CN109928713A - MXene hydrogel and its liquid phase assemble method - Google Patents
MXene hydrogel and its liquid phase assemble method Download PDFInfo
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Abstract
A kind of MXene hydrogel and its liquid phase assemble method, the hydrogel is by including that the raw material of following content of component reacts to obtain, wherein, MXene (1~20) part, graphene oxide (0.5~1) part, initiator (0.1~0.5) part.The present invention is under the auxiliary of common reducing agent, MXene nanometer sheet is crosslinked using the graphene oxide layer of partial reduction, the liquid phase of directional guide MXene assembles, obtain the MXene hydrogel of three-dimensional structure stabilization, volume contraction, the three-dimensional liquid phase assemble method of MXene is developed, a kind of high method of strong flexibility, controllability is provided for building three-dimensional MXene macroscopic body, has greatly widened the application space of MXene base macroscopic material, it is of far-reaching significance to the further development of two-dimensional material MXene.
Description
Technical field
The invention belongs to two-dimensional material package technique field more particularly to a kind of MXene hydrogel and its liquid phase assembling sides
Method.
Background technique
MXene is a kind of New Two Dimensional transition metal carbide or nitride, passes through villiaumite and hydrochloric acid or hf etching
MAX is divided by active metallic element and removes to obtain, and uses Mn+1XnT is indicated.It has unique two-dimensional layered structure, this type
The graphene-structured of type provides diffusion admittance for the intercalation/deintercalation of ion, has in lithium ion battery and supercapacitor
Broad application prospect.Meanwhile MXene material has huge specific surface area, higher conductivity, the wetting of good electrolyte
Property and stronger tension resistance ability, higher density (3.7g/cm3), show it as electrode material for super capacitor
Superior chemical property, advantage is prominent especially in terms of volume performance.However, as other two-dimensional materials, the layer of MXene
Shape structure also brings a series of problems, because stacked in multi-layers greatly reduces the utilization rate of its specific surface area.It is some to be based on MXene
Composite material design and exploitation effectively improve this problem, such as using flexibility " Sanming City of alternately suction filtration method preparation
Control " structure Ti3C2Tx/CNT、Ti3C2Tx/rGO、Ti3C2Tx/ OLC composite membrane, but limited lamella distance regulation mode is still unfavorable
In the further development of MXene.
In energy storage field, MXene three-dimensional porous structure is designed, the assembling mode by regulating and controlling lamella constructs reasonable electronics
Conducting networks and ion transmission channel, promote its effective ratio area, reduce the tortuosity that material internal ion shuttles, optimize from
Sub- efficiency of transmission is the effective means for improving its energy storage device electrode thickness, is expected to solve close in the horizontal upper volume energy of device
Spend not high problem.In addition, three-dimensional assembling is common one of the strategy for improving two-dimensional material lamella stack-up issue, three-dimensional porous
Network has the characteristics that be mutually communicated ion channel, biggish specific surface area, aperture layer abundant time, in fields such as energy storage, absorption
Have a stronger advantage, thus how based on two-dimensional layer material building three-dimensional porous network to the application space for expanding MXene
It is particularly important.However, MXene material is since lamella flexibility is not so good as graphene, it is to be difficult to constitute three as graphene in itself
Tie up the graphene hydrogel of structure, but at present people it is highly desirable find a kind of method and construct out be similar to as graphene
Three-dimensional MXene structure.
Summary of the invention
In view of this, one of main object of the present invention is to propose a kind of MXene hydrogel and its liquid phase assemble method,
To at least be partially solved at least one of above-mentioned technical problem.
To achieve the goals above, as one aspect of the present invention, a kind of MXene hydrogel is provided, by including
The raw material of following content of component reacts to obtain, wherein MXene (1~20) part, graphene oxide (0.5~1) part, initiator
(0.1~0.5) part.
As another aspect of the present invention, a kind of MXene hydrogel liquid phase assemble method is additionally provided, including will be caused
Agent is added to reaction in MXene and graphene oxide mixed solution and obtains MXene hydrogel.
