CN109081323B - Hollow carbon nanosphere and preparation method thereof - Google Patents
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Abstract
The present disclosure relates to a hollow carbon nanoball and a method for preparing the same, wherein the outer diameter of the hollow carbon nanoball is 20-100 nm, the thickness of the ball shell is 0.4-3.2 nm, and the specific surface area is 600-900 m2In grams, the specific surface area is determined using standard methods of GB/T5816-1995. The hollow carbon nanosphere provided by the disclosure has the advantages of large specific surface area and good electrochemical performance; the preparation method of the hollow carbon nanosphere provided by the disclosure has low cost.
Description
Technical Field
The disclosure relates to the technical field of carbon nanomaterials, in particular to a hollow carbon nanosphere and a preparation method thereof.
Background
With the intensive research of researchers on different types of carbon materials, the thin-shell hollow carbon nanospheres are widely applied to the fields of catalyst carriers, separation materials, super capacitors, lithium ion battery electrode materials and the like due to high specific surface area, high pore volume, excellent conductivity and stable chemical properties. When the heteroatom is doped into the carbon material, the carbon material has wider application prospect in the field of energy storage.
Most of the methods currently used for synthesizing hollow carbon nanospheres are a template method, an organic high-temperature pyrolysis method, a vapor deposition method, a laser distillation method, an arc discharge method and the like. The template method is a mode with good shape controllability, is usually used for preparing thin-shell hollow carbon nano-carbon spheres, and is beneficial to adding doping elements.
In the literature of Template-free synthesis of interconnected porous carbon nanoparticles for high-performance and material in lithium-ion batteries (adv. energy materials, 2011,1, 798-801), Fu-Dong Han et al first put zinc and glucose as carbon source into a stainless steel autoclave, heat to 550 ℃ and keep 10h, wash with dilute hydrochloric acid after the reaction is finished, put into a 50 ℃ oven and dry for 10h, obtain hollow carbon nanospheres with the particle size of 80nm and the wall thickness of 10nm, and the specific surface area of 270m2g-1Can be used as an active material of a lithium battery negative electrode.
The existing hollow carbon nanospheres have the defects of low specific surface area, poor electrochemical performance, high cost, difficulty in large-scale application and the like.
Disclosure of Invention
The hollow carbon nanosphere provided by the disclosure has large specific surface area and good super-capacitance performance; the preparation method of the hollow carbon nanosphere provided by the disclosure has low cost.
In order to accomplish the above objects, the present disclosure provides a hollow carbon nanoball having an outer diameter of 20 to 100 nm and a ball shell thickness of 0.4 to 3.2 nmRice, specific surface area of 600-900 m2In grams, the specific surface area is determined using standard methods of GB/T5816-1995.
Optionally, the thickness of the spherical shell of the hollow carbon nanosphere is 1-2 nm.
Optionally, the atomic fraction of sulfur atoms in the hollow carbon nanosphere is 2.0-4.0% and the atomic fraction of nitrogen atoms in the hollow carbon nanosphere is 2.0-3.0% based on the total number of atoms in the hollow carbon nanosphere.
The present disclosure also provides a method for preparing the hollow carbon nanoball, which comprises:
a. dispersing residual oil and spherical nano magnesium oxide particles in an organic solvent to obtain a suspension; wherein the particle size of the spherical nano magnesium oxide particles is 20-100 nanometers;
b. removing the organic solvent in the suspension obtained in the step a to obtain a solid-liquid mixture containing residual oil and spherical nano magnesium oxide particles;
c. c, carbonizing the solid-liquid mixture obtained in the step b under a protective atmosphere to carbonize residual oil to obtain a solid product;
d. and c, carrying out acid washing treatment on the solid product obtained in the step c in an acid solution to remove spherical nano magnesium oxide particles, so as to obtain the hollow carbon nanosphere.
Optionally, in step a, the weight ratio of the residual oil, the organic solvent and the spherical nano magnesium oxide particles is 1: (10-80): (1-10).
Optionally, in step a, the weight ratio of the residual oil, the organic solvent and the spherical nano magnesium oxide particles is 1: (20-50): (2-5).
Optionally, the organic solvent is at least one selected from the group consisting of toluene, ethylbenzene, benzene and petroleum ether, and the residue is at least one selected from the group consisting of atmospheric residue, vacuum residue, deep-drawing wax oil, light deasphalted oil and coker wax oil.
Optionally, the step of removing the organic solvent in step b includes: the suspension is subjected to an oil bath at 80-150 ℃ for 8-14 hours.
Optionally, the carbonization conditions in step c include: the temperature of the carbonization treatment is 500-900 ℃, the time of the carbonization treatment is 1-3 hours, and the protective atmosphere is at least one selected from nitrogen, argon, helium and neon.
