CN110993908A - Vertical graphene/manganese dioxide composite material and preparation method and application thereof - Google Patents
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a vertical graphene/manganese dioxide composite material, a preparation method thereof and application of the composite material as a positive electrode material of a zinc ion battery, wherein a microwave plasma chemical vapor deposition method is adopted to react for 1-2 hours at the temperature of 750-850 ℃ to generate a carbon cloth-loaded vertical graphene sheet. And then, reacting for 1-6 hours at 120-160 ℃ by using potassium permanganate and water as reaction sources through a hydrothermal method, taking out and drying to obtain the vertical graphene/manganese dioxide composite material, wherein the manganese dioxide nanosheets are uniformly loaded on the surface of the vertical graphene to form a core-shell structure. The vertical graphene/manganese dioxide composite material has high specific capacitance, high rate performance and long cycle life, and has wide application prospect in the fields of mobile communication, electric automobiles, aerospace and the like.
Description
Technical Field
The invention relates to the field of positive electrode materials of zinc ion batteries, in particular to a vertical graphene/manganese dioxide composite material, a preparation method thereof and application of the composite material as a positive electrode material of a zinc ion battery.
Background
At present, lithium ion batteries occupy the largest commercial market, and have been widely applied to the fields of electric vehicles, mobile phone mobile communication and the like. However, lithium metal is a limited resource and expensive material. Meanwhile, the harsh conditions under which the battery must be manufactured in a water-free environment increase the production cost thereof. In addition, the organic electrolyte adopted by the lithium ion battery is usually toxic and flammable, and has potential safety hazards. The ionic conductivity of the aqueous electrolyte is 2 orders of magnitude higher than that of the organic electrolyte, so that the aqueous battery generally has higher power density, is easy to prepare and has low cost. In the currently studied aqueous lithium ion battery, a potential window in which protons can stably exist in an electrolyte is narrow, many side reactions such as co-intercalation reaction of protons and ions occur in the charging and discharging process, and an electrode material is easily dissolved in water, so that the development of the aqueous lithium ion battery is limited by the factors. Zinc has a low equilibrium potential and a high overpotential for hydrogen reaction, and is the lowest standard potential of all elements that can be efficiently reduced from aqueous solutions. Among the metallic elements that can be stabilized in aqueous solution, zinc is also the highest in energy. Meanwhile, the metal zinc has the advantages of abundant resources, low toxicity, easy treatment and the like. Therefore, the secondary zinc ion water system battery with low price, high safety, no environmental pollution and high power is an ideal green battery system.
The ionic radius of the zinc ion was 0.074nm, which is close to that of the lithium ion (0.076 nm). However, the zinc has large atomic mass, and the zinc ions and the crystal structure of the anode material have strong electrostatic interaction, so that the transport kinetics is slow, the coulombic efficiency is low, and the rate capability is poor. Therefore, the types of materials that can be used as positive electrode materials for zinc ion batteries are not many. At present, the types of positive electrode materials of zinc ion batteries mainly comprise three main types, namely manganese oxides, vanadium-based materials and prussian blue. The three types of materials have own advantages and disadvantages, and in comparison, the manganese-based material has higher energy density, and the vanadium-based material has higher power density. Manganese oxide is currently the most studied positive electrode material for zinc ion batteries. Wherein the delta-type manganese dioxide has a layered structure of 1 x infinity, can effectively accommodate rapid intercalation and deintercalation of zinc ions, and has high capacity. But the low conductivity of manganese oxide results in poor rate capability and cycle performance. The compounding of manganese dioxide with carbon materials is an effective way to improve the electrical conductivity and structural stability thereof. This is mainly due to the excellent properties of carbon materials such as light weight, high conductivity, and high specific surface area. Meanwhile, the contact area of the electrode material and the electrolyte is increased by the manganese dioxide nanosheets, so that the transmission of electrons and charges is facilitated, and high 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 dual advantages of the carbon material and the manganese dioxide, and is an effective strategy for constructing the high-performance zinc ion battery.
Disclosure of Invention
The invention aims to solve the problems of poor conductivity, poor rate performance and the like of the electrode material of the current zinc ion battery, and provides a vertical graphene/manganese dioxide composite material, a preparation method thereof and application of the composite material as a positive electrode material of the zinc ion battery.
