CN113745012A - Preparation method and application of MXene/rGO @ charcoal hydrogel composite material - Google Patents
Preparation method and application of MXene/rGO @ charcoal hydrogel composite material Download PDFInfo
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- CN113745012A CN113745012A CN202110856800.3A CN202110856800A CN113745012A CN 113745012 A CN113745012 A CN 113745012A CN 202110856800 A CN202110856800 A CN 202110856800A CN 113745012 A CN113745012 A CN 113745012A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 22
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- 238000000227 grinding Methods 0.000 claims description 11
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- 238000010438 heat treatment Methods 0.000 claims description 9
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- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
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- 239000000243 solution Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011363 dried mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
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- 239000002904 solvent Substances 0.000 claims description 4
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- 241001465754 Metazoa Species 0.000 claims description 3
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- 229910021641 deionized water Inorganic materials 0.000 claims description 3
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- 239000003990 capacitor Substances 0.000 abstract description 11
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 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
- H01G11/30—Electrodes characterised by their material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
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Abstract
A preparation method and application of MXene/rGO @ charcoal hydrogel composite material are disclosed, wherein the charcoal in the composite material and MXene/rGO form a three-dimensional porous conductive structure. The MXene/rGO hydrogel and the biochar framework are combined, the defect of MXene stacking can be effectively overcome by the innovative structure, the active sites of pseudo-capacitance are provided, pores are formed by carbonization and KOH activation, the specific surface area of the composite material is effectively increased, and the specific capacitance and the energy density when the composite material is applied to a super capacitor are improved.
Description
Technical Field
The invention relates to the technical field of electrochemical energy, in particular to a preparation method and application of an MXene/rGO @ charcoal hydrogel composite material.
Background
At present, one of the major trends in the electronics industry is the miniaturization, portability and high integration of electronic devices. Such electronic devices require the use of a miniature power supply and a miniature energy storage device. Among them, flexible electrochemical capacitors (also called supercapacitors) have great commercial potential due to high power density, fast charge and discharge and long cycle life. The supercapacitor stores electrochemical energy by absorbing ions in an electrolyte through the surface of an electrode material with high specific surface area, so that the supercapacitor can store and transmit a large amount of charges in a short time, and the service life is generally millions of cycles compared with a common rechargeable battery. However, one of the major challenges in making supercapacitor electrode sheets is increasing the energy density of the overall capacitor.
The biochar is used as an important raw material of an electric double layer electrochemical capacitor, is easy to collect, has low cost and no pollution to the environment, but has small density due to more pores and larger specific surface area, so that the biochar is not beneficial to being used on various micro supercapacitors.
MXene is a novel two-dimensional material and gradually becomes a new choice of a supercapacitor capacitance material. Compared with other two-dimensional materials, MXene has oxygen-rich surface groups and extremely high volume specific capacity, so that the energy density is effectively improved. However, MXene has the same disadvantages as other two-dimensional nanomaterials, resulting in stacking and accumulation of MXene nanoplatelets, such that electrochemical performance cannot be fully utilized. Therefore, a suitable electrode structure is needed to combine biochar and MXene materials to increase the specific surface area and energy density of the electrode sheet.