Optionally, the method further includes: c, carrying out heat treatment on the solid-liquid mixture obtained in the step b under a protective atmosphere, and then carrying out carbonization treatment; wherein the temperature of the heat treatment is 200-500 ℃, and the time is 0.5-3 hours.
Optionally, the temperature rise rate of the heat treatment is 100-.
Optionally, the acid solution in step d is a nitric acid solution.
Optionally, the acid washing conditions in step d include: the acid solution is 2-5 mol/L nitric acid solution, the acid washing treatment time is 1-4 hours, and the ratio of the weight of the solid product to the volume of the nitric acid solution is 2-10 g: 1 liter.
Optionally, the preparation method further comprises: and washing and drying the solid product after the acid washing treatment to obtain the hollow carbon nanosphere.
The hollow carbon nanosphere provided by the disclosure has the advantages of small outer diameter, thin thickness, large specific surface area, sulfur and nitrogen heteroatom content and high stability, and can be applied to the fields of electrode materials of super capacitors, negative electrode materials of lithium batteries and the like. In addition, the hollow carbon nanosphere is prepared by adopting cheap magnesium oxide and residual oil, so that the preparation cost is low, and the industrial production is convenient.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is a Scanning Electron Micrograph (SEM) of a hollow carbon nanoball prepared in example 1 of the present disclosure.
Fig. 2 is a high-resolution transmission electron micrograph (HRTEM) of the hollow carbon nanoball prepared in example 1 of the present disclosure.
Fig. 3X-ray photoelectron spectroscopy (XPS) of the hollow carbon nanoball prepared in example 1 of the present disclosure.
Fig. 4 is a result of a first cycle charge and discharge cycle performance test of hollow carbon nanoball prepared in example 1 of the present disclosure under different current densities; wherein, the abscissa is time, and the unit is: second(s), with voltage on the ordinate, in units of: volts (V).
Fig. 5 is a high-resolution transmission electron micrograph (HRTEM) of the hollow carbon nanoball prepared in example 2 of the present disclosure.
Fig. 6 is an X-ray photoelectron spectrum (XPS) of the hollow carbon nanoball prepared in example 2 of the present disclosure.
Fig. 7 is a result of a first cycle charge and discharge cycle performance test of hollow carbon nanoball prepared in example 2 of the present disclosure under different current densities; wherein, the abscissa is time, and the unit is: second(s), with voltage on the ordinate, in units of: volts (V).
Fig. 8 is a high-resolution transmission electron micrograph (HRTEM) of the hollow carbon nanoball prepared in example 3 of the present disclosure.
Fig. 9 is an X-ray photoelectron spectrum (XPS) of the hollow carbon nanoball prepared by example 3 of the present disclosure.
Fig. 10 is a result of a first cycle charge and discharge cycle performance test of hollow carbon nanoball prepared in example 3 of the present disclosure under different current densities; wherein, the abscissa is time, and the unit is: second(s), with voltage on the ordinate, in units of: volts (V).
Fig. 11 is a Scanning Electron Micrograph (SEM) of the hollow carbon nanoball prepared by comparative example 1 of the present disclosure.
Fig. 12 a High Resolution Transmission Electron Micrograph (HRTEM) of the hollow carbon nanoball prepared in comparative example 1 of the present disclosure.
Fig. 13 is a first cycle charge and discharge cycle performance test result of the hollow carbon nanoball prepared by comparative example 1 of the present disclosure at different current densities; wherein, the abscissa is time, and the unit is: second(s), with voltage on the ordinate, in units of: volts (V).
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a hollow carbon nanoball having an outer diameter (sphere diameter) of 20-100 nm, a shell thickness of 0.4-3.2 nm, preferably 1-2 nm, a specific surface area of 600-900 m2In grams, the specific surface area is determined using standard methods of GB/T5816-1995.
According to the present disclosure, hollow carbon nanospheres (hollow carbon nanospheres), also referred to as hollow nanocapsules (hollow carbon capsules), generally have a wall thickness of 4nm or more, a particle size of 100 nm or more, and a specific surface area of less than 300 m2And/gram, the electrochemical performance is poor, and the requirement of large-scale industrial production cannot be met. The hollow carbon nanosphere provided by the disclosure has the advantages of small outer diameter, thin thickness and large specific surface area, can be applied to the fields of electrode materials of super capacitors, lithium battery negative electrode materials and the like, and has good electrochemical performance.
According to the present disclosure, the residual oil is rich in sulfur and nitrogen, and the preparation of the hollow carbon nanoball using the residual oil is equivalent to doping treatment of the hollow carbon nanoball, for example, the atomic fraction of sulfur atoms in the hollow carbon nanoball is 2.0-4.0%, preferably 2.0-3.5%, and the atomic fraction of nitrogen atoms in the hollow carbon nanoball is 2.0-3.0%, preferably 2.0-2.8%, based on the total number of atoms in the hollow carbon nanoball. The sulfur element and the nitrogen element in the hollow carbon nanosphere can adjust the property of the electron donor of the hollow carbon nanosphere, improve the surface activity, and simultaneously can reduce the charge transfer resistance and improve the wettability, thereby enhancing the capacitance performance. In addition, compared with single doping, co-doping can improve the overall properties of the material through synergistic effect, and is convenient to control and obtain the high-performance energy storage material.
