CN108147464B - Rice-shaped manganese dioxide/titanium carbide composite material and preparation method thereof - Google Patents

Rice-shaped manganese dioxide/titanium carbide composite material and preparation method thereof Download PDF

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CN108147464B
CN108147464B CN201810107158.7A CN201810107158A CN108147464B CN 108147464 B CN108147464 B CN 108147464B CN 201810107158 A CN201810107158 A CN 201810107158A CN 108147464 B CN108147464 B CN 108147464B
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manganese dioxide
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titanium carbide
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CN108147464A (en
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朱建锋
李学林
王雷
武文玲
方园
张佩
卫丹
王芬
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Shaanxi University of Science and Technology
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Abstract

The invention provides a rice-shaped manganese dioxide/titanium carbide composite material and a preparation method thereof, and Ti is prepared by3C2The nano powder and the dopamine hydrochloride are respectively dispersed inMixing ultrapure water uniformly, and stirring under a shading condition; adding Tris-buffer solution, and continuously stirring under the shading condition; separating, washing and drying the obtained mixed solution to obtain Ti3C2@ PDA nano powder; mixing Ti3C2Adding the @ PDA nano powder into CTAB solution, adding KMnO after uniformly dispersing4Solution, carrying out liquid phase reaction; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material. The method can form uniformly distributed rice-shaped manganese dioxide on the surface of the titanium carbide, the obtained composite material has good electrochemical performance, the preparation method has low requirement on equipment, the operation is simple and convenient, the cost is low, and the method is favorable for realizing industrialized large-scale production.

Description

Rice-shaped manganese dioxide/titanium carbide composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of nano functional materials, and particularly relates to a rice-shaped manganese dioxide/titanium carbide composite material and a preparation method thereof.
Background
In recent years, the discovery of a class of materials known as MXene has expanded the family of two-dimensional materials, i.e., transition metal carbides or carbonitrides, whose structure is similar to that of graphene. MXene materials can be obtained by etching away the A-layer elements in the MAX phase of their precursors, and leaving the original MX structure unchanged, such as Ti3C2、Ti2C and the like. MXene has great application potential in the fields of lithium ion batteries, supercapacitors, photocatalysis, sensors and the like due to high conductivity, large specific surface area, multilayer structure, good chemical stability and environmental friendliness. However, Ti3C2The lamellar structure is easily stacked, thus reducing the specific surface area, affecting the diffusion of ions between the layers, degrading the electrochemical performance, and thus separating the lamellae. Mashtalir is etc[13]For Ti3C2Intercalation studies were performed on MXene materials using hydrazine and a mixture of hydrazine and dimethylformamide as the intercalating species, respectively, and the results of the tests showed that the interplanar spacing increased from 0.195nm to 0.2548 and 0.268nm, respectively. Naguib et al[20]It was found that the use of tetrabutylammonium hydroxide (TBAOH) makes delamination easier, thereby achieving MXene large scale delamination. Thus, chemical intercalation is an effective means for improving MXene nanosheet stacking, but such methods tend to be tedious in process and low in yield. The electrochemical performance of the single MXene sheet material is easily affected by stacking, another effective method for reducing the stacking of the sheet layer is to compound the sheet layer with other materials besides layering, and research on manufacturing the composite material by using MXene is also carried out. Zhao et al by sequential vacuum filtration of Ti3C2The suspension and the CNTs dispersion are repeated for a plurality of times to obtain flexible sandwich type Ti3C2the/CNT composite paper. Relatively pure Ti3C2In addition, the conductivity is more excellent, the volume capacitance is higher, and can reach about 350F/cm3And the volume capacitance is basically kept unchanged after 10000 times of cyclic charge and discharge.
In the electrode material of the existing super capacitor, the electrode material of the pseudo capacitor can perform continuous reversible Faraday redox reaction, so that the energy density of the electrode material of the pseudo capacitor is higher than that of the electrode material of the electric double layer capacitor. Therefore, by compounding MXene with pseudo-capacitance electrode materials (transition metal oxides, conductive polymers and the like), the problem that the MXene materials are easy to stack can be solved, and the electrochemical performance of the MXene materials can be remarkably improved. MnO2The material has low cost, wide source, good electrochemical performance and environmental protection, is widely applied to the battery industry, and has great application prospect as an active electrode material of an electrochemical capacitor. Pure manganese dioxide can reach 1370F/g of theoretical specific capacitance and is a potential electrode material. However, the poor cycle stability and low conductivity of pure manganese dioxide have caused difficulties in practical application of manganese dioxide. Studies have shown that manganese dioxide can be modified to achieve better capacitance performance.
