acid and carrying out ultrasonic treatment to obtain a monomer 2 solution with the concentration of 1-5mmol/L.
According to the present invention, preferably, the time of the ultrasonic treatment is 10-40min.
According to the invention, the concentration of the hydrochloric acid is preferably between 0.1 and 1mol/L.
According to the present invention, it is preferred that the monomer 1 is at least one of 2,2 '-bis (trifluoromethyl) diaminobiphenyl, 4' -diaminooctafluorobiphenyl, 2-trifluoromethyl-1, 4-phenylenediamine and 2,3,5, 6-tetrafluorobenzene-1, 4-diamine.
According to the present invention, it is preferred that the monomer 2 is at least one of trialdehyde phloroglucinol, trimesic aldehyde, 4' - ((4-bromophenyl) azepinyl) benzaldehyde, 1,3, 5-tris (p-formylphenyl) benzene, 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde, 2,4, 6-trichloro-1, 3, 5-benzenetricarboxylic aldehyde and tris (4-formylphenyl) amine.
According to the invention, the solvent is preferably prepared by standing and mixing water and a surfactant solution.
According to the invention, preferably, the volume ratio of water to surfactant solution is between 2000 and 4000:1.
in the invention, water is used as a dispersing agent, a monomolecular layer is formed on the surface of the water by utilizing a hydrophobic group of a surfactant, and the fluorine-containing covalent organic framework nano-film is prepared at a gas-liquid interface of a crystallizing dish by Schiff base reaction of a monomer 1 and a monomer 2.
According to the present invention, preferably, the time for the static mixing is 20 to 60min.
In the present invention, the water is selected from at least one of ultrapure water, deionized water, triple distilled water, and pure water.
According to the present invention, preferably, the method for preparing the surfactant solution comprises: and (3) mixing trichloromethane with a surfactant to obtain the surfactant solution with the concentration of 1-5mmol/L.
According to the present invention, preferably, the surfactant is selected from at least one of a sodium dodecylbenzene sulfonate solution (SDBS), a sodium Polystyrene Sulfonate Solution (PSS), and a sodium dodecyl sulfate solution (SDS).
The invention provides the fluorine-containing covalent organic framework nano-film prepared by the preparation method of the fluorine-containing covalent organic framework nano-film.
The third aspect of the invention provides an application of the fluorine-containing covalent organic framework nano-film in the preparation of a lithium metal battery.
The fourth aspect of the present invention provides a lithium metal battery comprising a positive plate, a separator, an electrolyte and a negative plate;
the membrane is prepared by transferring a fluorine-containing covalent organic framework nano membrane through a medium, covering the fluorine-containing covalent organic framework nano membrane on a base membrane and drying the base membrane;
the fluorine-containing covalent organic framework nano-film is the fluorine-containing covalent organic framework nano-film.
In the invention, the fluorine-containing covalent organic framework nano-film (F-COFNs) is used for modifying a lithium metal interface and adjusting the interface stability of a lithium metal negative electrode. The F-COFNs have a complete and long-range ordered porous structure, so that charge transfer can be met, and uniform deposition of lithium ions under high current density is ensured. Meanwhile, the strong electronegativity and lithium affinity of the F atom can effectively promote Li in the electrolyte + The desolvation capacity of the nano film can be improved, the migration kinetics of lithium ions can be improved, the polarization potential of the battery can be effectively reduced, the cycling stability of the lithium metal battery can be obviously improved, the cycling life of the battery can be prolonged, the occurrence rate of safety problems caused by the continuous growth of uncontrollable lithium dendrites can be reduced, and the feasibility guidance can be provided for the application of the covalent organic framework nano film in the lithium metal battery.
According to the present invention, preferably, the medium is at least one of teflon paper, filter paper, snow pear paper, and tissue paper.
According to the present invention, preferably, the base film is selected from at least one of a polypropylene membrane, a glass fiber membrane, a Nafion membrane, a polyethylene membrane, and a PET membrane.
According to the invention, the drying temperature is preferably 20-80 ℃ and the drying time is preferably 3-8h.