The present disclosure also provides a method for preparing the hollow carbon nanoball, which comprises: a. dispersing residual oil and spherical nano magnesium oxide particles in an organic solvent to obtain a suspension; wherein the particle size of the spherical nano magnesium oxide particles is 20-100 nanometers; b. removing the organic solvent in the suspension obtained in the step a to obtain a solid-liquid mixture containing residual oil and spherical nano magnesium oxide particles; c. c, carbonizing the solid-liquid mixture obtained in the step b under a protective atmosphere to carbonize residual oil to obtain a solid product; d. and c, carrying out acid washing treatment on the solid product obtained in the step c in an acid solution to remove spherical nano magnesium oxide particles, so as to obtain the hollow carbon nanosphere.
According to the present disclosure, the residual oil is viscous and is difficult to be uniformly mixed with spherical nano magnesium oxide particles to form hollow carbon nanospheres with good performance, and the carbonized residual oil can form uniform and property-controllable hollow carbon nanospheres after the residual oil is dispersed by an organic solvent. The mixing ratio of the residual oil, the organic solvent and the spherical nano magnesium oxide particles has a great influence on the properties of the hollow carbon nanoball. If the ratio of the residual oil to the spherical nano-magnesium oxide particles is too high, the thickness of the hollow carbon nano-spherical shell is too large, and if the ratio is too low, the thickness of the hollow carbon nano-spherical shell is too small, so that the ratio of the residual oil to the spherical nano-magnesium oxide particles can be determined through a large number of experiments. The present disclosure preferably selects the weight ratio of the residual oil, the organic solvent and the spherical nano magnesium oxide particles as 1: (10-80): (1-10), more preferably 1: (20-50): (2-5).
According to the present disclosure, in order to uniformly mix the residual oil, the organic solvent and the spherical nano magnesium oxide particles, it is preferable to mix the organic solvent with the residual oil first and then add the spherical nano magnesium oxide particles, so that the residual oil dispersed in the organic solvent is favorably adhered to the outer sides of the spherical nano magnesium oxide particles, and the dispersion effect is improved. In addition, in order to further enhance the dispersing effect, the dispersing process is preferably performed under stirring and/or ultrasonic conditions.
According to the present disclosure, the existing carbon source for preparing the hollow carbon nanosphere is generally a fine chemical product and is expensive, and the present disclosure adopts a relatively cheap petrochemical primary product as the carbon source, so that the preparation cost can be reduced. The residue is well known to those skilled in the art and has a complicated carbon chain, and specifically may be at least one selected from the group consisting of atmospheric residue, vacuum residue, deep-drawing wax oil, light deasphalted oil and coker wax oil. In addition, the spherical nano magnesium oxide particles with the particle size of 20-100 nanometers, preferably 30-70 nanometers are used as the template agent, the spherical nano magnesium oxide particles are very cheap and far lower than nano particles such as nano silicon oxide and the like under the condition of the same particle size, and the performance of the prepared hollow carbon nanospheres is better. The organic solvent is used for dispersing and uniformly mixing the residual oil and the spherical nano magnesium oxide particles, and the organic solvent capable of achieving the above functions can be used in the present disclosure, and for example, may be at least one selected from toluene, ethylbenzene, benzene and petroleum ether, and is preferably toluene.
According to the present disclosure, after the residual oil and the spherical nano magnesium oxide particles are uniformly dispersed in the organic solvent, the organic solvent needs to be removed to wrap the residual oil around the spherical nano magnesium oxide particles, for example, the step of removing the organic solvent in step b may include: the residual oil suspension is subjected to oil bath treatment at 80-150 deg.C for 8-14 hr, and other methods such as rotary evaporation, water bath, etc. can be adopted by those skilled in the art for removing the organic solvent.
According to the present disclosure, carbonization refers to a way of heating and decomposing organic substances under the condition of air isolation to obtain solid products, and the present disclosure refers to a residual oil dehydrogenation and carbonization process. The carbonization treatment conditions in the present disclosure are not particularly limited to obtain a solid product, and for example, the carbonization treatment conditions in step c may include: the temperature of the carbonization treatment is 500-900 ℃, the time of the carbonization treatment is 1-3 hours, the temperature rising speed of the carbonization treatment can be 100-300 ℃/hour, the protective atmosphere can be at least one atmosphere selected from nitrogen, argon, helium and neon, and the protective atmosphere is used for isolating air to prevent the residual oil from being oxidized. In addition, the method of the present disclosure may further include: c, carrying out heat treatment on the solid-liquid mixture obtained in the step b under a protective atmosphere, and then carrying out carbonization treatment; wherein, the temperature of the heat treatment is 200-500 ℃, the time is 0.5-3 hours, and the temperature rise speed of the heat treatment can be 100-500 ℃/hour. The adoption of the two-stage heating and slow heating mode is beneficial to removing part of the residual organic solvent in the solid-liquid mixture and the low-boiling-point components in the residual oil, and preventing the bumping of the solid-liquid mixture from influencing the uniformity of the finally obtained hollow carbon nanospheres.
