CN113130866A - Preparation method of boron-carbon thin-wall hollow sphere - Google Patents

Preparation method of boron-carbon thin-wall hollow sphere Download PDF

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CN113130866A
CN113130866A CN202110359220.3A CN202110359220A CN113130866A CN 113130866 A CN113130866 A CN 113130866A CN 202110359220 A CN202110359220 A CN 202110359220A CN 113130866 A CN113130866 A CN 113130866A
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boron
hollow sphere
carbon thin
precipitate
temperature
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CN113130866B (en
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王慧奇
王美
白娜
李莹
李海茹
曹红红
张会念
胡胜亮
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North University of China
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/625—Carbon or graphite
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a preparation method of a boron-carbon thin-wall hollow sphere, which takes tannic acid as a carbon source and nano calcium carbonate as a template to prepare the boron-carbon thin-wall hollow sphere through hydrothermal treatment, high-temperature carbonization and other steps. The method of the invention has the following advantages: the reaction process is simple, and the tannic acid can be coated on the surface of the calcium carbonate by controlling the stirring time of the solution at normal temperature; calcium carbonate is used as a hard template, and a porous structure is generated while the template is removed through high-temperature carbonization; the porous structure provides a larger electrode/electrolyte contact area for electrochemical reaction; the interconnected carbon structure and thin carbon wall provide a continuous electron transport path and shorten the diffusion distance of ions, and can be widely applied to lithium (sodium) ion batteries as an electrode material.

Description

Preparation method of boron-carbon thin-wall hollow sphere
Technical Field
The invention belongs to the field of battery negative electrode materials, and particularly relates to a preparation method of a boron-carbon thin-wall hollow sphere.
Disclosure of Invention
The modern degree of the modern society is higher and higher, and the demand for energy products is also higher and higher. With the limited reserves of fossil fuels (including coal, petroleum, natural gas and the like), fossil fuel resources are exhausted with the excessive use in recent years, and CO generated in the use process is exhausted2The gases can also cause seawater acidification and greenhouse effect, and extremely worsen the ecological environment. However, new energy sources such as solar energy, wind energy, geothermal energy, tidal energy, etc. are limited in geographical distribution or time and cannot stably provide usable electric energy. The battery as a portable energy storage tool not only can realize reversible conversion between electric energy and chemical energy, but also provides a medium for the use of the new energy. Lithium ion batteries, because of their high energy density and long cycle life, have rapidly developed and rapidly commercialized since the 90 s of the 20 th century, leading the consumer market for electronic products, but due to the limited lithium resources on earth, have severely restricted the application of LIBs in large-scale energy storage. In recent years, Sodium Ion Batteries (SIBs) are considered as a promising new technology that may replace LIBs due to low price and abundant natural reserves of sodium. The carbon material is used as the most extensive anode material, and the porous structure of the carbon material can have a remarkable influence on the performance in the reaction process, so that more active sites are provided for the reaction.
Tannin as a plant polyphenol has low price and wide source, and can be directly extracted from a plurality of plants, such as: tea, pomegranate, gallnut, etc. Because the coating material has rich pyrocatechol structures, the coating material can be complexed with metal ions or undergo self-polymerization reaction under the condition of oxygen-containing at room temperature, so that the coating material can be coated on the surfaces of a plurality of substances through Van der Waals force or chemical bonds, does not harm the environment in the coating process, and is a green and cheap coating material. Meanwhile, calcium carbonate is low in price and wide in source, and is widely used for hard template agents. In the carbonization process, calcium carbonate is decomposed into calcium oxide and carbon dioxide, so that the formation of pores on the carbon wall is promoted, and a porous structure is obtained after the template is removed.
Disclosure of Invention
The invention aims to provide a preparation method of a boron-carbon thin-wall hollow sphere, which has the advantages of low cost, simple process, mild condition, low equipment requirement, no toxicity and environmental protection. The preparation raw materials of the invention comprise: the tannin, the nano calcium carbonate and the naphthyl boric acid are prepared by controlling the stirring time of the solution and finally obtaining the nano calcium carbonate and the naphthyl boric acid through high-temperature carbonization.