The technical scheme of the invention has the following beneficial effects:
(1) Fluorine atoms in C-F bonds in the fluorine-containing covalent organic framework nanofilms (F-COFNs) prepared by the method have extremely strong electronegativity, can generate strong interaction with lithium cations, show extremely high lithium-philic property, and increase fluorine-containing covalent organic framework nanofilms (F-COFNs)Dissociation of electrolyte (e.g., lithium bistrifluoromethylsulfonate imide, liTFSI) molecules greatly facilitates Li + The desolvation allows more "free" lithium ions to be released, thereby increasing the conductivity of the lithium ions and significantly reducing the polarization voltage during cycling.
(2) The F-COFNs are large-size covalent organic framework nano films with complete, smooth and long-range ordered porous structures, can solve the problem that ions or charge transfer is blocked due to irregular accumulation caused by traditional COFs after-modification, inhibit the growth of lithium dendrites and realize the uniform deposition of lithium ions.
(3) The F-COFNs have regular one-dimensional pore passages and adjustable pore sizes, and the F-COFNs are used for modifying a lithium metal interface, so that a new strategy is provided for a lithium ion transfer path in a lithium metal battery and improving lithium ion migration dynamics, and methods for inhibiting large-scale lithium nucleation and lithium dendrite formation are enriched.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Fig. 1 shows a schematic diagram of a reaction between a monomer 1 solution and a monomer 2 solution in a method for preparing a fluorine-containing covalent organic framework nano-film according to embodiment 1 of the present invention, and a structural formula of the obtained fluorine-containing covalent organic framework nano-film (BbTp).
Fig. 2 shows the result of cycle stability test of CR2032 button cell-lithium symmetric cell provided in example 1 of the present invention ("bareli" denotes a control cell using only polypropylene base film as a separator, "BbTp @ Li" denotes a cell in which fluorine-containing covalent organic framework nano-film (BbTp) is coated on polypropylene base film as a separator, time denotes Time, and Voltage denotes Voltage).
Fig. 3 (a) - (e) show optical microscope images of the growth process of a fluorine-containing covalent organic framework nano-film provided in example 2 of the present invention.
Fig. 4 shows a schematic diagram of a reaction between a monomer 1 solution and a monomer 2 solution of a method for preparing a fluorine-containing covalent organic framework nano-film provided in embodiment 2 of the present invention, and a structural formula of the obtained fluorine-containing covalent organic framework nano-film (TdTb).
Fig. 5 shows the cycle stability test results of the CR2032 button cell-lithium symmetric cell provided in example 2 of the invention ("Bare Li" denotes a control cell using only polypropylene base film as the membrane, "TdTb @ Li" denotes a cell in which fluorine-containing covalent organic framework nano-film (TdTb) is coated on the polypropylene base film as the membrane).
Fig. 6 shows the results of the cycling stability test of CR2032 button cell-lithium-copper half cell provided in example 3 of the present invention ("barecu" denotes a control group lithium-copper half cell using only polypropylene base film as a separator, "TdTb @ Cu" fluorine-containing covalent organic framework nanomembrane (TdTb) coated on polypropylene base film as a separator lithium-copper half cell, and Coulombic efficiency denotes Coulombic efficiency).
Fig. 7 (a) - (b) show tem images of a fluorine-containing covalent organic framework nanomembrane provided in example 4 of the present invention.
Fig. 8 shows a schematic diagram of a reaction between a monomer 1 solution and a monomer 2 solution of a method for preparing a fluorine-containing covalent organic framework nano-film provided in embodiment 4 of the present invention and a structural formula of the obtained fluorine-containing covalent organic framework nano-film (DtBt).
Fig. 9 shows the results of the cycling stability test of CR2032 button cell-lithium symmetric cell provided in example 4 of the present invention ("bareli" denotes a control cell using only polypropylene base film as the separator, "DtBt (1 mmol/L) @ Li" denotes a cell in which a fluorine-containing covalent organic framework nano-film (DtBt) is coated on the polypropylene base film as the separator).
