CN117352637A - MOFs nano-array composite material grown in situ on copper foil and preparation method and application thereof - Google Patents
MOFs nano-array composite material grown in situ on copper foil and preparation method and application thereof Download PDFInfo
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- CN117352637A CN117352637A CN202311396634.9A CN202311396634A CN117352637A CN 117352637 A CN117352637 A CN 117352637A CN 202311396634 A CN202311396634 A CN 202311396634A CN 117352637 A CN117352637 A CN 117352637A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000011889 copper foil Substances 0.000 title claims abstract description 136
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 118
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 17
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 150000003754 zirconium Chemical class 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- QCWPXJXDPFRUGF-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 QCWPXJXDPFRUGF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 85
- -1 zirconium dichloride hexahydrate Chemical compound 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 90
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 56
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 45
- 239000003792 electrolyte Substances 0.000 description 30
- 210000004027 cell Anatomy 0.000 description 26
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 16
- 239000010949 copper Substances 0.000 description 15
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 210000001787 dendrite Anatomy 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 229910013872 LiPF Inorganic materials 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- VWYHCWVXCWCOPV-UHFFFAOYSA-L dilithium trifluoromethanesulfonate Chemical compound [Li+].[Li+].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F VWYHCWVXCWCOPV-UHFFFAOYSA-L 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000003491 array Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WLOADVWGNGAZCW-UHFFFAOYSA-N 3-phenyl-23H-porphyrin-2,18,20,21-tetracarboxylic acid Chemical compound OC(=O)C=1C(N2C(O)=O)=C(C(O)=O)C(=N3)C(C(=O)O)=CC3=CC(N3)=CC=C3C=C(N=3)C=CC=3C=C2C=1C1=CC=CC=C1 WLOADVWGNGAZCW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Manufacturing & Machinery (AREA)
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- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Composite Materials (AREA)
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Abstract
The embodiment of the invention relates to a MOFs nano-array composite material grown on a copper foil in situ, and a preparation method and application thereof, wherein the preparation method is to immerse a clean copper foil in hydrochloric acid to remove oxidized parts on the surface of the copper foil, and then to obtain the copper foil to be compounded through a first drying treatment; adding zirconium salt, benzoic acid and tetracarboxyl phenyl porphyrin TCPP into N, N-dimethylformamide, and stirring to obtain MOFs precursor solution of the metal organic framework compound; immersing the copper foil to be compounded into MOFs precursor solution, performing heat treatment to coordinate copper ions on the surface of the copper foil to be compounded with carboxyl groups in the MOFs precursor solution, and then performing washing, activating treatment and secondary drying treatment to obtain the MOFs nano-array composite material with the metal organic framework compound grown on the copper foil in situ.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a MOFs nano-array composite material grown in situ on a copper foil, a preparation method and application thereof.
Background
Lithium metal anodes are considered "holy cups" in lithium secondary battery anode materials because of their ultra-high theoretical specific capacity (3860 mAh/g) and lowest redox potential (-3.04V).
However, the lithium metal cathode is easy to form irregular lithium dendrites in the deposition process, and the generated lithium dendrites are easy to fall off to form dead lithium, so that the coulomb efficiency of the battery is reduced and side reactions are increased; on the other hand, the separator is extremely easy to puncture to cause internal short circuit, and great potential safety hazards exist, so that the practical application of the lithium metal battery is greatly hindered.
Therefore, researchers at home and abroad do some work to solve the problem. For example, by carrying out surface modification on the lithium metal cathode, the formation of lithium dendrites is inhibited, the cycle life of the lithium metal battery is prolonged, and the safety performance of the lithium metal battery is improved. However, a large amount of binder is needed in the process of surface modification, and the binder is decomposed in the charge and discharge processes of the lithium metal battery, so that side reactions are brought to influence the electrochemical performance of the lithium metal battery.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a MOFs nano-array composite material grown in situ on a copper foil, and a preparation method and application thereof.
In order to achieve the above object, in a first aspect, the present invention provides a method for preparing a MOFs nano-array composite material grown in situ on a copper foil, the method comprising:
immersing clean copper foil into hydrochloric acid to remove oxidized parts on the surface of the copper foil, and then performing primary drying treatment to obtain the copper foil to be compounded;
adding zirconium salt, benzoic acid and tetracarboxyl phenyl porphyrin TCPP into N, N-dimethylformamide, and stirring to obtain MOFs precursor solution of the metal organic framework compound;
immersing the copper foil to be compounded into the MOFs precursor solution, performing heat treatment to coordinate copper ions on the surface of the copper foil to be compounded with carboxyl groups in the MOFs precursor solution, and then performing washing, activating treatment and secondary drying treatment to obtain the MOFs nano-array composite material with the metal-organic framework compound grown on the copper foil in situ.
