CN113285070B - Preparation method and application of porous dense MXene membrane with adjustable pores - Google Patents

Preparation method and application of porous dense MXene membrane with adjustable pores Download PDF

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CN113285070B
CN113285070B CN202110482143.0A CN202110482143A CN113285070B CN 113285070 B CN113285070 B CN 113285070B CN 202110482143 A CN202110482143 A CN 202110482143A CN 113285070 B CN113285070 B CN 113285070B
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mxene
dispersion liquid
dense
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membrane
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CN113285070A (en
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陶莹
吴志坦
刘啸尘
尚童鑫
王宁
陈德容
杨全红
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Tianjin University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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Abstract

The invention belongs to the technical field of energy storage material preparation, and particularly relates to a preparation method of an MXene compact porous membrane with adjustable pores, which at least comprises the following steps: preparing an MXene microgel dispersion liquid with a nano-sheet crosslinked structure from the MXene dispersion liquid by using a crosslinking method; mixing the MXene microgel dispersion liquid and the MXene dispersion liquid according to a proportion, and uniformly mixing and dispersing the mixture by ultrasonic treatment to obtain a mixed dispersion liquid A; and carrying out vacuum filtration or air drying film forming operation on the mixed dispersion liquid A, and removing water through vacuum drying to obtain the MXene compact porous film. According to the invention, the porosity and density of the MXene compact porous membrane can be regulated and controlled by regulating the proportion of microgel, and the porous membrane is applied to the field of electrochemical energy storage, and finally the electrode material with both volume energy density and power density is obtained.

Description

Preparation method and application of porous dense MXene membrane with adjustable pores
Technical Field
The invention belongs to the technical field of energy storage material preparation, and particularly relates to a preparation method and application of an adjustable-pore MXene compact porous membrane.
Background
MXene is a metal carbide or nitride material with a two-dimensional layered structure, and is derived from a ternary layered ceramic material M n+1AXn (M is a transition metal element, A is a main group element, X is C or N, and N is generally 1-3). In the etching preparation process, a large amount of residual functional groups (-F, -OH, -O and the like) on the surface of the MXene endows the MXene with good hydrophilicity, and the MXene has excellent electrical conductivity (6000-8000 Scm -1), good thermal conductivity, adjustable band gap and excellent mechanical strength, so the MXene has wide application prospect in the fields of energy conversion and the like.
MXene has great potential in dense energy storage applications due to its greater intrinsic density and higher specific capacity. By stacking the MXene nanoplatelets into a film, a high density approaching 4g/cm 3 can be achieved, thereby greatly improving the volumetric energy density of the MXene-based energy storage device. However, in dense MXene films, the stacking of two-dimensional lamellae results in a decrease in the effective specific surface area and active site utilization of MXene, while in two-dimensional layered materials the ion transport path is long and slow, thus impeding the kinetics of the electrode reaction.
The macroporous structure is introduced into the MXene-based electrode by a structure assembly method, so that the ion transmission path can be obviously shortened, and the multiplying power performance of the corresponding energy storage device is improved. However, the introduction of macropores severely reduces the bulk density of the electrode material, thereby greatly damaging the volumetric energy density of the energy storage device. How to balance electrode pores and density, the construction of an energy storage device with both high volumetric energy density and high power density still presents a significant challenge.
In view of the above, the present invention aims to provide a method for preparing a dense porous membrane of MXene with adjustable pores and application thereof, so as to solve the above problems.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, a preparation method and application of an adjustable-pore MXene compact porous membrane are provided, so as to solve the problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of an adjustable-pore MXene dense porous membrane at least comprises the following steps:
MXene has the general formula M n+1XnTx, where M is a transition metal element (e.g., cr, ti, V, nb, mo, etc.), X is carbon and/or nitrogen, T x represents a surface functional group thereof (i.e., -OH, -O, -F, etc.), and n=1 to 4.
