阅读说明：本技术 一种碳化钛-碳核壳阵列负载垂直石墨烯/二氧化锰复合材料及其制备方法和应用 (Titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material and preparation method and application thereof ) 是由 夏新辉 张永起 于 2021-08-12 设计创作，主要内容包括：本发明提供了一种碳化钛-碳核壳阵列负载垂直石墨烯/二氧化锰复合材料及其制备方法和应用,其制备方法,包括以下步骤：将清洗后的基底放置在等离子体石英管中,通过化学气相沉积法制得碳化钛-碳核壳阵列；以碳化钛-碳核壳阵列为载体置于离子体石英管中,通过化学气相沉积法制得碳化钛-碳核壳阵列负载垂直石墨烯复合材料；将碳化钛-碳核壳阵列负载垂直石墨烯复合材料置于原子层沉积仪中,原子层沉积法制得碳化钛-碳核壳阵列负载垂直石墨烯/二氧化锰复合材料。本发明还包括采用上述方法制得的复合材料及其在锌离子电池中的应用。本发明的碳化钛-碳核壳阵列负载垂直石墨烯/二氧化锰复合电极材料具有高比容量、高倍率性能及高循环寿命。(The invention provides a titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: placing the cleaned substrate in a plasma quartz tube, and preparing a titanium carbide-carbon core-shell array by a chemical vapor deposition method; placing the titanium carbide-carbon core-shell array as a carrier in a plasma quartz tube, and preparing the titanium carbide-carbon core-shell array loaded vertical graphene composite material by a chemical vapor deposition method; and placing the titanium carbide-carbon core-shell array loaded vertical graphene composite material in an atomic layer deposition instrument, and preparing the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material by an atomic layer deposition method. The invention also comprises the composite material prepared by the method and the application of the composite material in zinc ion batteries. The titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite electrode material has high specific capacity, high rate capability and long cycle life.)

1. A preparation method of a titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material is characterized by comprising the following steps:

(1) placing the cleaned substrate in a plasma quartz tube, carrying a reaction carbon source of acetone into the plasma quartz tube by argon bubbling at the temperature of 600-;

(2) placing the titanium carbide-carbon core-shell array obtained in the step (1) as a carrier in a plasma quartz tube, taking a mixed gas of argon, hydrogen and methane as a plasma reaction gas, taking a reaction carbon source as methane, and cooling to obtain the titanium carbide-carbon core-shell array loaded vertical graphene composite material under the conditions of the temperature of 800 ℃ at 300-;

(3) and (3) placing the titanium carbide-carbon core-shell array loaded vertical graphene composite material obtained in the step (2) in an atomic layer deposition instrument, taking 0.01-0.1mol/L manganese nitrate and deionized water as reaction sources, reacting at the temperature of 100-200 ℃, wherein the atomic layer deposition period is 100-300 weeks, and then carrying out heat treatment at the temperature of 200-500 ℃ in an argon atmosphere for 3-6 hours to obtain the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material.

2. The method for preparing the titanium carbide-carbon core-shell array supported vertical graphene/manganese dioxide composite material according to claim 1, wherein the substrate is a titanium-aluminum-vanadium alloy sheet.

3. The method for preparing the titanium carbide-carbon core-shell array supported vertical graphene/manganese dioxide composite material as claimed in claim 1, wherein in the step (2), the flow rate of argon gas is 10-50sccm, the flow rate of hydrogen gas is 10-50sccm, and the flow rate of methane is 5-20 sccm.

4. The titanium carbide-carbon core-shell array-supported vertical graphene/manganese dioxide composite material prepared by the method for preparing the titanium carbide-carbon core-shell array-supported vertical graphene/manganese dioxide composite material according to any one of claims 1 to 3.

5. The titanium carbide-carbon core-shell array-loaded vertical graphene/manganese dioxide composite material of claim 4, wherein the titanium carbide-carbon core-shell array diameter is 200-600nm, and the vertical graphene/manganese dioxide thickness is 300-800 nm.