Fig. 10 shows the results of the cycling stability test of CR2032 button cell-lithium-copper half cell provided in example 5 of the present invention ("barecu" denotes a control group lithium-copper half cell using only polypropylene base film as the separator, "DtBt @ (1 mmol/L) Cu" denotes a lithium-copper half cell with fluorine-containing covalent organic framework nano-film (DtBt) coated on polypropylene base film as the separator).
Fig. 11 shows the results of the cycling stability test of CR2032 button cell-lithium symmetric cell provided in example 6 of the present invention ("bareli" denotes a control cell using only polypropylene base film as the separator, "DtBt (3 mmol/L) @ Li" denotes a cell in which a fluorine-containing covalent organic framework nanomembrane (DtBt) is coated on the polypropylene base film as the separator).
Fig. 12 shows the cycle stability test results of CR2032 button cell-lithium-copper half-cell provided in example 7 of the invention ("Bare Cu" represents a control group lithium-copper half-cell using only polypropylene base film as the membrane, "DtBt @ (3 mmol/L) Cu" represents a lithium-copper half-cell with fluorine-containing covalent organic framework nano-film (DtBt) coated on the polypropylene base film as the membrane).
Fig. 13 shows a schematic diagram of a reaction between a monomer 1 solution and a monomer 2 solution in a method for preparing a fluorine-containing covalent organic framework nano-film according to embodiment 8 of the present invention, and a structural formula of the obtained fluorine-containing covalent organic framework nano-film (DoTp).
Fig. 14 shows the results of the cycling stability test of CR2032 button cell-lithium symmetric cell provided in example 8 of the present invention ("bareli" denotes a control cell using only polypropylene base film as the separator, "DoTp (1 Layer) @ Li" denotes a cell in which fluorine-containing covalent organic framework nano-film (DoTp) is coated on polypropylene base film as the separator).
Fig. 15 shows the results of the cycle stability test of CR2032 button cell-lithium-copper half cell provided in example 9 of the present invention ("barecu" denotes a control group lithium-copper half cell using only polypropylene base film as a separator, "DoTp (1 Layer) @ Cu" denotes a lithium-copper half cell with fluorine-containing covalent organic framework nano-film (DoTp) coated on polypropylene base film as a separator).
Fig. 16 shows the results of the cycling stability test of CR2032 button cells-lithium symmetric cells provided in example 10 of the present invention ("bareli" denotes a control cell using only polypropylene base film as the separator, "DoTp (3 Layer) @ Li" denotes a cell in which a fluorine-containing covalent organic framework nanomembrane (DoTp) is coated on the polypropylene base film as the separator).
Fig. 17 shows the results of the cycle stability test of CR2032 button cell-lithium-copper half cell provided in example 11 of the present invention ("barecu" denotes a control group lithium-copper half cell using only polypropylene base film as a separator, "DoTp (3 Layer) @ Cu" denotes a lithium-copper half cell in which fluorine-containing covalent organic framework nano-film (DoTp) is coated on polypropylene base film as a separator).
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
The embodiment provides a preparation method of a fluorine-containing covalent organic framework nano-film, which comprises the following steps:
adding 50mL of ultrapure water into a crystallization vessel, adding 40 mu L of surfactant SDBS solution into the crystallization vessel, and standing and mixing the solution in a constant temperature box for 50min to obtain a solvent; the preparation method of the surfactant SDBS solution comprises the following steps: mixing trichloromethane with a surfactant SDBS to obtain a surfactant solution with the concentration of 3mmol/L;
taking a 2,2 '-bis (trifluoromethyl) diaminobiphenyl solution (prepared by mixing 2,2' -bis (trifluoromethyl) diaminobiphenyl with 0.12mol/L hydrochloric acid and carrying out ultrasonic treatment for 10-40 min), adding 1mmol/L and 700 mu L of the solution into a crystallization vessel containing the solvent, standing and mixing for 60min to obtain a mixed solution;
taking a trialdehyde phloroglucinol solution (prepared by mixing trialdehyde phloroglucinol with 0.12mol/L hydrochloric acid and carrying out ultrasonic treatment for 10-40 min), taking 1mmol/L,420 mu L and 2mL of acetic acid solution with the concentration of 0.03mol/L as catalysts, uniformly mixing with the mixed solution, and reacting for 5 days at 50 ℃ to prepare the fluorine-containing covalent organic framework nano-film (BbTp).
