CN112768253A - High-performance electrode material for super capacitor, preparation method of high-performance electrode material and super capacitor - Google Patents
High-performance electrode material for super capacitor, preparation method of high-performance electrode material and super capacitor Download PDFInfo
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- CN112768253A CN112768253A CN202011615547.4A CN202011615547A CN112768253A CN 112768253 A CN112768253 A CN 112768253A CN 202011615547 A CN202011615547 A CN 202011615547A CN 112768253 A CN112768253 A CN 112768253A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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- 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
Abstract
The invention discloses a high-performance electrode material for a super capacitor, a preparation method of the high-performance electrode material and the super capacitor. The electrode material comprises MXene material and graphene material. According to the invention, the MXene material is modified by the graphene material to form the composite material, so that the flexibility of the material is increased due to the existence of the graphene, and the MXene material (such as Ti) is relieved3C2TxMXene material) in the process of charging and discharging, and increases the contact between the material and electrolyte, improves the conductivity of the material, and improves the electrochemical performance of the material.
Description
Technical Field
The invention belongs to the field of new energy materials, and relates to a high-performance electrode material for a supercapacitor, a preparation method of the high-performance electrode material and the supercapacitor.
Background
The problems of continuous exhaustion of fossil fuels, environmental pollution and the like are increasingly serious nowadays, and efficient and environment-friendly alternative energy is urgently sought. Nowadays, the traditional lithium ion battery has become an indispensable part of human life, and provides power for the revolution of portable electronic products. However, for the applications such as electric vehicles and power grid storage with ever-expanding scale, the proliferation of electrochemical energy storage depends on the strict performance of the battery in the future, such as safety, energy density and cost requirements, which cannot be met by the performance of the conventional lithium ion battery. In view of these problems, in order to solve this problem, supercapacitors have received much attention due to their high safety, high energy density and long cycle life.
MXene material as a novel two-dimensional layered material is expected to be applied to the field of new energy, for example, CN111029172A discloses Ti3C2TxThe MXene material shell is used in the technical field of super capacitors, and further discloses a Ti-regulating and controlling material3C2TxAlso disclosed in CN111763213A is a metal phthalocyanine-MXene composite material, a preparation method thereof, and a supercapacitor using the composite material, the preparation method comprising 1) mixing metal phthalocyanine with a first solvent to obtain a metal phthalocyanine solution; adding the metal phthalocyanine solution into water to obtain a metal phthalocyanine nano-structure; (2) and mixing the metal phthalocyanine nano-structure, the MXene material and a second solvent to obtain the metal phthalocyanine-MXene composite material. But the specific capacity is lower and no relevant cycle performance study is carried out.
From the above, with Ti3C2TxMXene material is an example, which has the advantages of high specific surface area and high electron transmission rate, and becomes a great research hotspot in the field of energy storage materials nowadays. But Ti3C2TxMXene materials have poor mechanical properties resulting in short cycle life.
Therefore, it is necessary to provide a composite material based on MXene material, which has both high specific capacity and excellent cycling performance, so as to meet practical applications.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a high performance electrode material for a super capacitor, a preparation method thereof and a super capacitor.
The high-performance electrode material of the invention refers to: at 1A g-1The specific capacity obtained by constant current charging and discharging under the current density of (2) is 226F g-1Above, the capacity retention rate is 91% or more after 10000 cycles of circulation.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an electrode material for a supercapacitor, wherein the electrode material comprises an MXene material and a graphene material.
As a novel layered material, the MXene material has the advantages of high specific surface area and high electron transmission rate, and becomes a great research hotspot in the field of energy storage materials at present, but the MXene material has poor mechanical properties, is easy to break due to high brittleness, and has short cycle life.
Graphene is a carbon allotrope that typically has the characteristics of a two-dimensional crystal structure. Its carbon atom passing through sp2The hybridization orbitals and the pi-bonding compact surface regularly form a hexagonal honeycomb lattice structure with the thickness of only one atomic layer. The special crystal structure endows the graphene with excellent mechanical, thermal and electrical properties.
According to the invention, the MXene material is modified by the graphene material to form the composite material, so that the flexibility of the material is increased due to the existence of the graphene, and the MXene material (such as Ti) is relieved3C2TxMXene material) in the process of charging and discharging, and increases the contact between the material and electrolyte, improves the conductivity of the material, and improves the electrochemical performance of the material.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, the MXene material is two-dimensional layered Ti3C2TxMXene materials.