As an additional aspect of the present invention, additionally provide a kind of three-dimensional MXene block, three-dimensional MXene block be by
The hydrogel obtains after being dried with hydrogel prepared by the method.
As another aspect of the invention, three-dimensional MXene block is additionally provided in energy storage or the application of adsorbing domain.
Based on the above-mentioned technical proposal it is found that MXene hydrogel of the invention is compared with the existing technology at least with following excellent
One of gesture:
(1) present invention is under the auxiliary of common reducing agent, using the graphene oxide layer of partial reduction by MXene nanometers
Piece crosslinking, the liquid phase assembling of directional guide MXene obtain that three-dimensional structure based on MXene is stable, hydrogel of volume contraction,
Develop the three-dimensional liquid phase assemble method of MXene, provides a kind of strong flexibility, controllability for building three-dimensional MXene macroscopic body
High method；
(2) crosslinking and synergistic effect the invention proposes " amphiphilic " graphene oxide in the assembling of MXene liquid phase, has
Effect reduces the dispersion liquid concentration threshold for constructing MXene base three-dimensional networks, and then realizes two-dimensional nano piece stack-up issue
Efficiently inhibit；
(3) hydrogel obtained using the assemble method of the New Two Dimensional crystal MXene hydrogel, can also further be passed through
Completely different two kinds of three-dimensional porous materials --- the MXene foam of pore-size distribution, density is obtained to the regulation of moisture removal mode
With it is strong, MXene foam and the strong specific surface area of MXene are respectively 10~180m2/ g and 80~250m2/ g, density are respectively
20~30mg/cm3With 1.5~2.5g/cm3, the application space of MXene base macroscopic material has greatly been widened, to two-dimensional material
The further development of MXene is of far-reaching significance.
Detailed description of the invention
Fig. 1 is (left figure) (right figure) schematic diagram afterwards before MXene hydrogel plastic in the present invention；
Fig. 2 is MXene three-dimensional foam (A figure) and strong (B figure) the exterior appearance schematic diagram of MXene in the present invention；
Fig. 3 is the SEM structural characterization figure of MXene three-dimensional foam structure in the present invention；
Fig. 4 is the SEM structural characterization figure of the strong structure of MXene of the present invention.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
The invention discloses a kind of MXene hydrogels, react to obtain by the raw material for including following content of component,
In, MXene (1~20) part, graphene oxide (0.5~1) part, initiator (0.1~0.5) part.
Preferably, the mass ratio of MXene and graphene oxide is (1~10): 1.
Preferably, which includes ammonium hydroxide, ethylenediamine, sodium hydroxide, dithioglycol, phloroglucin, cysteine, resists
At least one of bad hematic acid, hydroiodic acid, sodium hydrogensulfite, vulcanized sodium.
Preferably, graphene oxide is made using Hummer ' the s method of improvement.
The invention also discloses a kind of liquid phase assemble methods of MXene hydrogel, comprising:
Initiator is added to reaction in MXene and graphene oxide mixed solution and obtains MXene hydrogel.
Preferably, MXene and graphene oxide mixed solution are MXene dispersion liquid and graphene oxide dispersion in argon gas
The uniform mixed dispersion liquid that ultrasound obtains under atmosphere, preferably MXene dispersion liquid and graphene oxide dispersion are led in ice-water bath
Argon gas ultrasound.
Preferably, initiator concentration is 10~100mmol/L.
Preferably, the concentration of MXene is 1~20mg/mL in mixed solution.
Preferably, the concentration of graphene oxide is 0.5~2mg/mL in mixed solution.
Preferably, MXene dispersion liquid is to be put into MAX raw material in the LiF solution for be dissolved in hydrochloric acid to etch to obtain.
Preferably, reaction condition be normal pressure constant temperature, thermostat temperature be 50~100 DEG C, duration of the reaction be 6~for 24 hours.
It is by doing MXene hydrogel as described above the invention also discloses a kind of three-dimensional MXene block
It is obtained after dry.
Preferably, drying means is that freeze-drying or capillary evaporation are dry.