Firstly, preparing an MXene microgel dispersion liquid with a nano-sheet crosslinked structure from the MXene dispersion liquid by using a crosslinking method;
the crosslinking method comprises a small molecule assembly method, an ion crosslinking method and an alkali treatment method.
Small molecule crosslinking method: uniformly mixing the MXene dispersion liquid and the Graphene Oxide (GO) dispersion liquid according to a proportion, adding a small molecular cross-linking agent, uniformly dispersing, and performing sealing and heating treatment to obtain the MXene hydrogel, wherein the cross-linking agent is any one of Ethylenediamine (EDA), L-cysteine, ammonia water (NH 3·H2 O), hydrazine hydrate (N 2H4·H2 O), sodium bisulphite (NaHSO 3), hydrogen Iodide (HI) and sodium sulfide (Na 2 S). The MXene hydrogel was transferred into water and ultrasonically dispersed by a cell pulverizer to obtain MXene microgel dispersion a.
Ionic crosslinking method: and mixing the MXene dispersion liquid with a divalent metal ion salt solution according to a certain proportion to obtain an ionic crosslinked gel, and carrying out centrifugal washing and uniform dispersion on the ionic crosslinked gel in water by a cell pulverizer to obtain the MXene microgel dispersion liquid B.
Alkali treatment method: the MXene dispersion is mixed with sodium hydroxide or potassium hydroxide solution according to a certain proportion and continuously stirred to obtain alkali treatment MXene dispersion, and the alkali treatment MXene dispersion is subjected to centrifugal water washing and is uniformly dispersed in water by a cell pulverizer to obtain MXene microgel dispersion C.
The microgel dispersion is microscopically in the form of particles due to crosslinking of the nanoplatelets, the particle size of the particles being about 500 to 600nm. The microgel has a negative Zeta potential and is therefore well dispersed in water and can be homogeneously mixed with an MXene dispersion. Because of the fewer surface functional groups, the Zeta potential is greater than that of the corresponding MXene dispersion.
Secondly, mixing the MXene microgel dispersion liquid obtained in the first step with the MXene dispersion liquid in proportion, and uniformly mixing and dispersing the mixture by ultrasonic treatment to obtain a mixed dispersion liquid D;
And thirdly, carrying out vacuum suction filtration or air drying film forming operation on the mixed dispersion liquid D obtained in the second step, and removing water through vacuum drying to obtain the MXene compact porous film.
In the processes of vacuum filtration or air drying film formation and drying moisture removal, microgel composed of three-dimensional crosslinked nano sheets is compressed by capillary force, so that on one hand, a compact film can be formed to maintain high density level, and on the other hand, certain mesopores can be introduced to improve ion transmission. Therefore, the invention can regulate and control the porosity and density of the MXene compact porous membrane by regulating the proportion of microgel, is applied to the field of electrochemical energy storage, and finally obtains the electrode material with both volume energy density and power density.
As an improvement of the preparation method of the porous dense MXene membrane with adjustable pores, in the small molecular crosslinking method, the mass concentration of MXene in the mixed dispersion liquid is 2-10 mg/mL, the concentration is too high, so that the stacking of MXene sheets is serious, the internal components of the hydrogel are uneven, and the gel formation is difficult due to the too low concentration; the mass concentration of the graphene oxide is 2-10 mg/mL, and too high concentration can lead to serious agglomeration of graphene oxide sheets, so that the internal components of the hydrogel are uneven, and too low concentration can lead to difficult gel formation; the mass ratio of MXene to graphene oxide is (0.1-9): 1, the mass ratio is too high and too low, which leads to difficult gelling; the mass ratio of the total mass of MXene and graphene oxide to the cross-linking agent is 1: (0.1-1), the mass ratio is too high, which causes difficulty in gelling, and too low, which causes excessive crosslinking agent and difficulty in removal; the sealing heating temperature is 80-95 ℃, the sealing heating duration is 1-20 h, the MXene is oxidized due to the over high temperature, the structure is damaged, and the hydrogel is difficult to form due to the over low temperature.
