WO2019104927A1 - 碳包覆二氧化铈空心球的制备方法 - Google Patents

碳包覆二氧化铈空心球的制备方法 Download PDF

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WO2019104927A1
WO2019104927A1 PCT/CN2018/081841 CN2018081841W WO2019104927A1 WO 2019104927 A1 WO2019104927 A1 WO 2019104927A1 CN 2018081841 W CN2018081841 W CN 2018081841W WO 2019104927 A1 WO2019104927 A1 WO 2019104927A1
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coated
silica
carbon
microspheres
ceria
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French (fr)
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吴文剑
张美丽
蔡丽蓉
邱永福
范洪波
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东莞理工学院
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Priority to US16/308,129 priority Critical patent/US10654020B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/203—Exchange of core-forming material by diffusion through the capsule wall
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1291—Process of deposition of the inorganic material by heating of the substrate
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating

Definitions

  • the invention relates to the technical field of new material preparation, in particular to a preparation method of carbon-coated ceria hollow spheres.
  • cerium oxide As a kind of rare earth metal oxide, cerium oxide has two unique oxidation states (Ce +3 and Ce +4 ), which has the unique chemical properties of redox, making it in catalysis, secondary batteries (such as lithium). Ion batteries, lithium-sulfur batteries, etc.) and supercapacitors and other fields have a very wide range of applications.
  • cerium oxide As a catalytic material or an electrode material, the performance of cerium oxide is greatly dependent on its specific surface area. Increasing the specific surface area of cerium oxide can greatly improve its performance in catalysis and its use as a storage electrode material. Therefore, it is a very effective method to increase the specific surface area by nanometerizing cerium oxide or forming cerium oxide into a hollow structure or the like.
  • strontium ions when cerium oxide is used as the electrode material, in the case of charge and discharge of the electrode, strontium ions have a volume expansion due to a change in the valence state, so that the electrode is easily collapsed and the performance is drastically lowered.
  • cerium oxide can not achieve good performance due to its poor conductivity.
  • cerium oxide when used as a supercapacitor electrode material, its specific capacity is due to its lower conductivity. Both rate performance and cycle stability are low. Therefore, in order to improve the performance and application of cerium oxide, it is still necessary to design a new structure to overcome the problems in the current application process.
  • a method for preparing a carbon-coated ceria hollow sphere comprises the following steps:
  • the silica dispersion is hydrothermally reacted with a cerium salt to obtain a cerium oxide-coated silica microsphere;
  • the ceria-coated silica microspheres are coated with a carbon source to obtain a primary product, the carbon source being dopamine;
  • the raw product is subjected to sintering treatment under a protective gas atmosphere to obtain carbon-coated cerium oxide microspheres;
  • the carbon-coated ceria microspheres are etched by an etchant to obtain a carbon-coated ceria hollow sphere.
  • FIG. 1 is a flow chart showing a method of preparing a carbon-coated ceria hollow sphere according to an embodiment
  • Example 2 is a scanning electron micrograph (a, b) and a transmission electron micrograph (c, d) of the carbon-coated ceria hollow sphere prepared in Example 1.
  • Example 3 is a scanning electron micrograph (a, b) and a transmission electron micrograph (c, d) of the carbon-coated ceria hollow sphere prepared in Example 5.
  • a method for preparing a carbon-coated ceria hollow sphere includes the following steps:
  • the silica has an average particle diameter of from 200 nm to 500 nm.
  • the solvent is selected from at least one of water, ethylene glycol, ethanol, and isopropyl alcohol.
  • the ratio of silica to solvent is from 1 mg/mL to 20 mg/mL.
  • the silica is dispersed in a solvent by stirring or ultrasonic dispersion.
  • the onium salt is selected from at least one of cerium nitrate, cerium acetylacetonate, cerium carbonate, cerium oxalate, and cerium sulfate.
  • the cerium salt is added to the silica dispersion as an aqueous solution of cerium salt, and the molar concentration of the cerium salt is from 1 mol/L to 3 mol/L. Further, the mass ratio of the lanthanum element in the silica to the cerium salt is 1:0.3 to 1:3.
  • the cerium salt and the silica dispersion were uniformly mixed and transferred to a polytetrafluoroethylene-lined stainless steel autoclave for hydrothermal reaction.
  • the temperature of the hydrothermal reaction solution is from 100 ° C to 180 ° C, and the hydrothermal reaction time is from 5 h to 20 h.
  • the temperature at which the hydrothermal reaction is carried out is from 110 ° C to 160 ° C.
  • the temperature of the hydrothermal reaction is low, which is favorable for improving the safety of the reaction and reducing the production cost, and controlling the temperature at 100 ° C to 180 ° C, or At 110 ° C to 160 ° C, it is possible to maintain a large amount of oxygen-containing groups on the surface of the silica, which is advantageous for forming a Si—O—Ce chemical bond on the surface of the silica.
  • the ceria-coated silica microspheres were washed alternately with water and ethanol. The number of times of washing with water and ethanol was 1 to 5 times.
  • the cerium oxide-coated silica microspheres are washed, centrifuged, and vacuum-dried at 50 ° C to 80 ° C.
  • the carbon source is selected from at least one of glucose, fructose, sucrose, and dopamine.
  • the step of coating the ceria-coated silica microspheres with a carbon source to obtain a primary product is: coating the ceria with silica
  • the microspheres are added to an aqueous solution of a carbon source and uniformly mixed, and then transferred to a hydrothermal kettle for hydrothermal reaction.
  • the temperature at which the hydrothermal reaction is carried out is from 160 ° C to 190 ° C, and the hydrothermal reaction is carried out for a period of from 2 h to 8 h.
  • the mass ratio of the carbon source to the silica-coated silica microspheres is 1:1 to 20:1.
  • the aqueous solution of the carbon source has a mass concentration of 1% by weight to 20% by weight.
  • the step of coating the ceria-coated silica microspheres with a carbon source to obtain a primary product is: adding ceria-coated silica microspheres to a pH of 7.4-9.0 After uniformly dispersing in the tris buffer solution, dopamine is added thereto for mixing for 1 h to 24 h to obtain an initial product.
  • the mass ratio of the cerium oxide-coated silica microspheres to the dopamine is from 4:1 to 1:3.
  • the ratio of the amount of the ceria-coated silica microspheres to the tris buffer is from 0.5 mg/mL to 20 mg/mL.
  • the mixing treatment is carried out by stirring, and the stirring speed is from 120 rad/min to 300 rad/min.
  • the above step of coating with dopamine as a carbon source is carried out at 15 ° C to 35 ° C.
  • the initial product is subjected to centrifugation, washing and drying.
  • the primary product was washed alternately with water and ethanol.
  • the number of times of washing with water and ethanol was 1 to 5 times.
  • the obtained solid is subjected to vacuum drying treatment at 50 to 80 °C.
  • the protective gas is selected from at least one of argon gas and nitrogen gas.
  • S170 etching the carbon-coated cerium oxide microspheres with an etchant to obtain a carbon-coated cerium oxide hollow sphere.
  • the etchant is selected from at least one of sodium hydroxide and hydrofluoric acid.
  • the etchant is an aqueous solution of sodium hydroxide or hydrofluoric acid. Further, the molar concentration of sodium hydroxide is from 2 mol/L to 5 mol/L; and the concentration of hydrofluoric acid is from 5% to 10%.
