CN112233914A - Preparation method and application of micronized cellulose/MXene composite film - Google Patents
Preparation method and application of micronized cellulose/MXene composite film Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 95
- 239000001913 cellulose Substances 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 55
- 239000006228 supernatant Substances 0.000 claims abstract description 45
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003990 capacitor Substances 0.000 claims abstract description 5
- 239000007773 negative electrode material Substances 0.000 claims abstract description 4
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 4
- 239000000084 colloidal system Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
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- 239000012459 cleaning agent Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
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- 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
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- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/30—Electrodes characterised by their material
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Abstract
A preparation method and application of a micronized cellulose/MXene composite film relate to a preparation method and application of an MXene composite film. The invention aims to solve the problems that the mechanical property and the capacitance of the existing MXene composite film are poor, and the conductivity of the MXene cellulose composite film is in a linear reduction trend along with the increase of nano-cellulose. The method comprises the following steps: first, prepare dark green few-layer Ti3C2TxA colloidal supernatant; II, preparing MFC @ Ti3C2TxMicrogel; thirdly, adding MFC @ Ti3C2TxAnd (3) carrying out vacuum filtration on the microgel through a mixed cellulose membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain the independently supported microfibrillated cellulose/MXene composite membrane. Independently supported microfibrillated cellulose/MXene composite film serving as filmThe negative electrode material of the capacitor is used. The invention can obtain a micro cellulose/MXene composite film.
Description
Technical Field
The invention relates to a preparation method and application of an MXene composite film.
Background
Ti3C2TxAs a new electrode material of super capacitor, consists ofThe hydrophilic polymer has strong hydrophilicity, high conductivity and high theoretical capacity, thereby causing wide attention of people. Ti with a thickness of about 3 μm is reported3C2TxThe tensile strength of the film is 22MPa, the Young modulus can reach 3.52GPa, and the tensile elongation is about 1%. Due to Ti3C2TxThe surface contains a large number of negatively charged-OH, -F, -O groups and can therefore be linked to the organic polymer by hydrogen bonds. The plasticity of the composite material can be improved by compounding the composite material with a polymer, and the tensile strength of the composite material can also be greatly improved. However, the conductivity of most cellulose composite films shows a linear decreasing trend with the increase of the nano-cellulose, which will cause the reduction of electrochemical performance. This may be due to the intercalation of nanocellulose into Ti3C2TxThe interlayer electron conductivity is rapidly reduced, and the electron transport in the vertical direction is greatly reduced due to the presence of the polymer, which is used for Ti3C2TxThe use of the supercapacitor of (a) is detrimental.
Disclosure of Invention
The invention aims to solve the problems that the mechanical property and the capacitance of the existing MXene composite film are poor, and the conductivity of the MXene cellulose composite film is in a linear reduction trend along with the increase of nano-cellulose, and provides a preparation method of an independently supported microfibrillated cellulose/MXene composite film.
A preparation method of an independently supported microfibrillated cellulose/MXene composite film is completed according to the following steps:
first, prepare dark green few-layer Ti3C2TxAnd (3) colloid supernatant fluid:
adding LiF into HCl solution, stirring at room temperature until the LiF is completely dissolved, and then adding Ti under the condition of ice-water bath3AlC2Reacting for 18-28 h at 30-35 ℃ in nitrogen atmosphere to obtain reaction liquid;
② firstly, deionized water is used as cleaning agent, the reaction liquid is centrifugally cleaned to pH value under the centrifugal speed of 3500 r/min-4000 r/min>6, pouring out the supernatant to obtain a precipitate; adding deionized water to the precipitateThen ultrasonic treatment is carried out, the mixture is centrifuged for 1 to 1.2 hours at the centrifugal speed of 3500 to 4000r/min, and supernatant fluid is collected to obtain dark green few-layer Ti3C2TxA colloidal supernatant;
secondly, a small number of greenish black Ti layers3C2TxAdding the colloid supernatant into the micronized cellulose solution, and shaking to obtain MFC @ Ti3C2TxMicrogel;
thirdly, adding MFC @ Ti3C2TxAnd (3) carrying out vacuum filtration on the microgel through a mixed cellulose membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain the independently supported microfibrillated cellulose/MXene composite membrane.