Preferably, it is MXene three-dimensional foam structure by the three-dimensional MXene block that freeze-drying method obtains, compares table
Area is 10~180m2/ g, density are 20~30mg/cm3；It is by the three-dimensional MXene block that capillary evaporation is dried to obtain
The strong structure of MXene, specific surface area are 80~250m2/ g, density are 1.5~2.5g/cm3。
Preferably, it is dried again after MXene hydrogel first being cleaned removal of impurities with deionized water.
The invention also discloses a kind of three-dimensional MXene blocks as described above in energy storage, the application of adsorbing domain.
In a preferred embodiment, the present invention adopts the following technical scheme:
Step 1: taking MAX raw material, etching obtains MXene dispersion liquid in the LiF solution for being dissolved in hydrochloric acid；
Step 2: obtaining graphene oxide dispersion using Hummer ' the s legal system of improvement；
Step 3: the MXene dispersion liquid that step 1 obtains is mixed with the graphene oxide dispersion that step 2 obtains, and
Lead to ultrasound 30min under argon gas protection in ice-water bath, obtains uniform mixed dispersion liquid one；
Step 4: the initiator being added in the mixed dispersion liquid that step 3 obtains, stirs evenly, mixed dispersion liquid is obtained
Two；
Step 5: the mixed dispersion liquid that step 4 is obtained is added to progress normal pressure isothermal reaction in closed container, obtain
Hydrogel based on MXene；
Step 6: carrying out freeze-drying after the hydrogel that step 5 obtains is cleaned removal of impurities with deionized water or capillary being steamed
Dry dry removing moisture obtains the three-dimensional foam based on MXene or strong (freeze-drying obtains macrocellular foam, and capillary evaporation is dry then
It is strong to obtain micropore).
As a kind of improvement of above-mentioned assemble method, in the mixed dispersion liquid one of step 3, MXene and graphene oxide
Mass ratio is (1~10): 1.
As a kind of improvement of above-mentioned assemble method, in the mixed dispersion liquid one of step 3, the concentration of graphene oxide is
0.5~2mg/mL.
As a kind of improvement of above-mentioned assemble method, in the mixed dispersion liquid one of step 3, the concentration of MXene is 1~
20mg/mL。
As a kind of improvement of above-mentioned assemble method, initiator described in step 4 includes ammonium hydroxide, ethylenediamine, hydroxide
At least one of sodium, dithioglycol, phloroglucin, cysteine, ascorbic acid, hydroiodic acid, sodium hydrogensulfite, vulcanized sodium.
As a kind of improvement of above-mentioned assemble method, initiator concentration described in step 4 is 10~100mmol/L.
As a kind of improvement of above-mentioned assemble method, the temperature of normal pressure isothermal reaction described in step 5 is 50~100
DEG C, duration of the reaction be 6~for 24 hours.
As a kind of improvement of above-mentioned assemble method, in step 6, MXene foam obtained by the different drying modes and
MXene strong specific surface area is respectively 10~180m2/ g and 80~250m2/ g, density are respectively 20~30mg/cm3With 1.5
~2.5g/cm3。
Explanation is further elaborated to technical solution of the present invention below by way of specific embodiment combination attached drawing.It should be noted that
, following specific embodiments are only as example, the scope of protection of the present invention is not limited thereto.
Chemicals used in following embodiments and raw material are commercially available gained or are made by oneself by well known preparation method
It obtains.
