Zinc manganate/milk carbon composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a zinc manganate/milk carbon composite material and a preparation method thereof.
Background
The zinc manganate is a transition metal oxide with a spinel structure, belongs to a tetragonal crystal system, and has stable physical and chemical properties, low price and environmental friendliness. Meanwhile, the nanometer silicon dioxide is an important inorganic functional semiconductor material, and has important research value and application prospect in the fields of biomedicine, gas sensitive elements, catalysts, solar cells, fuel cells, information materials and the like. The carbon material has the advantages of low price, no pollution, good conductivity, stable physical and chemical properties and the like. The zinc manganate and the carbon material can improve the conductivity, stability, electrochemical capacity and the like of the material, and can enhance the performance of the material as an electrode material of a lithium ion battery, a super capacitor and the like. Graphene, as a carbon material, is complex in preparation method and not easy to prepare.
In the existing preparation method of zinc manganate and graphene composite material, as disclosed in the patent of 'a preparation method of zinc manganate/graphene composite material' of publication No. 104934590a, a graphite oxide aqueous solution, a manganese salt and a zinc salt aqueous solution are uniformly mixed and subjected to hydrothermal reaction to generate the zinc manganate and graphene composite material. The method has the main problems that graphite oxide is required to be synthesized by a Hummers method and prepared into a graphite oxide aqueous solution, and the synthesis process is complicated and the operation is complex.
Biomass carbon refers to a carbon-rich solid substance produced by pyrolysis of carbon-rich biomass under oxygen-free or anoxic conditions. In general, a carbon material can be obtained by calcining a substance containing a relatively large amount of carbon elements in an inert atmosphere such as argon. Currently, biomass carbon sources used by researchers include sugar cane, peanut shells, rice shells, watermelon pulp, egg shells, pollen, milk, banana peels, grass juice, and the like. The biomass carbon sources are ubiquitous in life and low in price, and no precedent for compounding the biomass carbon with the zinc manganate exists at present.
Just at present, the zinc manganate milk carbon composite material is low in purity, agglomeration phenomenon easily occurs in the preparation process, the conductivity and stability of the zinc manganate milk carbon composite material are affected, collapse of a carbon structure is easily caused, the structure is unstable, the morphology is poor, the particle uniformity is poor, the overall distribution is not uniform enough, the specific surface area is small, and the conductivity is not ideal enough.
Disclosure of Invention
The first purpose of the invention is to provide a zinc manganate/milk carbon composite material.
The second purpose of the invention is to provide a preparation method of the zinc manganate/milk carbon composite material.
The purpose of the invention is realized by the following technical scheme:
the zinc manganate/milk carbon composite material consists of 75-80 wt% of zinc manganate and 20-25 wt% of milk carbon.
Furthermore, the particle size of the zinc manganate/milk carbon composite material is 25 nm-35 nm.
A preparation method of a zinc manganate/milk carbon composite material is characterized in that zinc manganate/milk carbon composite material is prepared by taking zinc chloride, potassium permanganate and sodium fluoride as raw materials and water as a solvent, mixing and stirring to form a zinc manganate precursor solution, adding pure milk into the zinc manganate precursor solution, mixing and stirring, hydrothermal synthesis, solid-liquid separation, centrifugal washing, drying and the like to form a zinc manganate/milk carbon precursor, and finally, calcining at a high temperature in one step to obtain the zinc manganate/milk carbon composite material.
Further, the mixing and stirring process includes adding zinc chloride, potassium permanganate, sodium fluoride and deionized water into a suitable container, mixing and stirring for 20-30 minutes, adding pure milk under magnetic stirring, wherein the rotating speed of the magnetic stirring is 200-300 r/min, and the stirring time is 15-30 minutes, so that a mixed solution is obtained.