  • the carbon-coated ceria microspheres were immersed in an etchant for 24 to 72 hours to remove the silica to obtain a carbon-coated ceria hollow sphere.
  • the method for preparing the carbon-coated ceria hollow spheres is to prepare a ceria-coated silica microsphere by using silica as a template, and then coating the carbon layer on the ceria-coated silica microsphere and Sintering treatment, and then removing the silicon dioxide by using an etchant to obtain a carbon-coated ceria hollow sphere, the hollow structure is such that the carbon-coated ceria hollow sphere has a high specific surface area; and the carbon layer is evenly filled to two A film is formed on the surface of the cerium oxide grain and a film is formed on the surface of the cerium oxide, and a Ce-OC chemical bond is formed between the carbon layer and the cerium oxide, which can inhibit the growth of cerium dioxide during sintering, and prevent the hollow
  • the collapse of the cerium oxide microspheres makes the prepared carbon-coated cerium oxide hollow spheres have better structural stability, and also makes the cerium oxide crystallites smaller (within 30 nm), which is favorable for the specific
  • the coating of the ceria-coated silica microspheres with dopamine as a carbon source can be carried out only at 15 ° C to 35 ° C, and dopamine can be achieved without hydrothermal reaction.
  • the coating of cerium oxide-coated silica microspheres is beneficial to improve production safety and reduce production cost; and dopamine is a nitrogen-containing compound, and the coated carbon obtained by using dopamine as a carbon source is nitrogen-doped graphitized carbon.
  • the conductivity and electrochemical activity of the carbon dioxide-coated hollow spheres of the final product can be further improved.
  • the method for preparing the carbon-coated ceria hollow sphere is carried out by carbon coating and sintering to form a graphitized carbon layer, and then removing the silica template to facilitate the ceria-coated silica microspheres. Dispersion in a hydrophilic solvent to form a uniformly dispersed solution, thereby facilitating uniform coating of the carbon layer, and the carbon layer is not simply mixed with the ceria-coated silica microspheres, and is coated with cerium oxide. The presence of the silica-coated microspheres facilitates the uniform filling of carbon in the ceria grain gap and the formation of a carbon layer on the surface.
  • steps S130 and S150 may be omitted.
  • a carbon-coated ceria hollow sphere is prepared by the above preparation method.
  • silica having an average particle diameter of 200 nm was weighed and dispersed in 35 ml of ethylene glycol until the silica was uniformly dispersed to obtain a silica dispersion; 2 mL of a molar concentration of 1 mol/ was added to the silica dispersion.
  • L aqueous solution of cerium nitrate is uniformly dispersed by ultrasonic dispersion, and then transferred to a stainless steel high pressure autoclave lined with polytetrafluoroethylene to carry out hydrothermal reaction to obtain cerium oxide-coated silica microspheres, and the temperature of hydrothermal reaction is 130.
  • the reaction time is 15h; after the reactor is naturally cooled to room temperature, the reaction solution is centrifuged to obtain cerium oxide-coated silica microspheres, and the cerium oxide-coated silica microspheres are alternately centrifuged with water and ethanol. The mixture was washed and purified, and finally the ceria-coated silica microsphere solid was placed at 70 ° C for vacuum drying for 12 h. 50 mg of ceria-coated silica microspheres were added to 35 g of a 1 wt% aqueous solution of glucose, mixed uniformly, and transferred to a polytetrafluoroethylene-lined stainless steel autoclave for hydrothermal reaction to obtain a primary product.
  • the temperature of the hydrothermal reaction is 180 ° C, and the hydrothermal reaction time is 3 h.
  • the reaction vessel is naturally cooled to room temperature, the reaction solution is vacuum filtered, washed alternately with water and ethanol, and then vacuum dried at 70 ° C.
  • the initial product was obtained; the primary product was placed in a tube furnace, heated to 800 ° C at a heating rate of 2 ° C / min under an argon atmosphere, and then kept for 5 h, and then naturally cooled to obtain carbon-coated cerium oxide.
  • Microspheres; carbon-coated cerium oxide microspheres were immersed in a 5 mol/L sodium hydroxide solution for 48 hours to remove silica to obtain carbon-coated cerium oxide hollow spheres.
  • Example 2 The scanning electron micrograph of the carbon-coated ceria hollow sphere prepared in Example 1 is shown in a) and b) of Fig. 2, and the transmission electron micrograph of the carbon-coated ceria hollow sphere is shown in Figure 2, c) and d. ) shown.
  • silica having an average particle diameter of 500 nm was weighed and dispersed in 35 ml of water until the silica was uniformly dispersed to obtain a silica dispersion; and 1 mL of a carbonic acid having a molar concentration of 1 mol/L was added to the silica dispersion.
  • the hydrazine aqueous solution is uniformly dispersed by ultrasonic dispersion, and then transferred to a polytetrafluoroethylene-lined stainless steel high-pressure reaction vessel for hydrothermal reaction to obtain cerium oxide-coated silica microspheres, and the temperature of the hydrothermal reaction is 110 ° C.
  • the time is 20h; after the reactor is naturally cooled to room temperature, the reaction solution is centrifuged to obtain cerium oxide-coated silica microspheres, and the cerium oxide-coated silica microspheres are alternately washed and purified by using water and ethanol.
  • the finally obtained cerium oxide-coated silica microsphere solid was vacuum-dried at 70 ° C for 12 h.
  • 350 mg of ceria-coated silica microspheres were added to 35 g of a 20 wt% aqueous solution of fructose, mixed uniformly, and transferred to a polytetrafluoroethylene-lined stainless steel autoclave for hydrothermal reaction to obtain a primary product.
  • the temperature of the hydrothermal reaction is 160 ° C, and the hydrothermal reaction time is 3 h.
  • the reaction vessel is naturally cooled to room temperature, the reaction solution is vacuum filtered, washed alternately with water and ethanol, and then vacuum dried at 50 ° C.
  • the initial product was obtained after treatment for 24 hours; the primary product was placed in a tube furnace, heated to 900 ° C at a heating rate of 2 ° C / min under an argon atmosphere, and then kept for 2 h, and then naturally cooled to obtain carbon-coated cerium oxide.
  • Microspheres; carbon-coated cerium oxide microspheres were further immersed in a 5 wt% hydrofluoric acid solution for 48 hours to remove silica to obtain carbon-coated cerium oxide hollow spheres.
  • silica having an average particle diameter of 300 nm was weighed and dispersed in 35 ml of ethanol until the silica was uniformly dispersed to obtain a silica dispersion; 0.43 mL of a molar concentration of 3 mol/L was added to the silica dispersion.
  • the aqueous solution of oxalic acid is uniformly dispersed by ultrasonic dispersion, and then transferred to a stainless steel high pressure autoclave lined with polytetrafluoroethylene to carry out hydrothermal reaction to obtain ceria-coated silica microspheres, and the temperature of the hydrothermal reaction is 180 ° C.
  • the reaction time is 5h; after the reaction vessel is naturally cooled to room temperature, the reaction solution is centrifuged to obtain cerium oxide-coated silica microspheres, and the cerium oxide-coated silica microspheres are alternately washed by water and ethanol. After purification, the finally obtained ceria-coated silica microsphere solid was vacuum-dried at 70 ° C for 12 h. 175 mg of ceria-coated silica microspheres were added to 35 g of a sucrose aqueous solution having a mass concentration of 5 wt%, uniformly mixed, and transferred to a polytetrafluoroethylene-lined stainless steel autoclave for hydrothermal reaction to obtain a primary product.
