CN112242512A - Preparation method of vanadium dioxide and graphene oxide composite material - Google Patents
Preparation method of vanadium dioxide and graphene oxide composite material Download PDFInfo
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- CN112242512A CN112242512A CN202011112484.0A CN202011112484A CN112242512A CN 112242512 A CN112242512 A CN 112242512A CN 202011112484 A CN202011112484 A CN 202011112484A CN 112242512 A CN112242512 A CN 112242512A
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- H01M4/00—Electrodes
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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 belongs to the technical field of electrochemistry, and particularly relates to a preparation method of a vanadium dioxide and graphene oxide composite material. Aiming at the problems of complex process, high energy consumption, difficult reaction condition achievement and the like of the existing method for preparing the vanadium dioxide and graphene oxide composite material, the invention provides a preparation method of the vanadium dioxide and graphene oxide composite material, which comprises the following steps: a. preparing ethylene glycol vanadyl; b. putting ethylene glycol vanadyl, graphene oxide and deionized water into a hydrothermal reaction kettle, carrying out heat preservation reaction at 120-220 ℃ for 12-24 h, cooling, soaking, and freeze-drying to obtain the vanadium dioxide and graphene oxide composite material. According to the invention, the vanadium dioxide and graphene oxide composite material is generated by one-step reaction of a ethylene glycol vanadyl hydrothermal method, the reaction process is short, the operation is simple, no toxic or harmful substance is generated in the preparation process, the preparation method is economic and environment-friendly, special large-scale equipment and harsh medium atmosphere are not required, and the large-scale industrial production is easy to realize.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a preparation method of a vanadium dioxide and graphene oxide composite material.
Background
The development of science and technology is driving the development of chemical power sources towards high capacity, low energy consumption, no pollution and the like. The development of chemical sources of electrical energy has mainly gone through several stages: lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries and lithium batteries. The lithium ion battery has the advantages of high energy density, long cycle life, small self-discharge rate, environmental protection and the like, and has attracted more and more attention, and the research and the performance improvement of the lithium ion battery become a research hotspot in the field of chemical power supplies. Negative electrode materials for lithium batteries are mainly classified into carbon materials and non-carbon materials, and non-carbon materials include metal oxides, intermetallic compounds, metal nitrides, and the like, and have higher capacity than carbon materials, but still need to be further improved in terms of cycle stability. The effective way to solve the above problems is to shorten the transmission distance of ions and electrons by reducing the particle size or to introduce conducting polymers, CNTs, graphene and the like to prepare composite materials to improve the conductivity of the materials. At present, the graphene composite material is partially adopted as a lithium battery negative electrode material in the industry.
The patent CN109192934A discloses a preparation method of a porous vanadium dioxide micron sphere composite material, which is prepared by adding NH4VO3Dispersing the powder in deionized water, adding HCl, and stirring until the HCl is dissolved; and adding hydrazine hydrate, stirring, finally adding a graphene oxide aqueous solution, stirring and dispersing, then freeze-drying, and calcining the obtained precursor for 1-4 hours at 400-500 ℃ under nitrogen to obtain the graphene-supported porous vanadium dioxide microsphere composite material.
The patent CN109473649A discloses a sodium ion battery composite negative electrode material and a preparation method thereof, which comprises the steps of firstly preparing a graphene foam material, growing a carbon nano tube on the graphene foam material, carrying out surface treatment on the prepared carbon nano tube-graphene foam composite material, completely placing the carbon nano tube-graphene foam composite material in a prepared vanadium dioxide nanosheet reaction solution, controlling the reaction temperature to be 175-185 ℃, reacting for 3-3.5 hours, washing a reaction product with deionized water and alcohol for several times, drying and annealing for 2-2.5 hours.
Patent CN109517217A discloses a tungsten-doped vanadium dioxide/graphene composite and a preparation method and application thereof, firstly weighing a proper amount of graphene oxide powder, vanadium pentoxide, organic acid and ammonium tungstate, adding into solvent deionized water, and uniformly mixing to obtain a precursor solution; and carrying out hydrothermal reaction, cooling, washing, centrifugal washing and drying on the precursor solution, and then calcining to obtain the tungsten-doped vanadium dioxide/graphene composite.
