CN111653760B - Two-dimensional metal sheet and preparation method and application thereof - Google Patents

Two-dimensional metal sheet and preparation method and application thereof Download PDF

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CN111653760B
CN111653760B CN202010360687.5A CN202010360687A CN111653760B CN 111653760 B CN111653760 B CN 111653760B CN 202010360687 A CN202010360687 A CN 202010360687A CN 111653760 B CN111653760 B CN 111653760B
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zinc
rolling
folding
dimensional
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CN111653760A (en
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陈立宝
武晨
韦伟峰
陈月皎
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Central South University
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

Abstract

The invention relates to a two-dimensional metal sheet and a preparation method and application thereof; the preparation method of the invention uses the surface passivation (mainly oxide) existing in the metal itself as the barrier layer, folds and/or laminates-rolls the pure metal or alloy sheet by mechanical plastic deformation, and then strips to prepare the two-dimensional metal sheet. The method of the invention can be used for large-scale preparation and has high efficiency. The zinc metal cathode with the hierarchical structure formed by performing carbon coating modification on the two-dimensional zinc metal sheet prepared by the method has excellent electrochemical performance and can realize stable circulation.

Description

Two-dimensional metal sheet and preparation method and application thereof
Technical Field
The invention relates to a two-dimensional metal sheet and a preparation method and application thereof, belonging to the technical field of two-dimensional material preparation.
Background
The traditional two-dimensional material is a material which consists of a single layer or a few layers of atoms or molecular layers, wherein the layers are connected by strong covalent bonds or ionic bonds, and the layers are combined by weak van der waals force, such as graphene, transition metal sulfide, black phosphorus, Mxene and the like. For materials such as metal which are not in a laminated structure, the difficulty of preparing the two-dimensional morphology is high due to the isotropy of metal bonds. Meanwhile, the performance of metals is closely related to the shape, structure, composition and the like of the metals, particularly, the two-dimensional metal nano material has a two-dimensional structure with the thickness of a plurality of unique metal atomic layers, has large specific surface area, surface energy and abundant surface metal active sites, and shows great application prospects in the fields of energy storage such as batteries, catalysis and the like, so that the preparation of the two-dimensional metal nano material becomes a hot spot. The method for preparing the two-dimensional metal nano material at the present stage mainly comprises a chemical method and a physical method, and comprises a two-dimensional template limited domain growth method, a seed crystal growth method, hydrothermal synthesis, a self-assembly method, mechanical pressing, a stripping method and the like. These methods are more used for the production of two-dimensional materials of precious metals, and for non-precious metals, it is an effective method to reduce the size by plastic deformation using mechanical pressing. The current mechanical pressing method is to use two metal foils such as gold/aluminum, silver/aluminum, aluminum/tin, etc. to roll-fold repeatedly, then etch off one of the components (aluminum, tin, etc.) with alkali or acid solution, and finally strip. For noble metals, this is a very effective method for preparing two-dimensional nanomaterials, but for amphoteric metals such as zinc, aluminum, or more active metals, the following limitations mainly exist: 1. selection of sacrificial metal foil: selecting a foil material with a similar deformation amount to a target metal material to prevent the metal foils of the two components from deforming in an inconsistent manner in the mechanical pressing process; 2. in the subsequent etching process, since zinc, aluminum, etc. are amphoteric metals themselves, and a part of the metals are etched away by acid or alkali, the preparation is not efficient.
Disclosure of Invention
In view of the shortcomings of the prior art, a first object of the present invention is to provide a method for preparing a two-dimensional metal sheet. The preparation method of the invention uses the surface passivation (mainly oxide) existing in the metal itself as the barrier layer, and adopts mechanical plastic deformation to fold and/or stack-roll the pure metal or alloy sheet; and then ultrasonic stripping is carried out to prepare the two-dimensional metal sheet, the preparation method is efficient, and the obtained two-dimensional metal sheet is high in purity.
The second purpose of the invention is to provide the two-dimensional metal sheet prepared by the preparation method.
The third purpose of the invention is to provide the application of the two-dimensional metal sheet prepared by the preparation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a preparation method of a two-dimensional metal sheet, which comprises the following steps: and folding and/or laminating the metal foil with the surface containing the passivation layer, then rolling, wherein the folding and/or laminating-rolling times are more than or equal to 1 time, and stripping the obtained product to obtain the two-dimensional metal sheet.