Preferably, the molar ratio of the zirconium salt, the benzoic acid and the TCPP is (4-5): (13-18): 1.
Preferably, the zirconium salt comprises one or more of zirconium chloride, zirconium dichloride hexahydrate, zirconium nitrate.
Preferably, the molar concentration of the hydrochloric acid is 2mol/L to 5mol/L.
Preferably, the first drying treatment is specifically performed in a vacuum drying oven at a temperature of 60-80 ℃ for 2-5 hours.
Preferably, the heat treatment is carried out in particular in a forced air drying oven at a temperature of 110℃to 130℃for a time of 12 hours to 16 hours.
Preferably, the second drying treatment is specifically performed in a vacuum drying oven at a temperature of 75-95 ℃ for 12-24 hours.
In a second aspect, the present invention provides a MOFs nano-array composite material grown in situ on a copper foil, where the MOFs nano-array composite material grown in situ on the copper foil is prepared by the preparation method of any one of the first aspects.
In a third aspect, the invention provides a negative electrode piece, which is the MOFs nano-array composite material grown in situ on the copper foil in the second aspect.
In a fourth aspect, the invention provides a lithium metal battery, which comprises the negative electrode plate in the third aspect.
According to the preparation method of the MOFs nano-array composite material grown in situ on the copper foil, provided by the embodiment of the invention, copper ions on the surface of the copper foil are coordinated with MOFs, so that MOFs are grown in situ on the copper surface of the copper foil. The MOFs metal node constructed in situ is zirconium, so that the MOFs metal node has good chemical stability; the ligand molecule is TCPP, the ligand center can be anchored by nitrogen with transition metal M, M-N 4 The structure has good lithium affinity, and can effectively induce metal lithium nucleation, so that the formation of lithium dendrite is inhibited, the coulomb efficiency of the lithium metal battery is improved, the short circuit incidence rate of the lithium metal battery is reduced, the cycle life of the lithium metal battery is prolonged, and the safety performance is improved. In addition, the MOFs of the invention have one-dimensional pore channels, the nano array of the MOFs has high crystallinity and high specific surface area and large pore channels, the contact area between an electrode and lithium can be increased, the lithium deposition efficiency is improved, and the metal lithium can be uniformly deposited, so that the metal lithium anode with excellent electrochemical performance is obtained. The excellent lithium affinity obviously reduces the interface impedance of the lithium metal anode, and activates the mass transfer kinetics of the anode interface, thereby greatly improving the cycle stability of the lithium metal battery.
Drawings
FIG. 1 is a flowchart of a preparation method of MOFs nano-array composite material grown in situ on a copper foil provided by an embodiment of the invention;
FIG. 2 is an SEM image of an in-situ grown MOFs (Co) nano-array composite on a copper foil provided in example 3 of the present invention;
FIG. 3 is an SEM image of lithium deposition on bare Cu provided by comparative example 1 of the present invention;
FIG. 4 is an SEM image of an in-situ grown MOFs (Co) nano-array composite material deposited on copper foil using lithium provided in example 3 of the present invention;
FIG. 5 is an XRD pattern of in situ growth of MOFs (M or H) nano-array composites on copper foil deposited with lithium as provided in examples 1-4 of the present invention;
FIG. 6 is a constant current charge-discharge graph of the copper lithium half-cell provided in comparative example 1 of the present invention;
fig. 7 is a constant current charge-discharge curve of the copper lithium half-cell provided in embodiment 3 of the present invention;
FIG. 8 is a graph showing the cycle performance of the copper lithium half-cell provided in comparative example 1 and example 3 of the present invention;
FIG. 9 is a graph showing the cycle performance of the symmetrical cell provided in comparative example 1 of the present invention;
FIG. 10 is a graph showing the cycle performance of the symmetrical battery according to example 3 of the present invention;
FIG. 11 is a graph showing the cycle performance of the full cell provided in comparative example 1 of the present invention;
fig. 12 is a cycle performance chart of a full cell provided in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
The embodiment of the invention provides a preparation method of MOFs nano-array composite material grown in situ on copper foil, which has the process shown in figure 1 and comprises the following steps:
step 110, immersing the clean copper foil into hydrochloric acid to remove oxidized parts on the surface of the copper foil, and then performing primary drying treatment to obtain the copper foil to be compounded;
specifically, the copper foil in the present application is understood to be a single-sided copper foil composed of a copper side and a base material. The clean copper foil is placed with its copper side facing up in a petri dish, the petri dish is placed in a vacuum environment such as a glove box, and hydrochloric acid is then added to the petri dish so that the copper foil is completely immersed in the hydrochloric acid. Wherein the molar concentration of the hydrochloric acid is specifically 2mol/L to 5mol/L, preferably 3 mol/L. The soaking time is 15 minutes to 25 minutes, preferably 20 minutes. The vacuum environment can prevent the surface of the copper foil from being oxidized again.