Disclosure of Invention
The invention aims to provide a preparation method and application of an MXene/rGO @ charcoal hydrogel composite material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of an MXene/rGO @ charcoal hydrogel composite material comprises the following steps:
firstly, immersing a freeze-dried biomass material into mixed dispersion liquid of MXene and GO to be fully absorbed, wherein the mass ratio of the biomass material to the MXene to the GO is 100: 1-9: 9-1;
then, adding ethylenediamine into the mixed dispersion liquid, wherein 150-250 mu L of ethylenediamine is required for every 20-30 mg of GO; then carrying out hydrothermal reaction, heating to 80-130 ℃, and preserving heat for 6-48 hours;
after the hydrothermal reaction, washing the incompletely reacted ethylenediamine with a mixed solution of deionized water and ethanol, vacuum-heating to 50-70 ℃ after washing, keeping the temperature until the ethylenediamine is dried, cooling to room temperature, and taking out to obtain a dried mixture;
sintering and carbonizing the dried mixture under the protection of inert gas, cooling to room temperature, and taking out; wherein the carbonization is required to be heated to 600-800 ℃ and kept for 1-2 hours;
grinding the carbonized mixture in a ball mill for 20-30 minutes, adding an activating agent and water after grinding, and uniformly mixing, wherein the mass ratio of the activating agent to the carbonized mixture is (2-4): 1;
then, drying at 40-60 ℃, and sintering and activating under the protection of inert gas after drying, wherein the sintering and activating requirements are that the temperature is heated to 600-800 ℃, and the temperature is kept for 1-2 hours;
and finally, grinding the product after sintering and activation to obtain the MXene/rGO @ charcoal hydrogel composite material.
The relevant content in the above technical solution is explained as follows:
1. in the scheme, the biomass material comprises animal or/and plant, and material derived from living body such as microorganism, such as Pleurotus eryngii, folium Nelumbinis, and crab shell.
2. In the scheme, the freeze-drying step is that the frozen food is frozen at the temperature of-40 to-60 ℃ and then is placed in a freeze dryer for freeze-drying for 24 to 60 hours.
3. In the scheme, the mixed dispersion liquid is formed by ultrasonically mixing 10mg/mL MXene dispersion liquid and 2mg/mL GO dispersion liquid.
4. In the scheme, the ultrasonic frequency of ultrasonic mixing is 35-45 KHz, and the ultrasonic power is 600-800W.
In order to achieve the purpose, the invention adopts another technical scheme that:
an electrode slice applying MXene/rGO @ charcoal hydrogel composite material comprises:
firstly, uniformly mixing the MXene/rGO @ charcoal hydrogel composite material, a conductive agent and polyvinylidene fluoride according to a mass ratio of 6-8: 2-1;
then adding N-methylpyrrolidone serving as a solvent into the mixed solution until the solution is in a critical state between a viscous state and a thin state, and magnetically stirring for 12-24 hours until the solution is uniformly stirred to obtain MXene/rGO @ charcoal hydrogel composite material slurry;
and finally, uniformly coating the composite material slurry on the surface of one side of the sheared current collector, and performing vacuum drying at the temperature of 50-70 ℃ for 12-24 hours to remove the N-methyl pyrrolidone so as to obtain the composite electrode slice.
The working principle and the advantages of the invention are as follows:
the invention relates to a preparation method of MXene/rGO @ charcoal hydrogel composite material, wherein the charcoal in the composite material and MXene/rGO form a three-dimensional porous conductive structure. The invention combines MXene/rGO hydrogel with a charcoal frame, the innovative structure can effectively overcome the defect of MXene self-stacking, provides the active site of pseudo-capacitance, carries out pore-forming by carbonization and KOH activation, effectively increases the specific surface area of the composite material, and improves the specific capacitance and energy density of the super capacitor.
Compared with the prior art, the invention has the following technical effects:
1. the biochar and MXene/rGO in the composite material form a three-dimensional porous conductive structure, and due to the synergistic effect of the layered structure, the defects of self stacking and accumulation of MXene can be effectively overcome, so that the circulation stability of the supercapacitor is greatly improved;
2. in the preparation process of the MXene/rGO hydrogel, a contraction effect is generated, so that the hydrogel is attached to the surface of the pleurotus eryngii, the hydrogel is tightly attached, the ion transmission of the composite material is not influenced, a new pore size distribution structure is generated, the existence of macropores is reduced, the integral density is increased, and the volume energy density is increased;
3. MXene can provide additional active sites, can promote the pseudo-capacitance characteristic of the electrode surface and improve the specific capacity of the material;
4. according to the invention, a biomass material and MXene/rGO hydrogel are combined, and a two-dimensional material with higher density is used for filling the structure of the biochar, so that the energy density of the whole device can be obviously improved, and a premise is created for the biochar trend flexibility and a wearable super capacitor device.