6. The titanium carbide-carbon core-shell array supported vertical graphene/manganese dioxide composite of claim 4, wherein the titanium carbide-carbon core-shell array supported vertical graphene/manganese dioxide composite has a diameter of 500nm to 1.5 μm.

7. The titanium carbide-carbon core-shell array supported vertical graphene/manganese dioxide composite material according to claim 4, wherein the titanium carbide-carbon core-shell array is of a core-shell nanorod structure, wherein titanium carbide is an inner core and carbon is an outer shell.

8. The titanium carbide-carbon core-shell array supported vertical graphene/manganese dioxide composite material according to claim 4, wherein the vertical graphene/manganese dioxide is in a core-shell structure, and manganese dioxide nanoparticles are uniformly coated on the vertical graphene.

9. Use of the titanium carbide-carbon core-shell array supported vertical graphene/manganese dioxide composite of any one of claims 4 to 8 in a zinc ion battery.

10. Use of the titanium carbide-carbon core-shell array supported vertical graphene/manganese dioxide composite material of any one of claims 4 to 8 in a zinc ion battery positive electrode material.

Technical Field

The invention belongs to the technical field of composite material preparation, and particularly relates to a titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material, and a preparation method and application thereof.

Background

With the rapid development of electric transportation, mobile communication and large-scale energy storage industries, electrochemical energy storage devices (such as lithium ion batteries) and materials are meeting a brand new development opportunity and are receiving market pursuit. But lithium metal is a limited resource and is unevenly distributed, resulting in high price. Meanwhile, the production cost of the lithium ion battery is higher due to the harsh condition that the lithium ion battery must be manufactured in a waterless environment. In addition, the organic electrolyte adopted by the lithium ion battery is usually toxic and flammable, and has potential safety hazards. In view of this, new high-safety aqueous zinc ion batteries have been attracting attention. The ion conductivity of the aqueous zinc ion battery electrolyte is 2 orders of magnitude higher than that of the organic electrolyte, so that the aqueous zinc ion battery electrolyte has higher power density, convenient manufacturing environment and lower cost. In addition, zinc has a low equilibrium potential and a high hydrogen evolution overpotential, and is a low-potential element that can be efficiently reduced from an aqueous solution. Meanwhile, among the metal elements that can be stabilized in an aqueous solution, zinc is also the highest in energy. The metal zinc has the advantages of rich resources, low toxicity, easy treatment and the like. Therefore, a secondary zinc ion aqueous battery which is inexpensive, highly safe, free from environmental pollution and high in power characteristics is an ideal green battery system.

The zinc has large atomic mass, and strong electrostatic interaction exists between zinc ions and the crystal structure of the anode material, so that the ion transport kinetics is slow, the coulombic efficiency is low, and the multiplying power performance is poor. Therefore, it is imperative to design and construct a new high-performance positive electrode material for zinc ion batteries. The manganese dioxide-based material has high zinc storage capacity and high energy density, and the internal layered structure of the crystal can effectively accommodate the rapid embedding and the extraction of zinc ions. However, manganese dioxide has a low electronic conductivity, resulting in poor rate capability and cycle performance.

Therefore, compounding manganese dioxide with carbon materials (such as titanium carbide-carbon core-shell arrays and vertical graphene) is an effective way to improve its electrical conductivity and structural stability. The carbon material mainly benefits from the excellent characteristics of high chemical stability, high conductivity, large specific surface area and the like of the carbon material (titanium carbide-carbon core-shell array and vertical graphene). Meanwhile, the contact area of the electrode material and the electrolyte is increased by the manganese dioxide nano-particle material, so that electron transmission is facilitated, and higher capacitance can be provided. In addition, the vertical graphene provides stable structural support for the manganese dioxide, so that the manganese dioxide keeps stable structure and is not easy to collapse in the electrochemical charging and discharging process, and good multiplying power and cycle performance are obtained. The scheme combines the double advantages of carbon materials such as titanium carbide-carbon core-shell arrays and vertical graphene and manganese dioxide, and is an effective strategy for constructing the high-performance zinc ion battery.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material, and a preparation method and application thereof.