The invention is realized by the following technical scheme:
a method for preparing a boron-carbon thin-wall hollow sphere comprises the following steps:
(1) adding 0.1-0.8 g of nano calcium carbonate into 10-30 mL of absolute ethyl alcohol, stirring for 0.5-2h, and then carrying out ultrasonic treatment for 0.5-1 h;
(2) adding 0.5-2g of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 1.5-3 g of sodium chloride into 50-120 mL of distilled water, adjusting the pH value of the solution to 7, adding the solution obtained in the step (1), stirring for 0.5-1h, adding 0.5-1 g of naphthyl boric acid and 0.5-2g of tannic acid, and continuously stirring for 12-36 h at normal temperature until the solution is dark brown;
(3) pouring the solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction for 8-24 h at 120-200 ℃, then centrifuging the hydrothermal product at a centrifugation speed of 8000-10000rpm for 8-15 min to obtain a precipitate, and then drying the precipitate in a vacuum drying oven for 8-12 h to obtain an active substance;
(4) putting the active substance obtained in the step (3) into a tube furnace, and carrying out high-temperature carbonization to obtain a carbonized product;
(5) and (3) etching the carbonized product obtained in the step (4) with hydrochloric acid for 0.5-2h, centrifuging at a centrifugal rate of 8000-10000rpm for 8-15 min to obtain a precipitate, and drying the precipitate in a vacuum drying oven for 8-12 h to obtain the boron-carbon thin-walled hollow sphere.
The method of the invention uses tannic acid as a carbon source, uses nano calcium carbonate as a template, and obtains the boron-carbon thin-wall hollow sphere through the steps of hydrothermal treatment, high-temperature carbonization and the like, and the structure of the boron-carbon thin-wall hollow sphere can be used as an electrode material of a battery and a super capacitor, and the method has the following advantages: the reaction process is simple, and the tannic acid can be coated on the surface of the calcium carbonate by controlling the stirring time of the solution at normal temperature; calcium carbonate is used as a hard template, and a porous structure can be generated by removing the template through high-temperature carbonization; the porous structure provides a larger electrode/electrolyte contact area for electrochemical reaction; the interconnected carbon structure and thin carbon walls provide a continuous electron transport path and shorten the diffusion distance of ions.
Further, in the steps (3) and (5), the temperature of vacuum drying is 60-80 ℃.
Further, in the step (4), the temperature of high-temperature carbonization is 700-1000 ℃, the heating rate is 5-10 ℃/min, the heat preservation time is 1-3 h, and the protective gas is high-purity argon or nitrogen.
Further, the concentration of the hydrochloric acid in the step (5) is 0.1-1 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
(1) the raw materials required by the experiment are wide in source, low in price, non-toxic, environment-friendly, simple in experiment operation process and low in equipment requirement.
(2) The boron-carbon thin-wall hollow sphere prepared by the invention has a unique interconnected carbon structure and thin carbon walls, can shorten the diffusion distance of ions, and improves the sodium storage performance of the battery.
(3) The method has simple and efficient process, and the obtained boron-carbon thin-wall hollow sphere has good circulation stability and high capacity, and can realize large-scale production and wide commercialization.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate exemplary embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is the scanning electron microscope picture of the boron-carbon thin-wall hollow sphere prepared by the invention.
FIG. 2 is the transmission electron microscope pictures of the boron-carbon thin-walled hollow sphere prepared by the present invention, wherein (a) is low power and (b) is high power.
FIG. 3 is a nitrogen adsorption and desorption curve diagram of the boron-carbon thin-wall hollow sphere prepared by the invention.
FIG. 4 is a mesoporous pore size distribution curve diagram of the boron-carbon thin-walled hollow sphere prepared by the invention.
