CN110813200B - Preparation method of two-dimensional layered transition metal nanosheet gel - Google Patents
Preparation method of two-dimensional layered transition metal nanosheet gel Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
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Abstract
The invention provides a preparation method of two-dimensional layered transition metal nanosheet gel, which comprises the following steps: providing a two-dimensional layered transition metal nanosheet with a specific functional group as a solute, and dissolving the two-dimensional layered transition metal nanosheet in a solvent to form a nano dispersion liquid; providing a cross-linking agent solution containing a metal ion cross-linking agent, wherein the metal ion cross-linking agent contains metal ions with positive two or positive three, mixing the cross-linking agent solution with the nano dispersion liquid, and mixing to form the two-dimensional layered transition metal nanosheet gel.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a preparation method of two-dimensional layered transition metal nanosheet gel.
Background
The two-dimensional layered transition metal nanosheet is a layered two-dimensional nanosheet with excellent conductivity, catalytic activity and adsorbability, the two-dimensional nanosheet is gelatinized, the utilization rate of the nanosheet is effectively improved, the hydrogel has the advantages, and the application prospect of the two-dimensional layered transition metal nanosheet in the fields of energy storage, catalysis, high-strength materials, electronics, chemistry, biological detection and the like can be expanded.
However, one of the most significant problems with two-dimensional materials compared to other zero-or one-dimensional materials is their tendency to "face-to-face" stacking. That is, the gel has a macroscopic appearance of gel, and microscopically, different degrees of agglomeration and stacking still exist, so that the prepared gel is easy to collapse, has an unstable structure and has obvious orientation. The thus-prepared gel has a low utilization rate of lamellae, and it is difficult to fully exert the performance of the gel even after the gel is assembled into a device. In contrast, highly isotropic hydrogels possess a more stable network structure that facilitates the transport of substances within the network and also allows the gel matrix network to have greater electrical conductivity in all directions. The two-dimensional layered transition metal nanosheet hydrogel is prepared by a self-assembly method, a solution mixing method, an in-situ polymerization method or a chemical reduction method, and the like, and the listed traditional preparation process has the disadvantages of long preparation time, complex preparation process, long time consumption and high cost, and is not beneficial to maintaining the excellent physicochemical properties of the two-dimensional layered transition metal nanosheet.
The hydrogel skeleton network with high isotropy has strong conductivity in all directions, has a stable structure, and facilitates the transmission of substances among networks, however, the preparation of the hydrogel skeleton network is difficult, and the isotropy of the hydrogel skeleton network is realized by constructing a stable three-dimensional network while ensuring the conductivity of the hydrogel by a traditional method. How to solve the above problems is considered by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a preparation method of the isotropic hydrogel, which is fast, efficient, green, environment-friendly, simple in process, low in cost and suitable for large-scale production.
The invention provides a preparation method of two-dimensional layered transition metal nanosheet gel, which comprises the following steps:
providing a two-dimensional layered transition metal nanosheet with a specific functional group as a solute, and dissolving the two-dimensional layered transition metal nanosheet in a solvent to form a nano dispersion liquid; and
providing a cross-linking agent solution containing a metal ion cross-linking agent, wherein the metal ion cross-linking agent contains metal ions with positive two or positive three, mixing the cross-linking agent solution with the nano dispersion liquid, and mixing to form the two-dimensional layered transition metal nanosheet gel.
Further, the two-dimensional layered transition metal nanosheet at least comprises a first element and a second element, the first element is at least one of Sc, Ti, Zr, V, Nb, Cr or Mo, and the second element is at least one of C or N.
Further, the specific functional group in the two-dimensional layered transition metal nanosheet is at least one of a carboxyl group, a hydroxyl group, an ether group, an ester group, a ketone group, a carbonyl group, an acid anhydride, an epoxy functional group, a fluorine group, a sulfonic acid group, an amino group, a secondary amine, a tertiary amine, and an aromatic functional group.
Further, the metal ion crosslinking agent contains at least Mn2+，Fe2+，Co2+，Ni2+， Cu2+，Zn2+，Be2+，Ca2 +，Sr2+，Ba2+And Ga3+At least one of (1).
Further, the solvent is at least one of water, acetone, ethanol, methanol, tetrahydrofuran, acrylic acid, 1, 4-dioxane, n-methylpyrrolidone (NMP), Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethylene glycol, glycerol, diglyme, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and 1, 3-dioxolane.