Embodiment 1
A kind of liquid phase assemble method of MXene hydrogel, comprising the following steps:
Step 1: taking MAX raw material, etching obtains MXene dispersion liquid in the LiF solution for being dissolved in hydrochloric acid；
Step 2: obtaining graphene oxide dispersion using Hummer ' the s legal system of improvement；
Step 3: the MXene dispersion liquid that step 1 obtains is mixed with the graphene oxide dispersion that step 2 obtains, and
Lead to ultrasound 30min under argon gas protection in ice-water bath；Uniform mixed dispersion liquid one is obtained, wherein the concentration of MXene is 2mg/
ML, the concentration of graphene oxide are 2mg/mL；
Step 4: ethylenediamine is added as crosslinking agent, stirring by 10mmol/L in the mixed dispersion liquid that step 3 obtains
Uniformly, mixed dispersion liquid two is obtained；
Step 5: the mixed dispersion liquid that step 4 is obtained be added in closed container at 95 DEG C carry out normal pressure constant temperature it is anti-
6h is answered, the hydrogel based on MXene is obtained；
Step 6: carrying out freeze-drying after the hydrogel that step 5 obtains is cleaned removal of impurities with deionized water or capillary being steamed
Dry dry removing moisture, obtains the three-dimensional foam or strong based on MXene.
Practice have shown that: MXene hydrogel shape is consistent with reaction vessel, and hydrogel is contracted to the 1/2 of original solution volume, remains
Remaining solution is colorless and transparent.The MXene three-dimensional foam specific surface area that this method obtains is 167m2/ g, density 21mg/cm3；It obtains
The strong specific surface area of MXene be 245m2/ g, density 1.62g/cm3；
Carry out electron microscope analysis strong to MXene three-dimensional foam and MXene, the structural representation of MXene three-dimensional foam in the secure execution mode (sem
Figure is as shown in figure 3, the strong structural schematic diagram in the secure execution mode (sem of MXene is as shown in Figure 4.In liquid phase assembling process, two-dimensional MXene
Nanometer sheet is cross-linked with each other with the graphene oxide sheet being reduced, graphene oxide sheet hydrophily gradually weaken during by piece interlayer
The collective effect of π-π active force and Van der Waals force is assembled in solid liquid interface, under the crosslinking traction of Flexible graphene piece,
MXene nanometer sheet assembles jointly therewith, forms stable continuous three-dimensional network.By the regulation of moisture removal process, change is obtained
The size of tractive force suffered by assembly three-dimensional network is obtained, and then obtains the different MXene three-dimensional block of density.
Embodiment 2
A kind of liquid phase assemble method of MXene hydrogel, comprising the following steps:
Step 1: taking MAX raw material, etching obtains MXene dispersion liquid in the LiF solution for being dissolved in hydrochloric acid；
Step 2: obtaining graphene oxide dispersion using Hummer ' the s legal system of improvement；
Step 3: the MXene dispersion liquid that step 1 obtains is mixed with the graphene oxide dispersion that step 2 obtains, and
Lead to ultrasound 30min under argon gas protection in ice-water bath；Uniform mixed dispersion liquid one is obtained, wherein the concentration of MXene is 5mg/
ML, the concentration of graphene oxide are 0.5mg/mL；
Step 4: ethylenediamine is added as crosslinking agent, stirring by 10mmol/L in the mixed dispersion liquid that step 3 obtains
Uniformly, mixed dispersion liquid two is obtained；
Step 5: the mixed dispersion liquid that step 4 is obtained be added in closed container at 95 DEG C carry out normal pressure constant temperature it is anti-
8h is answered, the hydrogel based on MXene is obtained；
Step 6: carrying out freeze-drying after the hydrogel that step 5 obtains is cleaned removal of impurities with deionized water or capillary being steamed
Dry dry removing moisture, obtains the three-dimensional foam or strong based on MXene.