As an improvement of the preparation method of the porous dense porous membrane with adjustable pores, in the ionic crosslinking method, the mass concentration of the MXene dispersion liquid is 5-20 mg/mL, and too high concentration can cause serious stacking of MXene sheets, so that the internal components of the hydrogel are uneven, and too low concentration can cause gelling difficulty; the concentration of the divalent metal ion salt solution is 0.1-3 mol/L, and too high concentration can lead to local rapid gel formation of the MXene lamellar, so that the internal structure of the hydrogel is uneven, and too low concentration can lead to difficult gel formation; the mass ratio of MXene to divalent metal ions is 1: (0.1 to 0.5), too high will result in insufficient crosslinking agent to form a gel, and too low will result in excessive agglomeration of the MXene platelets.
As an improvement of the preparation method of the porous dense porous membrane with adjustable pores, in the first step of the alkali treatment method, the mass concentration of the MXene dispersion liquid is 1-20 mg/mL, and too high concentration can cause serious stacking of MXene sheets, so that the alkali treatment effect is insufficient, and too low concentration can cause too thin solution, which is unfavorable for centrifugally collecting products; the concentration of the sodium hydroxide or potassium hydroxide solution is 0.5-2 mol/L, and the excessive concentration can lead to etching of the sheet layer, and the excessive concentration can lead to insufficient alkali treatment effect; the mass ratio of MXene to sodium hydroxide or potassium hydroxide is 1: (1-10), too high will result in insufficient alkali treatment effect, and too low will result in etching of the sheet; the continuous stirring time is 30-120 min after mixing, the alkali treatment effect is insufficient due to the too short time, and the sheet layer is etched due to the too long time.
As an improvement of the preparation method of the porous dense MXene membrane with adjustable pores, in the first step, the ultrasonic power of a cell pulverizer is 400-800W, the MXene sheet layer is destroyed due to the excessive power, a crosslinked structure cannot be maintained, the microgel cannot be completely dispersed in water due to the excessive power, and the duration of the ultrasonic wave is 30-120 min; the concentration of the obtained MXene microgel dispersion liquid is 1-10 mg mL -1, and too high concentration can lead to severe agglomeration of microgels, which is unfavorable for the next step of mixing and dispersion, and too low concentration can lead to excessive volume of dispersion liquid used for suction filtration, thereby prolonging the preparation time.
As an improvement of the preparation method of the porous dense membrane with adjustable pores, in the second step, the mass ratio of the MXene microgel to the MXene is 1: (0-9), too low a ratio will result in too little film porosity being formed; the power of ultrasonic treatment is 250-360W, and too low ultrasonic power can lead to uneven mixing of the MXene microgel and the MXene, and too high ultrasonic power can lead to destruction of the MXene sheet layer; the duration of the ultrasound is 30-120 min, too short a time will result in uneven mixing of the MXene microgel with the MXene, too long a time will result in oxidation of the MXene lamellae.
As an improvement of the preparation method of the porous dense MXene membrane with adjustable pores, in the third step, the drying temperature is 25-80 ℃, the drying temperature is too low to cause incomplete drying, and the temperature is too high to cause the oxidation of the sheet layer; the drying duration is 3-12 h, too short a drying time will result in incomplete drying and too high a temperature will result in the sheet being oxidized.
The invention also aims to provide the porous dense MXene membrane with adjustable pores, which is prepared by the method, and has an adjustable porous structure, a specific surface area of 5-70 m 2/g, a pore volume of 0.003-0.15 cm 3/g and a bulk density of 2-4 g/cm 3.
It is a further object of the present invention to provide the use of pore-tunable dense porous membranes of MXene as electrode materials for supercapacitors, as well as negative electrode materials for alkaline metal ion batteries, and as efficient carriers for active materials in lithium sulfur batteries and lithium air batteries in the energy storage field.
Wherein the mass energy density of the super capacitor is 2-15 Wh/kg, and the volume energy density is 8-40 Wh/L.