In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material comprises the following steps:

(1) placing the cleaned substrate in a plasma quartz tube, carrying a reaction carbon source of acetone into the plasma quartz tube by argon bubbling at the temperature of 600-;

(2) placing the titanium carbide-carbon core-shell array obtained in the step (1) as a carrier in a plasma quartz tube, taking a mixed gas of argon, hydrogen and methane as a plasma reaction gas, taking a reaction carbon source as methane, and cooling to obtain the titanium carbide-carbon core-shell array loaded vertical graphene composite material under the conditions of the temperature of 800 ℃ at 300-;

(3) and (3) placing the titanium carbide-carbon core-shell array loaded vertical graphene composite material obtained in the step (2) in an atomic layer deposition instrument, taking 0.01-0.1mol/L manganese nitrate and deionized water as reaction sources, reacting at the temperature of 100-200 ℃, wherein the atomic layer deposition period is 100-300 weeks, and then carrying out heat treatment at the temperature of 200-500 ℃ in an argon atmosphere for 3-6 hours to obtain the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material.

Further, the substrate is a titanium-aluminum-vanadium alloy sheet.

Further, in the step (2), the argon flow rate is 10-50sccm, the hydrogen flow rate is 10-50sccm, and the methane flow rate is 5-20 sccm.

The titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material prepared by the preparation method of the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material.

Further, the diameter of the titanium carbide-carbon core-shell array is 200-800 nm, and the thickness of the vertical graphene/manganese dioxide is 300-800 nm.

Further, the diameter of the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material is 500nm-1.5 microns.

Further, the titanium carbide-carbon core-shell array is of a core-shell nanorod structure, wherein titanium carbide is an inner core, and carbon is an outer shell.

Further, the vertical graphene/manganese dioxide is of a core-shell structure, wherein the manganese dioxide nanoparticles are uniformly coated on the vertical graphene.

The titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite electrode material can adjust reaction time, reaction concentration and reaction temperature to control the size, thickness and mutual component ratio of the titanium carbide-carbon core-shell array and the vertical graphene/manganese dioxide according to actual needs.

The titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite electrode material has high specific capacity, long cycle life and high rate performance, and has wide application prospects in the fields of small-sized mobile electronic equipment, electric automobiles, solar power generation, aerospace and the like.

The titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material is applied to a zinc ion battery.

The titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material is applied to a zinc ion battery anode material.

In summary, the invention has the following advantages:

1. according to the invention, a titanium carbide-carbon core-shell array synthesized by a plasma chemical vapor deposition method is taken as a carrier, and then the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite electrode material is prepared by the plasma chemical vapor deposition method and the atomic layer deposition method. The preparation method is convenient to operate, easy to control and high in preparation precision.

2. The titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite electrode material has excellent high-rate cycle life, the specific capacity reaches more than 270mAh/g under the condition of 2A/g working current density, and the capacity is kept more than 80% after 1000-cycle circulation.

3. The titanium carbide-carbon core-shell array and the vertical graphene in the composite material both have excellent chemical stability and high electronic conductivity. Meanwhile, the porous core-shell structure provides a larger and more effective active reaction area, provides a good ion and electron diffusion channel for electrochemical reaction, shortens the diffusion distance of ions, accelerates the electrochemical reaction process, and improves the cycle stability and the rate capability of the electrochemical reaction process, thereby realizing the novel zinc ion battery electrode material with high energy density, good cycle performance, reliability and safety.