Practice have shown that: MXene hydrogel shape is consistent with reaction vessel, and hydrogel is contracted to the 8/9 of original solution volume, remains
Remaining solution is colorless and transparent.The MXene three-dimensional foam specific surface area that this method obtains is 56m2/ g, density 30mg/cm3；It obtains
The strong specific surface area of MXene is 92m2/ g, density 2.5g/cm3。
Embodiment 3
A kind of liquid phase assemble method of MXene hydrogel, comprising the following steps:
Step 1: taking MAX raw material, etching obtains MXene dispersion liquid in the LiF solution for being dissolved in hydrochloric acid；
Step 2: obtaining graphene oxide dispersion using Hummer ' the s legal system of improvement；
Step 3: the MXene dispersion liquid that step 1 obtains is mixed with the graphene oxide dispersion that step 2 obtains, and
Lead to ultrasound 30min under argon gas protection in ice-water bath；Uniform mixed dispersion liquid one is obtained, wherein the concentration of MXene is 4mg/
ML, the concentration of graphene oxide are 1mg/mL；
Step 4: ethylenediamine is added as crosslinking agent, stirring by 10mmol/L in the mixed dispersion liquid that step 3 obtains
Uniformly, mixed dispersion liquid two is obtained；
Step 5: the mixed dispersion liquid that step 4 is obtained be added in closed container at 95 DEG C carry out normal pressure constant temperature it is anti-
6h is answered, the hydrogel based on MXene is obtained, as shown in Fig. 1 right figure；
Step 6: carrying out freeze-drying after the hydrogel that step 5 obtains is cleaned removal of impurities with deionized water or capillary being steamed
Dry dry removing moisture, obtains the three-dimensional foam (as shown in A figure in Fig. 2) or strong (as shown in B figure in Fig. 2) based on MXene.
Practice have shown that: MXene hydrogel shape is consistent with reaction vessel, and hydrogel is contracted to the 4/5 of original solution volume, remains
Remaining solution is colorless and transparent.The MXene three-dimensional foam specific surface area that this method obtains is 126m2/ g, density 27mg/cm3；It obtains
The strong specific surface area of MXene be 187m2/ g, density 2.2g/cm3。
Embodiment 4
A kind of liquid phase assemble method of MXene hydrogel, comprising the following steps:
Step 1: taking MAX raw material, etching obtains MXene dispersion liquid in the LiF solution for being dissolved in hydrochloric acid；
Step 2: obtaining graphene oxide dispersion using Hummer ' the s legal system of improvement；
Step 3: the MXene dispersion liquid that step 1 obtains is mixed with the graphene oxide dispersion that step 2 obtains, and
Lead to ultrasound 30min under argon gas protection in ice-water bath；Uniform mixed dispersion liquid one is obtained, wherein the concentration of MXene is 4mg/
ML, the concentration of graphene oxide are 1mg/mL；
Step 4: sodium hydrogensulfite is added as crosslinking agent by 50mmol/L in the mixed dispersion liquid that step 3 obtains,
It stirs evenly, obtains mixed dispersion liquid two；
Step 5: the mixed dispersion liquid that step 4 is obtained be added in closed container at 80 DEG C carry out normal pressure constant temperature it is anti-
6h is answered, the hydrogel based on MXene is obtained；
Step 6: carrying out freeze-drying after the hydrogel that step 5 obtains is cleaned removal of impurities with deionized water or capillary being steamed
Dry dry removing moisture, obtains the three-dimensional foam or strong based on MXene.
Practice have shown that: MXene hydrogel shape is consistent with reaction vessel, and hydrogel is contracted to the 1/3 of original solution volume, remains
Remaining solution is colorless and transparent.The MXene three-dimensional foam specific surface area that this method obtains is 138m2/ g, density 30mg/cm3；It obtains
The strong specific surface area of MXene be 198m2/ g, density 2.43g/cm3。
Embodiment 5
A kind of liquid phase assemble method of MXene hydrogel, comprising the following steps:
Step 1: taking MAX raw material, etching obtains MXene dispersion liquid in the LiF solution for being dissolved in hydrochloric acid；
Step 2: obtaining graphene oxide dispersion using Hummer ' the s legal system of improvement；
Step 3: the MXene dispersion liquid that step 1 obtains is mixed with the graphene oxide dispersion that step 2 obtains, and
Lead to ultrasound 30min under argon gas protection in ice-water bath；Uniform mixed dispersion liquid one is obtained, wherein the concentration of MXene is 4mg/
ML, the concentration of graphene oxide are 1mg/mL；
Step 4: dithioglycol is added as crosslinking agent by 100mmol/L in the mixed dispersion liquid that step 3 obtains, stir
It mixes uniformly, obtains mixed dispersion liquid two；
Step 5: the mixed dispersion liquid that step 4 is obtained be added in closed container at 90 DEG C carry out normal pressure constant temperature it is anti-
The hydrogel based on MXene should be obtained for 24 hours；
Step 6: carrying out freeze-drying after the hydrogel that step 5 obtains is cleaned removal of impurities with deionized water or capillary being steamed
Dry dry removing moisture, obtains the three-dimensional foam or strong based on MXene.