Drawings
FIG. 1 is a flow chart of a preparation method of an MXene/rGO @ charcoal hydrogel composite electrode plate in the embodiment of the invention;
FIG. 2 is an electrochemical test chart-CV diagram of the MXene/rGO @ charcoal hydrogel composite electrode sheet in the embodiment of the invention;
FIG. 3 is an electrochemical test chart-GCD chart of the MXene/rGO @ charcoal hydrogel composite electrode sheet in the embodiment of the invention;
FIG. 4 is an electrochemical test chart-EIS chart of the MXene/rGO @ charcoal hydrogel composite electrode sheet in the embodiment of the invention.
Detailed Description
The invention is further described with reference to the following figures and examples:
example (b): the present disclosure will be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the disclosure may be shown and described, and which, when modified and varied by the techniques taught herein, can be made by those skilled in the art without departing from the spirit and scope of the disclosure.
As used herein, the terms "comprising," "including," "having," and the like are open-ended terms that mean including, but not limited to.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
A preparation method of an MXene/rGO @ charcoal hydrogel composite electrode plate comprises the following steps:
step one, preparing MXene/rGO @ charcoal hydrogel composite material
First, the biomass material was freeze-dried at-60 ℃ for 48 hours and then taken out. The biomass material comprises materials derived from animals or/and plants, and living bodies such as microorganisms, such as Pleurotus eryngii, folium Nelumbinis, and crab shell.
Immersing the biomass material subjected to freeze-drying into mixed dispersion liquid of MXene and GO to be fully absorbed, wherein the mass ratio of the biomass material to the MXene to the GO is 100: 1-9: 9 to 1. The mixed dispersion liquid is formed by ultrasonically mixing 10mg/mL MXene dispersion liquid and 2mg/mL GO dispersion liquid. The ultrasonic frequency of ultrasonic mixing is 35-45 KHz, and the ultrasonic power is 600-800W.
Then, adding Ethylenediamine (EDA) into the mixed dispersion liquid, wherein 150-250 mu L of ethylenediamine is required for every 20-30 mg of GO; then carrying out hydrothermal reaction, heating to 80-130 ℃, and preserving heat for 6-48 hours.
After the hydrothermal reaction, cleaning and drying to obtain a dried mixture; wherein the volume ratio of the cleaning is 9: 1, washing off the incompletely reacted ethylenediamine, cleaning, heating to 60 ℃ in vacuum, keeping the temperature until the temperature is dry, cooling to room temperature, and taking out.
Sintering and carbonizing the dried mixture under the protection of inert gas (such as nitrogen or argon), cooling to room temperature, and taking out; wherein the carbonization is required to be heated to 600-800 ℃ and kept for 1-2 hours.
Grinding the carbonized mixture in a ball mill for 20-30 minutes, adding an activating agent and water after grinding, and uniformly mixing, wherein the mass ratio of the activating agent to the carbonized mixture is (2-4): 1; the added water needs to be over the surface of the mixture and the particles in the solution are uniformly distributed after uniform mixing. The activating agent can be potassium hydroxide, potassium bicarbonate, etc.
And then continuously drying, and sintering and activating under the protection of inert gas after drying, wherein the sintering and activating are required to be heated to 600-800 ℃, and the temperature is kept for 1-2 hours.
And finally, grinding the product after sintering and activation to obtain the MXene/rGO @ charcoal hydrogel composite material.
Step two, preparation of composite electrode slice
Firstly, uniformly mixing the MXene/rGO @ charcoal hydrogel composite material, a conductive agent and polyvinylidene fluoride according to a mass ratio of 6-8: 2-1; the conductive agent can be carbon black.