Preferably, the graphene material includes at least one of graphene and reduced graphene oxide.
Preferably, the mass ratio of the MXene material to the graphene material is 1-99: 1, such as 1:1, 5:1, 8:1, 10:1, 15:1, 20:1, 25:1, 28:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1 or 90:1, and if the MXene material is too little and the graphene material is too much, the ion transmission performance is reduced; if the MXene material is too much and the graphene material is too little, the conductivity and the mechanical property are reduced, and the electrochemical property is further influenced, and the ratio of MXene material to graphene material is preferably 1-50: 1, and more preferably 7-15: 1.
In a second aspect, the present invention provides a method for preparing an electrode material for a supercapacitor according to the first aspect, the method comprising the steps of:
(1) dissolving a graphene material and an MXene material in a solvent according to a formula amount to obtain a mixed solution;
(2) and carrying out hydrothermal reaction at 150-280 ℃ by adopting the mixed solution to obtain the electrode material for the supercapacitor.
The method is simple, has low requirement on equipment, can prepare the electrode material with good electrochemical performance by one-step compounding, and the electrode material shows high specific capacitance and good cycling stability when being used for the super capacitor.
In the method, the hydrothermal reaction is in a high-temperature high-pressure environment, the combination of the hydrothermal reaction and the porous material can be better realized within the temperature range of 150-280 ℃, a stable three-dimensional porous structure is formed, the ionic conduction is facilitated, and simultaneously, the good mechanical stability is considered, if the temperature is less than 150 ℃, the incomplete reaction can be caused, and the composite structure is unstable; if the temperature is higher than 280 ℃, the morphology of the material is affected, the specific surface area is reduced, and the efficient transmission of lithium ions is not facilitated.
As a preferred technical solution of the method of the present invention, the graphene material is at least one of graphene and reduced graphene oxide, and is preferably reduced graphene oxide. The reduced graphene oxide is obtained by reducing graphene oxideBecause the oxygen-containing functional group on the graphene oxide is difficult to completely remove, the method is favorable for reducing the graphene oxide and the two-dimensional layered Ti3C2TxMXene materials combine to form a more tightly bonded high performance composite.
Preferably, the MXene material is two-dimensional layered Ti3C2TxMXene materials.
As a preferable technical scheme of the method, the two-dimensional layered Ti3C2TxThe MXene material is prepared by the following method:
(a) mixing titanium powder, aluminum powder and graphite, ball milling, pressing into sheet, calcining at 1000-1800 deg.C (such as 1000 deg.C, 1100 deg.C, 1200 deg.C, 1250 deg.C, 1300 deg.C, 1400 deg.C, 1500 deg.C, 1600 deg.C, 1700 deg.C or 1800 deg.C) under the protection of protective gas, and grinding the calcined product to obtain polycrystalline MAX phase compound Ti3AlC2MXene powder;
(b) subjecting the Ti of step (a) to3AlC2MXene powder is dispersed in HF solution and stirred for reaction to obtain two-dimensional layered Ti3C2TxMXene materials.
In the preferred technical scheme, a polycrystalline MAX phase compound Ti is synthesized3AlC2The calcining temperature of MXene powder is increased to 1000-1800 ℃, which is beneficial to improving crystallinity and structure stability, and the stability of the charging and discharging process is improved when the electrode material synthesized by the MXene powder is applied to a super capacitor.
Preferably, in the step (a), the titanium powder, the aluminum powder and the graphite are mixed according to an atomic ratio of Ti, Al and C of 3 (1.05-1.2): 2, such as 3:1.05:2, 3:1.1:2, 3:1.15:2 or 3:1.2: 2.
Preferably, the graphite of step (a) is flake graphite.
Preferably, the protective gas of step (a) comprises at least one of nitrogen, argon and helium.
Preferably, the calcination in step (a) is carried out for a time of 2h to 5h, such as 2h, 3h, 4h, 4.5h or 5h, etc.
Preferably, the concentration of the HF solution of step (b) is 20% to 60%, such as 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, or the like.
Preferably, the stirring reaction time in step (b) is 16h to 30h, such as 16h, 18h, 20h, 22h, 24h, 25h, 27h or 30 h.
Preferably, the stirring reaction of step (b) is followed by the steps of separating, washing and drying.
Preferably, the drying temperature is 50 ℃ to 100 ℃, such as 50 ℃, 60 ℃, 65 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃ and the like; the drying time is 10h to 15h, such as 10h, 11h, 11.5h, 12h, 13h or 15 h.