Tang et al as Ti3C2Preparing MnO by using nano material as matrix and liquid phase precipitation method and heat treatment2-Ti3C2Nanocomposite material of MnO2Is granular and is applied to electrochemical capacitors, but the specific capacity of the electrochemical capacitor is smaller. Rakhi et al chemically synthesized deposit of epsilon-MnO on MXene sheets2Nano-whisker to improve specific capacity of MXene material, but MnO obtained by the direct chemical synthesis method2Tend to agglomerate easily in Ti3C2The surface distribution is not uniform, thereby affecting the electrochemical performance thereof. Liu et al vacuum filtered Ti3C2And MnO with MnO2Mixing the solution to obtain flexible composite paper for increasing Ti content3C2But this approach does not allow control over the structure of the composite.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a rice-shaped manganese dioxide/titanium carbide composite material and a preparation method thereof, wherein dopamine is utilized in Ti3C2Coating a thin Polydopamine (PDA) layer on the surface, and then adopting KMnO with lower cost4Preparing a manganese dioxide/titanium carbide composite material by using Cetyl Trimethyl Ammonium Bromide (CTAB) as a manganese source and a surfactant, wherein the manganese dioxide is in Ti3C2The surface is uniformly and firmly distributed, and the Ti content is effectively improved3C2Electrochemical properties of the nanomaterial.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method comprises the following steps:
a preparation method of rice-shaped manganese dioxide/titanium carbide composite material comprises the following steps:
step 1, preparing Ti3C2@ PDA nano powder;
step 2, preparing a CTAB solution; mixing Ti3C2@ PDA nano powder and KMnO4Adding the mixture into a CTAB solution, uniformly dispersing, heating to 50-90 ℃, stirring and reacting for 1-6 h to obtain rice-shaped manganese dioxideA titanium carbide composite material.
Preferably, step 1 specifically comprises: mixing Ti3C2Dispersing the nano powder and dopamine hydrochloride in water, uniformly mixing, and stirring under a shading condition; adding Tris-buffer solution, and stirring under the condition of shading; separating, washing and drying the obtained mixed solution to obtain Ti3C2@ PDA nano powder.
Preferably, the CTAB solution prepared in step 2 is specifically: preparing 50-500 mmol L-1Stirring to dissolve CTAB completely in water.
Preferably, KMnO in step 24By adopting KMnO4And (3) solution.
Further, CTAB solution and Ti in the step 23C2@ PDA nano powder and KMnO4The ratio of the solution is (5 to 50) mL: (10-100) mg: (5-50) mL, wherein the concentration of CTAB solution is 50-500 mmol L-1，KMnO4The concentration of the solution is 20-300 mmol L-1。
Preferably, Ti in step 23C2Adding the @ PDA nano powder into CTAB solution, adding KMnO after uniformly dispersing4。
Further, Ti in step 23C2Adding the @ PDA nano powder into CTAB solution, firstly performing ultrasonic dispersion, then uniformly stirring, and then adding KMnO4。
Preferably, the reaction in step (2) is carried out under water bath conditions.
The rice-shaped manganese dioxide/titanium carbide composite material prepared by the preparation method is provided.
