CN112421038A - Composite material of black phosphorus nanosheet coated with metal organic framework and preparation method and application thereof - Google Patents
Composite material of black phosphorus nanosheet coated with metal organic framework and preparation method and application thereof Download PDFInfo
- Publication number
- CN112421038A CN112421038A CN202011231954.5A CN202011231954A CN112421038A CN 112421038 A CN112421038 A CN 112421038A CN 202011231954 A CN202011231954 A CN 202011231954A CN 112421038 A CN112421038 A CN 112421038A
- Authority
- CN
- China
- Prior art keywords
- black phosphorus
- composite material
- phosphorus nanosheet
- organic framework
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a composite material of a metal organic framework coated black phosphorus nanosheet and a preparation method and application thereof. Wherein, the method comprises the following steps: (1) dispersing the black phosphorus nanosheets in a methanol solution of polyvinylpyrrolidone to obtain a first mixed solution; (2) mixing a metal salt with the first mixed solution to obtain a second mixed solution; (3) and mixing the organic ligand with the second mixed solution and reacting at normal temperature to obtain the composite material of the metal organic framework coated black phosphorus nanosheet. The preparation method can be carried out at normal temperature, is simple to operate and mild in condition, can avoid the oxidation of the black phosphorus nanosheet caused by high-temperature reaction conditions, and can improve the stability of the finally prepared composite material and widen the application range of the composite material.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a composite material of a metal organic framework coated black phosphorus nanosheet, and a preparation method and application thereof.
Background
In recent years, two-dimensional materials have received extensive attention and research, in which black phosphorus, which is one of the most stable allotropes of phosphorus, has a naturally folded layered structure like graphite, and van der waals forces act between layers thereof, and van der waals forces between layers of black phosphorus are weakened by exfoliation, so that black phosphorus becomes nano-black phosphorus. The nano black phosphorus has many excellent properties, such as adjustable direct band gap, high carrier mobility, good photoelectron performance and the like, and has good application prospects in the fields of field effect transistors, energy storage, catalysis, pulse lasers, flame retardance and the like. Compared with other two-dimensional materials, black phosphorus, especially a few-layer black phosphorus, exhibits poor environmental stability and thermal stability, and the application range of the black phosphorus is greatly limited. Therefore, how to overcome the technical barriers, play the role of the black phosphorus and improve the application value of the black phosphorus has important significance for promoting the development of black phosphorus materials.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a composite material of a black phosphorus nanosheet coated with a metal organic framework, and a preparation method and application thereof. The preparation method can be carried out at normal temperature, is simple to operate and mild in condition, can avoid the oxidation of the black phosphorus nanosheet caused by high-temperature reaction conditions, and can improve the stability of the finally prepared composite material and widen the application range of the composite material.
The present application is proposed based on the following findings of the inventors:
metal-organic frameworks (MOFs) are organic-inorganic hybrid materials with intramolecular pores and regular morphologies formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds. In the MOF, the arrangement of organic ligands and metal ions or clusters has obvious directionality, different framework pore structures can be formed, and the MOF has the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity and tailorability of topological structures and the like, and the properties can be applied to the fields of gas storage, chemical separation, light capture, chemical sensing, energy sources and the like. However, the existing technical scheme for preparing the organic metal framework-coated two-dimensional black phosphorus nanosheet is prepared under a high-temperature condition, for example, the nanosheet needs to be crystallized at 135-200 ℃ for several hours to several days, however, the high-temperature condition can accelerate the oxidation of black phosphorus and influence the thermal stability of the black phosphorus, so that the application of the black phosphorus composite material is influenced.
To this end, according to a first aspect of the invention, the invention proposes a method for preparing a composite material of black phosphorus nanoplates coated with a metal-organic framework. According to an embodiment of the invention, the method comprises:
(1) dispersing the black phosphorus nanosheets in a methanol solution of polyvinylpyrrolidone to obtain a first mixed solution;
(2) mixing a metal salt with the first mixed solution to obtain a second mixed solution;
(3) and mixing an organic ligand with the second mixed solution and reacting at normal temperature to obtain the composite material of the metal organic framework coated black phosphorus nanosheet.
According to the method for preparing the composite material of the black phosphorus nanosheet coated with the metal organic framework, the methanol solvent is adopted in advance to enable the polyvinylpyrrolidone to be adsorbed on the surface of the black phosphorus nanosheet, then the metal salt is combined with the polyvinylpyrrolidone adsorbed on the black phosphorus nanosheet and is coordinated with the organic ligand, and a layer of porous film can be formed on the surface of the black phosphorus nanosheet at normal temperature, so that the direct contact between the black phosphorus nanosheet and water and oxygen can be avoided, the black phosphorus nanosheet is prevented from being oxidized, the stability of the black phosphorus nanosheet is improved, and the carrier mobility, the photoelectron performance and the like of the black phosphorus nanosheet are not influenced. In conclusion, the method is simple to operate and mild in condition, can avoid oxidation of the black phosphorus nanosheet caused by high-temperature reaction conditions, and can ensure that the finally prepared composite material with the metal organic framework coated with the black phosphorus nanosheet has the advantages of good conductivity, energy storage capacity and the like, so that the composite material can be widely applied to the fields of photoelectrocatalysis, electrocatalysis, electrochemical energy storage and the like as a two-dimensional electrode material.