The structural formula of the reaction of the monomer 1 solution and the monomer 2 solution and the obtained fluorine-containing covalent organic framework nano-film (BbTp) is shown in figure 1.
The embodiment also provides a CR2032 button cell-lithium symmetrical cell, which comprises a positive plate, a diaphragm, electrolyte and a negative plate;
the membrane is prepared by transferring the fluorine-containing covalent organic framework nano membrane onto a polypropylene substrate membrane through polytetrafluoroethylene paper and covering the polytetrafluoroethylene paper with the fluorine-containing covalent organic framework nano membrane, and drying the membrane, and specifically comprises the following steps: adding ultra-pure water into a large flat-bottom crystallization dish with the specification of 200mm multiplied by 120mm to ensure that the water height can be ensured to be higher than that of the crystallization dish used for preparing the fluorine-containing covalent organic framework nano-film, then placing the small crystallization dish with the grown film into a large crystallization dish with the specification of 200mm multiplied by 120mm and containing water, and transferring the fluorine-containing covalent organic framework nano-film (BbTp-film) onto a polypropylene base film by using PTFE polytetrafluoroethylene paper as a medium. And (3) placing the polypropylene-based bottom film covered with the BbTp-film in a constant-temperature drying oven, and drying for 3h at the temperature of 50 ℃ to obtain the polypropylene diaphragm uniformly covered with the fluorine-containing covalent organic framework nano film, namely the diaphragm.
1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used with a polypropylene separator uniformly covered with a fluorine-containing covalent organic framework nanomembrane DME :V DOL = 1) electrolyte was assembled into a CR2032 button cell.
The CR2032 button cell obtained in this example was subjected to a cycle stability test, and a control group was set: using only a polypropylene base film as a separator, 1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used DME :V DOL = 1) electrolyte was assembled into a CR2032 button cell.
Set the battery program at 10mA cm -2 Current density of 1mAh cm -2 The constant current charge-discharge cycle test was carried out at the deposition amount of (2). The test results are shown in fig. 2: the lithium metal battery modified by the fluorine-containing covalent organic framework nano-film (BbTp) still has low polarization potential less than 50mV after being cycled for 500 hours, while the lithium metal battery of a control group has poorer cycle stability.
Example 2
This example provides a method for preparing a fluorine-containing covalent organic framework nano-film, and the only difference between this example and example 1 is that:
adding a monomer 1 solution of 2-trifluoromethyl-1, 4-phenylenediamine (1 mmol/L and 530 mu L) into a crystallization vessel containing the solvent, and standing and mixing for 50min to obtain a mixed solution;
the monomer 2 solution was 1,3, 5-tris (p-formylphenyl) benzene, 1mmol/L, 780. Mu.L;
and preparing the fluorine-containing covalent organic framework nano film (TdTb), wherein the optical microscope pictures of the growth process of the nano film (TdTb) for 1-5 days are sequentially shown in figures 3 (a) - (e).
The reaction between the monomer 1 solution and the monomer 2 solution and the structural formula of the obtained fluorine-containing covalent organic framework nano-film (TdTb) are shown in figure 4.
This example also provides a CR2032 button cell-lithium symmetric cell, and the cell of this example only differs from example 1 in that: the membrane is prepared by transferring the fluorine-containing covalent organic framework nano membrane (TdTb) to a polypropylene substrate membrane through polytetrafluoroethylene paper, covering the polytetrafluoroethylene paper with the membrane, and drying the membrane.
The CR2032 button cell obtained in this example was subjected to a cycle stability test, and a control group was set: using only a polypropylene base film as a separator, 1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used DME :V DOL = 1) assembling the electrolyte into a CR2032 button cell.