Further, the concentration of the two-dimensional layered transition metal nanoplates in the nanodispersion ranges from 1mg/mL to 100 mg/mL.
Further, the particle size of the two-dimensional layered transition metal nanosheet ranges from 1nm to 100 μm.
Further, the mass ratio of the two-dimensional layered transition metal nanosheets to the metal ion crosslinking agent ranges from 1:50 to 5000: 1.
further, the concentration of the metal ion crosslinker in the two-dimensional layered transition metal nanosheet gel ranges from 0.1mg/mL to 50 mg/mL.
Further, the reaction temperature range in the process of preparing the two-dimensional layered transition metal nanosheet gel by mixing the cross-linking agent solution and the nano dispersion liquid is 0.1 ℃ to 99 ℃.
Compared with the traditional preparation method of hydrogel, the preparation method of the two-dimensional layered transition metal nanosheet gel has at least the following advantages:
the two-dimensional layered transition metal nanosheet gel has the properties of high isotropy, structural stability, good conductivity and the like. A stable three-dimensional network is constructed by overlapping two-dimensional layered transition metal nanosheets with specific functional groups with a cross-linking agent, so that the isotropy of the gel is ensured. And the preparation process is extremely fast and short in time consumption, and the mass preparation of the two-dimensional layered transition metal nanosheet gel can be realized in a short time.
The preparation method of the two-dimensional layered transition metal nanosheet gel has low requirements on temperature and pH value of a solution, the preparation process is simpler and more environment-friendly, the introduction of impurities is avoided, the process for removing the impurities can be further omitted, and the preparation method is suitable for large-scale industrial production.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a two-dimensional layered transition metal nanosheet gel according to an embodiment of the present invention.
Fig. 2 is a schematic diagram of a two-dimensional layered transition metal nanosheet gel before and after gelling according to an embodiment of the present invention.
Fig. 3 is a representation diagram of a morphology structure of a material after moisture removal of a two-dimensional layered transition metal nanosheet gel in accordance with an embodiment of the present invention.
Fig. 4 is a transmission electron microscope image of a two-dimensional layered transition metal nanoplate gel with isotropy according to an embodiment of the invention.
Fig. 5 is a transmission electron microscope image of a two-dimensional layered transition metal nanoplate gel with anisotropy according to an embodiment of the invention.
Description of the main elements
| Step (ii) of | S1、S2 |
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention and the scope of the present invention is therefore not limited to the specific embodiments disclosed below.
The invention provides a preparation method of two-dimensional layered transition metal nanosheet gel, which comprises the following steps of:
step S1: providing a two-dimensional layered transition metal nanosheet (MXene nanosheet) with a specific functional group as a solute, and dissolving the two-dimensional layered transition metal nanosheet in a solvent to form a nano dispersion liquid.
Specifically, the specific functional group in the two-dimensional layered transition metal nanoplate having the specific functional group may be one or more of a carboxyl group, a hydroxyl group, an ether group, an ester group, a ketone group, a carbonyl group, an acid anhydride, an epoxy functional group, a fluorine group, a sulfonic acid group, an amino group, a secondary amine, a tertiary amine, and an aromatic functional group. The specific functional group in the two-dimensional layered transition metal nanosheet with the specific functional group can improve the dispersibility of the two-dimensional layered transition metal nanosheet in a solvent and the lap joint stability of the nanosheet, construct a stable three-dimensional network and ensure the isotropy of the gel.
Specifically, the two-dimensional layered transition metal nanosheet (MXene nanosheet) includes at least a first element (M) and a second element (X), the first element (M) may be a metal, specifically at least one of Sc, Ti, Zr, V, Nb, Cr, or Mo, and the second element (X) may be at least one of C or N.
Specifically, the particle size in the two-dimensional layered transition metal nanosheet ranges from 1nm to 100 μm.