In addition, the method for preparing the composite material of the metal organic framework coated black phosphorus nanosheet according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, step (1) satisfies at least one of the following conditions: the dispersion is carried out under ultrasonic conditions; the black phosphorus nanosheet is prepared by adopting an electrochemical stripping method; the black phosphorus nanosheet is a single-layer black phosphorus nanosheet and/or a few-layer black phosphorus nanosheet; in the methanol solution of the polyvinylpyrrolidone, the concentration of the polyvinylpyrrolidone is 10-15 g/L.
In some embodiments of the present invention, the black phosphorus nanosheet is prepared by: constructing a two-electrode system by using a blocky black phosphorus crystal as a working electrode, a Pt wire as a counter electrode and tetrabutylammonium bromide-DMF (dimethyl formamide) solution as an electrolyte for stripping treatment; washing the stripped product with isopropyl alcohol to remove electrolyte remained on the stripped product; and (3) carrying out high-speed centrifugation treatment on the washed stripping product so as to remove the un-stripped blocky black phosphorus crystals and obtain the single-layer and/or few-layer black phosphorus nanosheets.
In some embodiments of the invention, at least one of the following conditions is satisfied: the stripping treatment voltage is-5 to-10V, and the stripping time is 1 to 1.5 h; the concentration of the electrolyte is 0.5-1 mol/L; the rotation speed of the centrifugal treatment is not less than 10000 r/min.
In some embodiments of the invention, in step (2), the metal ion in the metal salt comprises a metal selected from Zn2+、Co2+、Cu2+、Ni2+、Fe2+At least one of (a).
In some embodiments of the invention, at least one of the following conditions is satisfied: in the step (2), the concentration of the metal salt after the metal salt is mixed with the first mixed solution is 0.5-2.8 mmol/L; in the step (3), the organic ligand is di-methylimidazole and/or terephthalic acid; in the step (3), the molar ratio of the organic ligand to the metal ions in the metal salt is (5-8): 1.
in some embodiments of the invention, at least one of the following conditions is satisfied: in the step (3), the reaction time is 2-6 h; and (3) mixing an organic ligand with the second mixed solution under the stirring condition, reacting at normal temperature, and centrifuging, washing and drying a reaction product to obtain the composite material of the metal organic framework coated black phosphorus nanosheet.
According to a second aspect of the invention, the invention provides a composite material of black phosphorus nanosheet coated with a metal organic framework. According to the embodiment of the invention, the composite material is obtained by adopting the preparation method. Compared with the prior art, the composite material has the advantages of good stability, conductivity, energy storage capacity and the like.
According to a third aspect of the invention, the invention provides the application of the composite material of the black phosphorus nanosheet coated with the metal organic framework or the composite material of the black phosphorus nanosheet coated with the metal organic framework obtained by the preparation method in the fields of photoelectrocatalysis, electrocatalysis and electrochemical energy storage. Therefore, the excellent performances of the black phosphorus nanosheet in the fields of photoelectrocatalysis, electrocatalysis and electrochemical energy storage can be fully exerted.
According to a fourth aspect of the present invention, a battery is provided. According to an embodiment of the invention, the negative electrode of the battery is provided with the composite material of the black phosphorus nanosheet coated with the metal organic framework or the composite material of the black phosphorus nanosheet coated with the metal organic framework obtained by the preparation method. Compared with the prior art, the battery has better conductivity and energy storage performance, and can obviously improve the discharge capacity and electrochemical performance of the battery.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a flow diagram of a method of making a metal-organic framework-coated black phosphorus nanoplate composite according to one embodiment of the present invention.
Fig. 2 is a scanning electron microscope photograph of the few-layer black phosphorus nanosheets prepared according to example 1 of the present invention.
FIG. 3 is a comparative transmission electron micrograph of the final products obtained in example 2 according to the present invention and comparative example 1, wherein FIG. 3(a) is a transmission electron micrograph of the final product obtained in example 2 and FIG. 3(b) is a transmission electron micrograph of the final product obtained in comparative example 1.
FIG. 4 is a photoelectron spectrum of the final product prepared in example 3.
Fig. 5 is a voltage-capacity graph of a battery in which the final product obtained in example 4 was used for a negative electrode of a potassium ion battery.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to a first aspect of the invention, the invention provides a method for preparing a composite material of black phosphorus nanosheet coated with a metal-organic framework. According to an embodiment of the invention, the method comprises: (1) dispersing the black phosphorus nanosheets in a methanol solution of polyvinylpyrrolidone to obtain a first mixed solution; (2) mixing a metal salt with the first mixed solution to obtain a second mixed solution; (3) and mixing the organic ligand with the second mixed solution and reacting at normal temperature to obtain the composite material of the metal organic framework coated black phosphorus nanosheet. The method is simple to operate, mild in condition, capable of avoiding oxidation of the black phosphorus nanosheet caused by high-temperature reaction conditions, capable of ensuring the conductivity, the energy storage performance and the like of the finally prepared composite material with the black phosphorus nanosheet coated by the metal organic framework, and capable of being widely applied to the fields of photoelectrocatalysis, electrocatalysis, electrochemical energy storage and the like as a two-dimensional electrode material.