Preferably, the drying is vacuum drying at a vacuum of-70 Kpa to-90 Kpa, such as-70 Kpa, -75Kpa, -80Kpa or-90 Kpa, etc.
As a preferred technical scheme of the method, the solvent in the step (1) is water.
Preferably, the mixed solution is stirred for 1 to 2 hours, for example, 1 hour, 1.2 hours, 1.5 hours, 1.8 hours or 2 hours before the hydrothermal reaction in step (2).
Preferably, the hydrothermal reaction time in step (2) is 15h to 25h, such as 15h, 16h, 18h, 19h, 20h, 22h, 23h, 24h or 25 h.
Preferably, the hydrothermal reaction in step (2) is followed by the steps of filtering, washing and drying.
Preferably, the reagents used for the washing include water and ethanol.
Preferably, the drying temperature is 50 ℃ to 100 ℃, such as 50 ℃, 60 ℃, 65 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃ and the like; the drying time is 10h to 15h, such as 10h, 11h, 11.5h, 12h, 13h or 15 h.
Preferably, the drying is vacuum drying with a vacuum of-70 to-90 Kpa, such as-70 Kpa, -75Kpa, -80Kpa or-90 Kpa, etc.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) preparation of reduced graphene oxide powder
Preparing a dispersed graphene aqueous solution by using graphite powder, reducing graphene oxide by using hydrogen peroxide to obtain reduced graphene oxide, and drying to obtain reduced graphene oxide powder;
(2) preparation of Ti3C2TxMXene material
The method comprises the following steps: taking titanium powder, aluminum powder and graphite, and mixing the titanium powder, the aluminum powder and the graphite in an atomic ratio of Ti: al: uniformly mixing C-3: 1.1:2, ball-milling for 1-3 h, and pressing under the pressure of 0.5-2 Gpa to prepare a wafer;
step two: putting the wafer pressed in the step one into a tube furnace, calcining for 2-5 h at 1000-1800 ℃ under the protection of inert gas, cooling to room temperature, taking out, grinding for 1h by using a mortar to obtain a polycrystalline MAX phase compound Ti3AlC2MXene powder;
step three: ti prepared in the second step3AlC2Dispersing MXene powder in an HF solution, and continuously stirring for 16-30 h at room temperature;
step four: after the reaction is finished, repeatedly washing the reaction product by deionized water, and centrifuging for 10 minutes at the rotating speed of 3800 rpm until the pH value of the supernatant is 6;
step five: vacuum drying the product washed in the fourth step at 50-100 ℃ for 10-15 h to obtain Ti3C2Tx MXene powder;
(3) preparation of electrode material for super capacitor
Step six: separately weighing Ti3C2TxDissolving MXene powder and reduced graphene oxide powder in deionized water, continuously stirring for 1-2 h, transferring to a high-pressure reaction kettle, and continuously reacting for 15-25 h at 150-280 ℃;
step seven: filtering the product obtained after the reaction in the sixth step, washing the product for 3 to 5 times by using pure water and ethanol, and finally drying the product for 10 to 15 hours in vacuum at the temperature of between 50 and 100 ℃ to obtain Ti3C2TxMXene/reduced graphene oxide composite material, namely electrode material for a supercapacitor.
In a third aspect, the present invention provides a supercapacitor comprising the electrode material of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the MXene material is modified by the graphene material to form the composite material, and the MXene material (such as Ti) is relieved by the graphene3C2TxMXene material) in the process of charging and discharging, and increases the contact between the material and electrolyte, improves the conductivity of the material, and improves the electrochemical performance of the material.
(2) The method is simple, has low requirement on equipment, can prepare the electrode material with good electrochemical performance by one-step compounding, and the electrode material shows high specific capacitance and good cycling stability when being used for the super capacitor.