According to a specific embodiment of the present disclosure, the carbonizing may include: firstly, the solid-liquid mixture obtained in the step b is transferred into an atmosphere furnace, then argon is introduced into the atmosphere furnace (such as a tube furnace) for 0.5 hour to remove air, then the atmosphere furnace is heated to 200-900 ℃ within 1-3 hours and is kept for 0.5-3 hours, finally the atmosphere furnace is heated to 500-900 ℃ within 2-4 hours and is kept for 1-3 hours, argon is introduced all the time during the carbonization treatment to keep the protective atmosphere, and the flow rate of the argon can be 50-160 ml/min.
According to the present disclosure, the solid product obtained in step c is carbon nanosphere-coated spherical nano magnesium oxide particles, and in order to remove the spherical nano magnesium oxide particles, an acid washing treatment is required, wherein the acid washing treatment is based on removal of the spherical nano magnesium oxide particles, for example, the acid solution may be a nitric acid solution, preferably a nitric acid solution of 2-5 mol/l, the acid washing treatment time may be 1-4 hours, and the ratio of the weight of the solid product to the volume of the nitric acid solution may be 2-10 g: 1 liter.
According to the present disclosure, the preparation method may further include: and washing and drying the solid product after the acid washing treatment to obtain the hollow carbon nanosphere. The purpose of the washing and drying is to remove an acid solution and moisture attached to the hollow carbon nanoball, so that the hollow carbon nanoball can be used as an electrode material. The conditions of washing and drying are not particularly limited in the present disclosure, and for example, the number of washing may be 3 to 6, the temperature of drying may be 60 to 100 ℃, and the time may be 8 to 14 hours.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
The specific surface area of the present disclosure was determined using the GB/T5816-1995 standard method.
The type of the scanning electron microscope is Zeiss Supra 55 (German Zeiss), and the test method comprises the following steps: and (5) observing the surface appearance.
The high-resolution transmission electron microscope disclosed by the invention is H800 (Hitachi, Japan), and the test method comprises the following steps: and (6) observing the internal appearance.
The X-ray photoelectron spectrum analyzer (XPS) adopted by the present disclosure is an ESCALB 220i-XL type ray electron spectrum analyzer which is produced by VG scientific company and is equipped with Avantage V5.926 software, and the X-ray photoelectron spectrum analysis test conditions are as follows: the excitation source is monochromatized A1K alpha X-ray, the power is 330W, and the basic vacuum is 3X 10 during analysis and test-9mbar。
The model of the XRD diffractometer adopted in the present disclosure is XRD-6000X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are as follows: cu target, KαThe radiation (wavelength λ ═ 0.154nm), the tube voltage was 40kV, the tube current was 200mA, and the scanning speed was 10 ° (2 θ)/min.
The first-cycle charge-discharge cycle performance test method of the hollow carbon nanospheres under different current densities comprises the following steps: mixing the hollow carbon nanospheres with PTFE (polytetrafluoroethylene) to prepare an electrode plate, performing constant-current charging and discharging in a three-electrode system, performing constant-current discharge test by using 6 mol/L potassium hydroxide solution as electrolyte and different current densities (1 ampere/g, 2 ampere/g, 5 ampere/g and 10 ampere/g), calculating specific capacitance Csp according to discharge time and a formula (Csp ═ I Δ t/Δ Vm), wherein the larger the specific capacitance is, the better the electrochemical performance of the hollow carbon nanospheres is.
Example 1
(1) Taking 23 g of toluene (analytically pure, the same below) and 1 g of residual oil (properties are shown in table 1, the same below), uniformly mixing, then adding 3 g of spherical nano magnesium oxide particles (from Beijing Hua Wei Rui chemical Co., Ltd., particle size is 50 nm), and performing ultrasonic dispersion to form stable and uniform suspension;
(2) carrying out oil bath on the suspension prepared in the step (1) at 110 ℃ for 10 hours, stirring and evaporating a toluene solvent to obtain a solid-liquid mixture of spherical nano magnesium oxide particles and residual oil;
(3) transferring the solid-liquid mixture to a tube furnace for carbonization treatment, introducing argon for 0.5 hour to remove air, then heating to 300 ℃ within 100 minutes and preserving heat for 1 hour, and then heating to 800 ℃ within 170 minutes and preserving heat for 1 hour; during which the argon flow was kept at 100 ml/min;
(4) and after the carbonization treatment is finished, naturally reducing the temperature in the furnace to room temperature, stopping introducing argon, taking out a reaction product, weighing 0.15 g of the reaction product, placing the reaction product in 0.02 l of nitric acid solution with the concentration of 4 mol/l for pickling for 2 hours, performing suction filtration and washing for 5 times by using deionized water until the pH value is 7.0, and then drying for 10 hours at 80 ℃ to obtain the hollow carbon nanospheres.