The method for preparing the metal-organic framework-coated black phosphorus nanosheet composite of the above-described embodiment of the present invention is described in detail below with reference to fig. 1.
S100, dispersing the black phosphorus nanosheets in a methanol solution of polyvinylpyrrolidone to obtain a first mixed solution
According to the embodiment of the invention, the polyvinylpyrrolidone (PVP) is dissolved in the methanol in advance, and then the black phosphorus nanosheets are dispersed, so that the black phosphorus nanosheets and the polyvinylpyrrolidone can be in full contact, the PVP is uniformly coated on the surfaces of the black phosphorus nanosheets to serve as a protective agent, the growth of the metal organic framework material on the surfaces of the black phosphorus nanosheets is regulated, the coating layer is prevented from being too thick, the conductivity, the energy storage property and the like of the finally prepared composite material are further influenced, and meanwhile, the preparation of the composite material of the metal organic framework coated black phosphorus nanosheets at normal temperature is facilitated.
According to an embodiment of the invention, the black phosphorus nanosheet can be dispersed in a methanol solution of polyvinylpyrrolidone under ultrasonic conditions, so that sufficient contact between the black phosphorus nanosheet and PVP and uniformity of adsorption of PVP on the surface of the black phosphorus nanosheet can be further improved.
According to another embodiment of the present invention, the black phosphorus nanoplates may preferably be single-layer and/or few-layer black phosphorus nanoplates, more preferably single-layer nanoplates, thereby further improving the conductivity of the finally prepared composite material. The single-layer or few-layer black phosphorus nanosheets described in the present invention can be obtained by peeling off the block black phosphorus, the number of layers or the thickness of the few-layer black phosphorus nanosheets in the present invention is not particularly limited, and those skilled in the art can select the number of layers or the thickness according to actual needs, for example, the number of layers of the few-layer black phosphorus nanosheets may be 2 to 15 layers, or the thickness of the few-layer black phosphorus nanosheets may be 1 to 8nm, so that the conductivity, the energy storage performance, and the like of the finally prepared composite material can be further improved.
According to another embodiment of the invention, the black phosphorus nanosheet can be prepared by an electrochemical stripping method, for example, a two-electrode system can be constructed by taking a massive black phosphorus crystal as a working electrode, a Pt wire as a counter electrode and tetrabutylammonium bromide-DMF solution as an electrolyte for stripping treatment; washing the stripped product by using isopropanol after stripping is finished so as to remove electrolyte remained on the stripped product; and (3) carrying out high-speed centrifugal treatment on the washed stripping product so as to remove the un-stripped blocky black phosphorus crystal, and drying to finally obtain the single-layer and/or few-layer black phosphorus nanosheet. Wherein the voltage of the stripping treatment can be-5 to-10V, and the stripping time can be 1 to 1.5 h; the concentration of the electrolyte can be 0.5-1 mol/L; the rotating speed of the centrifugal treatment can be not lower than 10000r/min, and the stripping effect on the blocky black phosphorus can be further improved by controlling the process parameters of the electrochemical stripping method, so that the black phosphorus nanosheet with fewer layers or thinner thickness can be obtained.
According to another embodiment of the present invention, in the methanol solution of polyvinylpyrrolidone, the concentration of polyvinylpyrrolidone may be 10 to 15g/L, for example, 10g/L, 11g/L, 12g/L, 13g/L, 14g/L or 15g/L, if the concentration of PVP is too low or too high, the coating of the metal organic framework material on the surface of the black phosphorus nanosheet is not uniform or the thickness of the metal organic framework material is too large, and the porous coating layer structure of the prepared composite material and the conductivity, energy storage performance and the like of the composite material are finally affected, but in the present invention, by controlling polyvinylpyrrolidone to be in the above concentration range, not only a complete PVP coating layer can be formed on the surface of the black phosphorus nanosheet, but also an organic metal coating layer structure with a thinner thickness and uniform distribution can be further advantageously formed, thereby leading the composite material to have excellent conductivity, energy storage property and the like.
S200, mixing the metal salt with the first mixed solution to obtain a second mixed solution
According to the embodiment of the present invention, by uniformly mixing the metal salt with the first mixed liquid, the metal salt can be sufficiently brought into contact with the black phosphorus nanosheet.
According to one embodiment of the present invention, the metal salt used in the present invention may be includedIncluding being selected from Zn2+、Co2+、Cu2+、Ni2+、Fe2+At least one of (a). The inventors have found that when the metal ion is changed, the desired organic ligand is also changed, and the metal-organic framework coating layer can be prepared more advantageously by using a metal salt of the above kind in combination with the organic ligand di-methylimidazole and/or terephthalic acid in the present invention.