In the present invention, the metal foil is folded and/or laminated and then rolled, and then at least one of arbitrary folding and/or lamination is repeated and then rolled.
Preferably, the preparation method of the two-dimensional metal sheet comprises the following steps: and folding the metal foil with the surface containing the passivation layer, then rolling for more than or equal to 1 time, and placing the obtained product in a solution for ultrasonic stripping to obtain the two-dimensional metal sheet.
The invention relates to a preparation method of a two-dimensional metal sheet, wherein a passivation substance in a passivation layer comprises an oxide, and the oxide is obtained by air natural oxidation.
The metal in the metal foil according to the invention is suitable for all relatively reactive metal materials or amphoteric metals or alloys of these metal elements whose surface is susceptible to the formation of a thin layer of passivation (mainly oxides) in air.
For metals that tend to form passivation (primarily oxides) in air, the passivation layer formed is very thin and also dense, protecting the inner metal from oxidation. If other methods such as heating are used for oxidation, the oxide layer formed on the surface layer is too thick, and the subsequent rolling cannot be smoothly performed.
Preferably, in the method for producing a two-dimensional metal sheet according to the present invention, the metal in the metal foil is at least one selected from the group consisting of zinc, aluminum, copper, iron, nickel, magnesium, lead, and tin.
Further preferably, the metal in the metal foil is selected from at least one of zinc, aluminum, and copper.
The invention relates to a preparation method of a two-dimensional metal sheet, wherein the thickness of a metal foil is 10-100 mu m.
The method of the invention is to reduce the thickness by plastically deforming the metal foil by repeated mechanical pressing.
In the actual operation process, the metal foil is cut into a shape suitable for being folded in half, such as a rectangle, and is subjected to ultrasonic treatment in an acetone/ethanol solution for half an hour in advance to remove oil and impurities on the surface for later use.
Preferably, the invention relates to a method for producing a two-dimensional metal sheet, wherein the total reduction is equal to or less than 50% and the single-pass reduction is equal to or less than 50%, preferably the single-pass reduction is equal to or less than 20%, during said one-cycle folding and/or stacking-rolling operation.
The inventor finds that too large reduction can cause severe plastic deformation and uneven deformation of the metal, so that the metal sheet is adhered, and the subsequent peeling is difficult, therefore, the total reduction is controlled to be less than or equal to 50 percent in the folding and/or laminating-rolling operation process of one cycle, and the single-pass reduction is controlled to be less than or equal to 20 percent preferably by adopting multi-pass rolling, so that the better deformation uniformity of the metal can be ensured.
In the actual operation process, the cleaned metal foil is folded completely or a plurality of metal foils with the same shape and thickness are folded after being folded, or a plurality of metal foils with the same shape and thickness are laminated, and then a roller machine is adopted for mechanical rolling; and then repeating the folding and/or laminating operation, and continuing to perform mechanical rolling by using a roller machine.
Preferably, the present invention relates to a method for producing a two-dimensional metal sheet, wherein the number of folding and/or stacking-rolling is 1 to 100, preferably 5 to 20.
In the actual operation process, different folding and/or stacking-rolling times are required according to the thickness of the required two-dimensional metal sheet, if the thickness in the micrometer scale is required to be obtained, the folding and/or stacking-rolling times are selected less, and if the thickness in the nanometer scale is required to be obtained, the folding and/or stacking-rolling times are selected more.
Preferably, the method for preparing a two-dimensional metal sheet according to the present invention is a solution that does not have an oxidation effect on a metal, and is preferably at least one selected from the group consisting of ethanol, formamide, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), Dimethylsulfoxide (DMSO), isopropyl alcohol (IPA), and methanol (MeOH).
Preferably, in the preparation method of the two-dimensional metal sheet, the time of ultrasonic stripping is more than or equal to 1 hour, and preferably 2 to 4 hours.
The invention also provides the two-dimensional metal sheet prepared by the preparation method. The two-dimensional metal sheet is substantially defect free.
Preferably, the transverse dimension of the two-dimensional metal sheet can reach micron level, and the thickness is micron level or nanometer level.
The invention also provides application of the two-dimensional metal sheet prepared by the preparation method, and the two-dimensional metal sheet is used as a negative electrode material to be applied to a metal ion battery after being subjected to carbon coating modification.