Specifically, the solvent may be at least one of water, acetone, ethanol, methanol, tetrahydrofuran, acrylic acid, 1, 4-dioxane, n-methylpyrrolidone (NMP), Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethylene glycol, glycerol, diglyme, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and 1, 3-dioxolane. The surface energies of the two-dimensional layered transition metal nanosheets with the special functional groups are different, and the solvents of the components can be matched with parts with different surface energies, so that the two-dimensional layered transition metal nanosheets with the special functional groups can be uniformly dispersed in the solvents to form a dispersion liquid. And the solvent has good dispersibility for the cross-linking agent, so that the two-dimensional layered transition metal nanosheet with the special functional group and the cross-linking agent can be quickly mixed in a mixed solution, and the gelling speed of the gel is further improved. The gel has high gelling speed, is beneficial to reducing the agglomeration tendency of the nano-sheets in the assembling process and is beneficial to constructing isotropic two-dimensional layered transition metal nano-sheet hydrogel.
Specifically, the concentration range of the two-dimensional layered transition metal nanosheets in the nanodispersion is 1mg/mL to 100 mg/mL. The solubility of the two-dimensional layered transition metal nanosheets of different sizes or different specific functional groups has a certain difference, and the concentration of the two-dimensional layered transition metal nanosheets can also range from 1mg/mL to 10mg/mL, from 11mg/mL to 20mg/mL, from 21mg/mL to 40mg/mL, from 41mg/mL to 60mg/mL, from 61mg/mL to 80mg/mL, or from 81mg/mL to 100mg/mL, while ensuring the performance of the nanodispersion.
Step S2: providing a cross-linking agent solution containing a metal ion cross-linking agent, mixing the cross-linking agent solution with the nano dispersion liquid, and forming the two-dimensional layered transition metal nanosheet gel within 1 second after mixing.
Specifically, the metal ion crosslinking agent contains at least Mn2+，Fe2+，Co2+，Ni2+， Cu2+，Zn2+，Be2+，Sr2+，Ba2+，Ga3+One or more of (a).
Wherein, the divalent metal ions have more crosslinking sites than the monovalent metal ions, the divalent metal ions can exist between the layers of the two-dimensional layered transition metal nanosheets in a stable manner, and the monovalent metal ions cannot exist between the layers of the two-dimensional layered transition metal nanosheets in a stable manner. The binding capacity of monovalent metal ions and the specific functional groups on the surface of the two-dimensional layered transition metal nanosheet is weak, the number of active sites is small, the two-dimensional layered transition metal nanosheet cannot be gelatinized, and only the two-dimensional layered transition metal nanosheet can be crosslinked into a stacked state of a surface and a surface; part of the trivalent metal cation (e.g. Fe)3+，Co3+) The two-dimensional layered transition metal nanosheets are oxidized due to strong oxidizability; thus, the metal crosslinker provided by the invention comprises divalent metal ions (such as Mn)2+，Fe2+， Co2+，Ni2+，Cu2+，Zn2+，Be2+，Sr2+，Ba2+) And trivalent metal ions having a weak oxidizing power (e.g., Ga)3+). Compared with trivalent metal ions, the oxidation of divalent metal ions is generally lower, and the divalent metal ions are used as a cross-linking agent to effectively prevent the gel from being oxidized.
The metal ion crosslinking agent can quickly break the static balance of the nano dispersion liquid, so that the metal ion crosslinking agent and the two-dimensional layered transition metal nanosheet are quickly mixed in the mixed solution, the gelling speed of the gel can be effectively increased, and the gel is further prevented from being prone to agglomeration in the preparation process as far as possible. And the molecular structure of the metal ion crosslinking agent is small, so that the adverse effect on the conductivity of the two-dimensional layered transition metal nanosheet is avoided, and the assembled hydrogel still has very high conductivity.
The metal ion crosslinking agent containing divalent metal ions and the two-dimensional layered transition metal nanosheets are crosslinked into glue, so that the two-dimensional layered transition metal nanosheets can be different from a layered stacking mode and tend to have a three-dimensional structure, the structure is more favorable for material transmission in a network, the obtained gel has stronger isotropy, and the gel electrons have stronger conductivity in all directions. Univalent metal ions cannot exist between the layers of the two-dimensional layered transition metal nanosheets stably, the cross-linking effect between the univalent metal ions and the two-dimensional layered transition metal nanosheets is unstable, gel obtained by cross-linking the univalent metal ions and the two-dimensional layered transition metal nanosheets into glue is prone to agglomeration, unstable in spatial structure and poor in isotropy, and the divalent metal ions can be used for effectively avoiding the adverse phenomena.