According to another embodiment of the present invention, the concentration of the metal salt after the metal salt is mixed with the first mixed solution can be 0.5 to 2.8mmol/L, for example, 0.5mmol/L, 0.8mmol/L, 1.1mmol/L, 1.5mmol/L, 1.8mmol/L, 2.1mmol/L, 2.5mmol/L or 2.8mmol/L, etc., and the inventors have found that the metal-organic framework coating layer is advantageous in its own porous structure, the porous structure can greatly enhance the specific surface area of the material and accelerate the migration of ions in the porous structure, however, the metal organic framework is actually an organic matter, and if the coating layer of the metal organic framework is too thick, the conductivity, the energy storage performance and the like of the finally prepared composite material are influenced, and therefore, in the actual preparation process, the porous structure of the metal organic framework coating layer is not influenced, and the conductivity, the energy storage performance and the like of the black phosphorus nanosheet are not influenced; in addition, the inventor also finds that when the concentration of the metal salt is too low after the metal salt is mixed with the first mixed solution, an effective metal organic framework porous coating layer is difficult to form on the surface of the black phosphorus nanosheet, and when the concentration of the metal salt is too high after the metal salt is mixed with the first mixed solution, the metal organic framework is not only caused to spontaneously nucleate and agglomerate, but also the finally prepared metal organic framework coating layer is too thick and even completely seals the black phosphorus nanosheet, so that the performances of the conductivity and the like of the black phosphorus nanosheet are seriously influenced, and the invention can be more favorable for forming a layer of uniform, thin and porous metal organic framework coating layer similar to the surface appearance of the black phosphorus nanosheet on the surface of the black phosphorus nanosheet by controlling the metal salt to be in the above concentration range, so that the metal organic framework coating layer has rich pore structures, and the performances of the conductivity, the energy storage performance and the like, therefore, the finally prepared composite material can be further ensured to have better performances such as stability, conductivity, energy storage capacity and the like.
S300, mixing the organic ligand and the second mixed solution and reacting at normal temperature to obtain the composite material of the metal organic framework coated black phosphorus nanosheet
According to the embodiment of the invention, the organic ligand and the second mixed solution can be mixed and then react at normal temperature to realize coordination of metal ions and the organic ligand, and the organic ligand and the second mixed solution are preferably mixed and stirred, so that the reaction rate and the reaction uniformity can be further improved, and a uniform porous metal organic framework coating layer can be formed on the surface of the black phosphorus nanosheet. Further, the organic ligand and the second mixed solution can be mixed and stirred for a certain time, and then centrifugation, washing, drying and other treatments are carried out, so as to obtain the composite material of the metal organic framework coated black phosphorus nanosheet.
According to one embodiment of the invention, the reaction time of the organic ligand and the second mixed solution can be 2-6 h, and the inventor finds that if the reaction time is too short, the formation of a uniform porous metal organic framework coating layer on the surface of the black phosphorus nanosheet is not facilitated, and if the reaction time is too long, the finally formed metal organic framework coating layer is too thick, so that the exertion of the conductivity, the energy storage performance and the like of the black phosphorus nanosheet is influenced.
According to yet another embodiment of the invention, the organic ligand may be di-methylimidazole and/or terephthalic acid, for example, when the metal salt ion contains Zn2+And/or Co2+When the organic ligand is bis-methylimidazole; when the metal salt ions contain Cu2+、Ni2+、Fe2+The organic ligand may be terephthalic acid, and when the metal salt ion contains Zn2+And/or Co2+And also contains Cu2+、Ni2+、Fe2+When at least one of (1) above, the organic ligand may be bis-methylimidazoleAnd terephthalic acid, thereby further ensuring that the metal salt is able to successfully coordinate with the organic ligand and form a metal-organic framework coating.
According to another embodiment of the present invention, the molar ratio of the organic ligand to the metal ion in the metal salt may be (5-8): 1 may be, for example, 5/1, 6/1, 7/1, 8/1, or the like. The inventor finds that if the molar ratio of the organic ligand to the metal ions is too small, the formation of a uniform metal-organic framework coating layer is not facilitated, and if the molar ratio of the organic ligand to the metal ions is too large, the finally obtained metal-organic framework coating layer is too thick or the pore diameter of the porous coating layer is too small, so that the performance of the conductivity and the like of the black phosphorus nanosheet is influenced.
In summary, according to the method for preparing the composite material of the black phosphorus nanosheet coated with the metal organic framework in the embodiment of the present invention, the methanol solvent is adopted in advance to make the polyvinylpyrrolidone adsorbed on the surface of the black phosphorus nanosheet, and then the metal salt is combined with the polyvinylpyrrolidone adsorbed on the black phosphorus nanosheet and coordinated with the organic ligand, so that a porous film can be formed on the surface of the black phosphorus nanosheet at normal temperature, thereby not only preventing the black phosphorus nanosheet from directly contacting with water and oxygen and preventing the black phosphorus nanosheet from being oxidized, and thus improving the stability of the black phosphorus nanosheet, but also not affecting the carrier mobility, the optoelectronic properties and the like of the black phosphorus nanosheet. In conclusion, the method is simple to operate and mild in condition, can avoid oxidation of the black phosphorus nanosheet caused by high-temperature reaction conditions, and can ensure that the finally prepared composite material with the metal organic framework coated with the black phosphorus nanosheet has the advantages of good conductivity, energy storage capacity and the like, so that the composite material can be widely applied to the fields of photoelectrocatalysis, electrocatalysis, electrochemical energy storage and the like as a two-dimensional electrode material.