A preparation method of a vertical graphene/manganese dioxide composite material comprises the following steps:
(1) pretreating a carbon cloth substrate material, activating by concentrated sulfuric acid, and then cleaning for several times by deionized water and ethanol to obtain a pretreated carbon cloth substrate material;
(2) placing the pretreated carbon cloth substrate material obtained in the step (1) in a tubular furnace, vacuumizing, heating to 450-550 ℃, generating hydrogen plasma when the microwave power reaches 550-650W in a hydrogen atmosphere, treating the carbon cloth with the plasma, heating to 750-850 ℃ in a hydrogen and methane mixed atmosphere, preserving heat for 1-2 hours, and taking out to obtain a vertical graphene material growing on the carbon cloth substrate;
(3) and (3) soaking the vertical graphene material obtained in the step (2) in a potassium permanganate aqueous solution, then carrying out hydrothermal reaction, cooling the reaction kettle, taking out a reaction product, and drying to obtain the vertical graphene/manganese dioxide composite material.
In the step (1), the carbon cloth substrate material is pretreated, and the method specifically comprises the following steps: activating the carbon cloth substrate material by concentrated sulfuric acid, and then cleaning the carbon cloth substrate material by deionized water and ethanol for several times.
The activating condition of the concentrated sulfuric acid is as follows: the temperature is 70-90 ℃, the concentration of concentrated sulfuric acid is 5-10 mol/L, and the activation time is 60-120 minutes.
In the step (2), the pressure is vacuumized to reach 5-15 mTorr, and most preferably, the pressure is vacuumized to reach 10 mTorr.
The volume ratio of methane to hydrogen is 5-15: 1.
in the step (3), the concentration of the potassium permanganate aqueous solution is 0.02-0.1 mol/L. According to actual needs, the content change can be controlled by adjusting the reaction concentration and materials.
The conditions of the hydrothermal reaction are as follows: carrying out hydrothermal reaction for 2-6 hours at 120-160 ℃.
The vertical graphene/manganese dioxide composite electrode material (namely, the vertical graphene/manganese dioxide composite material) comprises vertical graphene and manganese dioxide nanosheets, wherein the graphene vertically grows on the surface of a carbon cloth substrate material, the diameter of the graphene is 500-600 nm, the thickness of the graphene is 5-10 nm, and the manganese dioxide nanosheets are uniformly loaded on the surface of the graphene.
The vertical graphene/manganese dioxide composite electrode material can be used as a positive electrode material of a zinc ion battery. The zinc ion battery vertical graphene/manganese dioxide composite electrode material has high specific capacity, long cycle life and high rate performance, and has wide application prospect in the fields of small-sized mobile electronic equipment, electric automobiles, solar power generation, aerospace and the like. Meanwhile, the electrode material growing on the carbon cloth substrate has excellent flexibility, can be assembled into a flexible energy storage device, and is applied to the field of wearable electronic devices.
Compared with the prior art, the invention has the following advantages:
according to the invention, vertical graphene is used as a carbon material, and a hydrothermal method is used for preparing the vertical graphene/manganese dioxide composite material. The preparation method is simple and convenient, and is easy to control.
According to the vertical graphene/manganese dioxide composite electrode material for the zinc ion battery, which is prepared by the invention, the vertical graphene material has higher conductivity, and meanwhile, the manganese dioxide nanosheets provide larger and more effective active reaction area, provide good ion and electron diffusion channels for electrochemical reaction, shorten the diffusion distance of ions, accelerate the electrochemical reaction process, and improve the cycle stability and rate capability of the electrochemical reaction process, so that the novel electrode material for the zinc ion battery, which has high energy density, excellent cycle performance, reliability and safety, is realized. Meanwhile, the electrode material has excellent flexibility, can be assembled into a flexible energy storage device, and is applied to the field of wearable electronic devices.
Drawings
Fig. 1 is a scanning electron micrograph of the vertical graphene prepared in example 1;
FIG. 2 is a scanning electron micrograph of a vertical graphene/manganese dioxide composite prepared in example 1;
fig. 3 is a transmission electron micrograph of the vertical graphene and vertical graphene/manganese dioxide composite prepared in example 1, in which (a) in fig. 3 is a transmission electron micrograph of the vertical graphene, and (b) in fig. 3 is a transmission electron micrograph of the vertical graphene/manganese dioxide.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Example 1
Activating the carbon cloth substrate material by concentrated sulfuric acid, wherein the activating conditions of the concentrated sulfuric acid are as follows: and (3) cleaning for several times by using deionized water and ethanol at the temperature of 70 ℃, the concentration of concentrated sulfuric acid of 5mol/L and the activation time of 120 minutes to obtain the pretreated carbon cloth substrate.