Compared with the prior art, the invention has at least the following advantages:
Firstly, the invention utilizes microgel to regulate and control the pore structure of the MXene membrane, greatly shortens the ion transmission path in the membrane electrode, and improves the specific surface area and the active site utilization rate of the MXene, thereby improving the multiplying power performance of the MXene membrane electrode.
Secondly, the invention can realize the accurate design of the pore structure of the MXene compact porous membrane by controlling the microgel content, thereby balancing the porosity and the density of the membrane electrode and realizing the combination of high volume energy density and high power density of the energy storage device. In addition, the method has the advantages of mild condition, simple operation, green and pollution-free performance and easy realization of large-scale preparation.
And thirdly, the invention utilizes a vacuum filtration or room temperature air drying film forming method, and regulates and controls the pore structure of the MXene film by introducing microgel, thereby improving the ion transmission characteristic of the membrane electrode while ensuring the compactness of the membrane electrode, and effectively improving the volume energy density of the material in high-rate energy storage application. The MXene compact porous membrane is used for performance test of the water system super capacitor, and the mass energy density is 2-15 Wh/kg, and the volume energy density is 8-40 Wh/L.
Drawings
The present invention and its advantageous technical effects will be described in detail below with reference to the accompanying drawings and detailed description.
FIG. 1 is an SEM image of a dense porous membrane of MXene prepared in example 1;
FIG. 2 is a graph of nitrogen adsorption and desorption isotherms (77K) for the dense porous membrane of MXene prepared in example 1;
FIG. 3 is a graph of pore size distribution of the dense porous membrane of MXene prepared in example 1;
FIG. 4 is a cyclic voltammogram of the dense porous membrane of MXene prepared in example 1 in 3mol/L sulfuric acid electrolyte;
FIG. 5 is a graph showing charge and discharge of the MXene film prepared in example 1 in 3mol/L sulfuric acid electrolyte;
FIG. 6 is an external appearance map of the dense porous MXene membrane prepared in example 1.
Detailed Description
The following specific examples are given to illustrate the technical aspects of the present invention, but the scope of the present invention is not limited thereto.
Example 1
The preparation method of the porous dense MXene membrane with adjustable pores provided by the embodiment comprises the following steps:
Firstly, adding 100 mu L of ethylenediamine crosslinking agent into 40mL of mixed dispersion liquid containing 9mg/mL of MXene dispersion liquid and 2mg/mL of Graphene Oxide (GO) to uniformly disperse, and sealing and heating at 95 ℃ for 6 hours to obtain MXene hydrogel; in this embodiment, the MXene is specifically Ti 3C2Tx.
Secondly, transferring the MXene hydrogel obtained in the first step into water, and performing ultrasonic dispersion for 30min at the power of 600W through a cell pulverizer to obtain 2mg/mL MXene microgel dispersion liquid;
Thirdly, 3.75mL of the 2mg/mL MXene microgel dispersion liquid obtained in the second step and 3.75mL of the 2mg/mL MXene dispersion liquid are taken, and are uniformly mixed and dispersed through ultrasonic treatment with 300W power for 70min, so as to obtain a mixed dispersion liquid A;
and fourthly, carrying out vacuum filtration on the mixed dispersion liquid A obtained in the third step to form a film, and carrying out vacuum drying at 70 ℃ for 8 hours to remove water to obtain the MXene compact porous film.
The specific surface area of the MXene compact porous membrane is 29.5m 2/g, the pore volume is 0.039cm -3/g, and the bulk density is 3.32g/cm 3.
FIG. 1 is an SEM image of a dense porous membrane of MXene prepared in example 1; as can be seen from fig. 1: the MXene dense porous membrane microscopically exhibits the morphology of a stack of nanoplatelets. This is because capillary forces generated by moisture removal during vacuum filtration and drying act to compress microgels and MXene nanoplatelets, thereby reducing dead space while retaining certain pores and increasing bulk density.