Preferably, the metal in the two-dimensional metal sheet is zinc.
Further preferably, the two-dimensional metal sheet is a zinc micron sheet.
Preferably, the metal-ion battery is a zinc-ion battery.
Preferably, the negative electrode material is a carbon-coated two-dimensional metal sheet, preferably a carbon-coated zinc micron sheet.
Preferably, the specific process of the carbon coating modification is as follows: and dispersing the two-dimensional metal sheet by using a solution containing a carbon binder precursor, then depositing the carbon binder precursor and the two-dimensional metal sheet on a stainless steel net together, and then carrying out carbonization treatment in an inert atmosphere.
In the present invention, carbon-containing binder precursors of the prior art are all suitable for use in the present invention.
Further preferably, the carbon-containing binder precursor is selected from at least one of carboxymethyl cellulose, sodium alginate and gelatin.
Further preferably, the temperature of the carbonization treatment is 300-400 ℃, preferably 350 ℃, the time is more than or equal to 1h, preferably 1h, and the temperature rise rate is 1-10 ℃/min, preferably 1 ℃/min.
Principles and advantages
The invention provides a preparation method of a two-dimensional metal sheet. The preparation method of the invention uses the surface passivation (mainly oxide) existing in the metal itself as the barrier layer, adopts mechanical plastic deformation to carry out multiple folding and/or laminating-rolling on the pure metal or alloy, and then carries out ultrasonic stripping on the obtained product to prepare the two-dimensional metal sheet.
The active metal such as zinc and aluminum can spontaneously form a thin oxide film on the surface in the air, and can be used as a barrier layer to prevent adjacent metal layers from forming metal bonds for bonding in the rolling process, and the adjacent oxide layers cannot form chemical bonds in the room-temperature rolling and laminating process, so that the adjacent metal layers can be easily separated by ultrasonic waves in the subsequent ultrasonic stripping process. By utilizing the oxide layer, metal foil can be repeatedly folded and/or laminated-rolled, metal is rolled by mechanical pressure, the metal foil reaches the micron level or even the nanometer level by changing the times of folding and/or laminating-rolling, and then the rolled laminated metal is put into ethanol, formamide or other solutions which are not easy to cause metal oxidation for stripping under the assistance of ultrasound, so that the high-purity two-dimensional metal sheet with the thickness of the nanometer level or the micrometer level and the transverse dimension of the micrometer level is obtained. The preparation method does not need an etching step, reduces the consumption of target metal as much as possible, and is more efficient.
In addition, the prepared zinc micron sheet is deposited on a stainless steel net by using carbon precursor binders such as carboxymethyl cellulose, and then the carboxymethyl cellulose binders are carbonized in situ under inert atmosphere to prepare the carbon-coated zinc micron sheet cathode, so that the carbon-coated zinc micron sheet cathode can obtain good performance when being applied to a zinc ion battery.
Drawings
FIG. 1 is a process flow diagram of the present invention, wherein FIG. 1a shows a preparation flow diagram, by multiple fold-rolling; finally, preparing the two-dimensional metal material by ultrasonic. Fig. 1b shows a schematic diagram of a preparation process and a finished product of the carbon-coated zinc micron sheet cathode, which is a multilayer structure.
FIG. 2 is a graph of XPS-Zn2p showing the surface of the zinc foil in example 1.
FIG. 3 is a scanning electron microscope photograph of a cross section of example 1 after folding-rolling was performed 15 times.
Fig. 4 is a phase XRD pattern of zinc nanoplates obtained after 3 hours of sonication with ethanol in example 1.
Fig. 5 is a transmission electron microscopy image and a selected area electron diffraction pattern of the morphology of the zinc nanoplates prepared in example 1.
FIG. 6 is a high resolution image of the zinc nanoplates prepared in example 1, with a measured interplanar spacing of 0.247 nm, consistent with the (002) interplanar spacing of the hexagonal zinc phase (JCPDS No. 65-5973).
Fig. 7 is an atomic force microscope image of the zinc nanoplates prepared in example 1, measured to a thickness of 42.77 nm.
Fig. 8 is a phase diagram of the zinc nanoplatelets and the carbon-coated zinc nanoplatelets prepared in example 2.