According to a second aspect of the invention, the invention provides a composite material of black phosphorus nanosheet coated with a metal organic framework. According to the embodiment of the invention, the composite material is obtained by adopting the preparation method. Compared with the prior art, the composite material has the advantages of good stability, conductivity, energy storage capacity and the like. It should be noted that the characteristics and effects described for the method for preparing the composite material in which the metal organic framework coats the black phosphorus nanosheet are also applicable to the composite material in which the metal organic framework coats the black phosphorus nanosheet, and are not described in detail here.
According to a third aspect of the invention, the invention provides the application of the composite material of the black phosphorus nanosheet coated with the metal organic framework or the composite material of the black phosphorus nanosheet coated with the metal organic framework obtained by the preparation method in the fields of photoelectrocatalysis, electrocatalysis and electrochemical energy storage. Therefore, the excellent performances of the black phosphorus nanosheet in the fields of photoelectrocatalysis, electrocatalysis and electrochemical energy storage can be fully exerted. It should be noted that, the characteristics and effects described in the composite material in which the metal organic framework is coated with the black phosphorus nanosheet and the method for preparing the composite material in which the metal organic framework is coated with the black phosphorus nanosheet are also applicable to the use of the composite material in which the metal organic framework is coated with the black phosphorus nanosheet, and are not described in detail here.
According to a fourth aspect of the present invention, a battery is provided. According to an embodiment of the invention, the negative electrode of the battery is provided with the composite material of the black phosphorus nanosheet coated with the metal organic framework or the composite material of the black phosphorus nanosheet coated with the metal organic framework obtained by the preparation method. Compared with the prior art, the battery has better energy storage performance, and can obviously improve the discharge capacity and electrochemical performance of the battery. The type of the battery is not particularly limited, and may be, for example, a potassium ion battery, a lithium ion battery, or the like, and may be selected by those skilled in the art according to actual needs. In addition, it should be noted that the characteristics and effects described for the composite material in which the metal-organic framework is coated with the black phosphorus nanosheet and the method for preparing the composite material in which the metal-organic framework is coated with the black phosphorus nanosheet are also applicable to the battery, and are not described in detail herein.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(1) Stripping the blocky black phosphorus by adopting an electrochemical stripping method, wherein the stripping voltage is-5V, the stripping time is 1h, and the electrolyte concentration is 0.5 mol/L;
(2) weighing 50mg of stripped black phosphorus nanosheet, adding the nanosheet into 150mL of PVP methanol solution with the concentration of 10g/L, and ultrasonically dispersing for 10min under the power of 400W;
(3) adding Zn (NO)3)2·6H2O metal salt with the concentration of 2mmol/L is placed on a stirring table to be stirred for 2 hours, and the stirring speed is 200 r/min;
(4) adding organic ligand 2-methylimidazole into the solution, wherein the molar ratio of the ligand to the metal salt is 6, and continuously stirring at room temperature for 4 hours;
(5) and centrifuging and washing the obtained product, and then placing the product in a vacuum drying oven for drying for 12 hours to obtain the final product.
Fig. 2 is a scanning electron microscope photograph of the black phosphorus nanosheet obtained by peeling in example 1, and it can be seen that the nanosheet is very thin, and few layers of black phosphorus nanosheets are present.
Example 2
(1) Stripping the blocky black phosphorus by adopting an electrochemical stripping method, wherein the stripping voltage is-5V, the stripping time is 1h, and the electrolyte concentration is 0.5 mol/L;
(2) weighing 50mg of stripped black phosphorus nanosheet, adding the nanosheet into 150mL of PVP methanol solution with the concentration of 10g/L, and ultrasonically dispersing for 10min under the power of 400W;
(3) adding Zn (NO)3)2·6H2O metal salt with the concentration of 1mmol/L is placed on a stirring table to be stirred for 2 hours, and the stirring speed is 200 r/min;
(4) adding organic ligand 2-methylimidazole into the solution, wherein the molar ratio of the ligand to the metal salt is 6, and continuously stirring at room temperature for 4 hours;
(5) and centrifuging and washing the obtained product, and then placing the product in a vacuum drying oven for drying for 12 hours to obtain the final product.
Comparative example 1
(1) Stripping the blocky black phosphorus by adopting an electrochemical stripping method, wherein the stripping voltage is-5V, the stripping time is 1h, and the electrolyte concentration is 0.5 mol/L;
(2) weighing 50mg of stripped black phosphorus nanosheet, adding the nanosheet into 150mL of PVP methanol solution with the concentration of 10g/L, and ultrasonically dispersing for 10min under the power of 400W;
(3) adding Zn (NO)3)2·6H2O metal salt with the concentration of 3mmol/L is placed on a stirring table to be stirred for 2 hours, and the stirring speed is 200 r/min;
(4) adding organic ligand 2-methylimidazole into the solution, wherein the molar ratio of the ligand to the metal salt is 6, and continuously stirring at room temperature for 4 hours;
(5) and centrifuging and washing the obtained product, and then placing the product in a vacuum drying oven for drying for 12 hours to obtain the final product.
Fig. 3 is a transmission electron microscope photograph of the composite material of black phosphorus nanosheet coated with metal organic framework material prepared in example 2 (corresponding to fig. 3(a)) and comparative example 1 (corresponding to fig. 3(b)), and it can be seen that when the concentration of metal ions is relatively low (within the normal range), the surface of the coating layer of metal organic framework material is smooth, and the morphology is similar to that of black phosphorus nanosheet. When the concentration of the metal salt is too high, small particles of about 20-50nm are attached to the surface of the black phosphorus nanosheet, and the metal ions begin to nucleate and grow due to the too high concentration of the metal ions. It is further demonstrated that too high a concentration of metal ions can seriously affect the uniformity of the final composite coating.