FIG. 2 shows the nitrogen adsorption/desorption isotherm (77K) of the dense porous membrane of MXene prepared in example 1, as can be seen from FIG. 2: the specific surface area of the MXene dense porous membrane is 29.5m 2/g.
FIG. 3 is a pore size distribution curve of the dense porous membrane of MXene prepared in example 1. As can be seen from fig. 3: the porous structure of the dense porous membrane of MXene is mainly mesoporous with the diameter of 3-5 nm.
Example 2
The embodiment is the same as in example 1, except that in step three, the mixed dispersion A is obtained by mixing 5mL of 2mg/mL MXene microgel dispersion and 2.5mL of MXene dispersion and then subjecting to ultrasonic treatment with a power of 300W.
The specific surface area of the MXene compact porous membrane is 53.7m 2/g, the pore volume is 0.102cm -3/g, and the bulk density is 2.94g/cm 3.
Example 3
The embodiment is the same as in example 1, except that in step three, the mixed dispersion A is obtained by mixing 2.5mL of 2mg/mL MXene microgel dispersion and 5mL of MXene dispersion and then subjecting to ultrasonic treatment with a power of 300W.
The specific surface area of the MXene compact porous membrane is 15.3m 2/g, the pore volume is 0.013cm -3/g, and the bulk density is 3.64g/cm 3.
Example 4
The embodiment is the same as in example 1, except that in step three, the mixed dispersion A consists of only 7.5mL of 2mg/mL MXene microgel dispersion.
The specific surface area of the MXene compact porous membrane is 65.4m 2/g, the pore volume is 0.121cm -3/g, and the bulk density is 2.58g/cm 3.
Example 5
The embodiment is the same as in example 1, except that in step one, the crosslinking agent used is NaHSO 3.
The specific surface area of the MXene compact porous membrane is 32.5m 2/g, the pore volume is 0.046cm -3/g, and the bulk density is 3.21g/cm 3.
Example 6
The embodiment is different from example 1 in that in the fourth step, the film forming mode is air drying film forming.
The specific surface area of the MXene compact porous membrane is 35.8m 2/g, the pore volume is 0.049cm -3/g, and the bulk density is 3.09g/cm 3.
Comparative example 1
The embodiment is the same as in example 1 except that in step three, the mixed dispersion A consists of only 7.5mL of 2mg/mL MXene dispersion.
A dense MXene film was finally obtained, having a specific surface area of 8.4m 2/g, a pore volume of 0.007cm -3/g and a bulk density of 3.98g/cm 3.
Electrochemical performance test
The target materials prepared in examples 1 to 6 and comparative example 1 were applied to supercapacitors, and the specific steps for preparing the supercapacitors were as follows:
(1) Milling a target material into a wafer with the diameter of 10mm, and directly taking the wafer as an electrode;
(2) And (3) sequentially placing the prepared pole piece according to the sequence of the negative electrode shell, the spring piece, the gasket, the negative electrode, the diaphragm, the positive electrode and the positive electrode shell, dripping a certain amount of electrolyte, sealing the assembled capacitor under the pressure of 50MPa by using a sealing machine, thus obtaining the button capacitor, and standing for 6 hours for electrochemical performance test. The electrolyte used in this example was 3mol/L H 2SO4.
The cyclic voltammogram (FIG. 4) was tested at a sweep rate of 20mV/s over a voltage window of 0-1V, and it was seen that the MXene dense porous membrane exhibited significant pseudocapacitive properties. Constant-current charge and discharge tests are carried out under the current density of 1A/g, and the charge and discharge curves are shown in FIG. 5, so that ideal capacitance behaviors are shown;
FIG. 6 is an appearance diagram of the dense porous membrane of MXene prepared in example 1, showing that the dense porous membrane of MXene has a self-supporting macroscopic structure, can be directly used as an electrode, has certain flexibility, and is expected to be used in the flexible energy storage field.