Practice have shown that: MXene hydrogel shape is consistent with reaction vessel, and hydrogel is contracted to the 9/10 of original solution volume,
Surplus solution is colorless and transparent.The MXene three-dimensional foam specific surface area that this method obtains is 92m2/ g, density 20mg/cm3；It obtains
The strong specific surface area of MXene be 162m2/ g, density 1.95g/cm3。
Embodiment 6
A kind of liquid phase assemble method of MXene hydrogel, comprising the following steps:
Step 1: taking MAX raw material, etching obtains MXene dispersion liquid in the LiF solution for being dissolved in hydrochloric acid；
Step 2: obtaining graphene oxide dispersion using Hummer ' the s legal system of improvement；
Step 3: the MXene dispersion liquid that step 1 obtains is mixed with the graphene oxide dispersion that step 2 obtains, and
Lead to ultrasound 30min under argon gas protection in ice-water bath；Uniform mixed dispersion liquid one is obtained, wherein the concentration of MXene is 20mg/
ML, the concentration of graphene oxide are 2mg/mL；
Step 4: ethylenediamine is added as crosslinking agent, stirring by 30mmol/L in the mixed dispersion liquid that step 3 obtains
Uniformly, mixed dispersion liquid two is obtained；
Step 5: the mixed dispersion liquid that step 4 is obtained be added in closed container at 95 DEG C carry out normal pressure constant temperature it is anti-
8h is answered, the hydrogel based on MXene is obtained；
Step 6: carrying out freeze-drying after the hydrogel that step 5 obtains is cleaned removal of impurities with deionized water or capillary being steamed
Dry dry removing moisture, obtains the three-dimensional foam or strong based on MXene.
Practice have shown that: MXene hydrogel shape is consistent with reaction vessel, and hydrogel is contracted to the 19/20 of original solution volume,
Surplus solution is colorless and transparent.The MXene three-dimensional foam specific surface area that this method obtains is 34m2/ g, density 30mg/cm3；It obtains
The strong specific surface area of MXene be 108m2/ g, density 2.48g/cm3。
Embodiment 7
A kind of liquid phase assemble method of MXene hydrogel, comprising the following steps:
Step 1: taking MAX raw material, etching obtains MXene dispersion liquid in the LiF solution for being dissolved in hydrochloric acid；
Step 2: obtaining graphene oxide dispersion using Hummer ' the s legal system of improvement；
Step 3: the MXene dispersion liquid that step 1 obtains is mixed with the graphene oxide dispersion that step 2 obtains, and
Lead to ultrasound 30min under argon gas protection in ice-water bath；Uniform mixed dispersion liquid one is obtained, wherein the concentration of MXene is 10mg/
ML, the concentration of graphene oxide are 2mg/mL；
Step 4: ethylenediamine is added as crosslinking agent, stirring by 20mmol/L in the mixed dispersion liquid that step 3 obtains
Uniformly, mixed dispersion liquid two is obtained；
Step 5: the mixed dispersion liquid that step 4 is obtained be added in closed container at 95 DEG C carry out normal pressure constant temperature it is anti-
6h is answered, the hydrogel based on MXene is obtained；
Step 6: carrying out freeze-drying after the hydrogel that step 5 obtains is cleaned removal of impurities with deionized water or capillary being steamed
Dry dry removing moisture, obtains the three-dimensional foam or strong based on MXene.