The first drying treatment may be carried out in particular in a vacuum oven, at a temperature of in particular 60℃to 80℃and preferably 70 ℃. The time is specifically 2 hours to 5 hours, preferably 3 hours to 4 hours.
As a preferred scheme, dust, oil stains and the like on the surface of the copper foil can be cleaned by deionized water and absolute ethyl alcohol before the copper foil is immersed in hydrochloric acid, so that a clean copper foil is obtained.
Step 120, adding zirconium salt, benzoic acid and tetra-carboxyl phenyl porphyrin TCPP into N, N-dimethylformamide, and stirring to obtain metal organic framework compound MOFs precursor solution;
specifically, the molar ratio of zirconium salt, benzoic acid and TCPP is (4-5): (13-18): 1. The zirconium salt may specifically include one or more of zirconium chloride, zirconium dichloride hexahydrate, zirconium nitrate. Zirconium salt is used as a metal node and has good chemical stability.
Wherein, ligand center of tetracarboxy phenyl porphyrin TCPP can be introduced with no metal (represented by H) or can be introduced with transition metals such as Fe, co, N i, cu and the like (represented by M), and the transition metals can coordinate with nitrogen atoms, so that M-TCPP has M-N with lithium 4 The structure can effectively induce the nucleation of the metal lithium, thereby inhibiting the formation of lithium dendrite, improving the coulomb efficiency of the lithium metal battery, reducing the short circuit incidence rate of the lithium metal battery, prolonging the cycle life of the lithium metal battery and improving the safety performance.
And 130, immersing the copper foil to be compounded in MOFs precursor solution, performing heat treatment to coordinate copper ions on the surface of the copper foil to be compounded with carboxyl groups in the MOFs precursor solution, and performing washing, activating treatment and secondary drying treatment to obtain the MOFs nano-array composite material with the metal-organic framework compound grown on the copper foil in situ.
Specifically, the heat treatment may specifically be: firstly, transferring a precursor solution into a reaction kettle, and immersing a copper foil to be compounded into the precursor solution; the reaction vessel was then placed in a forced air drying oven. The temperature of the heat treatment may in particular be 110℃to 130℃and preferably 120 ℃. The time may be in particular from 12 hours to 16 hours, preferably 14 hours.
The washing can be performed by washing the copper foil with deionized water and absolute ethyl alcohol multiple times to remove the surface unreacted TCPP molecules or simply physically adhered arrays of MOFs.
The activation treatment is specifically to immerse the coordinated copper foil in acetone for 8-12 minutes, take out and then wash with acetone, and repeat the above steps for a plurality of times to remove N, N-dimethylformamide and other impurities in MOFs pore channels.
The second drying treatment is carried out in particular in a vacuum oven at a temperature of in particular 75℃to 95℃and preferably 80 ℃. The time is in particular 12 hours to 24 hours, preferably 18 hours.
MOFs grow in situ on the copper face in the copper foil by complexing a portion of the copper ions on the copper foil with carboxyl groups. The MOFs of the application have one-dimensional pore channels, have high crystallinity of the nano array, have high specific surface area and large pore channels, can increase the contact area of an electrode and lithium, improve the lithium deposition efficiency, and enable the metal lithium to be uniformly deposited, thereby obtaining the metal lithium anode with excellent electrochemical performance.
According to the preparation method of the MOFs nano-array composite material grown in situ on the copper foil, provided by the embodiment of the invention, copper ions on the surface of the copper foil are coordinated with MOFs, so that MOFs are grown in situ on the copper surface of the copper foil. The MOFs metal node constructed in situ is zirconium, so that the MOFs metal node has good chemical stability; the ligand molecule is TCPP, the ligand center can be anchored by nitrogen with transition metal M, M-N 4 The structure has good lithium affinity, and can effectively induce metal lithium nucleation, so that the formation of lithium dendrite is inhibited, the coulomb efficiency of the lithium metal battery is improved, the short circuit incidence rate of the lithium metal battery is reduced, the cycle life of the lithium metal battery is prolonged, and the safety performance is improved. In addition, the MOFs of the invention have one-dimensional pore channels, the nano array of the MOFs has high crystallinity and high specific surface area and large pore channels, the contact area between an electrode and lithium can be increased, the lithium deposition efficiency is improved, the metal lithium can be uniformly deposited, and the MOFs are prepared from the metal lithiumAnd a metallic lithium anode excellent in electrochemical properties is obtained. The excellent lithium affinity obviously reduces the interface impedance of the lithium metal anode, and activates the mass transfer kinetics of the anode interface, thereby greatly improving the cycle stability of the lithium metal battery.