And then adding N-methylpyrrolidone serving as a solvent into the mixture until the solution is in a viscous and thin intermediate critical state, and magnetically stirring for 12-24 hours until the solution is uniformly stirred to obtain MXene/rGO @ charcoal hydrogel composite material slurry.
And finally, uniformly coating the composite material slurry on the surface of one side of the sheared current collector, and performing vacuum drying at the temperature of 50-70 ℃ for 12-24 hours to remove the N-methyl pyrrolidone so as to obtain the composite electrode slice. The current collector can be carbon paper, carbon cloth, foam nickel, foam copper and the like.
The invention also relates to a super capacitor, which comprises the composite material prepared by the preparation method provided by the invention and used as a working electrode of the super capacitor.
The general formula of MXene of the present invention is Mn +1XnTx or Mn +1Xn, wherein M represents a transition metal, X represents carbon or nitrogen, Tx represents a surface functional group including-O, -OH and-F, and n is 1, 2 or 3.
The following Ti is selected for MXene3C2TxThe specific case description is as follows:
a preparation method of a super capacitor comprises the following steps:
step one, Ti3C2TxThe preparation process of the/rGO @ charcoal hydrogel composite material is shown in figure 1:
the biomass material was freeze-dried at-60 ℃ for 48 hours and then removed. Immersing the biomass material in Ti3C2TxAnd GO in the mixed dispersion liquid, the mass ratio is 100: 9: 1, adding EDA to carry out hydrothermal reaction after full absorption, heating to 95 ℃, and keeping the temperature for 12 hours.
After the hydrothermal reaction, the product is washed by a mixed solution of deionized water and alcohol and then dried in vacuum at 60 ℃. And after the temperature is reduced to the room temperature, sintering and carbonizing the dried mixture under the protection of nitrogen or argon, heating to 600 ℃, preserving the heat for 1 hour, then cooling to the room temperature, and taking out.
Mixing activating agent after grinding, drying, sintering and activating under the protection of nitrogen or argon again, heating to 700 ℃, preserving heat for 1 hour, carefully grinding to obtain Ti3C2Txthe/rGO @ charcoal hydrogel composite material.
Step two, preparing the composite electrode slice, wherein the flow is shown in figure 1:
mixing Ti3C2TxUniformly mixing the/rGO @ charcoal hydrogel composite material, the carbon black and the polyvinylidene fluoride according to the mass ratio of 8:1:1, adding N-methyl pyrrolidone serving as a solvent, and fully and uniformly stirring to obtain Ti3C2Txthe/rGO @ charcoal hydrogel composite material slurry;
mixing the above Ti3C2TxUniformly coating the slurry of the/rGO @ charcoal hydrogel composite material on the surface of the sheared carbon paper, and drying the carbon paper in vacuum at the temperature of 60 ℃ for 12 hours to completely remove the N-methylpyrrolidone to obtain the composite electrode slice.
Step three, three-electrode system assembly, the flow is shown in figure 1:
ti for three-electrode test system3C2Txthe/rGO @ charcoal hydrogel composite electrode plate is used for a working electrode, high-purity graphite is used for a counter electrode, and Ag/AgCl is used for a reference electrode; test System adopted 3M H2SO4As an electrolyte.
The electrochemical performance of the super capacitor is tested by adopting a conventional battery testing instrument and method as follows: the specific capacitance is about 238F/g at a sweeping speed of 2 mv/s. After the sweep rate is increased to 50 times (100mv/s), the specific capacitance is about 234F/g, the electrochemical cycle charge-discharge performance is stable, the internal resistance is small, the CV curve is shown in FIG. 2, the GCD curve is shown in FIG. 3, and the EIS curve is shown in FIG. 4.