Further, the molar weight ratio of the zinc chloride, the potassium permanganate and the sodium fluoride is 0.6-0.8: 1.2-1.6: 1.2-1.6, wherein the unit is mmol, and the molar volume ratio of the zinc chloride to the deionized water is 0.6-0.8: 60-80, wherein the unit is mmol/ml, and the molar volume ratio of the zinc chloride to the pure milk is 0.6-0.8: 1.5-3, unit is mmol/ml.
Further, the hydrothermal reaction is carried out for 20-24 hours by placing the prepared mixed solution in a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and setting the temperature to be 180-200 ℃.
Further, the solid-liquid separation and the centrifugal washing are implemented by placing the cooled mixed solution after the hydrothermal reaction in a centrifuge for solid-liquid separation, collecting the precipitate after the solid-liquid separation, adding deionized water into the precipitate for centrifugal washing three times, wherein the mass ratio of the precipitate to the volume of the deionized water is 1: 60-200, after washing, collecting, combining and precipitating, and then centrifugally washing with absolute ethyl alcohol for three times, wherein the mass of the precipitate and the volume of the absolute ethyl alcohol are 1: 60-200, collecting, combining and precipitating for later use; the centrifugal rotating speed is 11000r/min, and the centrifugal time is 3-5 min.
Further, the drying is to take the collected and combined precipitate, place the precipitate in a drying box, and dry the precipitate for 8 to 48 hours at the temperature of 60 to 80 ℃ to prepare the zinc manganate/milk carbon precursor.
Further, the step of high-temperature calcination is to calcine the prepared zinc manganate/milk carbon precursor for 1-2 hours at the temperature of 400-700 ℃ in an air atmosphere, so as to obtain the zinc manganate/milk carbon composite material.
The invention has the following beneficial effects:
the zinc manganate/milk carbon composite material has high purity which can reach 99.3 percent, good appearance, good particle uniformity, uniform integral distribution, large specific surface area and high conductivity; the method can be widely applied to the preparation of zinc manganate/milk carbon functional materials, the agglomeration phenomenon can not occur in the preparation process, the structural stability is good, and the carbon structure collapse can not occur.
Drawings
Fig. 1 is an XRD pattern of zinc manganate/milk carbon composite prepared in example 1 of the present invention.
Fig. 2 is a FESEM view of the zinc manganate/milk carbon composite prepared in example 1 of the present invention.
Fig. 3 is a TEM image of a zinc manganate/milk carbon composite prepared in example 1 of the present invention.
Fig. 4 is a graph of the cycle profile of the zinc manganate/milk carbon composite prepared in example 1 of the present invention.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-described disclosure.
Example 1
Weighing 0.8mmol of zinc chloride, 1.6mmol of potassium permanganate and 1.6mmol of sodium fluoride, dissolving in 80mL of deionized water, mixing and stirring to form a uniform solution, adding 3mL of pure milk under vigorous magnetic stirring after 30 minutes, and continuing stirring for 30 minutes to prepare a uniformly dispersed mixed solution; then moving the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 24 hours at the temperature of 200 ℃, carrying out centrifugal washing on the cooled mixed solution after the hydrothermal reaction for three times by using deionized water and ethanol respectively, collecting precipitates of each time, placing the precipitates in a drying box, and drying the precipitates for 24 hours at the temperature of 60 ℃ to obtain a zinc manganate/milk carbon precursor; and finally, placing the precursor in a tubular furnace, and calcining for 2 hours at 500 ℃ in an air atmosphere at the heating rate of 5 ℃/min to obtain the zinc manganate/milk carbon composite material.
Figure 1 is an XRD pattern obtained from the zinc manganate/milk carbon composite prepared in this example, as measured by an XRD diffractometer. As can be seen from the figure, the XRD pattern of the sample prepared by the method is consistent with the peak position of a standard zinc manganate card, and the main characteristic peaks are well matched with the standard diffraction peak, and only one or two miscellaneous peaks exist, so that the product has high purity which can reach 99.3%.