  • the temperature of the hydrothermal reaction is 190 ° C, and the hydrothermal reaction time is 3 h.
  • the reaction vessel is naturally cooled to room temperature, the reaction solution is vacuum filtered, washed alternately with water and ethanol, and then vacuum dried at 80 ° C.
  • the initial product was obtained; the primary product was placed in a tube furnace, heated to 900 ° C at a heating rate of 5 ° C / min under an argon atmosphere, and then kept for 2 h, and then naturally cooled to obtain carbon-coated cerium oxide.
  • Microspheres; carbon-coated cerium oxide microspheres were immersed in a 5 mol/L sodium hydroxide solution for 48 hours to remove silica to obtain carbon-coated cerium oxide hollow spheres.
  • silica having an average particle diameter of 400 nm was weighed and dispersed in 35 ml of isopropyl alcohol until the silica was uniformly dispersed to obtain a silica dispersion; 0.32 mL of a molar concentration of 1.5 was added to the silica dispersion.
  • the mol/L aqueous solution of arsenic sulfate is uniformly dispersed by ultrasonic dispersion, and then transferred to a stainless steel high-pressure reaction vessel lined with polytetrafluoroethylene to carry out hydrothermal reaction to obtain cerium oxide-coated silica microspheres, hydrothermal reaction.
  • the temperature is 110 ° C, the reaction time is 16 h; after the reactor is naturally cooled to room temperature, the reaction solution is centrifuged to obtain cerium oxide-coated silica microspheres, and water and ethanol are alternately coated with cerium oxide-coated silica micro The ball was purified by centrifugal washing, and the finally obtained ceria-coated silica microsphere solid was vacuum-dried at 70 ° C for 12 h. 87.5mg of cerium oxide-coated silica microspheres were added to 35g of a 1% by weight aqueous solution of glucose and mixed uniformly, and then transferred to a polytetrafluoroethylene-lined stainless steel high-pressure reactor for hydrothermal reaction.
  • the product has a hydrothermal reaction temperature of 180 ° C and a hydrothermal reaction time of 3 h.
  • the reaction solution is vacuum filtered, washed alternately with water and ethanol, and then placed at 60 ° C for vacuum. Drying treatment for 18h to obtain the initial product; then the initial product was placed in a tube furnace, heated to 500 ° C at a heating rate of 1 ° C / min under argon atmosphere for 10 h, then naturally cooled to obtain carbon coated dioxide ⁇ microspheres; carbon-coated cerium oxide microspheres were immersed in 2 mol/L sodium hydroxide solution for 72 hours to remove silica to obtain carbon-coated cerium oxide hollow spheres.
  • silica dispersion Weigh 35 mg of silica having an average particle diameter of 200 nm and disperse it in 35 ml of ethylene glycol and stir until the silica is uniformly dispersed to obtain a silica dispersion; and add 0.56 mL of a molar concentration of 1 mol to the silica dispersion.
  • cerium oxide-coated silica microspheres were added to 100 mL of trimethylolamine buffer buffer of pH 7.4, and then uniformly dispersed at 22 ° C, 12.5 mg of dopamine was added thereto at a rotation speed.
  • the initial product was obtained by magnetic stirring at 120 rad/min for 20 hours; the reaction solution was vacuum filtered, washed alternately with water and ethanol, and then vacuum dried at 70 ° C for 12 h to obtain the initial product; then the initial product was placed in the tube.
  • the temperature is raised to 500 ° C at a heating rate of 2 ° C / min and then kept for 5 h, and then naturally cooled to obtain carbon-coated ceria microspheres; then carbon coated ceria microspheres
  • the silica was immersed in a 5 wt% hydrofluoric acid solution for 48 hours to remove carbon dioxide to obtain a carbon-coated cerium oxide hollow sphere.
  • silica having an average particle diameter of 500 nm was weighed and dispersed in 35 ml of ethylene glycol until the silica was uniformly dispersed to obtain a silica dispersion; and 1 mL of a molar concentration of 1 mol/ was added to the silica dispersion.
  • the aqueous solution of L-oxalate is uniformly dispersed by ultrasonic dispersion, and then transferred to a stainless steel high-pressure reaction vessel lined with polytetrafluoroethylene to carry out hydrothermal reaction to obtain ceria-coated silica microspheres, and the temperature of the hydrothermal reaction is 130.
  • the reaction time is 15h; after the reactor is naturally cooled to room temperature, the reaction solution is centrifuged to obtain cerium oxide-coated silica microspheres, and the cerium oxide-coated silica microspheres are alternately centrifuged with water and ethanol. The mixture was washed and purified, and finally the ceria-coated silica microsphere solid was placed at 70 ° C for vacuum drying for 12 h. 10 mg of cerium oxide-coated silica microspheres were added to 100 mL of trimethylolamine buffer buffer having a pH of 8.5, and then 30 mg of dopamine was added thereto at 35 ° C.
  • the initial product was obtained by magnetic stirring at 300 rad/min for 5 hours; the reaction solution was vacuum filtered, washed alternately with water and ethanol, and then vacuum dried at 70 ° C for 12 h to obtain the initial product; then the initial product was placed in a tube.
  • the temperature is raised to 600 ° C at a heating rate of 2 ° C / min and then kept for 5 h, and then naturally cooled to obtain carbon-coated cerium oxide microspheres; then carbon coated cerium oxide microspheres
  • the silica was immersed in a 5 mol/L sodium hydroxide solution for 48 hours to remove carbon dioxide to obtain a carbon-coated cerium oxide hollow sphere.
  • silica dispersion Weigh 35 mg of silica having an average particle diameter of 200 nm and disperse it in 35 ml of ethylene glycol and stir until the silica is uniformly dispersed to obtain a silica dispersion; and add 0.56 mL of a molar concentration of 1 mol to the silica dispersion.
  • cerium oxide-coated silica microspheres were added to 10 mL of trimethylolamine buffer buffer of pH 9.0, and 50 mg of dopamine was added thereto at 25 ° C.
  • the initial product was obtained by magnetic stirring at 120 rad/min for 20 hours; the reaction solution was vacuum filtered, washed alternately with water and ethanol, and then vacuum dried at 70 ° C for 12 h to obtain the initial product; then the initial product was placed in a tube.
  • the temperature is raised to 500 ° C at a heating rate of 2 ° C / min and then kept for 5 h, and then naturally cooled to obtain carbon-coated ceria microspheres; then carbon coated ceria microspheres
  • the silica was immersed in a 5 wt% hydrofluoric acid solution for 48 hours to remove carbon dioxide to obtain a carbon-coated cerium oxide hollow sphere.
  • silica having an average particle diameter of 500 nm was weighed and dispersed in 35 ml of ethylene glycol until the silica was uniformly dispersed to obtain a silica dispersion; and 1 mL of a molar concentration of 1 mol/ was added to the silica dispersion.
  • L aqueous solution of cerium nitrate is uniformly dispersed by ultrasonic dispersion, and then transferred to a stainless steel high pressure autoclave lined with polytetrafluoroethylene to carry out hydrothermal reaction to obtain cerium oxide-coated silica microspheres, and the temperature of hydrothermal reaction is 130.