The MOFs nano-array composite material grown in situ on the copper foil provided by the embodiment of the invention can be directly applied to electrodes of lithium metal batteries, and a binder is not required to be used, so that side reactions caused by decomposition of the binder in the traditional lithium metal electrodes are avoided.
In order to better understand the technical scheme provided by the invention, the following specific processes of preparing MOFs nano-array composite materials in situ on the copper foil by applying the method provided by the embodiment of the invention and the electrochemical characteristics of the MOFs nano-array composite materials in situ on the prepared copper foil are respectively described in a plurality of specific examples.
Example 1
Firstly, taking 2 cm by 2 cm copper foil, wiping the surface of the copper foil with deionized water and ethanol, placing the copper surface of the copper foil in a culture dish upwards, placing the culture dish in a vacuum glove box, adding 3mol/L hydrochloric acid into the culture dish, and soaking the copper foil for 20 minutes at room temperature. And then taking out the copper foil, and drying the copper foil in a vacuum drying oven with the temperature of 70 ℃ for 3 hours to obtain the copper foil to be compounded.
And secondly, weighing 0.12g of zirconium chloride, 0.22g of benzoic acid and 0.07g of TCPP without a metal center according to the molar ratio of zirconium salt to benzoic acid to TCPP of 5:18:1, adding the zirconium chloride, the benzoic acid and the TCPP into 50mL of N, N-dimethylformamide, stirring and dissolving the mixture, and obtaining a metal organic framework compound MOFs precursor solution.
And thirdly, transferring the precursor solution into a reaction kettle, immersing the copper foil to be compounded into the MOFs precursor solution, and then placing the reaction kettle into a blast drying box for heat treatment, wherein the heat treatment temperature is 120 ℃ and the time is 14 hours.
And fourthly, taking out the copper foil, flushing the copper foil with deionized water for three times, and flushing the copper foil with absolute ethyl alcohol for three times. The copper foil was immersed in acetone for 10 minutes, taken out, and then washed with acetone three times.
And fifthly, placing the copper foil in a vacuum drying oven for drying at the temperature of 80 ℃ for 18 hours. Thus, MOFs (H) nano-array composite material which is grown in situ on the copper foil is obtained and is abbreviated as MOFs (H) @ Cu.
The metal organic framework compound MOFs nano-array composite MOFs (H) @ Cu in situ grown on the copper foil prepared by the embodiment of the application is used for respectively assembling and testing half batteries, symmetrical batteries and full batteries, and the method comprises the following steps of:
assembling a copper-lithium half cell: first, the obtained MOFs (H) @ Cu was cut into positive electrode sheets of 13 mm. And secondly, assembling the lithium copper half battery by utilizing the positive electrode plate. Wherein, the electrolyte of the assembled lithium-copper half cell is 1mol/L lithium bistrifluoromethyl sulfonate imide (LiTFSI), the solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), and the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. The lithium sheet is the negative electrode. Then, at a current density of 2mA/cm 2 Cut-off capacity of 2mAh/cm 2 And under the condition, performing constant-current charge and discharge test.
Assembling a symmetrical battery: first, 5mAh of lithium was deposited on MOFs (H) @ Cu to give +.>Second, by +.>In the form of an assembled symmetrical battery. The assembled symmetrical electric electrolyte is 1mol/L lithium bistrifluoromethane sulfonate (LiTFSI), the solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), and the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. Then, at a current density of 1mA/cm 2 Cut-off capacity of 1mAh/cm 2 And under the condition, performing constant-current charge and discharge test.
And (3) assembling a full battery: firstly, uniformly mixing lithium iron phosphate, polyvinylidene fluoride (PVDF) and Super P according to the mass ratio of 90:5:5, adding into 500 mu L of N-methyl pyrrolidone (NMP), ball-milling to uniform slurry, coating on aluminum foil, then placing into a vacuum oven, drying at 80 ℃ for 12 hours, and then cutting into pole pieces with the diameter of 10mm, namely lithium iron phosphate (LFP) positive pole pieces. Second, by +.>Is a negative electrode, LFP is a positive electrode, and is assembled +.>And (3) a full battery. Lithium hexafluorophosphate LiPF with electrolyte of 1mol/L in full cell 6 The solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), wherein the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. Then, a constant current charge and discharge test was performed under the condition that the charge and discharge magnification was 0.5C.
Example 2
Firstly, taking 2 cm by 2 cm copper foil, wiping the surface of the copper foil with deionized water and ethanol, placing the copper surface of the copper foil in a culture dish upwards, placing the culture dish in a vacuum glove box, adding 2mol/L hydrochloric acid into the culture dish, and soaking the copper foil for 15 minutes at room temperature. And then taking out the copper foil, and drying the copper foil in a vacuum drying oven at the temperature of 60 ℃ for 4 hours to obtain the copper foil to be compounded.