Set the battery program at 4mA cm -2 Current density of 1mAh cm -2 The constant current charge-discharge cycle test was carried out at the deposition amount of (2). The test results are shown in fig. 5: the lithium metal battery modified by the fluorine-containing covalent organic framework nano-film (TdTb) still has low polarization potential less than 50mV after being cycled for 340 hours, while the lithium metal battery of a control group has poorer cycle stability.
Example 3
This example also provides a CR2032 button cell, lithium-copper half cell, and only differs from example 2 in that: this example is a lithium-copper half cell.
The CR2032 button cell obtained in this example was subjected to a cycle stability test, and a control group was set: using only a polypropylene base film as a separator, 1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used DME :V DOL = 1) assembling the electrolyte into a CR2032 button cell.
Set the battery program at 0.5mA cm -2 Current density of 1mAh cm -2 The constant current charge-discharge cycle test was performed at the deposition amount of (2). The test results are shown in fig. 6: the lithium metal battery modified by the fluorine-containing covalent organic framework nano-film (TdTb) has lower nucleation overpotential, and still maintains 98.2% of coulombic efficiency after 130 cycles of cycling, while the lithium metal battery of a control group has poorer cycling stability.
Example 4
The present embodiment provides a method for preparing a fluorine-containing covalent organic framework nano-film, and the difference between the present embodiment and embodiment 1 is only that:
adding 50mL of ultrapure water into a crystallization vessel, adding 30 mu L of surfactant SDBS solution into the crystallization vessel, and standing and mixing the solution in a constant temperature box for 50min to obtain a solvent;
adding monomer 1 solution of 2,3,5, 6-tetrafluoro-1, 4-phenylenediamine (1 mmol/L,540 μ L) into a crystallizing dish containing the solvent, standing and mixing for 50min to obtain a mixed solution;
the monomer 2 solution is 2,4, 6-tri (4-aldehyde phenyl) -1,3, 5-triazine, 1mmol/L,787 mu L and 2mL of acetic acid solution with the concentration of 0.03mol/L are used as catalysts, the mixed solution is uniformly mixed, and the mixture reacts for 6 days at the temperature of 50 ℃ to prepare the fluorine-containing covalent organic framework nano-film (DtBT), and transmission electron microscope images of the nano-film are shown in figures 7 (a) - (b).
The structural formula of the reaction of the monomer 1 solution and the monomer 2 solution and the obtained fluorine-containing covalent organic framework nano-film (DtBT) is shown in figure 8.
This example also provides a CR2032 button cell-lithium symmetric cell, and the cell of this example only differs from example 1 in that: the membrane is prepared by transferring the fluorine-containing covalent organic framework nano membrane (DtBT) to a polypropylene substrate membrane through polytetrafluoroethylene paper, and drying (drying for 6h at 40 ℃).
The CR2032 button cell obtained in this example was subjected to a cycle stability test, and a control group was set: using only a polypropylene base film as a separator, 1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used DME :V DOL = 1) assembling the electrolyte into a CR2032 button cell.
Set the battery program at 4mA cm -2 Current density of 8mAh cm -2 The constant current charge-discharge cycle test was carried out at the deposition amount of (2). The test results are shown in fig. 9: the lithium metal battery modified by the fluorine-containing covalent organic framework nano-film (DtBT) still has low polarization potential of 32mV after being cycled for 350 hours, while the lithium metal battery of a control group has poorer cycle stability.
Example 5
This example also provides a CR2032 button cell, lithium-copper half cell, and only differs from example 4 in that: this example is a lithium-copper half cell.
The CR2032 button cell obtained in this example was subjected to a cycle stability test, and a control group was set: using only a polypropylene base film as a separator, 1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used DME :V DOL = 1) electrolyte was assembled into a CR2032 button cell.
Set the battery program at 1mA cm -2 Current density of 1mAh cm -2 The constant current charge-discharge cycle test was performed at the deposition amount of (2). The test results are shown in FIG. 10 as l: the lithium metal battery modified by the fluorine-containing covalent organic framework nano-film (DtBT) has lower nucleation overpotential, still maintains 96.8 percent of coulombic efficiency after 120 cycles of circulation, and the lithium metal battery of a control group has poorer circulation stability.