Example 7
The preparation method of the porous dense MXene membrane with adjustable pores provided by the embodiment comprises the following steps:
Firstly, adding 50mg of L-cysteine cross-linking agent into 40mL of mixed dispersion liquid containing 4mg/mL of MXene dispersion liquid and 6mg/mL of Graphene Oxide (GO) to uniformly disperse, and sealing and heating at 85 ℃ for 4 hours to obtain MXene hydrogel; in this embodiment, MXene is specifically V 2CTx.
Secondly, transferring the MXene hydrogel obtained in the first step into water, and performing ultrasonic dispersion for 90 minutes by a cell pulverizer at a power of 500W to obtain MXene microgel dispersion liquid;
thirdly, 4mL of the MXene microgel dispersion liquid obtained in the second step and 4mL of the MXene dispersion liquid are taken, and are uniformly mixed and dispersed through ultrasonic treatment with 320W power for 60min, so as to obtain a mixed dispersion liquid A;
And fourthly, carrying out vacuum filtration on the mixed dispersion liquid A obtained in the third step to form a film, and carrying out vacuum drying at 60 ℃ for 10 hours to remove water to obtain the MXene compact porous film.
Example 8
The preparation method of the porous dense MXene membrane with adjustable pores provided by the embodiment comprises the following steps:
Firstly, adding 70 mu L of ammonia water (NH 3·H2 O) cross-linking agent into 40mL of mixed dispersion liquid containing 7mg/mL of MXene dispersion liquid and 8mg/mL of Graphene Oxide (GO) to uniformly disperse, and sealing and heating at 82 ℃ for 10 hours to obtain MXene hydrogel; in this embodiment, the MXene is specifically Ti 2CTx.
Secondly, transferring the MXene hydrogel obtained in the first step into water, and performing ultrasonic dispersion for 45min at 650W power through a cell pulverizer to obtain MXene microgel dispersion liquid;
Thirdly, 4mL of the MXene microgel dispersion liquid obtained in the second step and 4mL of the MXene dispersion liquid are taken, and are uniformly mixed and dispersed through ultrasonic treatment with the power of 280W for 80min, so as to obtain a mixed dispersion liquid A;
and fourthly, carrying out vacuum filtration on the mixed dispersion liquid A obtained in the third step to form a film, and carrying out vacuum drying at 55 ℃ for 4.5 hours to remove water to obtain the MXene compact porous film.
Example 9
The preparation method of the porous dense MXene membrane with adjustable pores provided by the embodiment comprises the following steps:
Firstly, adding 60 mu L of hydrazine hydrate (N 2H4·H2 O) cross-linking agent into 40mL of mixed dispersion liquid containing 3.5mg/mL of MXene dispersion liquid and 5.5mg/mL of Graphene Oxide (GO) to uniformly disperse, and sealing and heating at 92 ℃ for 15 hours to obtain MXene hydrogel; in this embodiment, the MXene is specifically Ti 3CNTx.
Secondly, transferring the MXene hydrogel obtained in the first step into water, and performing ultrasonic dispersion for 55min by using a cell pulverizer at the power of 450W to obtain MXene microgel dispersion liquid;
Thirdly, 4mL of the MXene microgel dispersion liquid obtained in the second step and 4mL of the MXene dispersion liquid are taken, and are uniformly mixed and dispersed through ultrasonic treatment with 310W power for 40min, so as to obtain a mixed dispersion liquid A;
And fourthly, carrying out vacuum filtration on the mixed dispersion liquid A obtained in the third step to form a film, and carrying out vacuum drying at 65 ℃ for 6.5h to remove water to obtain the MXene compact porous film.
Example 10
The preparation method of the porous dense MXene membrane with adjustable pores provided by the embodiment comprises the following steps:
Firstly, rapidly adding 5mL of MXene dispersion liquid with the concentration of 10mg/mL into 0.1mL of FeCl 2 solution with the concentration of 2mol/L to obtain MXene ionomer gel; in this embodiment, the MXene is specifically Ti 3C2Tx.