Drawings
FIG. 1 shows Ti prepared in example 13C2TxSEM pictures of MXene material;
FIG. 2 shows Ti prepared in example 13C2TxA specific capacity change diagram of the MXene/reduced graphene oxide composite material electrode under different current densities;
FIG. 3 shows Ti prepared in example 13C2TxCycle performance diagram of MXene/reduced graphene oxide composite electrode.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
The embodiment provides an electrode material for a supercapacitor and a preparation method thereof, and the preparation method specifically comprises the following steps:
(1) 2g of graphite powder and 1g of NaNO were added in sequence in a 250mL beaker in an ice-water bath state3And 46mLH2SO4And stirred well. Slowly adding 6g of potassium permanganate, controlling the temperature of the solution to be 20-50 ℃, keeping the solution under the condition of continuously stirring for 5min, adding 92mL of water, continuously stirring for 15min, increasing the water temperature to about 98 ℃, adding 80mL of water30 wt% hydrogen peroxide solution at 60 deg.c, centrifuging the liquid at 7200r/min for 30min, and washing with hot water until the pH value of the upper suspension is about 7. And dispersing the obtained powder into deionized water again, performing ultrasonic treatment for 15min, filtering, and drying to obtain the reduced graphene oxide.
(2) Titanium powder, aluminum powder and graphite are mixed according to the atomic ratio of Ti: al: mixing C in an atomic ratio of 3:1.1:2, ball-milling for 1h, pressing the mixture into a disk shape, calcining at 1400 ℃ in a tube furnace in an argon atmosphere for 2h, cooling to room temperature, and grinding for 1h by using a mortar. Grinding Ti3AlC2Soaking the powder in 40 wt% HF solution, stirring at room temperature for 24 hr, repeatedly washing with deionized water after reaction, centrifuging at 3500r/min for 10min until the pH of the supernatant exceeds 6, and vacuum drying at 80 deg.C for 12 hr to obtain Ti3C2TxMXene powder.
(3) 0.9g of Ti was weighed out separately by an electronic balance3C2TxDissolving MXene material and 0.1g of reduced graphene oxide in 25mL of deionized water, magnetically stirring for 30min, transferring to a stainless steel high-pressure reaction kettle, standing at 210 ℃ for 18h, filtering a product after reaction, washing with pure water and ethanol for 3 times, and finally vacuum drying at 80 ℃ for 12h to obtain Ti3C2TxMXene/reduced graphene oxide composite material (abbreviated as Ti)3C2Tx MXene/RGO)。
And (3) testing:
for Ti3C2TxMorphology test is carried out on the MXene/reduced graphene oxide composite material, and FIG. 1 shows Ti of the embodiment3C2TxSEM pictures of MXene material.
Ti prepared as described above3C2TxUniformly mixing MXene/reduced graphene oxide composite material, conductive carbon (SP) and PVDF according to the mass ratio of 8:1:1, adding a proper amount of NMP, fully grinding, then coating the slurry on a foamed nickel current collector, carrying out vacuum drying at 45 ℃ for 12h, respectively selecting a Pt electrode as a counter electrode, Hg/HgO as a reference electrode and an electrolyte as 6M KOH solution. The charge-discharge voltage is-1.0V-0V,at 1A g-1、2A g-1、3A g-1、4A g-1、5A g-1And 10A g-1Constant current charging and discharging was carried out at a current density of 1, and the test results are shown in fig. 2, which is at 1A g-1The specific capacity of the lower test can reach 242.3F g-1And the circulation performance of 10000 times of circulation is tested, the test result is shown in figure 3, and after 10000 times of charge-discharge circulation, the capacity is still as high as 238.9F g-1The retention rate reaches 98.6%, and excellent cycle stability is shown.
Example 2
The difference from example 1 is that Ti weighed in step (3)3C2TxThe mass of MXene material and reduced graphene oxide were 0.95g and 0.05g, respectively, when Ti was present3C2TxThe mass ratio of the MXene material to the reduced graphene oxide was 19.
Capacitor assembly and same conditions testing was performed using the same method as example 1, which was at 1A g-1The specific capacity of the lower test can reach 226.1F g-1(ii) a After 10000 times of charge-discharge cycles, the capacity retention rate reaches 91.4 percent.
Example 3
The difference from example 1 is that Ti weighed in step (3)3C2TxThe mass of MXene material and reduced graphene oxide were 0.85g and 0.15g, respectively, at which time Ti3C2TxThe mass ratio of the MXene material to the reduced graphene oxide was 5.7.
Capacitor assembly and same conditions testing was performed using the same method as example 1, which was at 1A g-1The specific capacity of the lower test can reach 232.8F g-1(ii) a After 10000 times of charge-discharge cycles, the capacity retention rate reaches 93.7 percent.
As can be seen by comparing examples 1 to 3, Ti3C2TxThe mass ratio of MXene material to graphene material is in a preferred range, and Ti3C2TxWhen the mass ratio of the MXene material to the graphene material is within the range of 7-15: 1, higher specific capacity and better cycling stability can be obtained.