The pretreated carbon cloth substrate was placed in a tube furnace and evacuated to a system pressure of 10 mtorr. Subsequently, the temperature was raised to 450 ℃ and plasma was generated when the microwave power reached 550W under a hydrogen atmosphere. After the carbon cloth is treated by plasma, the temperature is raised to 750 ℃ in the atmosphere of methane and hydrogen (the volume ratio is 5: 1) and the temperature is kept for 1 hour, so that the vertical graphene material growing on the carbon cloth substrate is prepared. Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) analysis of the obtained perpendicular graphene was performed, as shown in fig. 1 and 3, it can be seen that: the average diameter of the graphene sheet is 50nm, the thickness of the graphene sheet is about 8nm, and the graphene uniformly grows on the surface of the carbon cloth.
Then 3.16g of potassium permanganate is weighed and dissolved in 1000ml of deionized water, and the potassium permanganate solution is prepared by stirring until the potassium permanganate solution is completely dissolved. And then 50ml of potassium permanganate aqueous solution is put into a polytetrafluoroethylene high-pressure hydrothermal tank, the vertical graphene material is put into the tank, the autoclave is sealed, and the hydrothermal reaction is carried out for 2 hours at the temperature of 120 ℃. And cooling to room temperature of 25 ℃ after reaction, washing with deionized water and drying to obtain the vertical graphene/manganese dioxide composite material. Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) analyses were performed on the obtained vertical graphene/manganese dioxide composite material, as shown in fig. 2 and 3, it can be seen that: manganese dioxide nanosheets uniformly grow on the surface vertical to the graphene to form a core-shell structure.
Example 2
Activating the carbon cloth substrate material by concentrated sulfuric acid, wherein the activating conditions of the concentrated sulfuric acid are as follows: and (3) cleaning for several times by using deionized water and ethanol at the temperature of 80 ℃, the concentration of concentrated sulfuric acid of 8mol/L and the activation time of 90 minutes to obtain the pretreated carbon cloth substrate.
The pretreated carbon cloth substrate was placed in a tube furnace and evacuated to a system pressure of 10 mtorr. Subsequently, the temperature is raised to 500 ℃, and plasma is generated when the microwave power reaches 600W under the hydrogen atmosphere. After the carbon cloth is treated by plasma, the temperature is raised to 800 ℃ in the atmosphere of methane and hydrogen (the volume ratio is 10: 1) and the temperature is kept for 1.5 hours, so that the vertical graphene material growing on the carbon cloth substrate is prepared.
Weighing 7.9g of potassium permanganate, dissolving in 1000ml of deionized water, and stirring until the potassium permanganate is completely dissolved to prepare a 0.05mol/L potassium permanganate solution. And then 50ml of potassium permanganate aqueous solution is put into a polytetrafluoroethylene high-pressure hydrothermal tank, the prepared vertical graphene substrate is put into the tank, the autoclave is sealed, and hydrothermal reaction is carried out for 4 hours at the temperature of 140 ℃. And cooling to room temperature of 25 ℃ after reaction, washing with deionized water and drying to obtain the vertical graphene/manganese dioxide composite material.
Example 3
Activating the carbon cloth substrate material by concentrated sulfuric acid, wherein the activating conditions of the concentrated sulfuric acid are as follows: and (3) cleaning for several times by using deionized water and ethanol at the temperature of 90 ℃, the concentration of concentrated sulfuric acid of 10mol/L and the activation time of 60 minutes to obtain the pretreated carbon cloth substrate.
The pretreated carbon cloth substrate was placed in a tube furnace and evacuated to a system pressure of 10 mtorr. Subsequently, the temperature was raised to 550 ℃ and plasma was generated when the microwave power reached 650W under a hydrogen atmosphere. After the carbon cloth is treated by plasma, the temperature is raised to 850 ℃ in the atmosphere of methane and hydrogen (the volume ratio is 15: 1) and the temperature is kept for 2 hours, so that the vertical graphene material growing on the carbon cloth substrate is prepared.
Weighing 15.8g of potassium permanganate to dissolve in 1000ml of deionized water, and stirring until the potassium permanganate is completely dissolved to prepare a 0.1mol/L potassium permanganate solution. And then 50ml of potassium permanganate aqueous solution is put into a polytetrafluoroethylene high-pressure hydrothermal tank, the prepared vertical graphene substrate is put into the tank, the autoclave is sealed, and hydrothermal reaction is carried out for 6 hours at 160 ℃. And cooling to room temperature of 25 ℃ after reaction, washing with deionized water and drying to obtain the vertical graphene/manganese dioxide composite material.
Performance testing
The performance of the zinc ion battery is respectively tested in a two-electrode system by using the vertical graphene/manganese dioxide composite material prepared in the above examples 1-3 as the positive electrode of the zinc ion battery and the metal zinc sheet as the negative electrode. The electrolyte is 2mol/L zinc sulfate and 0.2mol/L manganese sulfate solution, the charging and discharging voltage is 1.0-1.8V, and the reversible charging and discharging specific capacitance, the charging and discharging cycle performance and the high rate characteristic of the vertical graphene/manganese dioxide composite material are measured in a circulating manner in an environment of 25 +/-1 ℃.