Example 3
(1) Stripping the blocky black phosphorus by adopting an electrochemical stripping method, wherein the stripping voltage is-5V, the stripping time is 1h, and the electrolyte concentration is 0.5 mol/L;
(2) weighing 50mg of stripped black phosphorus nanosheet, adding the nanosheet into 150mL of PVP methanol solution with the concentration of 10g/L, and ultrasonically dispersing for 10min under the power of 400W;
(3) adding Zn (NO)3)2·6H2O metal salt with the concentration of 2mmol/L is placed on a stirring table to be stirred for 2 hours, and the stirring speed is 200 r/min;
(4) adding organic ligand 2-methylimidazole into the solution, wherein the molar ratio of the ligand to the metal salt is 6, and continuously stirring for 2 hours at room temperature;
(5) and centrifuging and washing the obtained product, and then placing the product in a vacuum drying oven for drying for 12 hours to obtain the final product.
Fig. 4 is a photoelectron spectrum of the black phosphorus nanosheet composite coated with the metal-organic framework material prepared in example 3. As can be seen from the figure, the final product contains five elements, namely Zn, O, C, N and P.
Example 4
(1) Stripping the blocky black phosphorus by adopting an electrochemical stripping method, wherein the stripping voltage is-5V, the stripping time is 1h, and the electrolyte concentration is 0.5 mol/L;
(2) weighing 50mg of stripped black phosphorus nanosheet, adding the nanosheet into 250mL of PVP methanol solution with the concentration of 10g/L, and ultrasonically dispersing for 10min under the power of 400W;
(3) adding Zn (NO)3)2·6H2O metal salt with the concentration of 2mmo/L is placed on a stirring table to be stirred for 2 hours, and the stirring speed is 200 r/min;
(4) adding an organic ligand 2-methylimidazole into the solution, wherein the molar ratio of the ligand to the metal salt is 8, and continuously stirring at room temperature for 4 hours;
(5) and centrifuging and washing the obtained product, and then placing the product in a vacuum drying oven for drying for 12 hours to obtain the final product.
The final product obtained in example 4, that is, the composite material of the black phosphorus nanosheet coated with the metal organic framework material, was coated on a copper foil to serve as a working electrode of a potassium ion battery, the metal potassium sheet was a counter electrode, Whatman GF/F was a separator, and a mixed solution of ethylene carbonate and diethyl carbonate containing 1.0mol/L of KFSI (potassium bis fluorosulfonylimide) was used as an electrolyte, and the ion battery was assembled in a glove box. Wherein, fig. 5 is a voltage-capacity curve of the assembled potassium ion battery, it can be seen that the discharge capacity is as high as 290mAh/g at a current density of 50mA/g, and the battery has excellent energy storage properties.
Example 5
(1) Stripping the blocky black phosphorus by adopting an electrochemical stripping method, wherein the stripping voltage is-5V, the stripping time is 1h, and the electrolyte concentration is 0.5 mol/L;
(2) weighing 50mg of stripped black phosphorus nanosheet, adding the nanosheet into 250mL of PVP methanol solution with the concentration of 10g/L, and ultrasonically dispersing for 10min under the power of 400W;
(3) adding 1mmo/L Zn (NO)3)2·6H2O and 1mmo/L Co (NO)3)2·6H2O metal salt, then placing the mixture on a stirring table to stir for 2 hours, wherein the stirring speed is 200 r/min;
(4) adding an organic ligand 2-methylimidazole into the solution, wherein the molar ratio of the ligand to the metal salt is 8, and continuously stirring at room temperature for 4 hours;
(5) and centrifuging and washing the obtained product, and then placing the product in a vacuum drying oven for drying for 12 hours to obtain the final product.
After transmission electron microscope analysis is carried out on the final product prepared in example 5, the metal organic framework material coating layer with smooth surface and similar appearance to the black phosphorus nanosheet can be obtained when the concentration of the metal salt is 2 mmo/L.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for preparing a composite material of a black phosphorus nanosheet coated with a metal organic framework is characterized by comprising the following steps:
(1) dispersing the black phosphorus nanosheets in a methanol solution of polyvinylpyrrolidone to obtain a first mixed solution;
(2) mixing a metal salt with the first mixed solution to obtain a second mixed solution;
(3) and mixing an organic ligand with the second mixed solution and reacting at normal temperature to obtain the composite material of the metal organic framework coated black phosphorus nanosheet.
2. The method of claim 1, wherein step (1) satisfies at least one of the following conditions:
the dispersion is carried out under ultrasonic conditions;
the black phosphorus nanosheet is prepared by adopting an electrochemical stripping method;
the black phosphorus nanosheet is a single-layer black phosphorus nanosheet and/or a few-layer black phosphorus nanosheet;
in the methanol solution of the polyvinylpyrrolidone, the concentration of the polyvinylpyrrolidone is 10-15 g/L.