Example 6
This example provides a method for preparing a fluorine-containing covalent organic framework nano-film, and the only difference between this example and example 4 is that:
the monomer 1 solution is 2,3,5, 6-tetrafluoro-1, 4-phenylenediamine, 3mmol/L and 540 mu L;
the monomer 2 solution is 2,4, 6-tri (4-aldehyde phenyl) -1,3, 5-triazine, 3mmol/L, 787. Mu.L;
and preparing the fluorine-containing covalent organic framework nano film (DtBT).
This example also provides a CR2032 button cell-lithium symmetric cell.
The CR2032 button cell obtained in this example was subjected to a cycle stability test, and a control group was set: using only a polypropylene base film as a separator, 1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used DME :V DOL = 1) assembling the electrolyte into a CR2032 button cell.
Set the battery program at 4mA cm -2 Current density of 2mAh cm -2 The constant current charge-discharge cycle test was performed at the deposition amount of (2). The test results are shown in fig. 11: the lithium metal battery modified by the fluorine-containing covalent organic framework nano-film (DtBT) still has low polarization potential of 40mV after 650 hours of circulation, while the lithium metal battery of a control group has poorer circulation stability.
Example 7
This example also provides a CR2032 button cell, a lithium-copper half cell, and differs from example 6 only in that: this example is a lithium-copper half cell.
The CR2032 button cell obtained in this example was subjected to a cycle stability test, and a control group was set: using only a polypropylene base film as a separator, 1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used DME :V DOL = 1) electrolyte was assembled into a CR2032 button cell.
Set the battery program at 1mA cm -2 Current density of 1mAh cm -2 The constant current charge-discharge cycle test was carried out at the deposition amount of (2). The test results are shown in fig. 12: the lithium metal battery modified by the fluorine-containing covalent organic framework nano-film (DtBT) has lower nucleation overpotential, and still maintains 98.6 percent of coulombic efficiency after 120 cycles of circulation, while the lithium metal battery of a control group has poorer circulation stability.
Example 8
This example provides a method for preparing a fluorine-containing covalent organic framework nano-film, and the only difference between this example and example 1 is that:
adding 50mL of ultrapure water into a crystallization vessel, adding 20 mu L of surfactant SDBS solution into the crystallization vessel, and standing and mixing the solution in a constant temperature box for 30min to obtain a solvent;
adding the monomer 1 solution of 4,4' -diaminooctafluorobiphenyl (1 mmol/L,985 mu L) into a crystallization dish containing the solvent, and standing and mixing for 50min to obtain a mixed solution;
and the monomer 2 solution is trialdehyde phloroglucinol, 1mmol/L,420 mu L and 2mL of acetic acid solution with the concentration of 0.03mol/L are used as catalysts, the mixture is uniformly mixed with the mixed solution, and the mixture reacts for 5 days at the temperature of 50 ℃ to prepare the fluorine-containing covalent organic framework nano-film (DoTp).
The reaction of the monomer 1 solution and the monomer 2 solution and the structural formula of the obtained fluorine-containing covalent organic framework nano-film (DoTp) are shown in figure 13.
This example also provides a CR2032 button cell-lithium symmetric cell, and the cell of this example only differs from example 1 in that: the membrane is prepared by transferring the fluorine-containing covalent organic framework nano membrane (DoTp) to a polypropylene substrate membrane through polytetrafluoroethylene paper, and drying (drying for 6 hours at 40 ℃).
The CR2032 button cell obtained in this example was subjected to a cycle stability test, and a control group was set: using only a polypropylene base film as a separator, 1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used DME :V DOL = 1) electrolyte was assembled into a CR2032 button cell.
Set the battery program at 20mA cm -2 Current density of 1mAh cm -2 The constant current charge-discharge cycle test was carried out at the deposition amount of (2). The test results are shown in fig. 14: the lithium metal battery modified by the fluorine-containing covalent organic framework nano-film (DoTp) still has a low polarization potential of 70mV after 750 hours of circulation, while the lithium metal battery of the control group has poorer circulation stability.