  • the reaction time is 15h; after the reactor is naturally cooled to room temperature, the reaction solution is centrifuged to obtain cerium oxide-coated silica microspheres, and the cerium oxide-coated silica microspheres are alternately centrifuged with water and ethanol. The mixture was washed and purified, and finally the ceria-coated silica microsphere solid was placed at 70 ° C for vacuum drying for 12 h.
  • 100 mg of cerium oxide-coated silica microspheres were added to 100 mL of a hydroxymethylaminomethane buffer having a pH of 8.0, and then uniformly dispersed, and then 50 mg of dopamine was added thereto at 35 ° C at a rotation speed of
  • the initial product was obtained by magnetic stirring at 300 rad/min for 5 hours; the reaction solution was vacuum filtered, washed alternately with water and ethanol, and then vacuum dried at 70 ° C for 12 h to obtain the initial product; then the initial product was placed in a tube.
  • the temperature is raised to 600 ° C at a heating rate of 2 ° C / min and then kept for 5 h, and then naturally cooled to obtain carbon-coated cerium oxide microspheres; then carbon coated cerium oxide microspheres
  • the silica was immersed in a 5 mol/L sodium hydroxide solution for 48 hours to remove carbon dioxide to obtain a carbon-coated cerium oxide hollow sphere.
  • silica having an average particle diameter of 200 nm was weighed and dispersed in 35 ml of ethylene glycol until the silica was uniformly dispersed to obtain a silica dispersion; 2 mL of a molar concentration of 1 mol/ was added to the silica dispersion.
  • L aqueous solution of cerium nitrate is uniformly dispersed by ultrasonic dispersion, and then transferred to a stainless steel high pressure autoclave lined with polytetrafluoroethylene to carry out hydrothermal reaction to obtain cerium oxide-coated silica microspheres, and the temperature of hydrothermal reaction is 130.
  • the reaction time is 15h; after the reactor is naturally cooled to room temperature, the reaction solution is centrifuged to obtain cerium oxide-coated silica microspheres, and the cerium oxide-coated silica microspheres are alternately centrifuged with water and ethanol. The mixture was washed and purified, and finally the ceria-coated silica microsphere solid was placed at 70 ° C for vacuum drying for 12 h. The cerium oxide-coated silica microspheres were further immersed in a 5 mol/L sodium hydroxide solution for 48 hours to remove silica to obtain hollow cerium oxide microspheres.
  • cerium oxide hollow spheres were added to 35 g of a 1% by weight aqueous solution of glucose and mixed uniformly, and then transferred to a polytetrafluoroethylene-lined stainless steel high-pressure autoclave for hydrothermal reaction to obtain an initial product, hydrothermal reaction.
  • the temperature is 180 ° C
  • the hydrothermal reaction time is 3 h; after the reaction vessel is naturally cooled to room temperature, the reaction solution is vacuum filtered, washed alternately with water and ethanol, and then vacuum dried at 70 ° C for 12 h to obtain the initial product.
  • the primary product was placed in a tube furnace, heated to 800 ° C at a heating rate of 2 ° C / min under an argon atmosphere, and then incubated for 5 h, and then naturally cooled to obtain a carbon-coated ceria hollow sphere.
  • silica having an average particle diameter of 200 nm was weighed and dispersed in 35 ml of ethylene glycol until the silica was uniformly dispersed to obtain a silica dispersion; 2 mL of a molar concentration of 1 mol/ was added to the silica dispersion.
  • L aqueous solution of cerium nitrate is uniformly dispersed by ultrasonic dispersion, and then transferred to a stainless steel high pressure autoclave lined with polytetrafluoroethylene to carry out hydrothermal reaction to obtain cerium oxide-coated silica microspheres, and the temperature of hydrothermal reaction is 130.
  • the reaction time is 15h; after the reactor is naturally cooled to room temperature, the reaction solution is centrifuged to obtain cerium oxide-coated silica microspheres, and the cerium oxide-coated silica microspheres are alternately centrifuged with water and ethanol. The mixture was washed and purified, and finally the ceria-coated silica microsphere solid was placed at 70 ° C for vacuum drying for 12 h.
  • the ceria-coated silica microspheres were placed in a muffle furnace, heated to 500 ° C at a heating rate of 2 ° C/min in an air atmosphere, and then incubated for 5 h, and then naturally cooled to room temperature.
  • the cerium oxide-coated silica microspheres were further immersed in a 5 mol/L sodium hydroxide solution for 48 hours to remove silica to obtain hollow cerium oxide microspheres.
  • silica having an average particle diameter of 200 nm was weighed and dispersed in 35 ml of ethylene glycol until the silica was uniformly dispersed to obtain a silica dispersion; 2 mL of a molar concentration of 1 mol/ was added to the silica dispersion.
  • L aqueous solution of cerium nitrate is uniformly dispersed by ultrasonic dispersion, and then transferred to a stainless steel high pressure autoclave lined with polytetrafluoroethylene to carry out hydrothermal reaction to obtain cerium oxide-coated silica microspheres, and the temperature of hydrothermal reaction is 130.
  • the reaction time is 15h; after the reactor is naturally cooled to room temperature, the reaction solution is centrifuged to obtain cerium oxide-coated silica microspheres, and the cerium oxide-coated silica microspheres are alternately centrifuged with water and ethanol. The mixture was washed and purified, and finally the ceria-coated silica microsphere solid was placed at 70 ° C for vacuum drying for 12 h. 50 mg of ceria-coated silica microspheres were added to 35 g of a 1 wt% aqueous solution of glucose, mixed uniformly, and transferred to a polytetrafluoroethylene-lined stainless steel autoclave for hydrothermal reaction to obtain a primary product.
  • the temperature of the hydrothermal reaction is 180 ° C, and the hydrothermal reaction time is 3 h.
  • the reaction vessel is naturally cooled to room temperature, the reaction solution is vacuum filtered, washed alternately with water and ethanol, and then vacuum dried at 70 ° C.
  • the initial product was obtained; the primary product was placed in a tube furnace, heated to 800 ° C at a heating rate of 2 ° C / min under an argon atmosphere, and then kept for 5 h, and then naturally cooled to obtain carbon-coated cerium oxide. Microspheres.
  • the products prepared in the above Examples 1 to 11 were subjected to a specific surface area test using a specific surface area tester and applied to a supercapacitor: the obtained product, carbon black and polytetrafluoroethylene were mass ratio 7: 2:1 was thoroughly mixed, and absolute ethanol was added dropwise to form a paste, which was uniformly spread on foamed nickel, and vacuum-dried at 65 ° C for 8 hours to obtain an electrode.
  • the electrode prepared above is used as a working electrode, mercury/mercury oxide is used as a reference electrode, platinum wire electrode is a counter electrode, and 6 mol/L KOH solution is used as an electrolyte to form a three-electrode system.
  • the capacity and magnification are compared on the CHI660E electrochemical workstation. The performance and cycle stability were tested and the results are shown in Table 1.
  • the coated carbon obtained by using dopamine as a carbon source is nitrogen-doped graphitized carbon, the preparation method is simpler, and nitrogen-doped graphitized carbon can be generated, which can further improve the conductivity of the carbon dioxide-coated hollow sphere of the final product. Sexual and electrochemical activity.