Compared with the prior art, the invention has the following beneficial technical effects:
the poly-dopamine is an environment-friendly biological macromolecular product obtained by auto-oxidation polymerization of dopamine monomers in a weakly alkaline environment. Research shows that the autoxidation polymerization of dopamine can form polydopamine coating on the surface of many organic or inorganic substrates, and the polydopamine coating has strong bonding force with the substrates (such as ceramics, metal oxides, polymers and the like) and has a structure containing polydopamineAnd a large number of nitrogen-containing groups and phenolic hydroxyl groups exist, and polydopamine can be used as a good secondary reaction platform. The invention firstly utilizes the autoxidation polymerization of dopamine in a weak alkaline environment in Ti3C2Coating very thin PDA layer on the surface to obtain Ti3C2@ PDA composite material, then with Ti3C2@ PDA as matrix, KMnO4As manganese source, cetyl trimethyl ammonium bromide is used as surfactant, and the rice-shaped manganese dioxide/titanium carbide composite material is prepared through simple liquid phase reaction. On the one hand, due to the fact that in KMnO4During the high temperature reaction of (2), Ti3C2In the Ti, Ti is also partially oxidized to form TiC, thereby destroying Ti3C2Resulting in a decrease in electrochemical performance, the present invention is in Ti3C2Surface coating with PDA, coating layer with PDA can protect Ti3C2Structural integrity, avoidance of Ti therein by KMnO4The oxidation causes structural damage, which affects the electrochemical performance. On the other hand, Mn7+The ion outer layer has an empty electron orbit, two phenolic hydroxyl groups of the catechol group of the PDA can provide two pairs of lone pair electrons, and the catechol group and Mn in a neutral or alkaline environment7+The ions can form stable chelating ligand, the existence of the chelation provides a site for the growth or deposition of metal compounds on the surface of PDA, namely the PDA can react with Mn7+Is fixed on Ti3C2The surface of the sheet layer, and PDA itself has weak reducibility, Mn can be converted7 +Reduction to Mn4+In MnO2Form distribution in Ti3C2The surface of the lamella and the presence of catechol groups on PDA make the PDA have strong adhesion, so that the generated rice-grain manganese dioxide can be firmly adhered to Ti3C2The surface of the lamella is not easy to agglomerate, thereby being coated on Ti3C2The surface of the sheet layer can be uniformly distributed for a long time. In addition, CTAB was dissolved and then ionized to give CTA+，CTA+The front end of the CTAB is a positively charged hydrophilic group, the tail end of the CTAB is a long-chain hydrophobic group, and when the concentration of the CTAB in a solution reaches the Critical Micelle Concentration (CMC), micelles can be formed; when potassium permanganate is initially added, CTAB is oxidized by the strong oxidizing property of potassium permanganateAfter the potassium manganate is gradually reduced, the residual CTAB reaches the critical micelle concentration, and spherical micelles are formed; MnO as the reaction proceeds2After nucleation, the aggregates to the outer layer of spherical micelles, MnO2The growth of the manganese dioxide particles starts to be preferred orientation and becomes rice-shaped, and the content of the rice-shaped manganese dioxide increases along with the increase of the CTAB dosage. The obtained composite material has excellent electrochemical performance, and lays a foundation for further application in the fields of super capacitors, lithium ion batteries and the like. In addition, the simple pyrolysis method has the advantages of low requirement on equipment, simple and convenient operation, low cost and the like, and is favorable for realizing industrialized large-scale production.
Drawings
FIG. 1 is a SEM image (a) and an XRD image (b) (abscissa is X-ray incidence angle and ordinate is intensity) of the rice-shaped manganese dioxide/titanium carbide composite material prepared in example 2.
FIG. 2 is a graph of CV curves (voltage on the abscissa and current density on the ordinate) for the rice-grain manganese dioxide/titanium carbide composite (a) prepared in example 2 at different sweep rates (0.002V/s-0.2V/s); (b) the capacity is plotted against the scan rate (scan rate on the abscissa and unit capacitance on the ordinate).
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
The preparation method comprises the following steps:
step one, ternary layered Ti3AlC2Preparing ceramic powder;
synthesizing ternary layered Ti according to the method of patent ZL201310497696.93AlC2The preparation method of the ceramic powder comprises the following steps: firstly, the experimental raw materials of TiC, Ti and Al powder are TiC: ti: al 2.0: 1.0: 1.2, mixing materials; secondly, mixing the mixed material, alumina ball stone and absolute ethyl alcohol according to the proportion of 1: 3: 1, ball milling in a corundum ball milling tank, wherein absolute ethyl alcohol is used as a ball milling auxiliary agent, alumina ball stones are used as grinding media, the rotating speed of the ball mill is 300r/min, and the ball is milled for 4 hours by a wet method and then dried for 24 hours in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is mixedPlacing into corundum crucible, vacuum pressureless sintering in vacuum hot-pressing carbon tube furnace at a heating rate of 8 deg.C/min, heating to 1350 deg.C, maintaining for 1 hr with vacuum degree less than 10-2Pa, cooling to room temperature along with the furnace after heat preservation is finished; and finally, carrying out dry high-energy ball milling on the sintered powder for 2 hours at the rotating speed of 400r/min, wherein the ratio of the powder to the ball stone is 1: 10, sieving the ground powder by a 400-mesh sieve to obtain Ti with the particle size of less than 38 mu m3AlC2Ceramic powder.