Example 9
This example also provides a CR2032 button cell, a lithium-copper half cell, and differs from example 8 only in that: this example is a lithium-copper half cell.
The CR2032 button cell obtained in this example was subjected to a cycle stability test, and a control group was set: using only a polypropylene base film as a separator, 1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used DME :V DOL = 1) assembling the electrolyte into a CR2032 button cell.
Set the battery program at 0.5mA cm -2 Current density of 1mAh cm -2 The constant current charge-discharge cycle test was carried out at the deposition amount of (2). The test results are shown in fig. 15: the lithium metal battery modified by the fluorine-containing covalent organic framework nano film (DoTp) has lower nucleation overpotential, and still maintains 97.8 percent of coulombic efficiency after 130 cycles of circulation, while the lithium metal battery of a control group has poorer circulation stability.
Example 10
This example provides a CR2032 button cell-lithium symmetric cell, and differs from example 5 only in that:
the diaphragm is: adding ultra-pure water into a large flat-bottom crystallization dish with the specification of 200mm multiplied by 120mm ensures that the water height can exceed that of the crystallization dish used for preparing the fluorine-containing covalent organic framework nano-film in example 5, then placing the small crystallization dish with the grown film in example 5 into a large crystallization dish with the specification of 200mm multiplied by 120mm, and transferring the fluorine-containing covalent organic framework nano-film (DoTp) onto a polypropylene base film by using PTFE polytetrafluoroethylene paper as a medium. And (3) drying the polypropylene-based base film covered with the DoTp in a constant-temperature drying box for 6h at 40 ℃, covering the dried polypropylene-based base film covered with the DoTp again, drying the polypropylene-based base film in the constant-temperature drying box for 6h at 40 ℃, and repeating the drying process again after the polypropylene-based base film is dried to obtain the polypropylene diaphragm uniformly covering the 3 layers of fluorine-containing covalent organic framework nano-films.
The CR2032 button cell obtained in this example was subjected to a cycle stability test, and a control group was set: using only a polypropylene base film as a separator, 1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used DME :V DOL = 1) assembling the electrolyte into a CR2032 button cell.
Set the battery program at 20mA cm -2 Current density of 1mAh cm -2 The constant current charge-discharge cycle test was carried out at the deposition amount of (2). The test results are shown in fig. 16: the lithium metal battery modified by the fluorine-containing covalent organic framework nano-film (DoTp) still has a low polarization potential of 65mV after being cycled for 500 hours, while the lithium metal battery of a control group has poorer cycle stability.
Example 11
This example also provides a CR2032 button cell-lithium-copper half cell, and only differs from example 10 in that: this example is a lithium-copper half cell.
The CR2032 button cell obtained in this example was subjected to a cycle stability test, and a control group was set: using only a polypropylene base film as a separator, 1.0M LiTFSI (solvent V) with 2wt% lithium nitrate added was used DME :V DOL = 1) electrolyte was assembled into a CR2032 button cell.
Set the battery program at 1mA cm -2 Current density of 1mAh cm -2 The constant current charge-discharge cycle test was carried out at the deposition amount of (2). The test results are shown in fig. 17: the lithium metal battery modified by the fluorine-containing covalent organic framework nano film (DoTp) has lower nucleation overpotential, and still maintains 98.0 percent of coulombic efficiency after 140 cycles of circulation, while the lithium metal battery of a control group has poorer circulation stability.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A preparation method of a fluorine-containing covalent organic framework nano-film is characterized by comprising the following steps: and uniformly mixing the monomer 1 solution, the monomer 2 solution, the solvent and the acetic acid catalyst, and standing to prepare the fluorine-containing covalent organic framework nano-film.
2. The method for preparing the fluorine-containing covalent organic framework nanomembrane according to claim 1, wherein the method comprises the following steps: firstly, standing and mixing the monomer 1 solution and the solvent for 50-100min to obtain a mixed solution, then uniformly mixing the monomer 2 solution, the acetic acid catalyst and the mixed solution, and standing to obtain the fluorine-containing covalent organic framework nano-film.