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Abstract

一种碳包覆二氧化铈空心球的制备方法，包括以下步骤：S110、将二氧化硅分散在溶剂中得到二氧化硅分散液；S120、将二氧化硅分散液与铈盐进行水热反应得到二氧化铈包覆二氧化硅微球；S140、再采用碳源对二氧化铈包覆二氧化硅微球进行包覆得到初产物，碳源为多巴胺；S160、在保护性气体气氛下，将初产物进行烧结处理得到碳包覆二氧化铈微球；及S170、采用刻蚀剂对碳包覆二氧化铈微球进行刻蚀处理得到碳包覆二氧化铈空心球。

Description

碳包覆二氧化铈空心球的制备方法 技术领域：
本发明涉及新材料制备技术领域，特别是涉及碳包覆二氧化铈空心球的制备方法。
背景技术：
二氧化铈作为一种稀土金属氧化物，由于铈存在着两种氧化态(Ce +3和Ce +4)，具有氧化还原这一独特的化学特性，使其在催化、二次电池(如锂离子电池、锂硫电池等)和超级电容器等领域具有非常广泛的应用。
二氧化铈不论作为催化材料，还是电极材料，其性能极大的依赖于其比表面积，增加二氧化铈的比表面积能够极大的提高其在催化及其作为储能电极材料的性能。因此，通过把二氧化铈纳米化或将二氧化铈做成空心结构等以提高其比表面积是一种非常有效的方法。然而，当二氧化铈作为电极材料时，电极在充放电情况下，铈离子由于价态的变化而存在着体积膨胀，使得电极容易坍塌而导致性能急剧下降。
二氧化铈在应用过程中，由于其导电性能较差，其性能并不能达到较好的效果，例如，当二氧化铈作为超级电容器电极材料时，由于较低的导电性，使其比容量、倍率性能和循环稳定性均较低。因此，为了提高二氧化铈的性能及其应用，仍需设计新型的结构来克服当前应用过程中所存在的问题。
发明内容：
基于此，有必要针对二氧化铈材料易发生体积膨胀而坍塌及导电性能不佳的问题，提供一种碳包覆二氧化铈空心球的制备方法。
一种碳包覆二氧化铈空心球的制备方法，包括以下步骤：
将二氧化硅分散在溶剂中得到二氧化硅分散液；
所述二氧化硅分散液与铈盐进行水热反应得到二氧化铈包覆二氧化硅微球；
再采用碳源对所述二氧化铈包覆二氧化硅微球进行包覆得到初产物，所述碳源为多巴胺；
在保护性气体气氛下，将所述初产物进行烧结处理得到碳包覆二氧化铈微球；及
采用刻蚀剂对所述碳包覆二氧化铈微球进行刻蚀处理得到碳包覆二氧化铈空心球。
本发明的一个或多个实施例的细节在下面的附图和描述中提出。本发明的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。
附图说明
图1为一实施方式的碳包覆二氧化铈空心球的制备方法的流程图；
图2为实施例1制备得到的碳包覆二氧化铈空心球的扫描电镜图(a,b)和透射电镜图(c,d)；
图3为实施例5制备得到的碳包覆二氧化铈空心球的扫描电镜图(a,b)和透射电镜图(c,d)。
具体实施方式
下面将结合具体实施方式及附图对碳包覆二氧化铈空心球及其制备方法做进一步的详细说明。
请参阅图1，一实施方式的碳包覆二氧化铈空心球的制备方法，包括以下步骤：
S110、将二氧化硅分散在溶剂中得到二氧化硅分散液。
在其中一个实施方式中，二氧化硅的平均粒径为200nm-500nm。溶剂选 自水、乙二醇、乙醇和异丙醇中的至少一种。二氧化硅与溶剂的用量比为1mg/mL～20mg/mL。将二氧化硅分散在溶剂中采用搅拌或者超声波分散的方式进行。
S120、二氧化硅分散液与铈盐进行水热反应得到二氧化铈包覆二氧化硅微球。
在其中一个实施方式中，铈盐选自硝酸铈、乙酰丙酮化铈、碳酸铈、草酸铈和硫酸亚铈中的至少一种。铈盐以铈盐水溶液的形式加入到二氧化硅分散液中，铈盐的摩尔浓度为1mol/L～3mol/L。进一步的，二氧化硅与铈盐中铈元素的质量比为1:0.3～1:3。
将铈盐与二氧化硅分散液混合均匀后转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应。进行水热反应液的温度为100℃～180℃，进行水热反应的时间为5h～20h。优选的，进行水热反应的温度为110℃～160℃。
制备得到二氧化铈包覆二氧化硅微球的步骤中，进行水热反应的温度较低，有利于提高反应的安全性和降低生产成本，且将温度控制在100℃～180℃，也可以在110℃～160℃下，能够保持二氧化硅表面含有较多的含氧基团，有利于在二氧化硅表面形成Si-O-Ce化学键。
S130、将二氧化铈包覆二氧化硅微球进行离心、洗涤和干燥处理。
采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行洗涤。进行水洗及乙醇洗的次数为1～5次。对二氧化铈包覆二氧化硅微球进行洗涤后进行离心处理，再置于50℃～80℃下进行真空干燥处理。
S140、再采用碳源对二氧化铈包覆二氧化硅微球进行包覆得到初产物。
在其中一个实施方式中，碳源选自葡萄糖、果糖、蔗糖和多巴胺中的至少一种。
当碳源选自葡萄糖、果糖和蔗糖中的至少一种时，采用碳源对二氧化铈包覆二氧化硅微球进行包覆得到初产物的步骤为：将二氧化铈包覆二氧化硅微球加入到碳源的水溶液中混合均匀后转移至水热釜中进行水热反应。进行水热反应的温度为160℃～190℃，进行水热反应的时间为2h～8h。碳源与二氧 化铈包覆二氧化硅微球的质量比为1:1～20:1。碳源的水溶液的质量浓度为1wt％～20wt％。
当碳源为多巴胺时，采用碳源对二氧化铈包覆二氧化硅微球进行包覆得到初产物的步骤为：将二氧化铈包覆二氧化硅微球加入到pH值为7.4～9.0的三羟甲基氨基甲烷缓冲液中分散均匀后，再向其中加入多巴胺混合处理1h～24h得到初产物。二氧化铈包覆二氧化硅微球与多巴胺的质量比为4:1～1:3。二氧化铈包覆二氧化硅微球与三羟甲基氨基甲烷缓冲液的用量比为0.5mg/mL～20mg/mL。采用搅拌的方式进行混合处理，搅拌的转速为120rad/min～300rad/min。上述采用多巴胺作为碳源进行包覆的步骤在15℃～35℃下进行。
S150、将初产物进行离心、洗涤和干燥处理。
采用水和乙醇交替对初产物进行洗涤。进行水洗及乙醇洗的次数为1～5次。将经过水和乙醇交替洗涤后的初产物进行离心后，将得到的固体置于50℃～80℃下进行真空干燥处理。
S160、在保护性气体气氛下，将初产物进行烧结处理得到碳包覆二氧化铈微球。
保护性气体选自氩气和氮气中的至少一种。进行烧结处理时升温至500℃～900℃，并保温2h～10h。进行烧结处理时在管式炉中进行，且升温速率为1℃/min～5℃/min。
S170、采用刻蚀剂对碳包覆二氧化铈微球进行刻蚀处理得到碳包覆二氧化铈空心球。
刻蚀剂选自氢氧化钠和氢氟酸中的至少一种。刻蚀剂为氢氧化钠或氢氟酸的水溶液。进一步的氢氧化钠的摩尔浓度为2mol/L～5mol/L；氢氟酸的质量浓度为5％～10％。
将碳包覆二氧化铈微球浸渍在刻蚀剂中24h～72h以除去二氧化硅得到碳包覆二氧化铈空心球。