FIG. 5 is a charge-discharge curve diagram of the sodium ion battery with boron-carbon thin-wall hollow spheres prepared by the invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, a more complete and complete description of the present invention is provided below in conjunction with the accompanying drawings and embodiments. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example 1
A method for preparing a boron-carbon thin-wall hollow sphere comprises the following steps:
(1) adding 0.25g of nano calcium carbonate into 15mL of absolute ethyl alcohol, stirring for 0.5h, and then carrying out ultrasonic treatment for 0.5 h;
(2) adding 1.25g of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 1.5g of sodium chloride into 50mL of distilled water, adjusting the pH of the solution to 7, adding the solution obtained in the step (1) thereto, stirring for 0.5h, adding 0.8g of naphthylboric acid and 1.5g of tannic acid, and continuously stirring for 12h at normal temperature until the solution is dark brown;
(3) pouring the solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, then centrifuging the hydrothermal product at a centrifugal rate of 8000rpm for 8 minutes to obtain a precipitate, then putting the precipitate into a vacuum drying oven for drying for 8 hours, wherein the vacuum drying temperature is 65 ℃ to obtain an active substance;
(4) putting the active substance obtained in the step (3) into a tube furnace, and carrying out high-temperature carbonization at the temperature of 900 ℃, the heating rate of 5 ℃/min, the heat preservation time of 2h, and the protective gas of high-purity argon to obtain a carbonized product;
(5) and (3) etching the carbonized product obtained in the step (4) with hydrochloric acid for 1.5h, wherein the concentration of the hydrochloric acid is 0.1mol/L, centrifuging at the centrifugal speed of 8000rpm for 10min to obtain a precipitate, and then drying the precipitate in a vacuum drying oven for 12h at the vacuum drying temperature of 80 ℃ to obtain the boron-carbon thin-walled hollow sphere.
Example 2
A method for preparing a boron-carbon thin-wall hollow sphere comprises the following steps:
(1) adding 0.5g of nano calcium carbonate into 20mL of absolute ethyl alcohol, stirring for 0.5h, and then carrying out ultrasonic treatment for 0.5 h;
(2) adding 1.05g of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 2g of sodium chloride into 50mL of distilled water, adjusting the pH of the solution to 7, adding the solution obtained in the step (1) and stirring for 0.5h, then adding 1g of naphthylboric acid and 2g of tannic acid, and continuously stirring for 24h at normal temperature until the solution is dark brown;
(3) pouring the solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24h, then centrifuging the hydrothermal product at a centrifugal rate of 8000rpm for 10min to obtain a precipitate, then putting the precipitate into a vacuum drying oven for drying for 10h, wherein the vacuum drying temperature is 80 ℃ to obtain an active substance;
(4) putting the active substance obtained in the step (3) into a tube furnace, and carrying out high-temperature carbonization at the temperature of 800 ℃, at the heating rate of 5 ℃/min for 1h, wherein the protective gas is high-purity nitrogen, so as to obtain a carbonized product;
(5) and (3) etching the carbonized product obtained in the step (4) with hydrochloric acid for 1h, wherein the concentration of the hydrochloric acid is 0.5mol/L, centrifuging at a centrifugation speed of 10000rpm for 10min to obtain a precipitate, and then drying the precipitate in a vacuum drying oven for 12h at the vacuum drying temperature of 75 ℃ to obtain the boron-carbon thin-walled hollow sphere.
Example 3
A method for preparing a boron-carbon thin-wall hollow sphere comprises the following steps:
(1) adding 0.5g of nano calcium carbonate into 20mL of absolute ethyl alcohol, stirring for 0.5h, and then carrying out ultrasonic treatment for 0.5 h;
(2) adding 1.25g of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 2.8g of sodium chloride into 60mL of distilled water, adjusting the pH of the solution to 7, adding the solution obtained in the step (1) and stirring for 1h, then adding 0.5g of naphthylboric acid and 1.5g of tannic acid, and continuously stirring for 36h at normal temperature until the solution is dark brown;
(3) pouring the solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction for 12h at 200 ℃, then centrifuging the hydrothermal product at a centrifugal rate of 8000rpm for 15min to obtain a precipitate, then putting the precipitate into a vacuum drying oven for drying for 12h, wherein the vacuum drying temperature is 75 ℃, and thus obtaining an active substance;
(4) putting the active substance obtained in the step (3) into a tubular furnace, and carrying out high-temperature carbonization at the temperature of 900 ℃, the temperature rise rate of 5 ℃/min, the heat preservation time of 3h, and the protective gas of high-purity nitrogen to obtain a carbonized product;
(5) and (3) etching the carbonized product obtained in the step (4) with hydrochloric acid for 2h, wherein the concentration of the hydrochloric acid is 0.7mol/L, centrifuging at the centrifugal speed of 8000rpm for 10min to obtain a precipitate, and then drying the precipitate in a vacuum drying oven for 8h at the vacuum drying temperature of 70 ℃ to obtain the boron-carbon thin-walled hollow sphere.