3. The method for preparing a fluorine-containing covalent organic framework nanomembrane according to claim 1 or 2, wherein,
the molar ratio of the monomer 1 solution to the monomer 2 solution is as follows: 1:1-4;
the concentration of the acetic acid catalyst is 0.01-0.05mol/L;
the equipment for standing treatment is a constant temperature incubator or a constant temperature drying room, the temperature is 10-80 ℃, and the time is 2-10 days.
4. The method for preparing a fluorine-containing covalent organic framework nanomembrane according to claim 1 or 2, wherein,
the preparation method of the monomer 1 solution comprises the following steps: mixing the monomer 1 with hydrochloric acid and carrying out ultrasonic treatment to obtain a monomer 1 solution with the concentration of 1-6mmol/L;
the preparation method of the monomer 2 solution comprises the following steps: and mixing the monomer 2 with hydrochloric acid and carrying out ultrasonic treatment to obtain a monomer 2 solution with the concentration of 1-5mmol/L.
5. The method for preparing fluorine-containing covalent organic framework nanomembranes according to claim 4, wherein,
the ultrasonic treatment time is 10-40min;
the concentration of the hydrochloric acid is 0.1-1mol/L;
the monomer 1 is at least one of 2,2 '-bis (trifluoromethyl) diaminobiphenyl, 4' -diaminooctafluorobiphenyl, 2-trifluoromethyl-1, 4-phenylenediamine and 2,3,5, 6-tetrafluorobenzene-1, 4-diamine;
the monomer 2 is at least one of trialdehyde phloroglucinol, trimesic aldehyde, 4' - ((4-bromophenyl) azepinyl) benzaldehyde, 1,3, 5-tri (p-formylphenyl) benzene, 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde, 2,4, 6-trichloro-1, 3, 5-benzenetricarboxylic aldehyde and tri (4-formylphenyl) amine.
6. The method of preparing a fluorine-containing covalent organic framework nanomembrane according to claim 1, wherein,
the solvent is prepared by standing and mixing water and a surfactant solution;
the volume ratio of the water to the surfactant solution is 2000-4000:1;
standing for 20-60min;
the preparation method of the surfactant solution comprises the following steps: mixing trichloromethane with a surfactant to obtain a surfactant solution with the concentration of 1-5mmol/L;
the surfactant is at least one selected from sodium dodecyl benzene sulfonate solution, sodium polystyrene sulfonate solution and sodium dodecyl sulfate solution.
7. The fluorine-containing covalent organic framework nano-film prepared by the preparation method of the fluorine-containing covalent organic framework nano-film according to any one of claims 1 to 6.
8. Use of the fluorine-containing covalent organic framework nanomembrane of claim 7 for the preparation of a lithium metal battery.
9. A lithium metal battery is characterized by comprising a positive plate, a diaphragm, electrolyte and a negative plate;
the membrane is prepared by transferring a fluorine-containing covalent organic framework nano membrane through a medium, covering the fluorine-containing covalent organic framework nano membrane on a base membrane and drying the base membrane;
the fluorine-containing covalent organic framework nanomembrane of claim 7.
10. The lithium metal battery according to claim 9,
the medium is at least one of polytetrafluoroethylene paper, filter paper, snow pear paper and cotton paper;
the base film is selected from at least one of a polypropylene diaphragm, a glass fiber diaphragm, a Nafion diaphragm, a polyethylene diaphragm and a PET diaphragm;
the drying temperature is 20-80 ℃ and the drying time is 3-8h.
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| CN115863924A (en) * | 2023-02-24 | 2023-03-28 | 东营昆宇电源科技有限公司 | COFs modified AAO membrane, preparation method thereof and sodium-ion battery |
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| WO2022061666A1 (en) * | 2020-09-24 | 2022-03-31 | 浙江大学 | Method for preparing hollow covalent organic framework material |
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| CN115073802A (en) * | 2022-06-24 | 2022-09-20 | 福州大学 | Organic polymerization monolithic column containing fluorine functional covalent organic framework nanosheet and application thereof |
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