上述碳包覆二氧化铈空心球的制备方法，先以二氧化硅为模板制备二氧 化铈包覆二氧化硅微球，再在二氧化铈包覆二氧化硅微球上包覆碳层并进行烧结处理，再采用刻蚀剂除去二氧化硅以得到碳包覆二氧化铈空心球，空心结构使得碳包覆二氧化铈空心球具有较高的比表面积；另外碳层均匀的填充到二氧化铈晶粒缝隙中并在二氧化铈表面形成一层薄膜，且碳层与二氧化铈之间形成Ce-O-C化学键，可以抑制二氧化铈在烧结过程中晶粒的生长，防止了空心二氧化铈微球的坍塌，使得制备得到的碳包覆二氧化铈空心球具有较好的结构稳定性；同时也使得二氧化铈晶粒较小(30nm内)，有利于比表面积的提高。另外，所形成的碳层为石墨化碳，具有较高的导电性，与CeO 2包覆并化学结合后，能够极大的提高CeO 2的导电性，从而提高其电化学性能。
需要强调的是，采用多巴胺作为碳源对二氧化铈包覆二氧化硅微球进行包覆时只需在15℃～35℃下进行即可，不需要进行水热反应即可实现多巴胺在二氧化铈包覆二氧化硅微球的包覆，有利于提高生产的安全性并降低生产成本；且多巴胺为含氮化合物，采用多巴胺作为碳源得到的包覆碳为氮掺杂的石墨化碳，能够进一步提高终产物碳包覆二氧化铈空心球的导电性和电化学活性。
另外，上述碳包覆二氧化铈空心球的制备方法，在进行碳包覆并烧结形成石墨化碳层后再进行去除二氧化硅模板的步骤，有利于二氧化铈包覆二氧化硅微球在亲水性溶剂中的分散，从而形成分散均匀的溶液，从而有利于碳层的均匀包覆，而且碳层并不是与二氧化铈包覆二氧化硅微球简单混合，以二氧化铈包覆二氧化硅微球的形式存在能够有利于碳在二氧化铈晶粒缝隙中均匀的填充并在表面形成碳层。
需要说明的是，上述碳包覆二氧化铈空心球的制备方法中，步骤S130和S150均可以省略。
一种碳包覆二氧化铈空心球通过上述制备方法制备得到。
下面是具体实施例的说明，以下实施例如无特殊说明，则不含有除不可避免的杂质以外的其他未明确指出的组分。
实施例1
称取250mg的平均粒径为200nm的二氧化硅分散在35ml的乙二醇中搅拌至二氧化硅分散均匀得到二氧化硅分散液；向二氧化硅分散液中加入2mL的摩尔浓度为1mol/L的硝酸铈水溶液，通过超声波分散混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到二氧化铈包覆二氧化硅微球，水热反应的温度为130℃，反应时间为15h；反应釜自然冷却至室温后，反应液通过离心得到二氧化铈包覆二氧化硅微球，并采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行离心洗涤纯化，最后得到的二氧化铈包覆二氧化硅微球固体再置于70℃下进行真空干燥处理12h。将50mg的二氧化铈包覆二氧化硅微球加入到35g质量浓度为1wt％的葡萄糖水溶液中混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到初产物，水热反应的温度为180℃，水热反应的时间为3h；反应釜自然冷却至室温后，反应液通过真空抽滤，并采用水和乙醇交替洗涤，再置于70℃下进行真空干燥处理12h得到初产物；再将初产物放置于管式炉中，在氩气的气氛下，以2℃/min的升温速率升温至800℃后保温5h，然后自然冷却得到碳包覆二氧化铈微球；再将碳包覆二氧化铈微球置于5mol/L的氢氧化钠溶液中浸渍48h除去二氧化硅得到碳包覆二氧化铈空心球。实施例1制备得到的碳包覆二氧化铈空心球的扫描电镜图如图2中a)和b)所示，碳包覆二氧化铈空心球的透射电镜图如图2中c)和d)所示。
实施例2
称取250mg的平均粒径为500nm的二氧化硅分散在35ml的水中搅拌至二氧化硅分散均匀得到二氧化硅分散液；向二氧化硅分散液中加入1mL的摩尔浓度为1mol/L的碳酸铈水溶液，通过超声波分散混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到二氧化铈包覆二氧化硅微球，水热反应的温度为110℃，反应时间为20h；反应釜自然冷却至室温后，反应液通过离心得到二氧化铈包覆二氧化硅微球，并采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行离心洗涤纯化，最后得到的二氧化铈包覆二氧 化硅微球固体再置于70℃下进行真空干燥处理12h。将350mg的二氧化铈包覆二氧化硅微球加入到35g质量浓度为20wt％的果糖水溶液中混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到初产物，水热反应的温度为160℃，水热反应的时间为3h；反应釜自然冷却至室温后，反应液通过真空抽滤，并采用水和乙醇交替洗涤，再置于50℃下进行真空干燥处理24h得到初产物；再将初产物放置于管式炉中，在氩气的气氛下，以2℃/min的升温速率升温至900℃后保温2h，然后自然冷却得到碳包覆二氧化铈微球；再将碳包覆二氧化铈微球置于5wt％的氢氟酸溶液中浸渍48h除去二氧化硅得到碳包覆二氧化铈空心球。
实施例3
称取450mg的平均粒径为300nm的二氧化硅分散在35ml的乙醇中搅拌至二氧化硅分散均匀得到二氧化硅分散液；向二氧化硅分散液中加入0.43mL的摩尔浓度为3mol/L的草酸铈水溶液，通过超声波分散混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到二氧化铈包覆二氧化硅微球，水热反应的温度为180℃，反应时间为5h；反应釜自然冷却至室温后，反应液通过离心得到二氧化铈包覆二氧化硅微球，并采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行离心洗涤纯化，最后得到的二氧化铈包覆二氧化硅微球固体再置于70℃下进行真空干燥处理12h。将175mg的二氧化铈包覆二氧化硅微球加入到35g质量浓度为5wt％的蔗糖水溶液中混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到初产物，水热反应的温度为190℃，水热反应的时间为3h；反应釜自然冷却至室温后，反应液通过真空抽滤，并采用水和乙醇交替洗涤，再置于80℃下进行真空干燥处理6h得到初产物；再将初产物放置于管式炉中，在氩气的气氛下，以5℃/min的升温速率升温至900℃后保温2h，然后自然冷却得到碳包覆二氧化铈微球；再将碳包覆二氧化铈微球置于5mol/L的氢氧化钠溶液中浸渍48h除去二氧化硅得到碳包覆二氧化铈空心球。
实施例4