Example 4
The difference from example 1 is that the temperature of the reaction vessel in step (3) is 140 ℃.
Capacitor assembly and same conditions testing was performed using the same method as example 1, which was at 1A g-1The specific capacity of the lower test can reach 217F g-1(ii) a After 10000 times of charge-discharge cycles, the capacity retention rate reaches 93.1 percent.
Example 5
The difference from example 1 is that the temperature of the reaction vessel in step (3) is 300 ℃.
Capacitor assembly and same conditions testing was performed using the same method as example 1, which was at 1A g-1The specific capacity of the lower test can reach 228F g-1(ii) a After 10000 times of charge-discharge cycles, the capacity retention rate reaches 95.2 percent.
It can be seen from the comparison between example 1 and examples 4-5 that there is a preferable range of the temperature of the hydrothermal reaction, and both too low and too high of the temperature can affect the electrochemical performance of the electrode material, which may be because the difference of the hydrothermal temperature can affect the binding stability and morphology of the composite material.
Example 6
The difference from example 1 is that the calcination temperature in step (2) in a tube furnace under an argon atmosphere was 800 ℃.
Capacitor assembly and same conditions testing was performed using the same method as example 1, which was at 1A g-1The specific capacity of the lower test can reach 201F g-1(ii) a After 10000 times of charge-discharge cycles, the capacity retention rate reaches 91.4 percent.
It is understood from the comparison between example 1 and example 6 that too high a calcination temperature affects the crystallinity of the material, reduces the structural stability of the material, and further affects the structural collapse of the material during charge and discharge, thereby affecting the electrochemical performance.
Comparative example 1
The electrode material for a supercapacitor of this comparative example was Ti prepared in step (2) of example 13C2TxMXene powder, distinguished from example 1 by not being complexed with graphene oxide.
Capacitor assembly and same conditions testing was performed using the same method as example 1, which was at 1A g-1The specific capacity of the lower test can reach 178.4F g-1(ii) a After 10000 times of charge-discharge cycles, the capacity retention rate reaches 78.6 percent.
Comparative example 2
The electrode material for a supercapacitor of this comparative example was Ti prepared in step (2) of example 13C2TxMXene powder, the difference with example 1 is that the biological carbon material prepared by high temperature calcination of ginkgo leaves under inert atmosphere is compounded.
Capacitor assembly and same conditions testing was performed using the same method as example 1, which was at 1A g-1The specific capacity of the lower test can reach 163.9F g-1(ii) a After 10000 times of charge-discharge cycles, the capacity retention rate reaches 72.6 percent.
Comparative example 3
The electrode material for a supercapacitor of this comparative example was Ti prepared in step (2) of example 13C2TxMXene powder, the difference from example 1 is that the biocarbon material prepared by high temperature calcination of shrimp shells under inert atmosphere is compounded.
Capacitor assembly and same conditions testing was performed using the same method as example 1, which was at 1A g-1The specific capacity of the lower test can reach 180.1F g-1(ii) a After 10000 times of charge-discharge cycles, the capacity retention rate reaches 79.6 percent.
As can be seen from the comparison between example 1 and comparative examples 1 to 3, the introduction of the carbon material in the form of graphene oxide is very important for obtaining a high-performance electrode material for a supercapacitor, and the excellent electrochemical performance of the present invention cannot be achieved unless graphene oxide is added to the raw material or replaced with another carbon source.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The electrode material for the super capacitor is characterized by comprising an MXene material and a graphene material.
2. The electrode material for the supercapacitor according to claim 1, wherein the MXene material is two-dimensional layered Ti3C2TxMXene material;
preferably, the graphene material includes at least one of graphene and reduced graphene oxide.
3. The electrode material for the supercapacitor according to claim 1 or 2, wherein the mass ratio of the MXene material to the graphene material is 1-99: 1, preferably 1-50: 1, and more preferably 7-15: 1.
4. A method for preparing the electrode material for a supercapacitor according to any one of claims 1 to 3, comprising the steps of:
(1) dissolving a graphene material and an MXene material in a solvent according to a formula amount to obtain a mixed solution;
(2) and carrying out hydrothermal reaction at 150-280 ℃ by adopting the mixed solution to obtain the electrode material for the supercapacitor.