Specifically, the mass ratio of the two-dimensional layered transition metal nanosheet to the metal ion cross-linking agent may be in a range of 1:50 to 5000:1, further may be, 1:50 to 1:1, 1:1 to 10:1, 11:1 to 100:1, 101:1 to 1000:1, 1001:1 to 2500:1, 2501:1 to 5000: 1. The content of the metal ion crosslinking agent can determine the overlapping degree of interaction between skeleton molecules and further influence the internal structure and stability of the formed gel, and the mass ratio of the two-dimensional layered transition metal nanosheets to the metal ion crosslinking agent is in the range of 1:50 to 5000:1, the obtained two-dimensional layered transition metal nanosheet gel has a stable structure and does not have the phenomenon of agglomeration or gel collapse.
Specifically, the concentration range of the metal ion crosslinking agent in the two-dimensional layered transition metal nanosheet gel may be 0.1mg/mL to 50mg/mL, and further may be 0.1mg/mL to 1mg/mL, 1.1mg/mL to 10mg/mL, 10.1mg/mL to 20mg/mL, 20.1mg/mL to 35mg/mL, or 35.1mg/mL to 50 mg/mL.
Specifically, in the process of preparing the two-dimensional layered transition metal nanosheet gel by mixing the cross-linking agent solution and the nano dispersion solution, the reaction temperature of the reaction system may range from 0.1 ℃ to 99 ℃, and further may range from 0.1 ℃ to 1 ℃, from 1.1 ℃ to 10 ℃, from 10.1 ℃ to 30 ℃, from 30.1 ℃ to 60 ℃, from 60.1 ℃ to 90 ℃, and from 90.1 ℃ to 99 ℃. When the temperature range of the reaction system is 0.1-99 ℃, the temperature has weak influence on the intermolecular interaction in the reaction system, and has small negative influence on the rapid formation of the two-dimensional layered transition metal nanosheet gel.
Fig. 2 is a schematic diagram of a two-dimensional layered transition metal nanosheet gel according to an embodiment of the present invention before and after gelling. As shown in fig. 3, it is a characteristic diagram of a morphology structure of a material after moisture removal of a two-dimensional layered transition metal nanosheet gel according to an embodiment of the present invention.
Compared with the traditional preparation method of hydrogel, the preparation method of the two-dimensional layered transition metal nanosheet gel has at least the following advantages:
the two-dimensional layered transition metal nanosheet gel has the properties of high isotropy, structural stability, good conductivity and the like. A stable three-dimensional network is constructed by overlapping two-dimensional layered transition metal nanosheets with specific functional groups with a cross-linking agent, so that the isotropy of the gel is ensured. And the preparation process is extremely fast and short in time consumption, and the mass preparation of the two-dimensional layered transition metal nanosheet gel can be realized in a short time.
The preparation method of the two-dimensional layered transition metal nanosheet gel has low requirements on temperature and pH value of a solution, the preparation process is simpler and more environment-friendly, the introduction of impurities is avoided, the process for removing the impurities can be further omitted, and the preparation method is suitable for large-scale industrial production.