The patent CN110627055A discloses a vanadium dioxide and graphene composite film structure and a preparation method and application thereof, wherein graphene oxide is reduced on a sapphire substrate in a spin coating manner, a vanadium film is sputtered in a magnetron sputtering manner, then rapid oxidation annealing is carried out in a rapid annealing furnace, and finally acid corrosion is carried out to form graphene-VO2Nanoparticle composite film structures.
The method for preparing the vanadium dioxide/graphene oxide composite material has the defects of long reaction steps, complex process flow, high energy consumption, harsh reaction conditions and the like. Therefore, the development of a preparation method of the vanadium dioxide/graphene oxide composite material with short flow, low energy consumption and mild reaction conditions is urgently needed.
Disclosure of Invention
The invention provides a preparation method of a vanadium dioxide and graphene oxide composite material, aiming at the problems that the existing preparation method of the vanadium dioxide and graphene oxide composite material is complex in process, high in energy consumption, difficult to achieve reaction conditions and the like. The method comprises the following steps:
a. preparation of ethylene glycol vanadyl
Mixing a vanadium source and ethylene glycol according to a mass ratio of 1: 1-20, stirring and reacting at 30-200 ℃ for 2-12 h, cooling to room temperature, and filtering to obtain an ethylene glycol vanadyl solution;
b. preparation of vanadium dioxide/graphene oxide composite material
Putting the ethylene glycol vanadyl solution, the graphene oxide solution and deionized water into a hydrothermal reaction kettle according to the volume ratio of 1:1: 3-10, carrying out heat preservation reaction at 120-220 ℃ for 12-24 h, cooling, soaking the reaction product in the deionized water for 24h, and freeze-drying to obtain the vanadium dioxide and graphene oxide composite material.
In the preparation method of the vanadium dioxide and graphene oxide composite material, the vanadium source in the step a comprises at least one of ammonium metavanadate, vanadium pentoxide or vanadyl sulfate.
In the preparation method of the vanadium dioxide and graphene oxide composite material, the concentration of the graphene oxide solution in the step b is 0.5-5 mg/mL.
In the preparation method of the vanadium dioxide and graphene oxide composite material, the lining of the hydrothermal reaction kettle in the step b is made of polytetrafluoroethylene.
In the preparation method of the vanadium dioxide and graphene oxide composite material, the soaking in the step b is repeated for 2-6 times.
In the preparation method of the vanadium dioxide and graphene oxide composite material, the specific method of freeze drying in the step b is as follows: freezing in cold hydrazine at-50 deg.C for 12 hr, and drying in a freeze dryer.
The invention has the beneficial effects that:
according to the invention, vanadyl glycol and graphene oxide solution are used as raw materials for preparing the vanadium dioxide and graphene oxide composite material for the first time, compared with vanadium pentoxide adopted in the prior art, the vanadium dioxide/graphene oxide composite material prepared by the prior art needs a process of reducing a pentavalent vanadium source and then roasting at a high temperature, and vanadyl glycol can be directly subjected to one-step reaction by adopting a hydrothermal method to generate the vanadium dioxide and graphene oxide composite material. The preparation method has the advantages of short reaction flow, simple operation, no generation of toxic and harmful substances in the preparation process, economy and environmental protection, no need of special large-scale equipment and harsh medium atmosphere, and easy large-scale industrial production, and the composite material prepared by the preparation method can be applied to the lithium battery cathode material and has excellent cycle stability and high rate performance.
Detailed Description
The invention provides a preparation method of a vanadium dioxide and graphene oxide composite material, which comprises the following steps:
a. preparation of ethylene glycol vanadyl
Mixing a vanadium source and ethylene glycol according to a mass ratio of 1: 1-20, stirring and reacting at 30-200 ℃ for 2-12 h, cooling to room temperature, and filtering to obtain an ethylene glycol vanadyl solution;
b. preparation of vanadium dioxide/graphene oxide composite material
Putting the ethylene glycol vanadyl solution, the graphene oxide solution and deionized water into a hydrothermal reaction kettle according to the volume ratio of 1:1: 3-10, carrying out heat preservation reaction at 120-220 ℃ for 12-24 h, cooling, soaking the reaction product in the deionized water for 24h, and freeze-drying to obtain the vanadium dioxide and graphene oxide composite material.