称取45mg的平均粒径为400nm的二氧化硅分散在35ml的异丙醇中搅拌至二氧化硅分散均匀得到二氧化硅分散液；向二氧化硅分散液中加入0.32mL的摩尔浓度为1.5mol/L的硫酸亚铈水溶液，通过超声波分散混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到二氧化铈包覆二氧化硅微球，水热反应的温度为110℃，反应时间为16h；反应釜自然冷却至室温后，反应液通过离心得到二氧化铈包覆二氧化硅微球，并采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行离心洗涤纯化，最后得到的二氧化铈包覆二氧化硅微球固体再置于70℃下进行真空干燥处理12h。将87.5mg的二氧化铈包覆二氧化硅微球加入到35g质量浓度为1wt％的葡萄糖水溶液中混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到初产物，水热反应的温度为180℃，水热反应的时间为3h；反应釜自然冷却至室温后，反应液通过真空抽滤，并采用水和乙醇交替洗涤，再置于60℃下进行真空干燥处理18h得到初产物；再将初产物放置于管式炉中，在氩气的气氛下，以1℃/min的升温速率升温至500℃后保温10h，然后自然冷却得到碳包覆二氧化铈微球；再将碳包覆二氧化铈微球置于2mol/L的氢氧化钠溶液中浸渍72h除去二氧化硅得到碳包覆二氧化铈空心球。
实施例5
称取35mg的平均粒径为200nm的二氧化硅分散在35ml的乙二醇中搅拌至二氧化硅分散均匀得到二氧化硅分散液；向二氧化硅分散液中加入0.56mL的摩尔浓度为1mol/L的乙酰丙酮化铈水溶液，通过超声波分散混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到二氧化铈包覆二氧化硅微球，水热反应的温度为160℃，反应时间为10h；反应釜自然冷却至室温后，反应液通过离心得到二氧化铈包覆二氧化硅微球，并采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行离心洗涤纯化，最后得到的二氧 化铈包覆二氧化硅微球固体再置于70℃下进行真空干燥处理12h。将50mg的二氧化铈包覆二氧化硅微球加入到100mL的pH值为7.4的三羟甲基氨基甲烷缓冲液中分散均匀后，在22℃下再向其中加入12.5mg的多巴胺，在转速为120rad/min下磁力搅拌混20h得到初产物；反应液通过真空抽滤，并采用水和乙醇交替洗涤，再置于70℃下进行真空干燥处理12h得到初产物；再将初产物放置于管式炉中，在氩气的气氛下，以2℃/min的升温速率升温至500℃后保温5h，然后自然冷却得到碳包覆二氧化铈微球；再将碳包覆二氧化铈微球置于5wt％的氢氟酸溶液中浸渍48h除去二氧化硅得到碳包覆二氧化铈空心球。
实施例6
称取250mg的平均粒径为500nm的二氧化硅分散在35ml的乙二醇中搅拌至二氧化硅分散均匀得到二氧化硅分散液；向二氧化硅分散液中加入1mL的摩尔浓度为1mol/L的草酸铈水溶液，通过超声波分散混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到二氧化铈包覆二氧化硅微球，水热反应的温度为130℃，反应时间为15h；反应釜自然冷却至室温后，反应液通过离心得到二氧化铈包覆二氧化硅微球，并采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行离心洗涤纯化，最后得到的二氧化铈包覆二氧化硅微球固体再置于70℃下进行真空干燥处理12h。将10mg的二氧化铈包覆二氧化硅微球加入到100mL的pH值为8.5的三羟甲基氨基甲烷缓冲液中分散均匀后，在35℃下再向其中加入30mg的多巴胺，在转速为300rad/min下磁力搅拌混5h得到初产物；反应液通过真空抽滤，并采用水和乙醇交替洗涤，再置于70℃下进行真空干燥处理12h得到初产物；再将初产物放置于管式炉中，在氩气的气氛下，以2℃/min的升温速率升温至600℃后保温5h，然后自然冷却得到碳包覆二氧化铈微球；再将碳包覆二氧化铈微球置于5mol/L的氢氧化钠溶液中浸渍48h除去二氧化硅得到碳包覆二氧化铈空心球。
实施例7
称取35mg的平均粒径为200nm的二氧化硅分散在35ml的乙二醇中搅拌至二氧化硅分散均匀得到二氧化硅分散液；向二氧化硅分散液中加入0.56mL的摩尔浓度为1mol/L的乙酰丙酮化铈水溶液，通过超声波分散混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到二氧化铈包覆二氧化硅微球，水热反应的温度为150℃，反应时间为12h；反应釜自然冷却至室温后，反应液通过离心得到二氧化铈包覆二氧化硅微球，并采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行离心洗涤纯化，最后得到的二氧化铈包覆二氧化硅微球固体再置于70℃下进行真空干燥处理12h。将50mg的二氧化铈包覆二氧化硅微球加入到10mL的pH值为9.0的三羟甲基氨基甲烷缓冲液中分散均匀后，在25℃下再向其中加入50mg的多巴胺，在转速为120rad/min下磁力搅拌混20h得到初产物；反应液通过真空抽滤，并采用水和乙醇交替洗涤，再置于70℃下进行真空干燥处理12h得到初产物；再将初产物放置于管式炉中，在氩气的气氛下，以2℃/min的升温速率升温至500℃后保温5h，然后自然冷却得到碳包覆二氧化铈微球；再将碳包覆二氧化铈微球置于5wt％的氢氟酸溶液中浸渍48h除去二氧化硅得到碳包覆二氧化铈空心球。
实施例8
称取250mg的平均粒径为500nm的二氧化硅分散在35ml的乙二醇中搅拌至二氧化硅分散均匀得到二氧化硅分散液；向二氧化硅分散液中加入1mL的摩尔浓度为1mol/L的硝酸铈水溶液，通过超声波分散混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到二氧化铈包覆二氧化硅微球，水热反应的温度为130℃，反应时间为15h；反应釜自然冷却至室温后，反应液通过离心得到二氧化铈包覆二氧化硅微球，并采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行离心洗涤纯化，最后得到的二氧化铈包 覆二氧化硅微球固体再置于70℃下进行真空干燥处理12h。将100mg的二氧化铈包覆二氧化硅微球加入到100mL的pH值为8.0的三羟甲基氨基甲烷缓冲液中分散均匀后，在35℃下再向其中加入50mg的多巴胺，在转速为300rad/min下磁力搅拌混5h得到初产物；反应液通过真空抽滤，并采用水和乙醇交替洗涤，再置于70℃下进行真空干燥处理12h得到初产物；再将初产物放置于管式炉中，在氩气的气氛下，以2℃/min的升温速率升温至600℃后保温5h，然后自然冷却得到碳包覆二氧化铈微球；再将碳包覆二氧化铈微球置于5mol/L的氢氧化钠溶液中浸渍48h除去二氧化硅得到碳包覆二氧化铈空心球。
实施例9
称取250mg的平均粒径为200nm的二氧化硅分散在35ml的乙二醇中搅拌至二氧化硅分散均匀得到二氧化硅分散液；向二氧化硅分散液中加入2mL的摩尔浓度为1mol/L的硝酸铈水溶液，通过超声波分散混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到二氧化铈包覆二氧化硅微球，水热反应的温度为130℃，反应时间为15h；反应釜自然冷却至室温后，反应液通过离心得到二氧化铈包覆二氧化硅微球，并采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行离心洗涤纯化，最后得到的二氧化铈包覆二氧化硅微球固体再置于70℃下进行真空干燥处理12h。再将二氧化铈包覆二氧化硅微球置于5mol/L的氢氧化钠溶液中浸渍48h除去二氧化硅得到空心二氧化铈微球。将50mg的二氧化铈空心球加入到35g质量浓度为1wt％的葡萄糖水溶液中混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到初产物，水热反应的温度为180℃，水热反应的时间为3h；反应釜自然冷却至室温后，反应液通过真空抽滤，并采用水和乙醇交替洗涤，再置于70℃下进行真空干燥处理12h得到初产物；再将初产物放置于管式炉中，在氩气的气氛下，以2℃/min的升温速率升温至800℃后保温5h，然后自然冷却得到碳包覆二氧化铈空心球。