Example 1
Dispersing two-dimensional layered transition metal nanosheets in water to prepare 2mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifugal tube, and adding FeCl2Adding 0.2mL of 5mg/mL FeCl serving as a metal ion crosslinking agent into a two-dimensional layered transition metal nanosheet aqueous solution2The solution was allowed to stand at room temperature. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Example 2
Dispersing two-dimensional layered transition metal nanosheets in water to prepare 3mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifugal tube, and adding FeCl2Adding 0.2mL of 5mg/mL FeCl serving as a metal ion crosslinking agent into a two-dimensional layered transition metal nanosheet aqueous solution2Solutions ofThe reaction temperature was room temperature, followed by standing. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Example 3
Dispersing two-dimensional layered transition metal nanosheets in water to prepare 5mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifugal tube, and adding FeCl2Adding 0.2mL of 5mg/mL FeCl serving as a metal ion crosslinking agent into a two-dimensional layered transition metal nanosheet aqueous solution2The solution was allowed to stand at room temperature. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Example 4
Dispersing two-dimensional layered transition metal nanosheets in water to prepare 100mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifugal tube, and adding FeCl2Adding 0.2mL of 5mg/mL FeCl serving as a metal ion crosslinking agent into a two-dimensional layered transition metal nanosheet aqueous solution2The solution was allowed to stand at room temperature. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Example 5
Dispersing two-dimensional layered transition metal nanosheets in water to prepare 5mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifugal tube, and adding FeCl2Adding 0.2mL of 1mg/mL FeCl serving as a metal ion crosslinking agent into a two-dimensional layered transition metal nanosheet aqueous solution2The solution was allowed to stand at room temperature. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Example 6
Dispersing two-dimensional layered transition metal nanosheets in water to prepare 50mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifugal tube, and adding FeCl2Is goldBelongs to an ion cross-linking agent, 0.2mL of FeCl of 0.1mg/mL is added into the aqueous solution of the two-dimensional layered transition metal nano-sheet2The solution was allowed to stand at room temperature. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Example 7
Dispersing two-dimensional layered transition metal nanosheets in water to prepare 5mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifugal tube, and adding FeCl2Adding 0.2mL of 50mg/mL FeCl serving as a metal ion crosslinking agent into a two-dimensional layered transition metal nanosheet aqueous solution2The solution was allowed to stand at room temperature. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Example 8
Dispersing two-dimensional layered transition metal nanosheets in water to prepare 5mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifugal tube, and adding FeCl2Adding 0.2mL of 1mg/mL FeCl serving as a metal ion crosslinking agent into a two-dimensional layered transition metal nanosheet aqueous solution2The solution was allowed to stand at 99 ℃. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Example 9
Dispersing two-dimensional layered transition metal nanosheets in water to prepare 5mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifugal tube, and adding FeCl2Adding 0.2mL of 1mg/mL FeCl serving as a metal ion crosslinking agent into a two-dimensional layered transition metal nanosheet aqueous solution2The solution was allowed to stand at 0.1 ℃. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Example 10
Dispersing the two-dimensional layered transition metal nano-sheet into water to prepare a 5mg/mL two-dimensional layered transition metal nano-sheet aqueous solution,measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the aqueous solution into a 5mL centrifuge tube, and adding FeCl2Adding 0.2mL of 1mg/mL FeCl serving as a metal ion crosslinking agent into a two-dimensional layered transition metal nanosheet aqueous solution2The solution was allowed to stand at 50 ℃. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Comparative example 1
Dispersing two-dimensional layered transition metal nanosheets in water to prepare 0.9mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifugal tube, and adding FeCl2Adding 0.2mL of FeCl of 0.0002mg/mL into the aqueous solution of the two-dimensional layered transition metal nanosheet as a metal ion crosslinking agent2The solution was allowed to stand at room temperature. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Comparative example 2
Dispersing the two-dimensional layered transition metal nanosheets in water to prepare 5mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifuge tube, adding no cross-linking agent, keeping the reaction temperature at room temperature, and then standing. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
Comparative example 3
Dispersing two-dimensional layered transition metal nanosheets in water to prepare 0.9mg/mL of two-dimensional layered transition metal nanosheet aqueous solution, measuring 2mL of two-dimensional layered transition metal nanosheet aqueous solution, placing the two-dimensional layered transition metal nanosheet aqueous solution in a 5mL centrifugal tube, and adding FeCl2Adding 0.2mL of 50mg/mL FeCl serving as a metal ion crosslinking agent into a two-dimensional layered transition metal nanosheet aqueous solution2The solution was allowed to stand at room temperature. The obtained product was subjected to conductivity tests in different directions and electrochemical tests.
The gels of examples 1 to 10 and comparative examples 1 to 3 were tested, the time was counted after the two-dimensional layered transition metal nanosheet aqueous solution was poured into and mixed with the metal ion crosslinking agent, and after a certain period of time, the centrifuge tube was then inverted and if the mixed solution became solid and stable and did not fall, the gel was considered to be obtained. If the horizontal and vertical conductivities of the freeze-dried gel are tested to be similar (the error is not more than 40S/cm), and the gel is directly made into a capacitor electrode, and the capacity is kept to be more than 200F/g at the sweep speed of 1V/S, the gel is considered to be formed into an isotropic gel.
TABLE 1 results of preparing gels in examples 1 to 10 and comparative examples 1 to 3
Tests conducted on embodiments 1 to 10 and comparative examples 1 to 3 show that a two-dimensional layered transition metal nanosheet gel can be obtained by the preparation method of the two-dimensional layered transition metal nanosheet gel, and the two-dimensional layered transition metal nanosheet isotropic gel has good conductive isotropy and electrochemical performance.