Drawings

FIG. 1 is a scanning electron micrograph of a titanium carbide-carbon core-shell array obtained in example 1;

FIG. 2 is a transmission electron micrograph of the titanium carbide-carbon core-shell array obtained in example 1;

FIG. 3 is a scanning electron microscope image of the titanium carbide-carbon core-shell array loaded with vertical graphene obtained in example 1;

FIG. 4 is a transmission electron microscope image of the titanium carbide-carbon core-shell array loaded with vertical graphene obtained in example 1;

FIG. 5 is a transmission electron microscope image of the titanium carbide-carbon core-shell array loaded with vertical graphene/manganese dioxide obtained in example 1;

fig. 6 is a graph of the cycling performance of the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide prepared in example 1 at a current density of 2A/g.

Detailed Description

Example 1

A titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material is prepared by the following steps:

(1) placing the cleaned titanium-aluminum-vanadium alloy sheet substrate in a plasma quartz tube, carrying a reaction carbon source of acetone into the plasma quartz tube by argon bubbling at the temperature of 600 ℃, under the vacuum degree of 10Pa and under the plasma strength of 300W, wherein the argon flow is 150sccm, the reaction time is 1h, and cooling to obtain a titanium carbide-carbon core-shell array;

(2) placing the titanium carbide-carbon core-shell array obtained in the step (1) as a carrier in a plasma quartz tube, taking a mixed gas of argon, hydrogen and methane as a plasma reaction gas under the conditions of 300 ℃ temperature, 5Pa vacuum degree and 300W plasma intensity, wherein the argon flow is 10sccm, the hydrogen flow is 10-sccm, the methane flow is 5sccm, a reaction carbon source is methane, the reaction time is 5min, and cooling to obtain the titanium carbide-carbon core-shell array loaded vertical graphene composite material;

(3) and (3) placing the titanium carbide-carbon core-shell array loaded vertical graphene composite material obtained in the step (2) in an atomic layer deposition instrument, taking 0.01mol/L manganese nitrate and deionized water as reaction sources, reacting at 100 ℃, performing atomic layer deposition for 100 weeks, and performing heat treatment at 200 ℃ for 3 hours in an argon atmosphere to obtain the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material.

And (3) analyzing the titanium carbide-carbon core-shell array obtained in the step (1) by a scanning electron microscope and a transmission electron microscope, wherein the results are respectively shown in a figure 1 and a figure 2.

As can be seen from fig. 1-2, the titanium carbide-carbon carrier is a core-shell nanorod structure, titanium carbide is a core, carbon is a shell, and the average diameter is 100 nm.

And (3) analyzing the titanium carbide-carbon core-shell array loaded vertical graphene composite material obtained in the step (2) by a scanning electron microscope and a transmission electron microscope, wherein the results are respectively shown in fig. 3 and fig. 4.

As shown in fig. 3-4, the vertical graphene is uniformly coated on the titanium carbide-carbon core-shell array carrier, and the diameter width of the vertical graphene is 200-300 nm.

The titanium carbide-carbon core-shell array-supported vertical graphene/manganese dioxide composite material obtained in example 1 was analyzed by transmission electron microscopy, as shown in fig. 5.

As can be seen from fig. 5, the manganese dioxide nanoparticles are uniformly compounded on the vertical graphene, and the diameter of the manganese dioxide nanoparticles is 20-50 nm; the diameter of the whole composite structure is about 600 nm; the ratio of manganese dioxide to vertical graphene and titanium carbide-carbon was 40:10: 50.

Example 2

A titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material is prepared by the following steps:

(1) placing the cleaned titanium-aluminum-vanadium alloy sheet substrate in a plasma quartz tube, carrying a reaction carbon source of acetone into the plasma quartz tube by argon bubbling at the temperature of 750 ℃, under the vacuum degree of 20Pa and under the plasma strength of 500W, wherein the argon flow is 225sccm, the reaction time is 3h, and cooling to obtain a titanium carbide-carbon core-shell array;