Fig. 9 is a morphology of the zinc nanoplatelets and the carbon-coated zinc nanoplatelets of example 2 and a cross-sectional view of the prepared electrodes. Wherein, fig. 9a is a profile of a scanning electron microscope for zinc nanoplatelets, fig. 9b is a profile of a scanning electron microscope for carbon-coated zinc nanoplatelets, fig. 9c is a profile and a high resolution of a transmission electron microscope for carbon-coated zinc nanoplatelets, and fig. 9d is a cross-sectional scanning electron microscope for prepared carbon-coated zinc nanoplatelets.
Fig. 10 is a graph of full cell performance of the carbon coated zinc micron sheet negative electrode paired with a pure zinc foil negative electrode symmetric cell and paired with manganese dioxide of example 2.
Fig. 11 is a phase structure topography of the aluminum nanosheet prepared in example 3, wherein fig. 11a is a phase XRD pattern, fig. 11b is a cross-sectional topography of the aluminum foil after 20 times of repeated folding-rolling, fig. 11c is a transmission electron microscopy pattern and a high resolution pattern of the topography of the prepared aluminum nanosheet, and fig. 11d is an atomic force microscopy pattern of the prepared aluminum nanosheet.
Fig. 12 is a phase structure morphology diagram of copper nanosheets in example 4, wherein fig. 12a is a phase XRD diagram. FIG. 12b is a cross-sectional profile of the copper foil after 20 times of repeated folding-rolling. Fig. 12c is a transmission electron microscopy image and a high resolution image of the morphology of the prepared copper nanoplate. Fig. 12d is an atomic force microscope image of the prepared copper nanoplates.
Fig. 13 is a cross-sectional profile of samples of zinc metal two-dimensional sheets of different thicknesses, wherein fig. 13a is an atomic force microscope image of the zinc metal sheet after 10 fold-rolling and ultrasonic peeling in example 5, and fig. 13b is a cross-sectional profile of the zinc metal layer sheet of the laminate after 5 fold-rolling in example 2.
FIG. 14 is a XRD pattern of the phase of zinc nanoplatelets prepared by exfoliation in example 6 using formamide as the ultrasonic solution.
Fig. 15 phase XRD pattern of zinc nanoplatelets prepared in comparative example 1.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
The main principle of the invention is that a surface ultra-thin layer passivation (mainly oxide) layer formed by more active metal or amphoteric metal and alloy in the air is used as a barrier layer, the metal foil is repeatedly folded and/or laminated-rolled to enable the thickness of the material to reach the micron/nanometer level, and then ultrasonic stripping is carried out to form micron/nanometer sheets.
The invention is described below by means of exemplary embodiments. It should be noted that the following examples are given by way of illustration only and are not meant to limit the invention in any way, as will be readily understood by those skilled in the art.
Example 1
The zinc metal nano-sheet and the zinc micron sheet are prepared by repeated folding-rolling and ultrasonic stripping treatment.
The thickness of the zinc metal foil before processing is 50 microns, the purity is 99.95 percent, and the zinc metal foil is cut into a rectangle;
the rolling equipment comprises: shenyang Kejing manual roller mill MR 350;
folding, wherein the rolling reduction of single pass is 20%, the total rolling reduction is controlled to be 50% of the original thickness by multiple rolling, then folding-rolling is carried out, and the cycle times are calculated according to the folding times;
number of folding-rolling times: 15 times;
the ultrasonic time is 3 h.
Zinc nanoplates having an average thickness of 42.77 nm were obtained.
FIG. 2 is a graph of XPS-Zn2p of a zinc foil surface showing the presence of oxides on the surface layer that can act as a barrier to the formation of chemical bonds between adjacent metal sheets during rolling.
Fig. 3 is a scanning electron microscope image of a cross section of the sheet after folding-rolling was performed 15 times, and it can be seen that the zinc sheets between the adjacent sheets were not bonded together.
Fig. 4 is a phase XRD pattern after 3 hours of sonication with ethanol, which shows that no other impurity phase is present and the purity is high.
Fig. 5 is a transmission electron microscope image of the morphology of the prepared zinc nanosheet and a selective area electron diffraction image, and it can be seen that the transverse dimension is about micron, which is a polycrystalline feature.
FIG. 6 is a high resolution image of the prepared zinc nanosheets, with a interplanar spacing of 0.247 nm, consistent with the (002) interplanar spacing of the hexagonal zinc phase (JCPDS No. 65-5973).