Step two, two-dimensional layered Ti3C2Preparing a nano material;
preparation of two-dimensional layered Ti according to the method of patent 201410812056.73C2The preparation method of the nano material comprises the following specific steps of mixing 5g of Ti prepared in the step (1)3AlC2Slowly immersing the powder in 100mL of 40 wt.% hydrofluoric acid solution, magnetically stirring for 24h at room temperature at the rotating speed of 1200r/min, centrifugally separating the corrosion product, centrifugally cleaning with ultrapure water at 4500r/min until the pH value of the supernatant is about 6, cleaning with absolute ethyl alcohol for 5 times, and drying the obtained precipitate in a vacuum drying oven at 40 ℃ for 24h to obtain the two-dimensional layered Ti3C2And (3) nano powder.
Preparing titanium carbide @ PDA nano powder;
firstly, mixing 300-500 mg Ti3C2Ultrasonically dispersing the nano powder in 30-300 mL of ultrapure water, and ultrasonically treating for 30 min; dissolving 0.1-1.0 g of dopamine hydrochloride in 10-100 mL of ultrapure water, adding the solution, and stirring at room temperature for 0.5-2 hours under the shading condition; or 300-500 mg of Ti3C2Adding 40-400 mL of nano powder into 12.5-14.0 mmol L-1Stirring the dopamine hydrochloride solution at room temperature in a shading mode for 0.5-2 hours; completing the liquid phase reaction;
then adding 10-100 mL of Tris-buffer solution (50mmol L)-1And the pH value is 8.5), stirring at room temperature for 12-48 h under the shading condition; centrifugally separating the obtained mixed solution, washing with deionized water until the supernatant is clear, transferring into a freeze dryer, and taking out after 48h to obtain Ti3C2@PDA。
Specifically, 500mg of Ti was added3C2Nano meterRespectively dispersing the powder and 0.25g of dopamine hydrochloride in ultrapure water, uniformly mixing, and stirring for 1h under the shading condition; then adding 25mL of Tris-buffer solution, and continuing stirring for 24h under the shading condition; separating, washing and drying the obtained mixed solution to obtain Ti3C2@ PDA nano powder.
Preparing a rice-shaped manganese dioxide/titanium carbide composite material;
firstly, 5-50 mL of 50-500 mmol L is prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 10-100 mg of Ti obtained in the step (1)3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after stirring uniformly, adding 5-50 mL of 20-300 mmol L-1KMnO4Heating the solution in a water bath at 50-90 ℃, and stirring for reaction for 1-6 h; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 1
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 30mg of Ti3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after stirring uniformly, 10mL of 50mmol L is added-1KMnO4Heating the solution in 70 ℃ water bath, and stirring for reaction for 3 hours; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 2
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 30mg of Ti3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after stirring uniformly, 10mL of 100mmol L is added-1KMnO4Heating the solution in 70 ℃ water bath, and stirring for reaction for 3 hours; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 3
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; will be provided with30mg of Ti3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after stirring evenly, 10mL of 200mmol L is added-1KMnO4Heating the solution in 70 ℃ water bath, and stirring for reaction for 3 hours; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 4
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 30mg of Ti3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after stirring uniformly, 10mL of 100mmol L is added-1KMnO4Heating the solution in 70 ℃ water bath, and stirring for reaction for 1 h; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 5
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 30mg of Ti3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after stirring uniformly, 10mL of 100mmol L is added-1KMnO4Heating the solution in 70 ℃ water bath, and stirring for reaction for 2 hours; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 6
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 30mg of Ti3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after stirring uniformly, 10mL of 100mmol L is added-1KMnO4Heating the solution in 70 ℃ water bath, and stirring for reaction for 4 hours; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 7
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 30mg of Ti3C2Adding @ PDA nano powder into CTAB solutionPerforming ultrasonic dispersion for 30min, and stirring for 1 h; after stirring uniformly, 10mL of 100mmol L is added-1KMnO4Heating the solution in 70 ℃ water bath, and stirring for reaction for 5 hours; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 8
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 30mg of Ti3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after stirring uniformly, 10mL of 100mmol L is added-1KMnO4Heating the solution in 70 ℃ water bath, and stirring for reaction for 6 hours; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 9
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 30mg of Ti3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after stirring uniformly, 10mL of 100mmol L is added-1KMnO4Heating the solution in water bath at 50 ℃, and stirring for reaction for 3 hours; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 10
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 30mg of Ti3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after stirring uniformly, 10mL of 100mmol L is added-1KMnO4Heating the solution in water bath at 60 ℃, and stirring for reaction for 3 hours; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 11
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 30mg of Ti3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after being stirred evenly, 10 portions are addedmL of 100mmol L-1KMnO4Heating the solution in water bath at 80 ℃, and stirring for reaction for 3 hours; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 12
First, 10mL of 100mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 30mg of Ti3C2Adding the @ PDA nano powder into the CTAB solution, performing ultrasonic dispersion for 30min, and stirring for 1 h; after stirring uniformly, 10mL of 100mmol L is added-1KMnO4Heating the solution in water bath at 90 ℃, and stirring for reaction for 3 hours; and naturally cooling after the reaction is finished to obtain the rice-grain-shaped manganese dioxide/titanium carbide composite material.