Secondly, weighing 0.12g of zirconium dichloride hexahydrate, 0.15g of benzoic acid and 0.08g of Fe-TCPP according to the mol ratio of zirconium salt to benzoic acid to TCPP of 4:13:1, adding the zirconium dichloride hexahydrate, the benzoic acid and the Fe-TCPP into 50mL of N, N-dimethylformamide, stirring and dissolving the mixture to obtain MOFs precursor solution of the metal organic framework compound.
And thirdly, transferring the precursor solution into a reaction kettle, immersing the copper foil to be compounded into the MOFs precursor solution, and then placing the reaction kettle into a blast drying box for heat treatment, wherein the heat treatment temperature is 110 ℃ and the time is 16 hours.
And fourthly, taking out the copper foil, flushing the copper foil with deionized water for three times, and flushing the copper foil with absolute ethyl alcohol for three times. The copper foil was immersed in acetone for 8 minutes, taken out, and then washed with acetone three times.
And fifthly, placing the copper foil in a vacuum drying oven for drying at the temperature of 95 ℃ for 12 hours. Thus, MOFs (Fe) nano-array composite material which is grown in situ on the copper foil is obtained and is abbreviated as MOFs (Fe) @ Cu, wherein Fe represents that the ligand center of the MOFs is an iron atom.
The metal organic framework compound MOFs nano-array composite MOFs (Fe) @ Cu grown in situ on the copper foil prepared in the embodiment of the application is used for respectively assembling and testing half batteries, symmetrical batteries and full batteries, and the method comprises the following steps of:
assembling a copper-lithium half cell: first, the obtained MOFs (Fe) @ Cu was cut into positive electrode sheets of 13 mm. And secondly, assembling the lithium copper half battery by utilizing the positive electrode plate. Wherein, the electrolyte of the assembled lithium-copper half cell is 1mol/L lithium bistrifluoromethyl sulfonate imide (LiTFSI), the solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), and the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. The lithium sheet is the negative electrode. Then, at a current density of 2mA/cm 2 Cut-off capacity of 2mAh/cm 2 And under the condition, performing constant-current charge and discharge test.
Assembling a symmetrical battery: first, 5mAh of lithium was deposited on MOFs (Fe) @ Cu to give +.>Second, byIn the form of an assembled symmetrical battery. The assembled symmetrical electric electrolyte is 1mol/L lithium bistrifluoromethane sulfonate imide LiTFSI, the solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), whereinThe volume ratio of DME to DOL was 1:1. The diaphragm is Celgard. Then, at a current density of 1mA/cm 2 Cut-off capacity of 1mAh/cm 2 And under the condition, performing constant-current charge and discharge test.
And (3) assembling a full battery: firstly, uniformly mixing lithium iron phosphate, polyvinylidene fluoride (PVDF) and Super P according to the mass ratio of 90:5:5, adding into 500 mu L of N-methyl pyrrolidone (NMP), ball-milling to uniform slurry, coating on aluminum foil, then placing into a vacuum oven, drying at 80 ℃ for 12 hours, and then cutting into pole pieces with the diameter of 10mm, namely lithium iron phosphate (LFP) positive pole pieces. Second, byIs a negative electrode, LFP is a positive electrode, and is assembled +.>And (3) a full battery. Lithium hexafluorophosphate LiPF with electrolyte of 1mol/L in full cell 6 The solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), wherein the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. Then, a constant current charge and discharge test was performed under the condition that the charge and discharge magnification was 0.5C.
Example 3
Firstly, taking 2 cm by 2 cm copper foil, wiping the surface of the copper foil with deionized water and ethanol, placing the copper surface of the copper foil in a culture dish upwards, placing the culture dish in a vacuum glove box, adding 5mol/L hydrochloric acid into the culture dish, and soaking the copper foil for 25 minutes at room temperature. And then taking out the copper foil, and drying the copper foil in a vacuum drying oven with the temperature of 80 ℃ for 5 hours to obtain the copper foil to be compounded.
And secondly, weighing 0.07g of zirconium nitrate, 0.18g of benzoic acid and 0.08g of Co-TCPP according to the molar ratio of zirconium salt to benzoic acid to TCPP of 4:15:1, adding into 50mL of N, N-dimethylformamide, stirring and dissolving to obtain a metal organic framework compound MOFs precursor solution.
And thirdly, transferring the precursor solution into a reaction kettle, immersing the copper foil to be compounded into the MOFs precursor solution, and then placing the reaction kettle into a blast drying box for heat treatment, wherein the heat treatment temperature is 130 ℃ and the time is 12 hours.
And fourthly, taking out the copper foil, washing with deionized water four times, and washing with absolute ethyl alcohol three times. The copper foil was immersed in acetone for 12 minutes, taken out, and then washed with acetone four times.