Fig. 7 is an atomic force microscope image of the prepared zinc nanoplates with a measured thickness of 42.77 nm.
Example 2
The other conditions were the same as in example 1 except that the number of folding-rolling times was 5, and finally zinc micro-meter sheets having a thickness of about micrometer were obtained.
Preparing carbon-coated zinc micron sheets:
depositing the prepared zinc micron sheet on a stainless steel net by using a carboxymethyl cellulose binder, and then carrying out in-situ carbonization treatment on the carboxymethyl cellulose binder in an argon-hydrogen (95/5, v/v) atmosphere to prepare the carbon-coated zinc micron sheet cathode, wherein the carbonization treatment temperature is 350 ℃, the time is 1h, and the heating rate is 1 ℃/min.
Fig. 8 is a phase diagram of zinc foil, prepared zinc nanoplatelets and carbon-coated zinc nanoplatelets without other heterogeneous phases.
Fig. 9 is a morphology diagram, and the adopted zinc micron sheet is a structure obtained by folding-rolling 5 times and then ultrasonically peeling, and it can be seen that a thin carbon layer is formed on the surface of the zinc micron sheet after the carboxymethyl cellulose is carbonized. The prepared electrode is in a multilayer structure.
Fig. 10 is a graph of full cell performance for a carbon-coated zinc micron sheet negative electrode, a pure zinc foil negative electrode symmetric cell, and paired with manganese dioxide. The composite material combines the multilayer structure of the micron sheet and the protection effect of the carbon layer, and shows good cycle performance in a water system weakly acidic symmetrical battery and a full battery matched with manganese oxide. ByThe symmetric battery composed of the carbon-coated zinc micron sheet negative electrode is 0.2mA/cm2And 0.1mAh/cm2Can be cycled for 850h under the condition of (1), and the voltage of a symmetrical battery with a pure zinc foil cathode is 0.2mA/cm2And 0.1mAh/cm2Can only be cycled for 67 hours under the condition (2); the full cell paired with the carbon-coated zinc micron sheet cathode and the manganese dioxide has the capacity of 217.4mA h/g after being cycled for 140 circles under the current density of 300mA/g, the coulombic efficiency is close to 100 percent, and the full cell paired with the pure zinc foil cathode and the manganese dioxide has the capacity of only 89.5mAh/g after being cycled for 55 circles under the current density of 300 mA/g.
Example 3:
and preparing the aluminum metal nanosheet by using a repeated folding-rolling mode and ultrasonic stripping treatment.
Before processing, the thickness of the aluminum metal foil is 20 microns, the purity is 99.9 percent, and the aluminum metal foil is cut into a rectangle;
equipment: shenyang Kejing manual roller mill MR 350;
folding, wherein the single-pass rolling reduction is 20%, the total rolling reduction is controlled to be 50% of the original thickness by multiple rolling, then folding-rolling is carried out, and the cycle times are calculated according to the folding times;
number of folding-rolling times: 20 times;
the ultrasonic time is 3 h.
Fig. 11 is a phase structure morphology diagram of the prepared aluminum nanosheet after folding-rolling for 20 times and ultrasonic peeling, wherein fig. 11a is a phase XRD diagram, and it can be seen that no other impurity phase exists and the purity is high. Fig. 11b is a cross-sectional profile of the aluminum foil after 20 times of repeated folding-rolling, with good separation between layers. FIG. 11c is a transmission electron microscopy image and a high resolution image of the morphology of the prepared aluminum nanoplate, showing that the transverse dimension is about 1 micron, and the measured interplanar spacing is 0.234 nm, which is consistent with the interplanar spacing of (111) of cubic aluminum phase (JCPDS No. 99-0005). Fig. 11d is an atomic force microscope image of the prepared aluminum nanoplates measuring 3.63 nm in thickness, about 13 layers of aluminum atoms thick.
Example 4
And preparing the copper metal nanosheet by using a repeated folding-rolling mode and ultrasonic stripping treatment.
Before processing, the thickness of the copper metal foil is 20 microns, the purity is 99.8%, and the copper metal foil is cut into a rectangle;
equipment: shenyang Kejing manual roller mill MR 350;
folding, wherein the single-pass rolling reduction is 20%, the total rolling reduction is controlled to be 50% of the original thickness by multiple rolling, then folding-rolling is carried out, and the cycle times are calculated according to the folding times;
number of folding-rolling times: 20 times;
the ultrasonic time is 3 h.