The resulting hollow carbon nanoball was tested: specific surface area of 719.828 m2Per gram. As can be seen from the scanning electron micrograph of the hollow carbon nanoball of fig. 1 magnified 20 ten thousand times, the hollow carbon nanoball is spherical, has a uniform particle diameter, and has an outer diameter of about 50 nm. It can be seen from the high-resolution transmission electron micrograph of the hollow carbon nanoball of fig. 2 that the thickness of the spherical shell of the hollow carbon nanoball is about 1 nm. It is calculated from the X-ray photoelectron spectrum of the hollow carbon nanoball of fig. 3 that the atomic fraction of nitrogen atom in the hollow carbon nanoball is 2.69%, the atomic fraction of sulfur atom is 2.35%, and no characteristic peak of magnesium oxide is represented by XRD.
The method comprises the steps of taking hollow carbon nanospheres as an electrode material, ultrasonically dispersing 2 mg of the hollow carbon nanospheres in alcohol, adding acetylene black and a binder into ethanol dispersion liquid of the electrode material according to the proportion of 8:1:1 (the electrode material: the acetylene black: PTFE), ultrasonically treating for 0.5 hour, selecting cleaned 1 x 4cm foamed nickel (which is ultrasonically washed by acetone, deionized water and alcohol for 30 minutes respectively and is placed in a vacuum oven at 80 ℃ for drying for standby) as a substrate, slowly dripping the ethanol dispersion liquid on the 1 x 1cm foamed nickel by using a liquid transfer gun, and placing in the vacuum oven at 120 ℃ for 12 hours after all dripping is finished. And taking out the electrode from the oven, rolling under 15Mpa by using a double-roller machine to obtain the electrode of the nickel net load electrode material, and carrying out charge and discharge tests on the material under 0-1 volt. The specific discharge capacitance was 58.1 Farad/g at a current density of 10A/g, 80.2 Farad/g at a current density of 5A/g, 121.5 Farad/g at a current density of 2A/g, and maintained at 203.35 Farad/g as the current density decreased to 1A/g (see FIG. 4 for test results).
TABLE 1 residual oil Properties
Example 2
(1) Mixing 34 g of toluene and 1 g of residual oil uniformly, adding 2 g of spherical nano magnesium oxide particles (from Beijing Wai Rui chemical Co., Ltd., particle size of 60 nm), and performing ultrasonic dispersion to form stable and uniform suspension;
(2) carrying out oil bath on the suspension prepared in the step (1) at 120 ℃ for 12 hours, stirring and evaporating a toluene solvent to obtain a solid-liquid mixture of spherical nano magnesium oxide particles and residual oil;
(3) transferring the solid-liquid mixture to a tubular furnace for carbonization treatment, introducing argon for 0.5 hour to remove air, heating to 400 ℃ within 60 minutes and keeping for 2 hours, and heating to 900 ℃ within 180 minutes and keeping for 2 hours; during which time the argon flow was maintained at 150 ml/min;
(4) and after the carbonization treatment is finished, naturally reducing the temperature in the furnace to room temperature, stopping introducing argon, taking out a reaction product, weighing 0.15 g of the reaction product, placing the reaction product in 0.02L of nitric acid solution with the concentration of 3 mol/L for pickling for 4 hours, performing suction filtration and washing for 3 times by using deionized water until the pH value is 7.0, and then drying for 8 hours at 100 ℃ to obtain the hollow carbon nanospheres.
The resulting hollow carbon nanoball was tested: specific surface area of 722.164 m2In terms of g, it can be seen from the high resolution tem photograph of the hollow carbon nanoball of fig. 5 that the thickness of the spherical shell of the hollow carbon nanoball is about 2 nm and the outer diameter is about 60 nm. It is calculated from the X-ray photoelectron spectrum of the hollow carbon nanoball of fig. 6 that the atomic fraction of nitrogen atom in the hollow carbon nanoball is 2.43% and the atomic fraction of sulfur atom in the hollow carbon nanoball is 2.23%, and no characteristic peak of magnesium oxide is represented by XRD.