Example 13
First, 5mL of 50mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; adding 10mg of Ti3C2Adding @ PDA nano powder into PEG solution, and ultrasonically dispersing for 30 min; then, 5mL of 20mmol L was added- 1KMnO4Heating the solution in water bath at 90 ℃, and stirring for reaction for 1 h; and naturally cooling after the reaction is finished to obtain the manganese dioxide nanosheet/titanium carbide composite material.
Example 14
First, 30mL of 50mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 50mg of Ti3C2Adding @ PDA nano powder into PEG solution, and ultrasonically dispersing for 30 min; then, 30mL of 200mmol L was added- 1KMnO4Heating the solution in water bath at 90 ℃, and stirring for reaction for 1 h; and naturally cooling after the reaction is finished to obtain the manganese dioxide nanosheet/titanium carbide composite material.
Example 15
First, 50mL of 300mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 70mg of Ti3C2Adding @ PDA nano powder into PEG solution, and ultrasonically dispersing for 30 min; then, 30mL of 300mmol L was added-1KMnO4Heating the solution in water bath at 90 ℃, and stirring for reaction for 1 h; naturally cooling after the reaction is finishedThus obtaining the manganese dioxide nano-sheet/titanium carbide composite material.
Example 16
First, 50mL of 500mmol L was prepared-1Stirring the CTAB solution at room temperature for 30min to completely dissolve the CTAB in the ultrapure water; 100mg of Ti3C2Adding @ PDA nano powder into PEG solution, and ultrasonically dispersing for 30 min; then, 50mL of 100mmol L was added-1KMnO4Heating the solution in water bath at 90 ℃, and stirring for reaction for 1 h; and naturally cooling after the reaction is finished to obtain the manganese dioxide nanosheet/titanium carbide composite material.
FIG. 1 is an SEM image and an XRD image of the rice-grain manganese dioxide/titanium carbide composite material obtained in example 2. It can be seen that the rice-grain manganese dioxide is uniformly distributed in Ti3C2The specific surface area of the layered material is obviously improved and the distance between the layers is increased on the two sides of the layers, so that the electrochemical performance of the rice-grain-shaped manganese dioxide/titanium carbide composite material is better than that of pure Ti3C2。
An electrode was prepared using the rice-grain manganese dioxide/titanium carbide composite obtained in example 2: firstly, 50mg of rice-grain manganese dioxide/titanium carbide composite material, conductive carbon black and a binder (PVDF) are mixed according to a mass ratio of 80:10:10, a proper amount of N-methyl-pyrrolidone is added, and the mixture is ground in an agate mortar for 10 min. Next, the suspension was dropped onto a 2cm by 1cm area of foamed nickel using a pipette, and the active material area was 1cm by 1 cm. Then, the mixture was dried in a vacuum oven at 120 ℃ for 12 hours. And finally, maintaining the pressure of the dried electrode slice under a press at 20Mpa for 1min to obtain the rice-shaped manganese dioxide/titanium carbide electrode.
Adopting a three-electrode testing system, assembling the prepared rice-grain-shaped manganese dioxide/titanium carbide electrode (working electrode), a platinum electrode (counter electrode) and a saturated calomel electrode (reference electrode) into a simple super capacitor in an electrolytic cell, wherein the electrolyte is 1.0mol/L Na2SO4The solution was used to test the electrochemical performance of the manganese dioxide/titanium carbide electrodes, such as cyclic voltammetry, constant current charging and discharging, ac impedance and cyclic life, using the electrochemical workstation of shanghai chenhua CHI 660E. FIG. 2 shows that (a) is manganese dioxide in the form of rice grainsCV curve diagram of titanium carbide under different sweep speeds (0.002V/s-0.2V/s), and (b) is the variation curve of the capacity with sweep speed, which shows that the capacity is purer than that of Ti3C2The method has great promotion.