The performance test results are as follows:
the specific discharge capacities of the vertical graphene/manganese dioxide composite electrode materials of the embodiments 1, 2 and 3 at a current density of 0.5A/g are respectively 180F/g, 245F/g and 276F/g, and the specific discharge capacity retention rate after 1000 cycles is more than 94%. Therefore, the prepared vertical graphene/manganese dioxide composite material for the zinc ion battery has high charge and discharge capacity and good cycle stability.
The specific discharge capacitance of the vertical graphene/manganese dioxide composite electrode materials of example 1, example 2 and example 3 at a current density of 5A/g was 165F/g, 221F/g and 248F/g, respectively. Therefore, the prepared vertical graphene/manganese dioxide composite electrode material for the zinc ion battery has good high-rate performance.
The conductivity of the whole composite material is improved due to the introduction of the vertical graphene material, the crosslinked manganese dioxide nanosheets are beneficial to increasing the contact area of the electrode and the electrolyte, a more effective active reaction area is provided, meanwhile, a good ion and electron diffusion channel is provided for the electrochemical reaction, the diffusion distance of ions is shortened, and the performance of the zinc ion battery is improved.
Therefore, the zinc ion battery vertical graphene/manganese dioxide composite electrode material has high specific capacity, long cycle life and high rate performance, and has wide application prospect in the fields of small-sized mobile electronic equipment, electric automobiles, solar power generation, aerospace and the like.
Claims (10)
1. The preparation method of the vertical graphene/manganese dioxide composite material is characterized by comprising the following steps:
(1) pretreating a carbon cloth substrate material, activating by concentrated sulfuric acid, and then cleaning for several times by deionized water and ethanol to obtain a pretreated carbon cloth substrate material;
(2) placing the pretreated carbon cloth substrate material obtained in the step (1) in a tubular furnace, vacuumizing, heating to 450-550 ℃, generating hydrogen plasma when the microwave power reaches 550-650W in a hydrogen atmosphere, treating the carbon cloth with the plasma, heating to 750-850 ℃ in a hydrogen and methane mixed atmosphere, preserving heat for 1-2 hours, and taking out to obtain a vertical graphene material growing on the carbon cloth substrate;
(3) and (3) soaking the vertical graphene material obtained in the step (2) in a potassium permanganate aqueous solution, then carrying out hydrothermal reaction, cooling the reaction kettle, taking out a reaction product, and drying to obtain the vertical graphene/manganese dioxide composite material.
2. The method for preparing a vertical graphene/manganese dioxide composite material according to claim 1, wherein in the step (1), the carbon cloth substrate material is pretreated, and the method specifically comprises the following steps: activating the carbon cloth substrate material by concentrated sulfuric acid, and then cleaning the carbon cloth substrate material by deionized water and ethanol for several times.
3. The method for preparing a vertical graphene/manganese dioxide composite material according to claim 2, wherein in the step (1), the concentrated sulfuric acid activation conditions are as follows: the temperature is 70-90 ℃, the concentration of concentrated sulfuric acid is 5-10 mol/L, and the activation time is 60-120 minutes.
4. The method for preparing the vertical graphene/manganese dioxide composite material according to claim 2, wherein in the step (2), the vacuum is pumped to make the pressure reach 5-15 mTorr.
5. The preparation method of the vertical graphene/manganese dioxide composite material according to claim 2, wherein in the step (2), the volume ratio of methane to hydrogen in the mixed atmosphere of hydrogen and methane is 5-15: 1.
6. the preparation method of the vertical graphene/manganese dioxide composite material according to claim 1, wherein in the step (3), the concentration of the potassium permanganate aqueous solution is 0.02-0.1 mol/L.
7. The method for preparing a vertical graphene/manganese dioxide composite material according to claim 1, wherein in the step (3), the hydrothermal reaction conditions are as follows: carrying out hydrothermal reaction for 2-6 hours at 120-160 ℃.
8. The vertical graphene/manganese dioxide composite material prepared by the preparation method according to any one of claims 1 to 7.
9. The vertical graphene/manganese dioxide composite material according to claim 8, which comprises vertical graphene and manganese dioxide nanosheets, wherein the graphene vertically grows on the surface of the carbon cloth substrate material, and the manganese dioxide nanosheets are uniformly loaded on the surface of the graphene.
10. Use of the vertical graphene/manganese dioxide composite material according to claim 8 or 9 as a positive electrode material for a zinc-ion battery.
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