Example 4
A method for preparing a boron-carbon thin-wall hollow sphere comprises the following steps:
(1) adding 0.8g of nano calcium carbonate into 10mL of absolute ethyl alcohol, stirring for 0.5h, and then carrying out ultrasonic treatment for 1 h;
(2) adding 1.75g of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 3g of sodium chloride into 100mL of distilled water, adjusting the pH of the solution to 7, adding the solution obtained in the step (1) and stirring for 0.5h, then adding 1g of naphthylboric acid and 1.5g of tannic acid, and continuously stirring for 36h at normal temperature until the solution is dark brown;
(3) pouring the solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 12h, then centrifuging the hydrothermal product at a centrifugal rate of 8000rpm for 15min to obtain a precipitate, then putting the precipitate into a vacuum drying oven for drying for 12h, wherein the vacuum drying temperature is 70 ℃ to obtain an active substance;
(4) putting the active substance obtained in the step (3) into a tube furnace, and carrying out high-temperature carbonization at the temperature of 900 ℃, the heating rate of 5 ℃/min, the heat preservation time of 3h and the protective gas of high-purity argon to obtain a carbonized product;
(5) and (3) etching the carbonized product obtained in the step (4) with hydrochloric acid for 2h, wherein the concentration of the hydrochloric acid is 0.9mol/L, centrifuging at the centrifugal speed of 8000rpm for 8min to obtain a precipitate, and then drying the precipitate in a vacuum drying oven for 12h, wherein the temperature of vacuum drying is 75 ℃, so that the boron-carbon thin-wall hollow sphere is obtained.
Example 5
A method for preparing a boron-carbon thin-wall hollow sphere comprises the following steps:
(1) adding 0.75g of nano calcium carbonate into 20mL of absolute ethyl alcohol, stirring for 2.5h, and then carrying out ultrasonic treatment for 1.5 h;
(2) adding 1.75g of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 2.4g of sodium chloride into 60mL of distilled water, adjusting the pH of the solution to 7, adding the solution obtained in the step (1) and stirring for 2.5 hours, then adding 1g of naphthylboric acid and 0.5g of tannic acid, and continuously stirring for 18 hours at normal temperature until the solution is dark brown;
(3) pouring the solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 12 hours, then centrifuging the hydrothermal product at a centrifugal rate of 10000rpm for 13 minutes to obtain a precipitate, then putting the precipitate into a vacuum drying oven for drying for 12 hours, and carrying out vacuum drying at the temperature of 60 ℃ to obtain an active substance;
(4) putting the active substance obtained in the step (3) into a tube furnace, and carrying out high-temperature carbonization at the temperature of 1000 ℃, at the temperature rise rate of 5 ℃/min for 1h, wherein the protective gas is high-purity argon to obtain a carbonized product;
(5) and (3) etching the carbonized product obtained in the step (4) with hydrochloric acid for 0.5h, wherein the concentration of the hydrochloric acid is 0.8mol/L, centrifuging at the centrifugal speed of 8000rpm for 10min to obtain a precipitate, and then drying the precipitate in a vacuum drying oven for 10h at the vacuum drying temperature of 60 ℃ to obtain the boron-carbon thin-wall hollow sphere.