Wherein, in order to obtain ethylene glycol vanadyl through better preparation, the vanadium source in the step a comprises at least one of ammonium metavanadate, vanadium pentoxide or vanadyl sulfate. The vanadium source generally requires that the content of V is within a range of 15-60 g/L, the proportion of the vanadium source to ethylene glycol is correspondingly adjusted according to different contents of V in the vanadium source, but the inventor determines through a large number of experiments that more ethylene glycol vanadyl can be prepared when the mass ratio of the vanadium source to the ethylene glycol is 1: 1-20. The ethylene glycol adopted by the invention is analytically pure.
And c, in order to avoid the problem that the viscosity of the graphene oxide solution is high due to overhigh concentration, the concentration of the graphene oxide solution in the step b is 0.5-5 mg/mL.
In the preparation method of the vanadium dioxide and graphene oxide composite material, the lining of the hydrothermal reaction kettle in the step b is made of polytetrafluoroethylene. The hydrothermal reaction kettle with the polytetrafluoroethylene lining can be used for a long time below 260 ℃, does not pollute a sample, and avoids introducing impurity silicon by using a glass lining.
In the preparation method of the vanadium dioxide and graphene oxide composite material, the soaking in the step b is repeated for 2-6 times.
In the preparation method of the vanadium dioxide and graphene oxide composite material, the specific method of freeze drying in the step b is as follows: freezing in cold hydrazine at-50 deg.C for 12 hr, and drying in a freeze dryer.
The vanadium dioxide/graphene oxide composite material is prepared by taking the ethylene glycol vanadyl solution as a raw material, generally, the raw material for preparing the vanadium dioxide/graphene oxide composite material is vanadium pentoxide, but the vanadium dioxide/graphene oxide composite material can be generated in situ in one step through hydrothermal reaction of the ethylene glycol vanadyl, and the reaction temperature is low. Therefore, the method can save the flow by adopting the raw material and is more beneficial to industrial production.
Meanwhile, after the ethylene glycol vanadyl solution is used as a raw material, the ethylene glycol vanadyl solution, the graphene oxide solution and the deionized water are specially arranged according to the volume ratio, and the temperature and the time of the hydrothermal reaction are determined through a large number of screening experiments, experiments show that the volume ratio is 1:1: 3-10, the reaction is carried out for 12-24 hours at the hydrothermal reaction temperature of 120-220 ℃, vanadium dioxide particles generated by decomposing the ethylene glycol vanadyl through a hydrothermal method are good in dispersity, can be uniformly coated by the graphene oxide, and are more beneficial to electron conduction.
According to the invention, a hydrothermal reaction method is innovatively adopted to produce the vanadium dioxide and graphene oxide composite material, compared with the existing roasting method, the method avoids the high energy consumption of the traditional method for preparing the vanadium dioxide by roasting, and the prepared product has more uniform granularity and better dispersibility.
The following examples are intended to illustrate specific embodiments of the present invention without limiting the scope of the invention to the examples.
Example 1 preparation of vanadium dioxide and graphene oxide composite Material by the method of the present invention
Mixing ammonium metavanadate and ethylene glycol according to the mass ratio of 1:15, stirring and reacting for 24 hours at 90 ℃, cooling to room temperature and filtering. And putting 10mL of the prepared ethylene glycol vanadyl solution, 10mL (with the concentration of 1mg/mL) of the graphene oxide solution and 50mL of deionized water into a hydrothermal reaction kettle, carrying out heat preservation reaction at 220 ℃ for 12 hours, naturally cooling, soaking in the deionized water for 24 hours, and then freeze-drying the product to prepare the lithium battery cathode material.
At a current density of 100mA g-1Under the condition (2), after 160 cycles, the specific discharge capacity is kept at 382mA · g-1The capacity is basically not attenuated, and the coulombic efficiency is always kept about 100 percent.
Example 2 preparation of vanadium dioxide and graphene oxide composite Material by the method of the present invention
Mixing vanadium pentoxide and ethylene glycol according to the mass ratio of 1:5, stirring and reacting at 170 ℃ for 12 hours, cooling to room temperature and filtering. And putting 10mL of the prepared ethylene glycol vanadyl solution, 10mL of the graphene oxide solution (with the concentration of 2.8mg/mL) and 50mL of deionized water into a hydrothermal reaction kettle, carrying out heat preservation reaction at 180 ℃ for 18 hours, naturally cooling, soaking in the deionized water for 24 hours, and then freeze-drying the product to prepare the lithium battery cathode material.