Fig. 12 is a phase structure morphology diagram of the prepared copper nanosheet after folding-rolling for 20 times and ultrasonic stripping, wherein fig. 12a is a phase XRD diagram, and it can be seen that no other impurity phase exists and the purity is high. Fig. 12b is a cross-sectional profile of the copper foil after 20 passes of iterative fold-rolling with good layer-to-layer separation. FIG. 12c is a transmission electron microscopy image and a high resolution image of the morphology of the prepared copper nanoplate, showing that the transverse dimension is about 1 micron, the measured interplanar spacing is 0.209 nm, and the interplanar spacing is consistent with the interplanar spacing of (111) cubic copper phase (JCPDS No. 85-1326). Fig. 12d is an atomic force microscope image of the copper nanoplates prepared, measuring 4.04 nm in thickness, about 16 layers of copper atoms thick.
Example 5
The other conditions were the same as in example 1 except that the number of folding-rolling times was 10, and finally zinc micro-sheets having a thickness of about several hundred nanometers were obtained.
Fig. 13 is a cross-sectional profile of a zinc metal two-dimensional sheet sample of different thickness, wherein fig. 13a is an atomic force microscope image of the zinc metal sheet after 10 folds-rolling and ultrasonic peeling in example 5, and the thickness can be seen to be about several hundred nanometers. Fig. 13b is a cross-sectional profile of the zinc metal sheet of example 2 after 5 fold-rolls and it can be seen that the individual zinc sheet dimensions are in the order of microns. This example illustrates that the thickness of a two-dimensional metal material can be varied by varying the number of folds and rolls.
Example 6
In example 1, a zinc metal two-dimensional sheet sample prepared by repeated folding-rolling and ultrasonic peeling treatments was ultrasonically peeled using 5 passes of rolling and a different solution, formamide. The XRD of the prepared sample phase is shown in figure 14, and the phase is relatively pure without other impurities.
In the course of the experiment, the invention also tried the following scheme:
1. after the metal foil is polished by abrasive paper to remove an oxide layer, the metal foil is folded and rolled under a protective atmosphere, and finally, the metal foil is not effectively stripped.
2. After a plurality of metal foils are laminated, the metal foils are rolled by one-time large rolling reduction, so that the peeling effect is poor, and large-area peeling is difficult to realize.
3. Stripping is more difficult during a single cycle of the fold-and-roll operation, with total reduction > 50% being controlled.
Comparative example 1
In example 1, the zinc foil and the aluminum foil with the same size are repeatedly folded and rolled for 5 times, then the aluminum foil is etched by using a sodium hydroxide solution, and then the aluminum foil is subjected to ultrasonic treatment to form the micron sheet, wherein the prepared zinc micron sheet contains more zinc oxide, and a phase XRD (X-ray diffraction) diagram is shown in figure 15.
The results of the examples and comparative examples show that the folding-rolling process using the oxide layer existing in the metal or alloy itself and the ultrasonic stripping are the method for preparing the high-efficiency and expandable high-purity metal nano/micron sheet.

Claims (3)

1. A preparation method of a two-dimensional metal sheet is characterized by comprising the following steps: the method comprises the following steps: folding the metal foil with the surface containing the passivation layer, and then rolling; the folding-rolling times are more than or equal to 1 time, and the obtained product is placed in a solution for ultrasonic stripping to obtain a two-dimensional metal sheet; the passivation in the passivation layer comprises an oxide obtained by natural oxidation of air;
in each folding-rolling operation process, the total reduction is 50%, and the single-pass reduction is less than or equal to 20%;
the number of folding-rolling times is 5-20;
the solution is at least one selected from ethanol, formamide, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, isopropanol and methanol.
2. A method of producing a two-dimensional metal sheet according to claim 1, wherein: the metal in the metal foil is at least one selected from zinc, aluminum, copper, iron, nickel, magnesium, lead and tin;
the thickness of the metal foil is 10-100 mu m.
3. A method of producing a two-dimensional metal sheet according to claim 1, wherein: the time of ultrasonic stripping is more than or equal to 1 h.
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