The method comprises the steps of taking hollow carbon nanospheres as an electrode material, ultrasonically dispersing 2 mg of the hollow carbon nanospheres in alcohol, adding acetylene black and a binder into ethanol dispersion liquid of the electrode material according to the proportion of 8:1:1 (the electrode material: the acetylene black: PTFE), ultrasonically treating for 0.5 hour, selecting cleaned 1 x 4cm foamed nickel (which is ultrasonically washed by acetone, deionized water and alcohol for 30 minutes respectively and is placed in a vacuum oven at 80 ℃ for drying for standby) as a substrate, slowly dripping the ethanol dispersion liquid on the 1 x 1cm foamed nickel by using a liquid transfer gun, and placing in the vacuum oven at 120 ℃ for 12 hours after all dripping is finished. And taking out the electrode from the oven, rolling under 15Mpa by using a double-roller machine to obtain the electrode of the nickel net load electrode material, and carrying out charge and discharge tests on the material under 0-1 volt. The specific capacitance was 41.4 Farad/g for a current density of 10A/g, 52.7 Farad/g for a current density of 5A/g, and 74.7 Farad/g for a current density of 2A/g, and remained at 95.6 Farad/g as the current density was reduced to 1A/g (test results are shown in FIG. 7).
Example 3
(1) Uniformly mixing 46 g of toluene and 1 g of residual oil, then adding 4 g of spherical nano magnesium oxide particles (from Beijing Wai Rui chemical Co., Ltd., particle size of 40 nm), and performing ultrasonic dispersion to form stable and uniform suspension;
(2) carrying out oil bath on the suspension prepared in the step (1) for 14 hours at 100 ℃, and stirring and evaporating a toluene solvent to obtain a solid-liquid mixture of spherical nano magnesium oxide particles and residual oil;
(3) transferring the solid-liquid mixture to a tube furnace for carbonization treatment, introducing argon for 0.5 hour to remove air, heating to 500 ℃ within 120 minutes and keeping for 3 hours, and heating to 700 ℃ within 210 minutes and keeping for 3 hours; during which time the argon flow was maintained at 50 ml/min;
(4) and after the carbonization treatment is finished, naturally cooling the temperature in the furnace to room temperature, stopping introducing argon, taking out a reaction product, weighing 0.15 g of the reaction product, putting the reaction product into 0.03 l of nitric acid solution with the concentration of 2 mol/l for acidification for 3 hours, performing suction filtration and washing for 4 times by using deionized water until the pH value is 7.0, and then drying for 6 hours at 120 ℃ to obtain the hollow carbon nanospheres.
The resulting hollow carbon nanoball was tested: specific surface area of 639.601 m2In grams, it can be seen from the high resolution TEM photograph of the hollow carbon nanoball of FIG. 8 that the thickness of the spherical shell of the hollow carbon nanoball is about 1.8 nm and the outer diameter of the hollow carbon nanoball isAbout 40 nm. It is calculated from the X-ray photoelectron spectrum of the hollow carbon nanoball of fig. 9 that the atomic fraction of nitrogen atom in the hollow carbon nanoball is 2.25% and the atomic fraction of sulfur atom in the hollow carbon nanoball is 3.19%, and no characteristic peak of magnesium oxide is represented by XRD.
The method comprises the steps of taking hollow carbon nanospheres as an electrode material, ultrasonically dispersing 2 mg of the hollow carbon nanospheres in alcohol, adding acetylene black and a binder into ethanol dispersion liquid of the electrode material according to the proportion of 8:1:1 (the electrode material: the acetylene black: PTFE), ultrasonically treating for 0.5 hour, selecting cleaned 1 x 4cm foamed nickel (which is ultrasonically washed by acetone, deionized water and alcohol for 30 minutes respectively and placed in a vacuum oven at 80 ℃ for drying for later use) as a substrate, slowly dripping the ethanol dispersion liquid on the 1 x 1cm foamed nickel by using a liquid transfer gun, and placing in the vacuum oven at 120 ℃ for 12 hours after all dripping is finished. Taking out the electrode from the oven, rolling under 15Mpa by a double-roller machine to obtain the electrode of the nickel net load electrode material, and carrying out charge and discharge test on the material under 0-0.9 volt. The specific capacitance was 31.5 Farad/g for a current density of 10A/g, 39.4 Farad/g for a current density of 5A/g, 66.9 Farad/g for a current density of 2A/g, and remained at 88.1 Farad/g as the current density decreased to 1A/g (test results are shown in FIG. 10).