(2) placing the titanium carbide-carbon core-shell array obtained in the step (1) as a carrier in a plasma quartz tube, taking a mixed gas of argon, hydrogen and methane as a plasma reaction gas, wherein the argon flow is 25sccm, the hydrogen flow is 25sccm, the methane flow is 15sccm, a reaction carbon source is methane, the reaction time is 15min, and cooling to obtain the titanium carbide-carbon core-shell array loaded vertical graphene composite material under the conditions of 600 ℃ temperature, 15Pa vacuum degree and 600W plasma intensity;

(3) and (3) placing the titanium carbide-carbon core-shell array loaded vertical graphene composite material obtained in the step (2) in an atomic layer deposition instrument, taking 0.05mol/L of manganese nitrate and deionized water as reaction sources, reacting at the temperature of 150 ℃, wherein the atomic layer deposition period is 200 weeks, and then carrying out heat treatment at the temperature of 350 ℃ for 4.5 hours in an argon atmosphere to obtain the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material.

Example 3

A titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material is prepared by the following steps:

(1) placing the cleaned titanium-aluminum-vanadium alloy sheet substrate in a plasma quartz tube, carrying a reaction carbon source of acetone into the plasma quartz tube by argon bubbling at the temperature of 900 ℃, under the vacuum degree of 30Pa and under the plasma strength of 700W, wherein the argon flow is 300sccm, the reaction time is 5h, and cooling to obtain a titanium carbide-carbon core-shell array;

(2) placing the titanium carbide-carbon core-shell array obtained in the step (1) as a carrier in a plasma quartz tube, taking a mixed gas of argon, hydrogen and methane as a plasma reaction gas, wherein the argon flow is 50sccm, the hydrogen flow is 50sccm, the methane flow is 20sccm, a reaction carbon source is methane, the reaction time is 30min, and cooling to obtain the titanium carbide-carbon core-shell array loaded vertical graphene composite material under the conditions of 800 ℃, 25Pa vacuum degree and 900W plasma intensity;

(3) and (3) placing the titanium carbide-carbon core-shell array loaded vertical graphene composite material obtained in the step (2) in an atomic layer deposition instrument, taking 0.1mol/L manganese nitrate and deionized water as reaction sources, reacting at 200 ℃, performing atomic layer deposition for 300 weeks, and performing heat treatment for 6 hours at 500 ℃ in an argon atmosphere to obtain the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material.

Examples of the experiments

The titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material obtained in the example 1-3 is used as a positive electrode of a zinc ion battery, a metal zinc sheet is used as a negative electrode, and the performance of the zinc ion battery is respectively tested in a two-electrode system. The electrolyte is 2mol/L zinc sulfate and 0.2mol/L manganese sulfate solution, the charge-discharge voltage is 1.0-1.8V, the reversible charge-discharge specific capacitance, the charge-discharge cycle performance and the high rate characteristic of the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material are measured circularly in an environment at 25 ℃, and the result is shown in figure 6.

As can be seen from FIG. 6, the capacity of the carbon spiral nanofiber/lithium titanate composite material is 280mA h g at the current densities of 0.5A/g, 1A/g and 2A/g^-1、261mA h g^-1、238mA h g^-1And excellent high power performance is shown. The capacity retention rate of more than 80% is still achieved after the lithium ion battery is cycled for 1000 times under the current density of 2A/g, and the lithium ion battery shows excellent cycling stability and long cycle life.

The conductivity of the whole composite material is improved due to the introduction of the titanium carbide-carbon core-shell array and the vertical graphene material, the crosslinked manganese dioxide nanoparticles are beneficial to increasing the contact area of an electrode and electrolyte, and provide a more effective active reaction area, and meanwhile, good ion and electron diffusion channels are provided for electrochemical reaction, the diffusion distance of ions is shortened, and the performance of a zinc ion battery is improved.

Therefore, the titanium carbide-carbon core-shell array loaded vertical graphene/manganese dioxide composite material has high specific capacity, long cycle life and high rate performance, and has wide application prospects in the fields of small mobile power grid energy storage, electronic equipment, electric automobiles, aerospace and the like.

While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.