And fifthly, placing the copper foil in a vacuum drying oven for drying at the temperature of 75 ℃ for 24 hours. Thus, MOFs (Co) nano-array composite material which is grown in situ on the copper foil is obtained and is abbreviated as MOFs (Co) @ Cu, wherein Co represents that the ligand center of the MOFs is cobalt atom.
The metal organic framework compound MOFs nano-array composite MOFs (Co) @ Cu grown in situ on the copper foil prepared in the embodiment of the application is used for respectively assembling and testing half batteries, symmetrical batteries and full batteries, and the method comprises the following steps of:
assembling a copper-lithium half cell: first, the obtained MOFs (Co) @ Cu was cut into positive electrode sheets of 13 mm. And secondly, assembling the lithium copper half battery by utilizing the positive electrode plate. Wherein, the electrolyte of the assembled lithium-copper half cell is 1mol/L lithium bistrifluoromethyl sulfonate imide (LiTFSI), the solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), and the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. The lithium sheet is the negative electrode. Then, at a current density of 2mA/cm 2 Cut-off capacity of 2mAh/cm 2 And under the condition, performing constant-current charge and discharge test.
Assembling a symmetrical battery: first, 5mAh of lithium was deposited on MOFs (Co) @ Cu to give +.>Second, byIn the form of an assembled symmetrical battery. The assembled symmetrical electric electrolyte is 1mol/L lithium bistrifluoromethane sulfonate (LiTFSI), the solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), and the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. Then, at a current density of 1mA/cm 2 Cut-off capacity of 1mAh/cm 2 And under the condition, performing constant-current charge and discharge test.
And (3) assembling a full battery: firstly, uniformly mixing lithium iron phosphate, polyvinylidene fluoride (PVDF) and Super P according to the mass ratio of 90:5:5, adding into 500 mu L of N-methyl pyrrolidone (NMP), ball-milling to uniform slurry, coating on aluminum foil, then placing into a vacuum oven, drying at 80 ℃ for 12 hours, and then cutting into pole pieces with the diameter of 10mm, namely lithium iron phosphate (LFP) positive pole pieces. Second, byIs a negative electrode, LFP is a positive electrode, and is assembled +.>And (3) a full battery. Lithium hexafluorophosphate LiPF with electrolyte of 1mol/L in full cell 6 The solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), wherein the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. Then, a constant current charge and discharge test was performed under the condition that the charge and discharge magnification was 0.5C.
Example 4
Firstly, taking 2 cm by 2 cm copper foil, wiping the surface of the copper foil with deionized water and ethanol, placing the copper surface of the copper foil in a culture dish upwards, placing the culture dish in a vacuum glove box, adding 4mol/L hydrochloric acid into the culture dish, and soaking the copper foil at room temperature for 22 minutes. And then taking out the copper foil, and drying the copper foil in a vacuum drying oven at the temperature of 75 ℃ for 4.5 hours to obtain the copper foil to be compounded.
And secondly, weighing 0.12g of zirconium chloride, 0.18g of benzoic acid and 0.08g of Ni-TCPP according to the molar ratio of zirconium salt to benzoic acid to TCPP of 5:15:1, adding into 50mL of N, N-dimethylformamide, stirring and dissolving to obtain a metal organic framework compound MOFs precursor solution.
And thirdly, transferring the precursor solution into a reaction kettle, immersing the copper foil to be compounded into the MOFs precursor solution, and then placing the reaction kettle into a blast drying box for heat treatment, wherein the heat treatment temperature is 125 ℃ and the time is 15 hours.
And fourthly, taking out the copper foil, washing with deionized water four times, and washing with absolute ethyl alcohol three times. The copper foil was immersed in acetone for 11 minutes, taken out, and then washed with acetone four times.
And fifthly, placing the copper foil in a vacuum drying oven for drying at 90 ℃ for 14 hours. Thus, MOFs (Ni) nano-array composite material which is grown in situ on the copper foil is obtained and is abbreviated as MOFs (Ni) @ Cu, wherein Ni represents that the ligand center of the MOFs is nickel atom.
The metal organic framework compound MOFs nano-array composite MOFs (Ni) @ Cu prepared by the embodiment of the application is used for respectively assembling and testing half batteries, symmetrical batteries and full batteries, and the metal organic framework compound MOFs nano-array composite MOFs (Ni) @ Cu is specifically as follows:
assembling a copper-lithium half cell: first, the obtained MOFs (Ni) @ Cu was cut into positive electrode sheets of 13 mm. And secondly, assembling the lithium copper half battery by utilizing the positive electrode plate. Wherein, the electrolyte of the assembled lithium-copper half cell is 1mol/L lithium bistrifluoromethyl sulfonate imide (LiTFSI), the solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), and the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. The lithium sheet is the negative electrode. Then, at a current density of 2mA/cm 2 Cut-off capacity of 2mAh/cm 2 And under the condition, performing constant-current charge and discharge test.