Comparative example 1
(1) Firstly, preparing a solution A: respectively measuring 9 ml of 28 wt% concentrated ammonia water, 16.25 ml of ethanol and 24.75 ml of water, mixing the three in a beaker, and magnetically stirring at the stirring speed of 1100 revolutions per minute;
(2) then, solution B was prepared: respectively measuring 4.5 ml of tetraethyl orthosilicate (TEOS) and 45.5 ml of ethanol, and uniformly mixing the two;
(3) after the solution A is stirred for 1 minute, quickly adding the solution B into the solution A, then reducing the stirring speed to 360 revolutions per minute, reacting for 2 hours, centrifuging, washing and drying to obtain silicon dioxide particles (the particle size is 350 nanometers) for later use;
(4) preparing a uniformly mixed solution by taking 46 g of toluene and 1 g of residual oil, then mixing 3 g of silicon dioxide particles, performing ultrasonic dispersion to form a stable and uniform suspension, and performing ultrasonic dispersion to form a stable and uniform suspension;
(5) carrying out oil bath on the solution obtained in the step (4) at 100 ℃ for 14 hours, and stirring and evaporating a toluene solvent to obtain a uniform mixture of silica particles and residual oil;
(6) after the uniform mixture is transferred to a magnetic boat, argon is used as a reaction atmosphere, argon is introduced into a chemical vapor deposition device for 0.5 hour to remove air, then the temperature is raised to 300 ℃ in 100 minutes, the flow rate of the argon is kept at 100 ml/min for 1 hour, and then the temperature is raised to 800 ℃ in 167 minutes for 1 hour;
(7) and etching the carbon-coated silica particles by using hydrofluoric acid with the mass fraction of 10 wt%, after lasting for 4 hours, centrifugally washing the carbon-coated silica particles for four times by using deionized water until the carbon-coated silica particles are neutral, and drying the carbon-coated silica particles for 10 hours at the temperature of 100 ℃ to obtain the hollow carbon nanospheres.
The resulting hollow carbon nanoball was tested: specific surface area of 81.722 m2And/g, as can be seen from the scanning electron micrograph of fig. 11, the obtained carbon spheres have obvious fragmentation phenomenon. It can be seen from the high-resolution transmission electron micrograph through the hollow carbon nanoball that fig. 12 shows that the thickness of the spherical shell of the hollow carbon nanoball is about 5 nm.
The doped hollow carbon nanospheres are adopted as an electrode material, 2 mg of ultrasonic dispersion is carried out in alcohol, then acetylene black and a binder are added into ethanol dispersion liquid of the electrode material according to the proportion of 8:1:1 (the electrode material: the acetylene black: PTFE), after 0.5 hour of ultrasonic treatment, cleaned 1 x 4cm of foamed nickel (which is respectively ultrasonically washed by acetone, deionized water and alcohol for 30 minutes and is placed in a vacuum oven at 80 ℃ for drying for standby) is selected as a substrate, the ethanol dispersion liquid is slowly dripped on the 1 x 1cm of foamed nickel by a liquid transfer gun, and the substrate is placed in the vacuum oven at 120 ℃ for 12 hours after all dripping is finished. Taking out the electrode from the oven, rolling under 15Mpa by a double-roller machine to obtain the electrode of the nickel net load electrode material, and carrying out charge and discharge test on the material under 0-0.6 volt. The specific capacitance was 3.1 Farad/g at a current density of 10A/g, 5.4 Farad/g at a current density of 5A/g, and 8.1 Farad/g at a current density of 2A/g, and remained at 8.8 Farad/g as the current density was reduced to 1A/g (test results are shown in FIG. 13).
Comparative example 2
(1) Taking 1 g of residual oil and 3 g of spherical nano magnesium oxide particles (from Beijing Warrei chemical Co., Ltd., particle size of 50 nm), directly mixing under heating condition to obtain a stable mixture;
(2) transferring the mixture to a tube furnace for carbonization treatment, introducing argon for 0.5 hour to remove air, heating to 300 ℃ within 100 minutes, keeping the temperature for 1 hour, and heating to 800 ℃ within 170 minutes and keeping the temperature for 1 hour; during which the argon flow was kept at 100 ml/min;
(4) and after the carbonization treatment is finished, naturally cooling the temperature in the furnace to room temperature, stopping introducing argon, and taking out a reaction product. The observation of the product revealed that the bottom of the porcelain boat was clearly in the form of white powder and black powder piled up. As is clear from the color, the spherical nano magnesium oxide particles are not coated with the carbon layer, and thus do not have the effect of serving as a template agent for the hollow carbon nanospheres.
Comparative example 3
The preparation method is basically the same as that of the example 1, except that hydrochloric acid solution is adopted for acid cleaning, other conditions are not changed, and the product after acid cleaning is subjected to XRD characterization, so that a characteristic peak of magnesium oxide exists.
Comparative example 4
The preparation method is basically the same as that of the example 1, except that the sulfuric acid solution is adopted for acid washing, other conditions are not changed, and the product after the acid washing is subjected to XRD characterization, so that a characteristic peak of magnesium oxide exists.