Practice have shown that: MXene hydrogel shape is consistent with reaction vessel, and hydrogel is contracted to the 5/6 of original solution volume, remains
Remaining solution is colorless and transparent.The MXene three-dimensional foam specific surface area that this method obtains is 89m2/ g, density 26mg/cm3；It obtains
The strong specific surface area of MXene is 174m2/ g, density 2.2g/cm3。
Embodiment 8
A kind of liquid phase assemble method of MXene hydrogel, comprising the following steps:
Step 1: taking MAX raw material, etching obtains MXene dispersion liquid in the LiF solution for being dissolved in hydrochloric acid；
Step 2: obtaining graphene oxide dispersion using Hummer ' the s legal system of improvement；
Step 3: the MXene dispersion liquid that step 1 obtains is mixed with the graphene oxide dispersion that step 2 obtains, and
Lead to ultrasound 30min under argon gas protection in ice-water bath；Uniform mixed dispersion liquid one is obtained, the concentration of MXene is 14mg/mL,
The concentration of graphene oxide is 2mg/mL；
Step 4: ethylenediamine is added as crosslinking agent, stirring by 25mmol/L in the mixed dispersion liquid that step 3 obtains
Uniformly, mixed dispersion liquid two is obtained；
Step 5: the mixed dispersion liquid that step 4 is obtained be added in closed container at 95 DEG C carry out normal pressure constant temperature it is anti-
8h is answered, the hydrogel based on MXene is obtained；
Step 6: carrying out freeze-drying after the hydrogel that step 5 obtains is cleaned removal of impurities with deionized water or capillary being steamed
Dry dry removing moisture, obtains the three-dimensional foam or strong based on MXene.
Practice have shown that: MXene hydrogel shape is consistent with reaction vessel, and hydrogel is contracted to the 4/5 of original solution volume, remains
Remaining solution is colorless and transparent.The MXene three-dimensional foam specific surface area that this method obtains is 76m2/ g, density 27mg/cm3；It obtains
The strong specific surface area of MXene is 151m2/ g, density 2.6g/cm3。
Comparative example 1
A kind of comparative situation for not adding initiator, comprising the following steps:
Step 1: taking MAX raw material, etching obtains MXene dispersion liquid in the LiF solution for being dissolved in hydrochloric acid；
Step 2: obtaining graphene oxide dispersion using Hummer ' the s legal system of improvement；
Step 3: the MXene dispersion liquid that step 1 obtains is mixed with the graphene oxide dispersion that step 2 obtains, and
Lead to ultrasound 30min under argon gas protection in ice-water bath；Uniform mixed dispersion liquid one is obtained, wherein the concentration of MXene is 4mg/
ML, the concentration of graphene oxide are 1mg/mL；
Step 4: the mixed dispersion liquid that step 3 is obtained be added in closed container at 95 DEG C carry out normal pressure constant temperature it is anti-
6h is answered, MXene hydrogel is unable to get.
Practice have shown that: when no initiator participates in, graphene oxide can not be cross-linked with each other with two kinds of nanometer sheets of MXene, in turn
Gelation.
Comparative example 2
This comparative example provides the comparative situation for not adding graphene oxide, comprising the following steps:
Step 1: taking MAX raw material, etching obtains MXene dispersion liquid in the LiF solution for being dissolved in hydrochloric acid；
Step 2: the MXene dispersion liquid that step 1 obtains to be made into the MXene dispersion liquid of 4mg/mL, and press 50mmol/L
Ethylenediamine is added as crosslinking agent, stirs evenly, obtains mixed dispersion liquid；
Step 3: the mixed dispersion liquid that step 2 is obtained be added in closed container at 95 DEG C carry out normal pressure constant temperature it is anti-
6h is answered, MXene hydrogel is unable to get.
Practice have shown that: when non-oxidation graphene participates in, MXene nanometer sheet can not be cross-linked with each other to form gel.
Comparative example 3
This comparative example provides the comparative situation for not adding MXene, comprising the following steps:
Step 1: obtaining graphene oxide dispersion using Hummer ' the s legal system of improvement；
Step 2: the MXene dispersion liquid that step 1 is obtained leads to ultrasound 30min under argon gas protection, oxidation in ice-water bath
The concentration of graphene is 0.5mg/mL；
Step 3: ethylenediamine is added as crosslinking by 10mmol/L in graphene oxide dispersion obtained in step 2
Agent stirs evenly, and obtains mixed dispersion liquid；
Step 4: the mixed dispersion liquid that step 3 is obtained be added in closed container at 95 DEG C carry out normal pressure constant temperature it is anti-
8h is answered, MXene hydrogel is unable to get.