Example 6
A method for preparing a boron-carbon thin-wall hollow sphere comprises the following steps:
(1) adding 0.25g of nano calcium carbonate into 30mL of absolute ethyl alcohol, stirring for 1h, and then carrying out ultrasonic treatment for 0.5 h;
(2) adding 1.05g of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 2.2g of sodium chloride into 80mL of distilled water, adjusting the pH of the solution to 7, adding the solution obtained in the step (1) and stirring for 0.5h, then adding 1g of naphthylboric acid and 1.75g of tannic acid, and continuously stirring for 24h at normal temperature until the solution is dark brown;
(3) pouring the solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 12h, then centrifuging the hydrothermal product at a centrifugal rate of 8000rpm for 13min to obtain a precipitate, then putting the precipitate into a vacuum drying oven for drying for 10h, wherein the vacuum drying temperature is 70 ℃ to obtain an active substance;
(4) putting the active substance obtained in the step (3) into a tube furnace, and carrying out high-temperature carbonization at the temperature of 800 ℃, at the temperature rise rate of 5 ℃/min for 3h, wherein the protective gas is high-purity nitrogen, so as to obtain a carbonized product;
(5) and (3) etching the carbonized product obtained in the step (4) with hydrochloric acid for 0.5h, wherein the concentration of the hydrochloric acid is 1mol/L, centrifuging at a centrifugation speed of 10000rpm for 15min to obtain a precipitate, and then drying the precipitate in a vacuum drying oven for 11h at the vacuum drying temperature of 65 ℃ to obtain the boron-carbon thin-walled hollow sphere.
Example 7
A method for preparing a boron-carbon thin-wall hollow sphere comprises the following steps:
(1) adding 0.6g of nano calcium carbonate into 25mL of absolute ethyl alcohol, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour;
(2) adding 1.05g of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 2.2g of sodium chloride into 100mL of distilled water, adjusting the pH of the solution to 7, adding the solution obtained in the step (1) thereto, stirring for 1h, adding 0.75g of naphthylboric acid and 0.5g of tannic acid, and continuously stirring for 12h at normal temperature until the solution is dark brown;
(3) pouring the solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 12h, then centrifuging the hydrothermal product at a centrifugal rate of 8000rpm for 10min to obtain a precipitate, then putting the precipitate into a vacuum drying oven for drying for 9h, wherein the vacuum drying temperature is 80 ℃ to obtain an active substance;
(4) putting the active substance obtained in the step (3) into a tube furnace, and carrying out high-temperature carbonization at the temperature of 800 ℃, at the heating rate of 5 ℃/min for 2h, wherein the protective gas is high-purity argon to obtain a carbonized product;
(5) and (3) etching the carbonized product obtained in the step (4) with hydrochloric acid for 1.5h, wherein the concentration of the hydrochloric acid is 0.3mol/L, centrifuging at the centrifugal speed of 8000rpm for 8min to obtain a precipitate, and then drying the precipitate in a vacuum drying oven for 12h at the vacuum drying temperature of 80 ℃ to obtain the boron-carbon thin-walled hollow sphere.
Example 8
A method for preparing a boron-carbon thin-wall hollow sphere comprises the following steps:
(1) adding 0.1g of nano calcium carbonate into 30mL of absolute ethyl alcohol, stirring for 1.5h, and then carrying out ultrasonic treatment for 0.5 h;
(2) adding 1.55g of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 3g of sodium chloride into 100mL of distilled water, adjusting the pH of the solution to 7, adding the solution obtained in the step (1) into the solution, stirring the solution for 1 hour, adding 0.8g of naphthyl boric acid and 2g of tannic acid, and continuously stirring the solution for 36 hours at normal temperature until the solution is dark brown;
(3) pouring the solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction for 12 hours at 200 ℃, then centrifuging the hydrothermal product at a centrifugal rate of 8000rpm for 10 minutes to obtain a precipitate, then putting the precipitate into a vacuum drying oven for drying for 11 hours, wherein the vacuum drying temperature is 65 ℃, and thus obtaining an active substance;
(4) putting the active substance obtained in the step (3) into a tube furnace, and carrying out high-temperature carbonization at the temperature of 800 ℃, at the heating rate of 5 ℃/min for 1h, wherein the protective gas is high-purity argon to obtain a carbonized product;
(5) and (3) etching the carbonized product obtained in the step (4) with hydrochloric acid for 1h, wherein the concentration of the hydrochloric acid is 0.4mol/L, centrifuging at the centrifugal speed of 8000rpm for 10min to obtain a precipitate, and then drying the precipitate in a vacuum drying oven for 8h at the vacuum drying temperature of 60 ℃ to obtain the boron-carbon thin-walled hollow sphere.