3. The method of claim 1 or 2, wherein the black phosphorus nanoplates are prepared by:
constructing a two-electrode system by using a blocky black phosphorus crystal as a working electrode, a Pt wire as a counter electrode and tetrabutylammonium bromide-DMF (dimethyl formamide) solution as an electrolyte for stripping treatment;
washing the stripped product with isopropyl alcohol to remove electrolyte remained on the stripped product;
and (3) carrying out high-speed centrifugation treatment on the washed stripping product so as to remove the un-stripped blocky black phosphorus crystals and obtain the single-layer and/or few-layer black phosphorus nanosheets.
4. A method according to claim 3, characterized in that at least one of the following conditions is fulfilled:
the stripping treatment voltage is-5 to-10V, and the stripping time is 1 to 1.5 h;
the concentration of the electrolyte is 0.5-1 mol/L;
the rotation speed of the centrifugal treatment is not less than 10000 r/min.
5. The method according to claim 1 or 4, wherein in step (2), the metal ion in the metal salt comprises Zn2+、Co2+、Cu2+、Ni2+、Fe2+At least one of (a).
6. The method of claim 5, wherein at least one of the following conditions is satisfied:
in the step (2), the concentration of the metal salt after the metal salt is mixed with the first mixed solution is 0.5-2.8 mmol/L;
in the step (3), the organic ligand is di-methylimidazole and/or terephthalic acid;
in the step (3), the molar ratio of the organic ligand to the metal ions in the metal salt is (5-8): 1.
7. the method according to claim 1 or 6, characterized in that at least one of the following conditions is fulfilled:
in the step (3), the reaction time is 2-6 h;
and (3) mixing an organic ligand with the second mixed solution under the stirring condition, reacting at normal temperature, and centrifuging, washing and drying a reaction product to obtain the composite material of the metal organic framework coated black phosphorus nanosheet.
8. A composite material of a black phosphorus nanosheet coated with a metal organic framework, which is prepared by the method of any one of claims 1 to 7.
9. Use of the metal organic framework-coated black phosphorus nanosheet composite material of claim 8 or the metal organic framework-coated black phosphorus nanosheet composite material prepared by the method of any one of claims 1 to 7 in the fields of photoelectrocatalysis, electrocatalysis and electrochemical energy storage.
10. A battery, characterized in that at least one electrode plate of the battery is provided with the composite material of black phosphorus nanosheet coated with metal organic framework as defined in claim 8 or the composite material of black phosphorus nanosheet coated with metal organic framework prepared by the method as defined in any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011231954.5A CN112421038A (en) | 2020-11-06 | 2020-11-06 | Composite material of black phosphorus nanosheet coated with metal organic framework and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011231954.5A CN112421038A (en) | 2020-11-06 | 2020-11-06 | Composite material of black phosphorus nanosheet coated with metal organic framework and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112421038A true CN112421038A (en) | 2021-02-26 |
Family
ID=74782068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011231954.5A Pending CN112421038A (en) | 2020-11-06 | 2020-11-06 | Composite material of black phosphorus nanosheet coated with metal organic framework and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112421038A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113699556A (en) * | 2021-08-27 | 2021-11-26 | 常州大学 | CoNiMOF-BP QDs/b-CNF composite material electrocatalyst and preparation method thereof |
| CN114381315A (en) * | 2022-01-19 | 2022-04-22 | 西安建筑科技大学 | Bidirectional composite black phosphorus quantum dot/copper-based metal organic framework lubricating additive and preparation method thereof |
| CN114574899A (en) * | 2022-03-30 | 2022-06-03 | 西安交通大学 | Water electrolysis bifunctional electrocatalyst and preparation method and application thereof |
| CN114614198A (en) * | 2022-02-28 | 2022-06-10 | 南京林业大学 | Phase change diaphragm for lithium-sulfur battery and preparation method thereof |
| CN115959639A (en) * | 2023-01-19 | 2023-04-14 | 厦门大学 | Preparation method of etched black phosphorus nanosheet and etched black phosphorus nanosheet |
| CN114574899B (en) * | 2022-03-30 | 2024-05-24 | 西安交通大学 | Electrolytic water dual-function electrocatalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109602919A (en) * | 2018-11-30 | 2019-04-12 | 东南大学 | A kind of black phosphorus quantum dot and the preparation method and application thereof of nucleocapsid metal organic frame cladding |
| CN110078034A (en) * | 2019-04-29 | 2019-08-02 | 厦门大学深圳研究院 | A kind of organic metal framework coats the preparation method of two-dimentional black phosphorus nanometer sheet |
| CN110455896A (en) * | 2019-08-27 | 2019-11-15 | 青岛大学 | The preparation method of metal organic framework compound ratio electrochemistry miR3123 aptamer sensor |
| CN110817816A (en) * | 2019-11-25 | 2020-02-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area thin-layer high-quality black phosphorus nanosheet and electrochemical stripping preparation method thereof |
-
2020
- 2020-11-06 CN CN202011231954.5A patent/CN112421038A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109602919A (en) * | 2018-11-30 | 2019-04-12 | 东南大学 | A kind of black phosphorus quantum dot and the preparation method and application thereof of nucleocapsid metal organic frame cladding |