In the second step, the ionomer gel was washed 3 times with centrifugal water at 4000rpm, and then the precipitate was dispersed in 10mL of water and ultrasonically dispersed by a cell pulverizer at a power of 500W for 60 minutes to obtain a microgel dispersion.
Thirdly, 4mL of the MXene microgel dispersion liquid obtained in the second step and 4mL of the MXene dispersion liquid are taken, and are uniformly mixed and dispersed through ultrasonic treatment with 320W power for 60min, so as to obtain a mixed dispersion liquid;
And fourthly, carrying out vacuum filtration on the mixed dispersion liquid obtained in the third step to form a film, and carrying out vacuum drying at 60 ℃ for 10 hours to remove water to obtain the MXene compact porous film.
Example 11
The embodiment is similar to example 10, except that in step one, the divalent metal salt solution used is a 2mol/L NiCl 2 solution
Example 12
The embodiment is the same as in example 10 except that in step one, the concentration of the MXene dispersion used is 20mg/mL.
Example 13
The preparation method of the porous dense MXene membrane with adjustable pores provided by the embodiment comprises the following steps:
Firstly, adding 10mL of NaOH solution with the concentration of 2mol/L into 40mL of MXene dispersion with the concentration of 5mg/mL to obtain alkali-treated MXene dispersion; in this embodiment, the MXene is specifically Ti 3C2Tx.
In the second step, the alkali-treated MXene dispersion was centrifuged and washed 3 times at 4000rpm, and then the precipitate was dispersed in 10mL of water and sonicated by a cell pulverizer at a power of 500W for 60 minutes to obtain a microgel dispersion.
Thirdly, 4mL of the MXene microgel dispersion liquid obtained in the second step and 4mL of the MXene dispersion liquid are taken, and are uniformly mixed and dispersed through ultrasonic treatment with 320W power for 60min, so as to obtain a mixed dispersion liquid;
And fourthly, carrying out vacuum filtration on the mixed dispersion liquid obtained in the third step to form a film, and carrying out vacuum drying at 60 ℃ for 10 hours to remove water to obtain the MXene compact porous film.
Example 14
The embodiment is different from example 13 in that in the first step, the alkali solution used is a 2mol/L KOH solution
Example 15
The embodiment is the same as in example 13 except that in step one, the concentration of the MXene dispersion used is 20mg/mL.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.

Claims (12)

1. A method for preparing an adjustable-pore MXene dense porous membrane, which is characterized by at least comprising the following steps:
Firstly, preparing an MXene microgel dispersion liquid with a nano-sheet crosslinked structure from the MXene dispersion liquid by using a crosslinking method;
secondly, mixing the MXene microgel dispersion liquid obtained in the first step with the MXene dispersion liquid in proportion, and uniformly mixing and dispersing the mixture by ultrasonic treatment to obtain a mixed dispersion liquid D;
thirdly, carrying out vacuum suction filtration or air drying film forming operation on the mixed dispersion liquid D obtained in the second step, and drying to remove water to obtain the MXene compact porous film;
The concentration of the MXene microgel dispersion liquid obtained in the first step is 1-10 mg mL -1; in the second step, the mass ratio of the MXene microgel to the MXene is 1: (0-9); the power of ultrasonic treatment is 250-360W, and the duration of ultrasonic treatment is 30-120 min.
2. The method for preparing a pore-tunable MXene dense porous membrane according to claim 1, wherein the crosslinking method comprises a small molecule crosslinking method, an ion crosslinking method and an alkali treatment method.
3. The method for preparing the porous dense membrane with adjustable pores, which is characterized in that the specific steps of the small molecule crosslinking method are as follows: uniformly mixing the MXene dispersion liquid and the graphene oxide dispersion liquid according to a proportion to obtain a mixed dispersion liquid, adding a small molecular cross-linking agent to uniformly disperse, performing sealing and heating treatment to obtain MXene hydrogel, transferring the MXene hydrogel into water, and performing ultrasonic dispersion through a cell pulverizer to obtain MXene microgel dispersion liquid A.