Comparative example 4
(on the basis of comparative example 3, the type and concentration of initiator are changed a number) is Step 1: using improvement
Hummer ' s legal system obtains graphene oxide dispersion；
Step 2: the MXene dispersion liquid that step 1 is obtained leads to ultrasound 30min under argon gas protection, oxidation in ice-water bath
The concentration of graphene is 1mg/mL；
Step 3: ethylenediamine is added as crosslinking by 20mmol/L in graphene oxide dispersion obtained in step 2
Agent stirs evenly, and obtains mixed dispersion liquid；
Step 4: the mixed dispersion liquid that step 3 is obtained be added in closed container at 95 DEG C carry out normal pressure constant temperature it is anti-
6h is answered, MXene hydrogel is unable to get.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to of the invention
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although being used in this specification
Some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (10)
1. a kind of MXene hydrogel reacts to obtain, wherein MXene (1~20) by the raw material for including following content of component
Part, graphene oxide (0.5~1) part, initiator (0.1~0.5) part.
2. MXene hydrogel according to claim 1, which is characterized in that
The mass ratio of the MXene and graphene oxide is (1~10): 1.
3. MXene hydrogel according to claim 1, which is characterized in that
The initiator includes ammonium hydroxide, ethylenediamine, sodium hydroxide, dithioglycol, phloroglucin, cysteine, ascorbic acid, hydrogen
At least one of acid iodide, sodium hydrogensulfite, vulcanized sodium.
4. MXene hydrogel according to claim 1, which is characterized in that
The graphene oxide is made using Hummer ' the s method of improvement.
5. such as the liquid phase assemble method of the described in any item MXene hydrogels of Claims 1 to 4, including initiator is added to
Reaction obtains MXene hydrogel in MXene and graphene oxide mixed solution.
6. assemble method according to claim 5, which is characterized in that
The initiator concentration is 10~100mmol/L；
Preferably, the concentration of MXene is 1~20mg/mL in the mixed solution；
Preferably, the concentration of graphene oxide is 0.5~2mg/mL in the mixed solution.
7. assemble method according to claim 5, which is characterized in that
The MXene and graphene oxide mixed solution be MXene dispersion liquid and graphene oxide dispersion under an argon atmosphere
Ultrasound obtains uniform mixed dispersion liquid；
Preferably, the MXene dispersion liquid and graphene oxide dispersion lead to argon gas ultrasound in ice-water bath in advance；
Preferably, the MXene dispersion liquid is to be put into MAX raw material in the LiF solution for be dissolved in hydrochloric acid to etch to obtain；
Preferably, the reaction condition be normal pressure constant temperature, thermostat temperature be 50~100 DEG C, duration of the reaction be 6~
24h。
8. a kind of three-dimensional MXene block, which is characterized in that will as the described in any item hydrogels of Claims 1 to 4 or with such as weigh
The hydrogel that benefit requires 5~7 described in any item assemble methods to be formed obtains after being dried.
9. three-dimensional MXene block according to claim 8, which is characterized in that
The drying means is that freeze-drying or capillary evaporation are dry；
Preferably, be three-dimensional MXene foaming structure by the three-dimensional MXene block that the freeze-drying method obtains, ratio
Surface area is 10~180m2/ g, density are 20~30mg/cm3；
Preferably, being the strong structure of MXene by the three-dimensional MXene block that capillary evaporation is dried to obtain, specific surface area is
80~250m2/ g, density are 1.5~2.5g/cm3；
Preferably, being dried again after MXene hydrogel is first cleaned removal of impurities with deionized water.
10. if the described in any item three-dimensional MXene blocks of claim 8 or 9 are in energy storage or the application of adsorbing domain.
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