An independently supported microfibrillated cellulose/MXene composite film is used as a negative electrode material of a capacitor.
The principle and the advantages of the invention are as follows:
firstly, the invention selects micron-sized Microfibrillated Cellulose (MFC) with diameter as Ti3C2TxReinforcing agent for mechanical properties, known as Ti3C2TxThe lateral dimension of the nanosheets is only a few microns at most, so when the two are combined, Ti3C2TxThe nanoplatelets can be attached to the one-dimensional cellulose to form a one-dimensional conductive channel, so that Ti is not influenced3C2TxElectronic transmission in the one-dimensional and two-dimensional directions of the nanosheets is realized, and the celluloses are mutually connected and built, so that the formed film has enhanced mechanical properties;
secondly, the invention adds the micro cellulose to ensure Ti3C2TxUnder the condition that the tensile strength is improved by 2-3 times, the conductivity and capacitance of the composite material can still be ensured not to be reduced; when the mass fraction of the microfibrillated cellulose (MFC) in the independently supported microfibrillated cellulose/MXene composite film is 10%, the capacitance can be increased from 362F/g to 451F/g, so that the addition of the easily-obtained microfibrillated cellulose for increasing Ti3C2TxThe combination of properties of the film is of great significance.
Drawings
FIG. 1 shows Ti in the second step of the example3C2TxThe microgel formation process is shown in figure 1, which shows a greenish black few-layer Ti3C2TxThe supernatant of colloid, 2 is a micronized cellulose solution, 3 is Ti3C2TxMicrogel;
FIG. 2 shows Ti prepared in comparative example3C2TxFilms and MFC @ Ti prepared in example one3C2TxComparative figures for thin films;
FIG. 3 is MFC @ Ti prepared in example one3C2TxA schematic diagram of the self-assembly of microgels;
FIG. 4 is a Zeta potential comparison diagram, in which 1 is Ti prepared in comparative example3C2TxFilm, 2 MFC @ Ti prepared in example one3C2TxA film;
FIG. 5 shows Ti prepared in comparative example3C2TxSEM image of the film;
FIG. 6 is an SEM image of MFC;
FIG. 7 is MFC @ Ti prepared in example one3C2TxSEM image of the film;
FIG. 8 is MFC @ Ti prepared in example one3C2TxTEM image of the thin film;
FIG. 9 is a graph showing tensile properties, in which 1 is Ti prepared in comparative example3C2TxFilm, 2 MFC @ Ti prepared in example one3C2TxFilm, 3 MFC @ Ti prepared in example two3C2TxFilm, 4 MFC @ Ti prepared in example III3C2TxA film;
FIG. 10 is an EIS diagram, in which 1 is Ti prepared in a comparative example3C2TxFilm, 2 MFC @ Ti prepared in example one3C2TxFilm, 3 MFC @ Ti prepared in example two3C2TxFilm, 4 MFC @ Ti prepared in example III3C2TxA film;
FIG. 11 is an enlarged view taken at A in FIG. 10;
FIG. 12 is a GCD curve of different films at a current density of 1A/g, wherein 1 is Ti prepared in comparative example3C2TxFilm, 2 MFC @ Ti prepared in example one3C2TxFilm, 3 MFC @ Ti prepared in example two3C2TxFilm, 4 MFC @ Ti prepared in example III3C2TxA film;
FIG. 13 is a CV diagram of 5mV/s sweep rate for various films, where 1 is Ti prepared in a comparative example3C2TxFilm, 2 MFC @ Ti prepared in example one3C2TxFilm, 3 MFC @ Ti prepared in example two3C2TxFilm, 4 MFC @ Ti prepared in example III3C2TxA film.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the embodiment is a preparation method of an independently supported microfibrillated cellulose/MXene composite film, which is completed by the following steps:
first, prepare dark green few-layer Ti3C2TxAnd (3) colloid supernatant fluid:
adding LiF into HCl solution, stirring at room temperature until the LiF is completely dissolved, and then adding Ti under the condition of ice-water bath3AlC2Reacting for 18-28 h at 30-35 ℃ in nitrogen atmosphere to obtain reaction liquid;
firstly, deionized water is used as a cleaning agent, reaction liquid is centrifugally cleaned at a centrifugal speed of 3500 r/min-4000 r/min until the pH value is more than 6, and supernatant liquid is poured out to obtain a precipitate; deionized water was added to the precipitated material,
then carrying out ultrasoundCentrifuging at 3500-4000 r/min for 1-1.2 h, collecting supernatant to obtain dark green Ti with few layers3C2TxA colloidal supernatant;
secondly, a small number of greenish black Ti layers3C2TxAdding the colloid supernatant into the micronized cellulose solution, and shaking to obtain MFC @ Ti3C2TxMicrogel;
thirdly, adding MFC @ Ti3C2TxAnd (3) carrying out vacuum filtration on the microgel through a mixed cellulose membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain the independently supported microfibrillated cellulose/MXene composite membrane.
The principle and advantages of the embodiment are as follows:
first, in the present embodiment, Microfibrillated Cellulose (MFC) with a micron-sized diameter is selected as Ti3C2TxReinforcing agent for mechanical properties, known as Ti3C2TxThe lateral dimension of the nanosheets is only a few microns at most, so when the two are combined, Ti3C2TxThe nanoplatelets can be attached to the one-dimensional cellulose to form a one-dimensional conductive channel, so that Ti is not influenced3C2TxElectronic transmission in the one-dimensional and two-dimensional directions of the nanosheets is realized, and the celluloses are mutually connected and built, so that the formed film has enhanced mechanical properties;
secondly, the embodiment adds the micro cellulose to ensure Ti3C2TxUnder the condition that the tensile strength is improved by 2-3 times, the conductivity and capacitance of the composite material can still be ensured not to be reduced; when the mass fraction of the microfibrillated cellulose (MFC) in the independently supported microfibrillated cellulose/MXene composite film is 10%, the capacitance can be increased from 362F/g to 451F/g, so that the addition of the easily-obtained microfibrillated cellulose for increasing Ti3C2TxThe combination of properties of the film is of great significance.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the concentration of the HCl solution in the first step is 8-10 mol/L. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the ratio of the mass of LiF to the volume of HCl solution in the first step (1 g-2 g) is 20 mL. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: ti described in step one3AlC2The ratio of the mass of (1) to the volume of the HCl solution (0.5g to 1.5g) was 20 mL. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the ultrasonic power is 100W-300W, and the ultrasonic time is 50 min-70 min; the small layer of greenish black Ti in the step one3C2TxThe concentration of the colloid supernatant is 5 mg/mL-6 mg/mL. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the mass fraction of the microfibrillated cellulose solution in the second step is 0.5-0.8%, and the solvent is water. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the shaking time in the step two is 5 min-10 min. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the mass fraction of the microfibrillated cellulose in the independently supported microfibrillated cellulose/MXene composite film in the third step is 10-30%. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the mass fraction of the microfibrillated cellulose in the independently supported microfibrillated cellulose/MXene composite film in the third step is 10-20%. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: in the present embodiment, an independently supported microfibrillated cellulose/MXene composite film is used as a negative electrode material for a capacitor.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: a preparation method of an independently supported microfibrillated cellulose/MXene composite film is completed according to the following steps:
first, prepare dark green few-layer Ti3C2TxAnd (3) colloid supernatant fluid:
adding 1.6g LiF into 20mL of 9mol/L HCl solution, stirring at room temperature until the LiF is completely dissolved, and then adding 1g Ti under the condition of ice-water bath3AlC2Reacting for 24 hours at 35 ℃ in nitrogen atmosphere to obtain reaction liquid;
② firstly, deionized water is used as cleaning agent, the reaction liquid is centrifugally cleaned to pH value at 3500r/min of centrifugal speed>6, pouring out the supernatant to obtain a precipitate; adding deionized water into the precipitate, performing ultrasonic treatment, centrifuging at 3500r/min for 1 hr, and collecting supernatant to obtain dark green Ti with few layers3C2TxA colloidal supernatant;
the ultrasonic power in the first step is 100W, and the ultrasonic time is 60 min;
the small layer of greenish black Ti in the step one3C2TxThe concentration of the colloid supernatant is 5 mg/mL;
secondly, a small number of greenish black Ti layers3C2TxAdding the colloid supernatant into the micronized cellulose solution, and shaking for 10min to obtain MFC @ Ti3C2TxMicrogel;
the mass fraction of the microfibrillated cellulose solution in the second step is 0.5 percent;
thirdly, adding MFC @ Ti3C2TxVacuum filtering the microgel through a mixed cellulose membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain an independently supported microfibrillated cellulose/MXene composite membrane;
the mass fraction of the microfibrillated cellulose in the independently supported microfibrillated cellulose/MXene composite film described in step three is 10%.
Example two: a preparation method of an independently supported microfibrillated cellulose/MXene composite film is completed according to the following steps:
first, prepare dark green few-layer Ti3C2TxAnd (3) colloid supernatant fluid:
adding 1.6g LiF into 20mL of 9mol/L HCl solution, stirring at room temperature until the LiF is completely dissolved, and then adding 1g Ti under the condition of ice-water bath3AlC2Reacting for 24 hours at 35 ℃ in nitrogen atmosphere to obtain reaction liquid;
② firstly, deionized water is used as cleaning agent, the reaction liquid is centrifugally cleaned to pH value at 3500r/min of centrifugal speed>6, pouring out the supernatant to obtain a precipitate; adding deionized water into the precipitate, performing ultrasonic treatment, centrifuging at 3500r/min for 1 hr, and collecting supernatant to obtain dark green Ti with few layers3C2TxA colloidal supernatant;
the ultrasonic power in the first step is 100W, and the ultrasonic time is 60 min;
the small layer of greenish black Ti in the step one3C2TxThe concentration of the colloid supernatant is 5 mg/mL;
secondly, a small number of greenish black Ti layers3C2TxAdding the colloid supernatant into the micronized cellulose solution, and shaking for 10min to obtain MFC @ Ti3C2TxMicrogel;
the mass fraction of the microfibrillated cellulose solution in the second step is 0.5 percent;
thirdly, adding MFC @ Ti3C2TxVacuum filtering the microgel through a mixed cellulose membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain an independently supported microfibrillated cellulose/MXene composite membrane;
the mass fraction of the microfibrillated cellulose in the independently supported microfibrillated cellulose/MXene composite film described in step three is 20%.