As is clear from comparative examples 1 to 10, the rate of formation of the isotropic gel of the two-dimensional layered transition metal nanoplate can be adjusted by the concentration of the two-dimensional layered transition metal nanoplate (skeleton) and the content of the metal ion crosslinking agent.
As can be seen from comparative examples 1 to 10, the isotropy of the conductivity of the two-dimensional layered transition metal nanosheet can be adjusted by the concentration of the two-dimensional layered transition metal nanosheet (framework) and the content of the metal ion crosslinking agent, and the specific capacity of the capacitor can be further improved.
Within the foregoing range, the higher the content of the metal ion crosslinking agent, the better the crosslinking degree of the two-dimensional layered transition metal nanosheet gel and the more stable the gel. The concentration of the two-dimensional layered transition metal nanosheet (skeleton) can greatly influence the formation rate of the two-dimensional layered transition metal nanosheet gel, and the higher the concentration of the two-dimensional layered transition metal nanosheet (skeleton), the faster the formation rate of the isotropic gel, the more isotropic the conductivity tends to be, and the higher the specific capacity of the capacitor is.
The preparation method of the two-dimensional layered transition metal nanosheet gel provided by the invention is simple in process and convenient for industrial mass production.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A preparation method of two-dimensional layered transition metal nanosheet gel is characterized by comprising the following steps:
providing a two-dimensional layered transition metal nanosheet with a specific functional group as a solute, wherein the specific functional group is at least one of a carboxyl group, a hydroxyl group, an ether group, an ester group, a ketone group, a carbonyl group, an acid anhydride, an epoxy functional group, a fluorine group, a sulfonic group, an amino group, a secondary amine, a tertiary amine and an aromatic functional group, and dissolving the two-dimensional layered transition metal nanosheet in a solvent to form a nano dispersion; and
providing a cross-linking agent solution containing a metal ion cross-linking agent, wherein the metal ion cross-linking agent contains metal ions with positive divalent or positive trivalent, mixing the cross-linking agent solution with the nano dispersion liquid, and mixing to form the two-dimensional layered transition metal nanosheet gel, wherein the mass ratio of the two-dimensional layered transition metal nanosheet to the metal ion cross-linking agent ranges from 1:1 to 5000: 1.
2. The method of preparing a two-dimensional layered transition metal nanoplatelet gel of claim 1, wherein the two-dimensional layered transition metal nanoplatelets comprise at least a first element and a second element, the first element being at least one of Sc, Ti, Zr, V, Nb, Cr, or Mo, and the second element being at least one of C or N.
3. The method of preparing a two-dimensional layered transition metal nanoplatelet gel of claim 1, wherein the metal ion crosslinker comprises at least Mn2+，Fe2+，Co2+，Ni2+，Cu2+，Zn2+，Be2+，Sr2+，Ba2+And Ga3+At least one of (1).
4. A method of preparing a two-dimensional layered transition metal nanoplate gel as defined in claim 1, wherein the solvent is at least one of water, acetone, ethanol, methanol, tetrahydrofuran, acrylic acid, 1, 4-dioxane, n-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, ethylene glycol, glycerol, diglyme, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and 1, 3-dioxolane.
5. The method of preparing a two-dimensional layered transition metal nanoplate gel of claim 1, wherein the concentration of the two-dimensional layered transition metal nanoplate in the nanodispersion ranges from 1mg/mL to 100 mg/mL.
6. The method of preparing a two-dimensional layered transition metal nanoplate gel of claim 1, wherein the two-dimensional layered transition metal nanoplate has a particle size in the range of 1nm to 100 μ ι η.
7. A method of preparing a two-dimensional layered transition metal nanoplate gel as claimed in claim 1 wherein the concentration of the metal ion crosslinker in the two-dimensional layered transition metal nanoplate gel is in the range of 0.1mg/mL to 50 mg/mL.
8. The method of preparing a two-dimensional layered transition metal nanoplate gel of claim 1, wherein the reaction temperature during the mixing of the crosslinker solution with the nanodispersion to prepare the two-dimensional layered transition metal nanoplate gel ranges from 0.1 ℃ to 99 ℃.
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