5. The method according to claim 4, wherein the graphene material is at least one of graphene and reduced graphene oxide, preferably reduced graphene oxide;
preferably, the MXene material is two-dimensional layered Ti3C2TxMXene materials.
6. The method of claim 5,the two-dimensional layered Ti3C2TxThe MXene material is prepared by the following method:
(a) mixing titanium powder, aluminum powder and graphite, pressing into sheets after ball milling, calcining at 1000-1800 ℃ under the protection of protective gas, grinding the calcined product to obtain a polycrystalline MAX phase compound Ti3AlC2MXene powder;
(b) subjecting the Ti of step (a) to3AlC2MXene powder is dispersed in HF solution and stirred for reaction to obtain two-dimensional layered Ti3C2TxMXene materials.
7. The method according to claim 6, wherein in the step (a), the titanium powder, the aluminum powder and the graphite are mixed according to the atomic ratio of Ti, Al and C of 3 (1.05-1.2): 2;
preferably, the graphite of step (a) is flake graphite;
preferably, the protective gas of step (a) comprises at least one of nitrogen, argon and helium;
preferably, the calcining time of the step (a) is 2-5 h;
preferably, the concentration of the HF solution in the step (b) is 20-60%;
preferably, the stirring reaction time of the step (b) is 16-30 h;
preferably, after the stirring reaction of step (b), the steps of separating, washing and drying are performed;
preferably, the drying temperature is 50-100 ℃, and the drying time is 10-15 h;
preferably, the drying is vacuum drying, and the vacuum degree is-70 Kpa to-90 Kpa.
8. The method according to any one of claims 4 to 7, wherein the solvent of step (1) is water;
preferably, before the hydrothermal reaction in the step (2), the mixed solution is stirred for 1 to 2 hours;
preferably, the hydrothermal reaction time in the step (2) is 15-25 h;
preferably, after the hydrothermal reaction in the step (2), filtering, washing and drying steps are carried out;
preferably, the reagents used for washing include water and ethanol;
preferably, the drying temperature is 50-100 ℃, and the drying time is 10-15 h;
preferably, the drying is vacuum drying, and the vacuum degree is-70 Kpa to-90 Kpa.
9. Method according to any of claims 4-8, characterized in that the method comprises the steps of:
(1) preparation of reduced graphene oxide powder
Preparing a dispersed graphene aqueous solution by using graphite powder, reducing graphene oxide by using hydrogen peroxide to obtain reduced graphene oxide, and drying to obtain reduced graphene oxide powder;
(2) preparation of Ti3C2TxMXene material
The method comprises the following steps: taking titanium powder, aluminum powder and graphite, and mixing the titanium powder, the aluminum powder and the graphite in an atomic ratio of Ti: al: uniformly mixing C-3: 1.1:2, ball-milling for 1-3 h, and pressing under the pressure of 0.5-2 Gpa to prepare a wafer;
step two: putting the wafer pressed in the step one into a tube furnace, calcining for 2-5 h at 1000-1800 ℃ under the protection of inert gas, cooling to room temperature, taking out, grinding for 1h by using a mortar to obtain a polycrystalline MAX phase compound Ti3AlC2MXene powder;
step three: ti prepared in the second step3AlC2Dispersing MXene powder in an HF solution, and continuously stirring for 16-30 h at room temperature;
step four: after the reaction is finished, repeatedly washing the reaction product by deionized water, and centrifuging for 10 minutes at the rotating speed of 3800 rpm until the pH value of the supernatant is 6;
step five: vacuum drying the product washed in the fourth step at 50-100 ℃ for 10-15 h to obtain Ti3C2Tx MXene powder;
(3) preparation of electrode material for super capacitor
Step six: separately weighing Ti3C2TxDissolving MXene powder and reduced graphene oxide powder in deionized water, continuously stirring for 1-2 h, transferring to a high-pressure reaction kettle, and continuously reacting for 15-25 h at 150-280 ℃;
step seven: filtering the product obtained after the reaction in the sixth step, washing the product for 3 to 5 times by using pure water and ethanol, and finally drying the product for 10 to 15 hours in vacuum at the temperature of between 50 and 100 ℃ to obtain Ti3C2TxMXene/reduced graphene oxide composite material, namely electrode material for a supercapacitor.
10. A supercapacitor, characterized in that it comprises an electrode material according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011615547.4A CN112768253B (en) | 2020-12-30 | 2020-12-30 | High-performance electrode material for super capacitor, preparation method of high-performance electrode material and super capacitor |
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