Example three: a preparation method of an independently supported microfibrillated cellulose/MXene composite film is completed according to the following steps:
first, prepare dark green few-layer Ti3C2TxAnd (3) colloid supernatant fluid:
adding 1.6g LiF into 20mL of 9mol/L HCl solution, stirring at room temperature until the LiF is completely dissolved, and then adding 1g Ti under the condition of ice-water bath3AlC2Reacting for 24 hours at 35 ℃ in nitrogen atmosphere to obtain reaction liquid;
② firstly, deionized water is used as cleaning agent, the reaction liquid is centrifugally cleaned to pH value at 3500r/min of centrifugal speed>6, pouring out the supernatant to obtain a precipitate; adding deionized water into the precipitate, performing ultrasonic treatment, centrifuging at 3500r/min for 1 hr, and collecting supernatant to obtain dark green Ti with few layers3C2TxA colloidal supernatant;
the ultrasonic power in the first step is 100W, and the ultrasonic time is 60 min;
the small layer of greenish black Ti in the step one3C2TxThe concentration of the colloid supernatant is 5 mg/mL;
secondly, a small number of greenish black Ti layers3C2TxAdding the colloid supernatant into the micronized cellulose solution, and shaking for 10min to obtain MFC @ Ti3C2TxMicrogel;
the mass fraction of the microfibrillated cellulose solution in the second step is 0.5 percent;
thirdly, adding MFC @ Ti3C2TxVacuum filtering the microgel through a mixed cellulose membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain an independently supported microfibrillated cellulose/MXene composite membrane;
the mass fraction of the microfibrillated cellulose in the independently supported microfibrillated cellulose/MXene composite film described in step three is 30%.
Comparative example: ti3C2TxPreparation of filmsThe method is completed according to the following steps:
first, prepare dark green few-layer Ti3C2TxAnd (3) colloid supernatant fluid:
adding 1.6g LiF into 20mL of 9mol/L HCl solution, stirring at room temperature until the LiF is completely dissolved, and then adding 1g Ti under the condition of ice-water bath3AlC2Reacting for 24 hours at 35 ℃ in nitrogen atmosphere to obtain reaction liquid;
② firstly, deionized water is used as cleaning agent, the reaction liquid is centrifugally cleaned to pH value at 3500r/min of centrifugal speed>6, pouring out the supernatant to obtain a precipitate; adding deionized water into the precipitate, performing ultrasonic treatment, centrifuging at 3500r/min for 1 hr, and collecting supernatant to obtain dark green Ti with few layers3C2TxA colloidal supernatant;
the ultrasonic power in the first step is 100W, and the ultrasonic time is 60 min;
the small layer of greenish black Ti in the step one3C2TxThe concentration of the colloid supernatant is 5 mg/mL;
secondly, a small number of greenish black Ti layers3C2TxFiltering the colloid supernatant with 0.22 μm mixed cellulose membrane under vacuum, and drying at room temperature to obtain Ti3C2TxA film.
Example two in one step a few layers of Ti of greenish black color were applied3C2TxAdding the colloidal supernatant into the microfibrillated cellulose solution, shaking for 10min, and then finding that the solution becomes a microgel visible to the naked eye within one minute, as shown in figure 1;
FIG. 1 shows Ti in the second step of the example3C2TxThe microgel formation process is shown in figure 1, which shows a greenish black few-layer Ti3C2TxThe supernatant of colloid, 2 is a micronized cellulose solution, 3 is Ti3C2TxMicrogels.
This indicates that Ti3C2TxThe nanosheets are due to strong electrostatic attraction and hydrogen bondingThe effect has been fully combined with cellulose, and the schematic diagram of self-assembly is shown in FIG. 3;
FIG. 3 is MFC @ Ti prepared in example one3C2TxA schematic diagram of the self-assembly of microgels;
FIG. 2 shows Ti prepared in comparative example3C2TxFilms and MFC @ Ti prepared in example one3C2TxComparative figures for thin films;
as can be seen from a comparison of FIG. 2, the original Ti3C2TxThe film surface is smooth, and MFC @ Ti3C2TxThe film surface is rough due to the inter-weaving of cellulose, which slows down the layer-to-layer stacking to some extent.
Testing of the original Ti3C2TxZeta potentials of the colloidal solution and the self-assembled microgel solution are shown in FIG. 4.
FIG. 4 is a Zeta potential comparison diagram, in which 1 is Ti prepared in comparative example3C2TxFilm, 2 MFC @ Ti prepared in example one3C2TxA film;
as can be seen from FIG. 4, the original Ti3C2TxThe colloidal solution was-23 mV, due to Ti3C2TxAnd (3) existence of a functional group with negative electricity on the surface of the nanosheet. When Ti is present3C2TxThe Zeta potential of the colloidal solution after complexing with MFC was-3 mV, demonstrating that these functional groups have bonded to a large number of hydroxyl groups on MFC and that the entire solution becomes electrically neutral.