The invention relates to a preparation method of an MXene/rGO @ charcoal hydrogel composite electrode plate for a supercapacitor. The invention combines MXene/rGO hydrogel with a charcoal frame, the innovative structure can effectively overcome the defect of MXene self-stacking, provides the active site of pseudo-capacitance, carries out pore-forming by carbonization and KOH activation, effectively increases the specific surface area of the composite material, and improves the specific capacitance and energy density of the super capacitor.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A preparation method of MXene/rGO @ charcoal hydrogel composite material is characterized by comprising the following steps: the method comprises the following steps:
firstly, immersing a freeze-dried biomass material into mixed dispersion liquid of MXene and GO to be fully absorbed, wherein the mass ratio of the biomass material to the MXene to the GO is 100: 1-9: 9-1;
then, adding ethylenediamine into the mixed dispersion liquid, wherein 150-250 mu L of ethylenediamine is required for every 20-30 mg of GO; then carrying out hydrothermal reaction, heating to 80-130 ℃, and preserving heat for 6-48 hours;
after the hydrothermal reaction, washing the incompletely reacted ethylenediamine with a mixed solution of deionized water and ethanol, vacuum-heating to 50-70 ℃ after washing, keeping the temperature until the ethylenediamine is dried, cooling to room temperature, and taking out to obtain a dried mixture;
sintering and carbonizing the dried mixture under the protection of inert gas, cooling to room temperature, and taking out; wherein the carbonization is required to be heated to 600-800 ℃ and kept for 1-2 hours;
grinding the carbonized mixture in a ball mill for 20-30 minutes, adding an activating agent and water after grinding, and uniformly mixing, wherein the mass ratio of the activating agent to the carbonized mixture is (2-4): 1;
then, drying at 40-60 ℃, and sintering and activating under the protection of inert gas after drying, wherein the sintering and activating requirements are that the temperature is heated to 600-800 ℃, and the temperature is kept for 1-2 hours;
and finally, grinding the product after sintering and activation to obtain the MXene/rGO @ charcoal hydrogel composite material.
2. The method of claim 1, wherein: the biomass material includes animal or/and plant derived material.
3. The method of claim 1, wherein: the freeze-drying step is that the frozen food is frozen at the temperature of minus 40 to minus 60 ℃ and then is placed in a freeze dryer for freeze-drying for 24 to 60 hours.
4. The method of claim 1, wherein: the mixed dispersion liquid is formed by ultrasonically mixing 10mg/mL MXene dispersion liquid and 2mg/mL GO dispersion liquid.
5. The method of claim 1, wherein: the ultrasonic frequency of ultrasonic mixing is 35-45 KHz, and the ultrasonic power is 600-800W.
6. An electrode slice using MXene/rGO @ charcoal hydrogel composite material is characterized in that: the method comprises the following steps:
firstly, uniformly mixing the MXene/rGO @ charcoal hydrogel composite material, a conductive agent and polyvinylidene fluoride according to a mass ratio of 6-8: 2-1;
then adding N-methylpyrrolidone serving as a solvent into the mixed solution until the solution is in a critical state between a viscous state and a thin state, and magnetically stirring for 12-24 hours until the solution is uniformly stirred to obtain MXene/rGO @ charcoal hydrogel composite material slurry;
and finally, uniformly coating the composite material slurry on the surface of one side of the sheared current collector, and performing vacuum drying at the temperature of 50-70 ℃ for 12-24 hours to remove the N-methyl pyrrolidone so as to obtain the composite electrode slice.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115116761A (en) * | 2022-06-09 | 2022-09-27 | 北京化工大学 | Preparation method of high-capacity MXene composite fiber electrode material |
Citations (5)
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| CN115116761A (en) * | 2022-06-09 | 2022-09-27 | 北京化工大学 | Preparation method of high-capacity MXene composite fiber electrode material |
| CN115116761B (en) * | 2022-06-09 | 2024-03-26 | 北京化工大学 | Preparation method of high-capacity MXene composite fiber electrode material |
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