At a current density of 100mA g-1Under the condition (1), after 160 cycles, the specific discharge capacity is 373mA g-1The capacity is basically kept unchanged, and the coulombic efficiency is always kept about 100%.
Example 3 preparation of vanadium dioxide and graphene oxide composite Material by the method of the present invention
Mixing vanadyl sulfate and ethylene glycol according to the mass ratio of 1:10, stirring and reacting at 150 ℃ for 18 hours, cooling to room temperature and filtering. And putting 10mL of the prepared ethylene glycol vanadyl solution, 10mL (with the concentration of 3mg/mL) of the graphene oxide solution and 50mL of deionized water into a hydrothermal reaction kettle, carrying out heat preservation reaction at 150 ℃ for 24 hours, naturally cooling, soaking in the deionized water for 24 hours, and then freeze-drying the product to prepare the lithium battery cathode material.
At a current density of 100mA g-1Under the condition (2), after 160 cycles, the specific discharge capacity is 348mA g-1And basically keeps unchanged, and the coulombic efficiency is always kept about 100 percent.
Comparative example 4 preparation of vanadium dioxide and graphene oxide composite Material by Using existing method
The vanadium dioxide and graphene oxide composite material is prepared by the method in the patent CN109192934A, a precursor is prepared from ammonium metavanadate, hydrazine hydrate and graphene oxide which are pentavalent vanadium sources, and then the precursor is roasted at 400-500 ℃ in a nitrogen atmosphere to prepare the composite material which is applied to a sodium-ion battery cathode material.
Compared with a comparative patent, the invention has the advantages that the reaction temperature is lower, the reaction atmosphere does not need to be controlled, and the cost is lower by synthesizing the composite material by a hydrothermal method.
Claims (6)
1. The preparation method of the vanadium dioxide and graphene oxide composite material is characterized by comprising the following steps:
a. preparation of ethylene glycol vanadyl
Mixing a vanadium source and ethylene glycol according to a mass ratio of 1: 1-20, stirring and reacting at 30-200 ℃ for 2-12 h, cooling to room temperature, and filtering to obtain an ethylene glycol vanadyl solution;
b. preparation of vanadium dioxide/graphene oxide composite material
Putting the ethylene glycol vanadyl solution, the graphene oxide solution and deionized water into a hydrothermal reaction kettle according to the volume ratio of 1:1: 3-10, carrying out heat preservation reaction at 120-220 ℃ for 12-24 h, cooling, soaking the reaction product in the deionized water for 24h, and freeze-drying to obtain the vanadium dioxide and graphene oxide composite material.
2. The preparation method of the vanadium dioxide and graphene oxide composite material according to claim 1, characterized in that: the vanadium source in the step a comprises at least one of ammonium metavanadate, vanadium pentoxide or vanadyl sulfate.
3. The preparation method of the vanadium dioxide and graphene oxide composite material according to claim 1, characterized in that: and c, the concentration of the graphene oxide solution in the step b is 0.5-5 mg/mL.
4. The preparation method of the vanadium dioxide and graphene oxide composite material according to claim 1, characterized in that: and c, the inner liner of the hydrothermal reaction kettle in the step b is made of polytetrafluoroethylene.
5. The preparation method of the vanadium dioxide and graphene oxide composite material according to claim 1, characterized in that: and c, repeating the soaking for 2-6 times.
6. The preparation method of the vanadium dioxide and graphene oxide composite material according to claim 1, characterized in that: the freeze drying method in the step b comprises the following specific steps: freezing in cold hydrazine at-50 deg.C for 12 hr, and drying in a freeze dryer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113066973A (en) * | 2021-03-15 | 2021-07-02 | 武汉理工大学 | Self-supporting vanadium graphene interface zinc storage material and preparation method and application thereof |
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Patent Citations (5)
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| US20130189592A1 (en) * | 2010-09-09 | 2013-07-25 | Farshid ROUMI | Part solid, part fluid and flow electrochemical cells including metal-air and li-air battery systems |
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