FIG. 5 shows Ti prepared in comparative example3C2TxSEM image of the film;
as can be seen from FIG. 5, Ti produced in comparative example3C2TxIs a thin nano-sheet structure.
FIG. 6 is an SEM image of MFC;
from the microscopic appearance of MFC observed in FIG. 6, it can be found that the micron-sized large framework of MFC is formed by one fiber with a diameter of tens of nanometers and an ultra-long length-diameter ratioCellulose, these smaller celluloses being Ti3C2TxThe enhancement of the mechanical property of the film provides guarantee.
FIG. 7 is MFC @ Ti prepared in example one3C2TxSEM image of the film;
from fig. 7 it can be seen that one piece of cellulose is cross-linked to each other and agglomerated.
FIG. 8 is MFC @ Ti prepared in example one3C2TxTEM image of the thin film;
from the TEM image of FIG. 8, it can be seen that the cellulose outer layer having a diameter of about 2 μm is coated with a layer of Ti3C2TxNanosheets, from which Ti was known3C2TxThe nanosheets have been attached to the surface of the microfibrillated cellulose by means of hydrogen bonding or the like.
FIG. 9 is a graph showing tensile properties, in which 1 is Ti prepared in comparative example3C2TxFilm, 2 MFC @ Ti prepared in example one3C2TxFilm, 3 MFC @ Ti prepared in example two3C2TxFilm, 4 MFC @ Ti prepared in example III3C2TxA film;
it can be seen from FIG. 9 that as the MFC content increases, the tensile strength Ti3C2TxThe stress and strain of the film are increased, the strain is mainly due to the existence of hydrogen bonds, the film can act as a 'movable pulley' to increase the sliding between the sheets and further increase the plasticity, and when the MFC content reaches 30%, MFC @ Ti is added3C2TxThe tensile strength of the film is virgin Ti3C2TxThree times as much film.
FIG. 10 is an EIS diagram, in which 1 is Ti prepared in a comparative example3C2TxFilm, 2 MFC @ Ti prepared in example one3C2TxFilm, 3 MFC @ Ti prepared in example two3C2TxFilm, 4 MFC @ Ti prepared in example III3C2TxA film;
FIG. 11 is an enlarged view taken at A in FIG. 10;
as can be seen from fig. 10 and 11, the high frequency region still appears as a negligible semicircle after adding MFC, demonstrating its excellent conductivity. Compared with the slope of the straight line in the high-frequency region, the slope is found to be smaller and the Weber impedance is reduced due to the introduction of the cellulose. This is because the addition of MFC alleviates the stacking phenomenon between sheets to greatly shorten the ion transport path, so that the utilization rate of the material is increased.
FIG. 12 is a GCD curve of different films at a current density of 1A/g, wherein 1 is Ti prepared in comparative example3C2TxFilm, 2 MFC @ Ti prepared in example one3C2TxFilm, 3 MFC @ Ti prepared in example two3C2TxFilm, 4 MFC @ Ti prepared in example III3C2TxA film;
it can be seen from FIG. 12 that the film discharge time for 10% MFC content is longer than the original Ti3C2TxThe film is grown and its capacitance, Ti, is calculated3C2TxThe specific capacities of 10% MFC, 20% MFC and 30% MFC were 362F/g, 451F/g, 367F/g and 333F/g, respectively. The increase in film capacitance for 10% MFC content is not only due to the increase in interlayer spacing, but also due to the reduced ion channels due to the mitigation of stacking phenomena.
FIG. 13 is a CV diagram of 5mV/s sweep rate for various films, where 1 is Ti prepared in a comparative example3C2TxFilm, 2 MFC @ Ti prepared in example one3C2TxFilm, 3 MFC @ Ti prepared in example two3C2TxFilm, 4 MFC @ Ti prepared in example III3C2TxA film.