As can be seen from the examples and comparative examples, the hollow carbon nanoball prepared by the disclosed method has good electrochemical properties. Among them, as can be seen from comparative example 1, the electrical properties of the hollow carbon nanoball prepared by using silica particles are inferior to those of the spherical nano-magnesia particles. As can be seen from comparative example 2, the direct heating mixing of the residual oil and the spherical nano-magnesia particles is difficult to obtain a uniform mixture, which is not favorable for obtaining the hollow carbon nanospheres. As can be seen from comparative examples 3 to 4, magnesium oxide in the carbonized-treated product was not removed by using both hydrochloric acid and sulfuric acid.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (14)
1. A hollow carbon nanosphere, the outer diameter of the hollow carbon nanosphere is 20-100 nanometers, the thickness of the spherical shell is 0.4-3.2 nanometers, and the specific surface area is 600-900 meters2In grams, the specific surface area is determined using standard methods of GB/T5816-1995.
2. A hollow carbon nanoball according to claim 1, wherein the thickness of the spherical shell of the hollow carbon nanoball is 1-2 nm.
3. The hollow carbon nanoball of claim 1, wherein the atomic fraction of sulfur atoms in the hollow carbon nanoball is 2.0-4.0% and the atomic fraction of nitrogen atoms is 2.0-3.0% by number of atoms based on the total number of atoms in the hollow carbon nanoball.
4. A method for preparing a hollow carbon nanoball of any one of claims 1 to 3, comprising:
a. dispersing residual oil and spherical nano magnesium oxide particles in an organic solvent to obtain a suspension; wherein the particle size of the spherical nano magnesium oxide particles is 20-100 nanometers;
b. removing the organic solvent in the suspension obtained in the step a to obtain a solid-liquid mixture containing residual oil and spherical nano magnesium oxide particles;
c. c, carbonizing the solid-liquid mixture obtained in the step b under a protective atmosphere to carbonize residual oil to obtain a solid product;
d. c, carrying out acid washing treatment on the solid product obtained in the step c in an acid solution to remove spherical nano magnesium oxide particles so as to obtain hollow carbon nanospheres;
the residual oil is at least one selected from atmospheric residual oil, vacuum residual oil, deep-drawing wax oil, light deasphalted oil and coker wax oil.
5. The preparation method according to claim 4, wherein in the step a, the weight ratio of the residual oil, the organic solvent and the spherical nano magnesium oxide particles is 1: (10-80): (1-10).
6. The preparation method according to claim 4, wherein in the step a, the weight ratio of the residual oil, the organic solvent and the spherical nano magnesium oxide particles is 1: (20-50): (2-5).
7. The production method according to claim 4, wherein the organic solvent is at least one selected from the group consisting of toluene, ethylbenzene, benzene, and petroleum ether.
8. The method of claim 4, wherein the step of removing the organic solvent in step b comprises: the suspension is subjected to an oil bath at 80-150 ℃ for 8-14 hours.
9. The production method according to claim 4, wherein the carbonization treatment conditions in step c include: the temperature of the carbonization treatment is 500-900 ℃, the time of the carbonization treatment is 1-3 hours, and the protective atmosphere is at least one selected from nitrogen, argon, helium and neon.
10. The production method according to claim 4 or 9, further comprising: c, carrying out heat treatment on the solid-liquid mixture obtained in the step b under a protective atmosphere, and then carrying out carbonization treatment; wherein the temperature of the heat treatment is 200-500 ℃, and the time is 0.5-3 hours.
11. The preparation method as claimed in claim 10, wherein the temperature-raising rate of the heat treatment is 100-500 ℃/hr, and the temperature-raising rate of the carbonization treatment is 100-300 ℃/hr.
12. The method according to claim 4, wherein the acid solution in step d is a nitric acid solution.
13. The method according to claim 4, wherein the acid washing treatment conditions in step d include: the acid solution is 2-5 mol/L nitric acid solution, the acid washing treatment time is 1-4 hours, and the ratio of the weight of the solid product to the volume of the nitric acid solution is 2-10 g: 1 liter.
14. The production method according to claim 4, further comprising: and washing and drying the solid product after the acid washing treatment to obtain the hollow carbon nanosphere.
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Non-Patent Citations (4)
| Title |
|---|
| Carbon Nanocages as Supercapacitor Electrode Materials;Ke Xie etc.;《Advanced Materials》;20111205;第24卷(第3期);347-352 * |
| Hollow Carbon Nanospheres with Superior Rate Capability for Sodium-Based Batteries;Kun Tang etc.;《Advanced Energy Materials》;20120731;第2卷(第7期);873-877 * |
| Template-Directed Synthesis of Pillared-Porous Carbon Nanosheet Architectures: High-Performance Electrode Materials for Supercapacitors;Zhuangjun Fan etc.;《Advanced Energy Materials》;20120430;第2卷(第4期);419-424 * |
| Template-Free Synthesis of Interconnected Hollow Carbon Nanospheres for High-Performance Anode Material in Lithium-Ion Batteries;Fu-Dong Han etc.;《Advanced Energy Materials》;20110819;第1卷(第5期);798-801 * |
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