实施例10
称取250mg的平均粒径为200nm的二氧化硅分散在35ml的乙二醇中搅拌至二氧化硅分散均匀得到二氧化硅分散液；向二氧化硅分散液中加入2mL的摩尔浓度为1mol/L的硝酸铈水溶液，通过超声波分散混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到二氧化铈包覆二氧化硅微球，水热反应的温度为130℃，反应时间为15h；反应釜自然冷却至室温后，反应液通过离心得到二氧化铈包覆二氧化硅微球，并采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行离心洗涤纯化，最后得到的二氧化铈包覆二氧化硅微球固体再置于70℃下进行真空干燥处理12h。将二氧化铈包覆二氧化硅微球放置于马弗炉中，在空气的气氛下，以2℃/min的升温速率升温至500℃后保温5h，然后自然冷却至室温。再将二氧化铈包覆二氧化硅微球置于5mol/L的氢氧化钠溶液中浸渍48h除去二氧化硅得到空心二氧化铈微球。
实施例11
称取250mg的平均粒径为200nm的二氧化硅分散在35ml的乙二醇中搅拌至二氧化硅分散均匀得到二氧化硅分散液；向二氧化硅分散液中加入2mL的摩尔浓度为1mol/L的硝酸铈水溶液，通过超声波分散混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到二氧化铈包覆二氧化硅微球，水热反应的温度为130℃，反应时间为15h；反应釜自然冷却至室温后，反应液通过离心得到二氧化铈包覆二氧化硅微球，并采用水和乙醇交替对二氧化铈包覆二氧化硅微球进行离心洗涤纯化，最后得到的二氧化铈包覆二氧化硅微球固体再置于70℃下进行真空干燥处理12h。将50mg的二氧化铈包覆二氧化硅微球加入到35g质量浓度为1wt％的葡萄糖水溶液中混合均匀后，转移至聚四氟乙烯内衬的不锈钢高压反应釜中进行水热反应得到初产物，水热反应的温度为180℃，水热反应的时间为3h；反应釜自然冷却至 室温后，反应液通过真空抽滤，并采用水和乙醇交替洗涤，再置于70℃下进行真空干燥处理12h得到初产物；再将初产物放置于管式炉中，在氩气的气氛下，以2℃/min的升温速率升温至800℃后保温5h，然后自然冷却得到碳包覆二氧化铈微球。
利用比表面积测试仪对上述实施例1～实施例11制备得到的产物进行比表面积测试，并将其应用于超级电容器中：将所获的产物、炭黑和聚四氟乙烯按质量比7：2：1充分混合，滴加无水乙醇形成糊状物，将其均匀涂抹在泡沫镍上，在65℃真空干燥8h得到电极。以上述制备的电极为工作电极，汞/氧化汞为参比电极，铂丝电极为对电极，6mol/L的KOH溶液为电解液构成三电极体系，利用CHI660E型电化学工作站上对比容量、倍率性能和循环稳定性进行测试，结果如表1所示。
表1
Figure PCTCN2018081841-appb-000001
采用多巴胺作为碳源得到的包覆碳为氮掺杂的石墨化碳，制备方法更简单，且能够生成氮掺杂的石墨化碳，能够进一步提高终产物碳包覆二氧化铈空心球的导电性和电化学活性。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (16)

  1. 一种碳包覆二氧化铈空心球的制备方法，包括以下步骤：
    将二氧化硅分散在溶剂中得到二氧化硅分散液；
    所述二氧化硅分散液与铈盐进行水热反应得到二氧化铈包覆二氧化硅微球；
    再采用碳源对所述二氧化铈包覆二氧化硅微球进行包覆得到初产物，所述碳源为多巴胺；
    在保护性气体气氛下，将所述初产物进行烧结处理得到碳包覆二氧化铈微球；及
    采用刻蚀剂对所述碳包覆二氧化铈微球进行刻蚀处理得到碳包覆二氧化铈空心球。
  2. 根据权利要求1所述的制备方法，其特征在于，所述再采用碳源对所述二氧化铈包覆二氧化硅微球进行包覆得到初产物的步骤具体为：
    将所述二氧化铈包覆二氧化硅微球加入到pH值为7.4～9.0的三羟甲基氨基甲烷缓冲液中；及
    在15℃～35℃下加入多巴胺混合处理1h～24h得到初产物。
  3. 根据权利要求2所述的制备方法，其特征在于，所述二氧化铈包覆二氧化硅微球与所述三羟甲基氨基甲烷缓冲液的用量比为0.5mg/mL～20mg/mL。
  4. 根据权利要求1所述的制备方法，其特征在于，所述二氧化铈包覆二氧化硅微球与所述多巴胺的质量比为4:1～1:3。
  5. 根据权利要求1所述的制备方法，其特征在于，所述溶剂选自水、乙二醇、乙醇和异丙醇中的至少一种。
  6. 根据权利要求1所述的制备方法，其特征在于，所述二氧化硅与所述溶剂的用量比为1mg/mL～20mg/mL。
  7. 根据权利要求1所述的制备方法，其特征在于，所述铈盐选自硝酸铈、乙酰丙酮化铈、碳酸铈、草酸铈和硫酸亚铈中的至少一种。
  8. 根据权利要求1所述的制备方法，其特征在于，所述二氧化硅与所述铈盐中铈元素的质量比为1:0.3～1:3。
  9. 根据权利要求1所述的制备方法，其特征在于，所述二氧化硅分散液与铈盐进行水热反应得到二氧化铈包覆二氧化硅微球的步骤中水热反应的温度为100℃～180℃，水热反应的时间为5h～20h。
  10. 根据权利要求9所述的制备方法，其特征在于，所述水热反应的温度为110℃～160℃。
  11. 根据权利要求1所述的制备方法，其特征在于，所述将所述初产物进行烧结处理得到碳包覆二氧化铈微球的步骤中，烧结处理时升温至500℃～900℃，并保温2h～10h。
  12. 根据权利要求11所述的制备方法，其特征在于，进行所述烧结处理时的升温速率为1℃/min～5℃/min。
  13. 根据权利要求1所述的制备方法，其特征在于，所述刻蚀剂选自氢氧化钠和氢氟酸中的至少一种。
  14. 根据权利要求13所述的制备方法，其特征在于，所述刻蚀剂为氢氧化钠水溶液，所述氢氧化钠水溶液的摩尔浓度为2mol/L～5mol/L。
  15. 根据权利要求13所述的制备方法，其特征在于，所述刻蚀剂为氢氟酸水溶液，所述氢氟酸水溶液的质量浓度为5％～10％。
  16. 根据权利要求1所述的制备方法，其特征在于，所述刻蚀处理的步骤具体为将所述碳包覆二氧化铈微球浸渍在所述刻蚀剂中24h～72h。
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