The preparation method of the rice-shaped manganese dioxide/titanium carbide composite material comprises the following steps: high-purity fine-grain ternary layered Ti3AlC2Synthesizing powder; treatment of Ti by etching with HF solution3AlC2Selective etching away of ternary layered Ti3AlC2Preparing two-dimensional layered Ti from the Al layer3C2A nanomaterial; with Ti3C2As a carrier, dopamine is firstly utilized to carry out auto-oxidative polymerization on Ti in a weak alkaline environment3C2Coating very thin PDA layer on the surface to obtain Ti3C2The coating layer PDA can prevent Ti in the Ti3C2 structure from being oxidized in the reaction process, so that the integrity of the Ti3C2 structure is protected; then with Ti3C2@ PDA as matrix, KMnO4The manganese source is cetyl trimethyl ammonium bromide is used as a surfactant, the rice-shaped manganese dioxide/titanium carbide composite material is prepared by simple liquid phase reaction, and the PDA structure contains a large amount of nitrogen-containing groups and phenolic hydroxyl groups, and the phenolic hydroxyl groups can react with Mn7+Fixing the manganese dioxide in the position by ion chelation, reducing the manganese dioxide into manganese dioxide, enabling PDA to have strong adhesion by phenolic hydroxyl, and firmly and uniformly distributing the rice-shaped manganese dioxide on Ti3C2The surfaces of the lamellae are not easy to agglomerate. CTAB added forms spherical micelles during the reaction, MnO2Aggregated to the outer layer of spherical micelles after nucleation, thereby MnO2The rice grains grow in a preferred orientation. The obtained composite material has excellent electrochemical performance. This is for expanding Ti3C2The application of the material in the fields of super capacitors, lithium ion batteries and the like has important practical significance. Compared with other reported preparation methods, the method has the advantages of simpler required experimental conditions, low cost and easy operation.

Claims (9)

1. The preparation method of the rice-shaped manganese dioxide/titanium carbide composite material is characterized by comprising the following steps of:
step 1, preparing Ti3C2@ PDA nano powder;
step 2, preparing a CTAB solution; mixing Ti3C2@ PDA nano powder and KMnO4Adding the mixture into a CTAB solution, uniformly dispersing, heating to 50-90 ℃, and stirring for reaction for 1-6 hours to obtain the rice-shaped manganese dioxide/titanium carbide composite material.
2. The method for preparing rice-shaped manganese dioxide/titanium carbide composite material according to claim 1, wherein the step 1 specifically comprises: mixing Ti3C2Dispersing the nano powder and dopamine hydrochloride in water, uniformly mixing, and stirring under a shading condition; adding Tris-buffer solution, and stirring under the condition of shading; separating, washing and drying the obtained mixed solution to obtain Ti3C2@ PDA nano powder.
3. The method for preparing a rice-shaped manganese dioxide/titanium carbide composite material as claimed in claim 1, wherein the CTAB solution prepared in the step 2 is specifically: preparing 50-500 mmol L-1Stirring to dissolve CTAB completely in water.
4. The method of claim 1, wherein KMnO is used in step 24By adopting KMnO4And (3) solution.
5. The method of claim 4, wherein the CTAB solution and Ti are added in step 23C2@ PDA nano powder and KMnO4The ratio of the solution is (5 to 50) mL: (10-100) mg: (5-50) mL, wherein the concentration of CTAB solution is 50-500 mmol L-1，KMnO4The concentration of the solution is 20-300 mmol L-1。
6. According to the claimsThe method of claim 1, wherein the step 2 is a step of preparing a rice-shaped manganese dioxide/titanium carbide composite material3C2Adding the @ PDA nano powder into CTAB solution, adding KMnO after uniformly dispersing4。
7. The method of claim 6, wherein the step 2 is performed in a manner such that Ti is present in the form of rice-grain manganese dioxide/titanium carbide composite3C2Adding the @ PDA nano powder into CTAB solution, firstly performing ultrasonic dispersion, then uniformly stirring, and then adding KMnO4。
8. The method of claim 1, wherein the step 2 is carried out in a water bath.
9. A rice-grain manganese dioxide/titanium carbide composite material obtained by the production method according to any one of claims 1 to 8.
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