Symmetrical battery packAnd (3) loading: first, 5mAh of lithium was deposited on MOFs (Ni) @ Cu to give +.>Second, byIn the form of an assembled symmetrical battery. The assembled symmetrical electric electrolyte is 1mol/L lithium bistrifluoromethane sulfonate (LiTFSI), the solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), and the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. Then, at a current density of 1mA/cm 2 Cut-off capacity of 1mAh/cm 2 And under the condition, performing constant-current charge and discharge test.
And (3) assembling a full battery: firstly, uniformly mixing lithium iron phosphate, polyvinylidene fluoride (PVDF) and Super P according to the mass ratio of 90:5:5, adding into 500 mu L of N-methyl pyrrolidone (NMP), ball-milling to uniform slurry, coating on aluminum foil, then placing into a vacuum oven, drying at 80 ℃ for 12 hours, and then cutting into pole pieces with the diameter of 10mm, namely lithium iron phosphate (LFP) positive pole pieces. Second, byIs a negative electrode, LFP is a positive electrode, and is assembled +.>And (3) a full battery. Lithium hexafluorophosphate LiPF with electrolyte of 1mol/L in full cell 6 The solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), wherein the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. Then, a constant current charge and discharge test was performed under the condition that the charge and discharge magnification was 0.5C.
Comparative example 1
The surface of the copper foil was wiped clean with deionized water and ethanol, the copper side of the copper foil was placed in a dish, the dish was placed in a vacuum glove box, 4mol/L hydrochloric acid was added to the dish, and the copper foil was immersed at room temperature for 22 minutes. Then, the copper foil was taken out and dried in a vacuum drying oven at 75℃for 4.5 hours to obtain a clean copper foil, abbreviated as bare Cu.
The assembly and testing of half cells, symmetrical cells and full cells were performed separately using clean copper foil, as follows:
assembling a copper-lithium half cell: first, the obtained bare Cu was cut into a positive electrode sheet of 13 mm. And secondly, assembling the lithium copper half battery by utilizing the positive electrode plate. Wherein, the electrolyte of the assembled lithium-copper half cell is 1mol/L lithium bistrifluoromethyl sulfonate imide (LiTFSI), the solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), and the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. The lithium sheet is the negative electrode. Then, at a current density of 2mA/cm 2 Cut-off capacity of 2mAh/cm 2 And under the condition, performing constant-current charge and discharge test.
Assembling a symmetrical battery: first, 5mAh of lithium was deposited on bare Cu to give +.>Second, by +.>In the form of an assembled symmetrical battery. The assembled symmetrical electric electrolyte is 1mol/L lithium bistrifluoromethane sulfonate (LiTFSI), the solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), and the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. Then, at a current density of 1mA/cm 2 Cut-off capacity of 1mAh/cm 2 And under the condition, performing constant-current charge and discharge test.
And (3) assembling a full battery: firstly, uniformly mixing lithium iron phosphate, polyvinylidene fluoride (PVDF) and Super P according to the mass ratio of 90:5:5, adding into 500 mu L of N-methyl pyrrolidone (NMP), ball-milling to uniform slurry, coating on aluminum foil, then placing into a vacuum oven, drying at 80 ℃ for 12 hours, and then cutting into pole pieces with the diameter of 10mm, namely lithium iron phosphate (LFP) positive pole pieces. Second, by +.>Is a negative electrode, LFP is a positive electrode, and is assembled +.> And (3) a full battery. Lithium hexafluorophosphate LiPF with electrolyte of 1mol/L in full cell 6 The solvent of the electrolyte is a mixed solution of dimethyl ether (DME) and Dioxolane (DOL), wherein the volume ratio of DME to DOL is 1:1. The diaphragm is Celgard. Then, a constant current charge and discharge test was performed under the condition that the charge and discharge magnification was 0.5C.
The results of the tests and electrochemical properties of the materials prepared in comparative example 1 and examples 1 to 4 are briefly described below in connection with fig. 2 to 12.
Fig. 2 is a scanning electron microscope image of in-situ growth of MOFs (Co) nano-array composite material on copper foil according to example 3 of the present invention, and it can be seen that MOFs (Co) nano-arrays are uniformly grown on copper foil.