As can be seen in FIG. 13, MFC @ Ti3C2TxThe film had the largest area, consistent with the GCD curve results.
Table 1 shows the comparison of the conductivities of composite films with different MFC contents, and it can be seen that the conductivity is smaller than that of the original Ti when the content is smaller3C2TxFilm is toThis is different from the immediate conductivity reduction caused by the addition of nanocellulose, which also illustrates the advantage of microfibrillated cellulose for improving the overall performance of the film: the mechanical property is improved under the condition of not reducing the conductivity.
TABLE 1
Claims (10)
1. A preparation method of a microfibrillated cellulose/MXene composite film is characterized in that the preparation method of the microfibrillated cellulose/MXene composite film is completed according to the following steps:
first, prepare dark green few-layer Ti3C2TxAnd (3) colloid supernatant fluid:
adding LiF into HCl solution, stirring at room temperature until the LiF is completely dissolved, and then adding Ti under the condition of ice-water bath3AlC2Reacting for 18-28 h at 30-35 ℃ in nitrogen atmosphere to obtain reaction liquid;
② firstly, deionized water is used as cleaning agent, the reaction liquid is centrifugally cleaned to pH value under the centrifugal speed of 3500 r/min-4000 r/min>6, pouring out the supernatant to obtain a precipitate; adding deionized water into the sediment, then carrying out ultrasonic treatment, centrifuging for 1-1.2 h at the centrifugal speed of 3500-4000 r/min, and collecting the supernatant to obtain dark green few-layer Ti3C2TxA colloidal supernatant;
secondly, a small number of greenish black Ti layers3C2TxAdding the colloid supernatant into the micronized cellulose solution, and shaking to obtain MFC @ Ti3C2TxMicrogel;
thirdly, adding MFC @ Ti3C2TxAnd (3) passing the microgel through a mixed cellulose membrane with the aperture of 0.22 mu m, performing vacuum filtration, and drying at room temperature to obtain the microfibrillated cellulose/MXene composite membrane.
2. The method for preparing a micronized cellulose/MXene composite film according to claim 1, wherein the HCl solution has a concentration of 8mol/L to 10mol/L in the first step.
3. The method for preparing the microfibrillated cellulose/MXene composite film according to claim 1, wherein the ratio of the mass of LiF to the volume of HCl solution in the first step (1 g-2 g) is 20 mL.
4. The method for preparing a micronized cellulose/MXene composite film according to claim 1, wherein Ti is as described in step one >3AlC2The ratio of the mass of (1) to the volume of the HCl solution (0.5g to 1.5g) was 20 mL.
5. The preparation method of the microfibrillated cellulose/MXene composite film according to claim 1, wherein the ultrasonic power in the first step is 100W-300W, and the ultrasonic time is 50 min-70 min; the small layer of greenish black Ti in the step one3C2TxThe concentration of the colloid supernatant is 5 mg/mL-6 mg/mL.
6. The method for preparing a microfibrillated cellulose/MXene composite film according to claim 1, wherein the mass fraction of the microfibrillated cellulose solution in the second step is 0.5-0.8%, and the solvent is water.
7. The method for preparing a micronized cellulose/MXene composite film according to claim 1, wherein the shaking time in the second step is 5min to 10 min.
8. The method for preparing the microfibrillated cellulose/MXene composite film according to claim 1, wherein the mass fraction of the microfibrillated cellulose in the microfibrillated cellulose/MXene composite film in the step three is 10-30%.
9. The method for preparing the microfibrillated cellulose/MXene composite film according to claim 8, wherein the mass fraction of the microfibrillated cellulose in the microfibrillated cellulose/MXene composite film in the step three is 10-20%.
10. The use of a microfibrillated cellulose/MXene composite film according to claim 1 for producing a capacitor negative electrode material.
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