4. The method for preparing the porous dense membrane with adjustable pores, which is characterized in that the mass concentration of the MXene in the mixed dispersion liquid in the small molecule crosslinking method is 2-10 mg/mL, and the mass concentration of the graphene oxide is 2-10 mg/mL;
the mass ratio of MXene to graphene oxide is (0.1-9): 1, a step of;
The cross-linking agent is any one of Ethylenediamine (EDA), L-cysteine, ammonia water (NH 3·H2 O), hydrazine hydrate (N 2H4·H2 O), sodium bisulphite (NaHSO 3), hydrogen Iodide (HI) and sodium sulfide (Na 2 S);
The mass ratio of the total mass of MXene and graphene oxide to the cross-linking agent is 1: (0.1 to 0.2);
The sealing heating temperature is 80-95 ℃, and the sealing heating duration is 1-20 h.
5. The method for preparing the porous dense membrane with adjustable pores, which is characterized in that the ion crosslinking method comprises the following specific steps: and mixing the MXene dispersion liquid with a divalent metal ion salt solution in proportion to obtain an ionic crosslinked gel, washing the ionic crosslinked gel by centrifugation, and performing ultrasonic dispersion by a cell pulverizer to obtain the MXene microgel dispersion liquid B.
6. The method for preparing a dense porous membrane of MXene with adjustable pores according to claim 5, characterized in that the mass concentration of the MXene dispersion in the ionic crosslinking method is 5-20 mg/mL; the divalent metal ion is any one of Fe 2+,Cu2+,Ni2+,Mg2+,Zn2+,Ca2+,Co2+; the concentration of the divalent metal ion salt solution is 0.1-3 mol/L; the mass ratio of MXene to divalent metal ions is 1: (0.1-0.5).
7. The method for preparing the porous dense membrane with adjustable pores, which is characterized in that the specific steps of the alkali treatment method are as follows: and mixing the MXene dispersion liquid with sodium hydroxide or potassium hydroxide solution according to a certain proportion and continuously stirring to obtain an alkali-treated MXene dispersion liquid, and performing centrifugal water washing and ultrasonic dispersion on the alkali-treated MXene dispersion liquid by a cell pulverizer to obtain an MXene microgel dispersion liquid C.
8. The method for preparing the porous dense membrane with adjustable pores of MXene according to claim 7, wherein the method comprises the following steps: the mass concentration of the MXene dispersion liquid in the alkali treatment method is 1-20 mg/mL; the concentration of the sodium hydroxide or potassium hydroxide solution is 0.5-2 mol/L; the mass ratio of MXene to sodium hydroxide or potassium hydroxide is 1: (1-10), and the continuous stirring time after mixing is 30-120 min.
9. The method for preparing a dense porous membrane of MXene with adjustable pores according to claim 3, 5 or 7, characterized in that in the first step, the power of the ultrasonic wave of the cell pulverizer is 400-800W, and the duration of the ultrasonic wave is 30-120 min; in the third step, the drying temperature is 50-80 ℃ and the drying duration is 3-12 h.
10. A pore-tunable MXene dense porous membrane prepared by the method of any one of claims 1-9, characterized in that: the MXene compact porous membrane has an adjustable porous structure, the specific surface area is 5-70 m 2/g, the pore volume is 0.007-0.15 cm 3/g, and the bulk density is 2.6-4 g/cm 3.
11. Use of an adjustable pore dense porous MXene membrane prepared by the method of any one of claims 1-9 in the energy storage field, characterized in that: the MXene dense porous membrane is useful as a supercapacitor electrode material, or as an alkali metal ion battery anode material, or as an effective carrier for active materials in lithium sulfur batteries and lithium air batteries.
12. The use according to claim 11, characterized in that: the mass energy density of the super capacitor is 2-15 Wh/kg, and the volume energy density is 8-40 Wh/L.
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