| CN110078034A (en) * | 2019-04-29 | 2019-08-02 | 厦门大学深圳研究院 | A kind of organic metal framework coats the preparation method of two-dimentional black phosphorus nanometer sheet |
| CN110455896A (en) * | 2019-08-27 | 2019-11-15 | 青岛大学 | The preparation method of metal organic framework compound ratio electrochemistry miR3123 aptamer sensor |
| CN110817816A (en) * | 2019-11-25 | 2020-02-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area thin-layer high-quality black phosphorus nanosheet and electrochemical stripping preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王练: "ZIF-8/BP纳米复合材料的制备及光催化降解甲基蓝的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 鲁昆昆等: "一步法合成的黑磷烯掺杂的金属有机框架用于氧还原反应", 《第三届中国国际复合材料科技大会》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113699556A (en) * | 2021-08-27 | 2021-11-26 | 常州大学 | CoNiMOF-BP QDs/b-CNF composite material electrocatalyst and preparation method thereof |
| CN114381315A (en) * | 2022-01-19 | 2022-04-22 | 西安建筑科技大学 | Bidirectional composite black phosphorus quantum dot/copper-based metal organic framework lubricating additive and preparation method thereof |
| CN114614198A (en) * | 2022-02-28 | 2022-06-10 | 南京林业大学 | Phase change diaphragm for lithium-sulfur battery and preparation method thereof |
| CN114574899A (en) * | 2022-03-30 | 2022-06-03 | 西安交通大学 | Water electrolysis bifunctional electrocatalyst and preparation method and application thereof |
| CN114574899B (en) * | 2022-03-30 | 2024-05-24 | 西安交通大学 | Electrolytic water dual-function electrocatalyst and preparation method and application thereof |
| CN115959639A (en) * | 2023-01-19 | 2023-04-14 | 厦门大学 | Preparation method of etched black phosphorus nanosheet and etched black phosphorus nanosheet |
| CN115959639B (en) * | 2023-01-19 | 2024-05-10 | 厦门大学 | Preparation method of etched black phosphorus nano-sheet and etched black phosphorus nano-sheet |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112421038A (en) | Composite material of black phosphorus nanosheet coated with metal organic framework and preparation method and application thereof | |
| Sun et al. | A review on recent advances for boosting initial coulombic efficiency of silicon anodic lithium ion batteries | |
| Xiao et al. | Electronic structure adjustment of lithium sulfide by a single-atom copper catalyst toward high-rate lithium-sulfur batteries | |
| JP3691482B2 (en) | Method for producing carbon active material coated with metal or metal oxide | |
| CN103682368B (en) | A kind of flexible lithium ion battery filled soon and the preparation method of electrode thereof | |
| Wu et al. | Defect Electrocatalysts and Alkaline Electrolyte Membranes in Solid‐State Zinc–Air Batteries: Recent Advances, Challenges, and Future Perspectives | |
| CN107579219B (en) | Graphene/zinc oxide negative electrode material for secondary zinc-based battery and preparation thereof | |
| CN112670543B (en) | Composite solid electrolyte membrane based on hollow MOF (metal organic framework) and preparation method and application thereof | |
| CN109148873A (en) | A kind of silicium cathode material of carbon nanotube cladding and negative electrode tab and preparation method thereof and lithium ion battery | |
| CN105390677A (en) | Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof | |
| Zhang et al. | Atomically dispersed materials for rechargeable batteries | |
| Cheng et al. | Porous MOF derived TiO2/ZnO/C@ CNTs composites for enhancing lithium storage performance | |
| Chen et al. | Designing of carbon cloth@ Co-MOF@ SiO2 as superior flexible anode for lithium-ion battery | |
| CN113363421A (en) | Lithium metal negative electrode layer and preparation method and application thereof | |
| CN114122368A (en) | Lithium supplement material, manufacturing method thereof, negative pole piece and battery | |
| CN112751008B (en) | Polyphenol modified zinc-iron based heterojunction oxide carbon nano lithium ion battery cathode composite material and preparation method thereof | |
| CN112117445B (en) | Stannous oxide/graphene heterojunction composite material, preparation method and application thereof, and metal lithium cathode taking stannous oxide/graphene heterojunction composite material as host | |
| Zhu et al. | A Highly-Lithiophilic Mn3O4/ZnO-Modified Carbon Nanotube Film for Dendrite-Free Lithium Metal Anodes | |
| Guo et al. | High‐Rate Lithium–Selenium Batteries Boosted by a Multifunctional Janus Separator Over a Wide Temperature Range of− 30° C to 60° C | |
| Fu et al. | Te-hybridized zeolitic imidazolate frameworks-derived core-shell design toward dendrite-free Zn anode for long-term aqueous zinc-ion batteries | |
| CN109786769A (en) | A kind of carbon supported noble metal oxide bifunctional catalyst and its preparation method and application | |
| CN104103808B (en) | A kind of lithium ion battery lamellar stannum carbon composite and preparation method thereof | |
| KR20210009468A (en) | Negative electrode active material for lithium secondary battery, method for manufacturing the same, and lithium secondary battery comprising the same | |
| CN115939498A (en) | Organic-inorganic quasi-solid composite electrolyte and preparation method and application thereof | |
| Li et al. | Fabrication of metal-organic frameworks-derived porous NiCo2O4 nanofibers for high lithium storage properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210226 |