Fig. 2 is an SEM image of the zinc manganate/milk carbon composite prepared in this example taken by a field emission scanning electron microscope. As can be seen from the figure, the zinc manganate/milk carbon nanoparticles have uniform size and average diameter of 20-35 nm.
Fig. 3 is a TEM image of the zinc manganate/milk carbon composite prepared in this example taken by a transmission electron microscope. As can be seen from the figure, the milk-derived carbon wraps the zinc manganate nanoparticles, and the particles are good in uniformity, uniform in overall distribution and large in specific surface area.
Fig. 4 is a graph of the cycle profile of the zinc manganate/milk carbon composite prepared in this example as a negative electrode material for a lithium ion battery. As can be seen from the figure, the first discharge specific capacity is 1285mAh/g, the charge specific capacity is 774mAh/g, and the coulombic efficiency is 60.26%; after the circulation is carried out for 100 times, the discharge specific capacity is 658mAh/g, the charge specific capacity is 648mAh/g, and the coulombic efficiency is 98.52%; after 100 times of circulation, the discharge specific capacity is 994mAh/g, the charge specific capacity is 978mAh/g, and the coulombic efficiency is 98.37%. Along with the increase of the cycle times, the charging and discharging specific capacity of the zinc manganate/milk carbon negative electrode material is gradually reduced until about 50 cycles, and the charging and discharging specific capacity begins to stably increase. Therefore, the preparation method improves the conductivity, specific surface area and stability of the composite material, and finally improves the electrochemical performance of the zinc manganate/milk carbon cathode material.
Example 2
Weighing 0.7mmol of zinc chloride, 1.4mmol of potassium permanganate and 1.4mmol of sodium fluoride, dissolving in 70mL of deionized water, mixing and stirring to form a uniform solution, adding 2mL of pure milk under vigorous magnetic stirring after 25 minutes, and continuing stirring for 25 minutes to prepare a uniformly dispersed mixed solution; then moving the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 22 hours at the temperature of 190 ℃, then respectively centrifugally washing the cooled mixed solution after the hydrothermal reaction with deionized water and ethanol for three times, collecting precipitates of each time, placing the precipitates in a drying box, and drying the precipitates for 32 hours at the temperature of 70 ℃ to obtain a zinc manganate/milk carbon precursor; and finally, placing the precursor in a tubular furnace, and calcining for 1h at 600 ℃ in an air atmosphere at the heating rate of 5 ℃/min to obtain the zinc manganate/milk carbon composite material.
The experiment is carried out according to the experimental method of the embodiment 1, and the experimental result shows that the product has high purity which can reach 99.3%, uniform size, average diameter of 20-35 nm, good particle uniformity, uniform overall distribution and large specific surface area.
Example 3
Weighing 0.6mmol of zinc chloride, 1.2mmol of potassium permanganate and 1.2mmol of sodium fluoride, dissolving in 60mL of deionized water, mixing and stirring to form a uniform solution, adding 1.5mL of pure milk under vigorous magnetic stirring after 20 minutes, and continuously stirring for 15 minutes to prepare a uniformly dispersed mixed solution; then moving the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 20 hours at the temperature of 180 ℃, then respectively centrifugally washing the cooled mixed solution after the hydrothermal reaction with deionized water and ethanol for three times, collecting precipitates of each time, placing the precipitates in a drying box, and drying the precipitates for 15 hours at the temperature of 60 ℃ to obtain a zinc manganate/milk carbon precursor; and finally, placing the precursor in a tubular furnace, and calcining for 2 hours at 400 ℃ in an air atmosphere at the heating rate of 5 ℃/min to obtain the zinc manganate/milk carbon composite material.
The experiment is carried out according to the experimental method of the embodiment 1, and the experimental result shows that the product has high purity which can reach 99.0%, uniform size, average diameter of 20-35 nm, good particle uniformity, uniform overall distribution and large specific surface area.