FIG. 3 is an SEM image of lithium deposition on bare Cu of comparative example 1, wherein the copper foil has a thickness of 50.5. Mu.m. The thickness of the deposited lithium was 26.3 μm in some cases and 8.1 μm in others; FIG. 4 is an SEM image of an in situ grown MOFs (Co) nanoarray composite with lithium deposition on copper foil of example 3, where the copper foil has a thickness of 49.4 μm and the deposited lithium has a thickness of 12.4. Mu.m. Therefore, MOFS (Co) grown in situ on the surface of the copper foil of example 3 can well guide uniform deposition of lithium, and thus can suppress growth of lithium dendrites, compared to comparative example 1 in which no MOFS is built on the surface of the copper foil.
FIG. 5 shows XRD patterns of MOFs (M or H) nano-array composites grown in situ on copper foil by lithium deposition as provided in examples 1-4 of the present invention, and it is understood from FIG. 5 that MOFs diffraction peaks grown on copper foil are unchanged regardless of whether the ligand center is incorporated with a metal atom.
As shown in fig. 6, the overpotential of the assembled copper lithium half cell of comparative example 1 increased from 55mV to 155mV after 100 cycles. While the assembled copper lithium half-cell of example 3 shown in fig. 7 remained at an overpotential of 50mV after 100 cycles. Referring again to fig. 8, and referring again to fig. 8, the coulombic efficiency of the copper lithium half-cell of comparative example 1 was significantly reduced after 60 cycles. While the coulombic efficiency of the copper lithium half-cell in example 3 remained above 98% after 290 cycles. This indicates that lithium deposition on copper foil grown with MOFs nano-arrays can form a more stable solid electrolyte interface.
In comparative example 1 shown in FIG. 9Symmetrical cell with polarization overpotential of 0.4V at 1mA/cm 2 Can only be cycled steadily for 100 turns at the current density, and the polarization overpotential increases suddenly after 100 turns. Whereas in example 3 shown in fig. 10 +.>Symmetrical cell with polarization overpotential of 0.08V capable of 1mA/cm 2 For more than 800 cycles of stable cycling at a current density, the polarization overpotential increases slowly after 800 cycles. Therefore, the lithium metal anode with the MOFs nano array can provide a more stable interface for deposition and stripping of lithium metal, so that the reaction kinetics of the lithium metal battery is improved.
As can be seen from FIG. 11, the comparative exampleFull cell: the initial discharge specific capacity is 129mAh/g, the initial effect is 93.4%, and the capacity retention rate after 50 circles of circulation is 84.73%. Embodiment->Full cell: the initial discharge specific capacity is 133mAh/g, the initial effect is 94.1%, and the capacity retention rate after 50 circles of circulation is 96.72%. Therefore, dendrite-free lithium deposited by the MOFs nano-array composite material grown in situ on the copper foil in example 3 can greatly improve the cycle stability of the lithium metal battery.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the MOFs nano-array composite material grown in situ on the copper foil is characterized by comprising the following steps of:
immersing clean copper foil into hydrochloric acid to remove oxidized parts on the surface of the copper foil, and then performing primary drying treatment to obtain the copper foil to be compounded;
adding zirconium salt, benzoic acid and tetracarboxyl phenyl porphyrin TCPP into N, N-dimethylformamide, and stirring to obtain MOFs precursor solution of the metal organic framework compound;
immersing the copper foil to be compounded into the MOFs precursor solution, performing heat treatment to coordinate copper ions on the surface of the copper foil to be compounded with carboxyl groups in the MOFs precursor solution, and then performing washing, activating treatment and secondary drying treatment to obtain the MOFs nano-array composite material with the metal-organic framework compound grown on the copper foil in situ.
2. The method according to claim 1, wherein the molar ratio of zirconium salt, benzoic acid and TCPP is (4-5): 13-18): 1.
3. The method of claim 1, wherein the zirconium salt comprises one or more of zirconium chloride, zirconium dichloride hexahydrate, zirconium nitrate.
4. The process according to claim 1, wherein the molar concentration of hydrochloric acid is 2mol/L to 5mol/L.
5. The preparation method according to claim 1, wherein the first drying treatment is performed in a vacuum drying oven, at a temperature of 60 ℃ to 80 ℃ for a time of 2 hours to 5 hours.
6. The preparation method according to claim 1, wherein the heat treatment is carried out in particular in a forced air drying oven at a temperature of 110 ℃ to 130 ℃ for a time of 12 hours to 16 hours.
7. The preparation method according to claim 1, wherein the second drying treatment is performed in a vacuum drying oven, at a temperature of 75-95 ℃ for 12-24 hours.
8. An in-situ grown MOFs nano-array composite material on a copper foil, characterized in that the in-situ grown MOFs nano-array composite material on a copper foil is prepared by the preparation method of any one of claims 1-7.
9. A negative electrode sheet, characterized in that the negative electrode sheet is a MOFs nano-array composite material grown in situ on the copper foil of claim 8.
10. A lithium metal battery comprising the negative electrode tab of claim 9.
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