Corresponding experimental detection is carried out on the boron-carbon thin-walled hollow sphere prepared by the method disclosed by the invention, as shown in fig. 1 to 5. According to the figures 1 and 2, the tannic acid is successfully coated on the surface of the calcium carbonate, the average coating thickness is 5.77nm, and the calcium carbonate is decomposed to release carbon dioxide to form a porous structure in the subsequent carbonization process; from FIGS. 3 and 4, it can be seen that the pore diameter is mainly mesoporous, and the size is between 3 and 20 nm; from the charge-discharge curve of FIG. 5, it can be seen that when it is used as an anode material for a sodium ion battery, it is at 0.1Ag-1Current density of about 200 mAhg after 200 cycles of charge and discharge capacity-1And the sodium storage performance is excellent.
The technical solutions in the embodiments of the present invention are clearly and completely described above, and the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (5)

1. The preparation method of the boron-carbon thin-wall hollow sphere is characterized by comprising the following steps of:
(1) adding 0.1-0.8 g of nano calcium carbonate into 10-30 mL of absolute ethyl alcohol, stirring for 0.5-2h, and then carrying out ultrasonic treatment for 0.5-1 h;
(2) adding 0.5-2g of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 1.5-3 g of sodium chloride into 50-120 mL of distilled water, adjusting the pH value of the solution to 7, adding the solution obtained in the step (1), stirring for 0.5-1h, adding 0.5-1 g of naphthyl boric acid and 0.5-2g of tannic acid, and continuously stirring for 12-36 h at normal temperature until the solution is dark brown;
(3) pouring the solution obtained in the step (2) into a reaction kettle, carrying out hydrothermal reaction for 8-24 h at 120-200 ℃, then centrifuging the hydrothermal product at a centrifugal rate of 8000-10000rpm for 8-15 min to obtain a precipitate, and then drying the precipitate in a vacuum drying oven for 8-12 h to obtain an active substance;
(4) putting the active substance obtained in the step (3) into a tube furnace, and carrying out high-temperature carbonization to obtain a carbonized product;
(5) and (3) etching the carbonized product obtained in the step (4) with hydrochloric acid for 0.5-2h, centrifuging at a centrifugal rate of 8000-10000rpm for 8-15 min to obtain a precipitate, and drying the precipitate in a vacuum drying oven for 8-12 h to obtain the boron-carbon thin-walled hollow sphere.
2. The method for preparing the boron-carbon thin-walled hollow sphere according to claim 1, wherein the method comprises the following steps: in the steps (3) and (5), the temperature of vacuum drying is 60-80 ℃.
3. The method for preparing the boron-carbon thin-walled hollow sphere according to claim 1 or 2, wherein the method comprises the following steps: in the step (4), the high-temperature carbonization temperature is 700-1000 ℃, the heating rate is 5-10 ℃/min, the heat preservation time is 1-3 h, and the protective gas is high-purity argon or nitrogen.
4. The method for preparing the boron-carbon thin-walled hollow sphere according to claim 1 or 2, wherein the method comprises the following steps: the concentration of the hydrochloric acid in the step (5) is 0.1-1 mol/L.
5. The method for preparing the boron-carbon thin-walled hollow sphere according to claim 3, wherein the method comprises the following steps: the concentration of the hydrochloric acid in the step (5) is 0.1-1 mol/L.
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