CN110931767A - SnO modified by carbon-coated FeCo alloy2Negative electrode material of sodium ion battery and preparation method thereof - Google Patents
SnO modified by carbon-coated FeCo alloy2Negative electrode material of sodium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of sodium ion batteries and discloses SnO modified by carbon-coated FeCo alloy2The negative electrode material of the sodium-ion battery and the preparation method thereof comprise the following formula raw materials: FeCo alloy modified nano SnO2Hollow microspheres, 3-aminophenol, phytic acid, potassium persulfate, a phosphorylation catalyst and a condensing agent. The carbon-coated FeCo alloy modified SnO2Negative electrode material of sodium ion battery and its preparation method, Fe-Co in SnO2The surface of the hollow microsphere forms alloy with Sn, so that the conductivity of the negative electrode material is enhanced, and Na + and electron diffusion are improvedDispersion and transmission rate, Fe-Co-Sn alloy inhibits nano SnO2Agglomerated into particles, and N-P-O co-doped porous carbon coated nano SnO2The hollow microspheres have the advantages that the N doping enhances the conductivity of the porous carbon material, the P doping enlarges the interlayer spacing of the porous carbon, a richer pore structure is formed, and Na is removed and embedded in the tin-based negative electrode material+In the process, the expansion buffer is improved, rich active defect sites are formed by doping O, and the sodium storage capacity of the cathode material is improved.
Description
Technical Field
The invention relates to the field of sodium ion batteries, in particular to SnO modified by carbon-coated FeCo alloy2A negative electrode material of a sodium ion battery and a preparation method thereof.
Background
The sodium ion battery is a rechargeable secondary battery mainlyRely on Na+Moving between positive and negative electrodes to work, Na during charging+The anode is in a sodium-rich state; na at discharge+The lithium ion battery is separated from the cathode, is inserted into the anode through the electrolyte, has a similar working principle as a lithium ion battery, and has various advantages compared with the lithium ion battery, such as rich sodium salt raw material reserves and low price; the sodium ion battery can use low-concentration electrolyte for work; na (Na)+The aluminum alloy does not form an alloy with aluminum, and the battery cathode material can adopt aluminum foil which is cheap and easy to obtain as a current collector; the sodium ion battery has no over-discharge characteristic and can discharge to zero volt.
The sodium ion battery mainly comprises a positive electrode material, a negative electrode material, electrolyte, a diaphragm and other materials, wherein the electrochemical performance of the negative electrode material directly influences the performance of the sodium ion battery; titanium-based compounds, e.g. TiO2、Li4Ti5O12、Na2Ti3O7(ii) a Alloy material such as SiNa alloy and Na15Sn4Alloys and the like; metal compound materials such as metal oxide Fe2O3Metallic sulfide SnS2Etc.; organic compounds such as nano-sized sodium terephthalate, 2, 5-dihydroxy-1, 4 benzoquinone disodium salt, etc.
Sn can form an alloy with higher specific capacity with Na, elemental tin, tin oxide and tin nano material can form a composite material with a carbon material, and the composite material is a sodium ion battery cathode material with great potential, but the existing sodium ion battery tin-based cathode material can be caused by Na in the charging and discharging processes+The method leads the volume of the matrix to expand and contract irreversibly, leads the cathode material to be worn or even decomposed, reduces the specific capacitance and the cycle stability of the cathode material, has low conductivity of the tin-based cathode material, hinders the migration and the transmission of Na + and electrons between the cathode material and an electrolyte, inhibits the forward progress of electrochemical reaction, and reduces the rate capability of the cathode material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides SnO modified by carbon-coated FeCo alloy2The negative electrode material of the sodium ion battery and the preparation method thereof solve the problems that a matrix is easy to expand and contract irreversibly to cause the loss and even decomposition of the negative electrode material in the charging and discharging processes of the tin-based negative electrode material, and simultaneously solve the problems that the conductivity of the tin-based negative electrode material is not high, and the migration and transmission of Na + and electrons between the negative electrode material and an electrolyte are inhibited.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: SnO modified by carbon-coated FeCo alloy2The negative electrode material of the sodium-ion battery and the preparation method thereof comprise the following formula raw materials in parts by weight: 12-30 parts of FeCo alloy modified nano SnO2Hollow microspheres, 18-22 parts of 3-aminophenol, 20-25 parts of phytic acid, 20-24 parts of potassium persulfate, 1-2 parts of a phosphorylation catalyst and 11-15 parts of a condensing agent.
Preferably, the phosphorylation catalyst is p-toluenesulfonic acid.
Preferably, the condensing agent isN,N"-diisopropylcarbodiimide.
Preferably, the FeCo alloy is modified with nano SnO2The preparation method of the hollow microsphere comprises the following steps:
(1) addition of SnCl to distilled water in reaction flask4And urea, placing a reaction bottle in an ultrasonic dispersion instrument, heating to 70-80 ℃, carrying out ultrasonic dispersion treatment for 1-2 h at the ultrasonic frequency of 20-25 KHz, adding an ethanol solvent, wherein the volume ratio of the ethanol solvent to distilled water is 2-2.5:1, transferring the solution into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle in a reaction kettle heating box, heating to 220-240 ℃, reacting for 18-20 h, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with a proper amount of distilled water, fully drying, and preparing to obtain the nano SnO2Hollow microspheres.
(2) Adding a proper amount of distilled water solvent into a reaction bottle, and then sequentially adding FeCl3、CoCl2Urotropin, citric acid dispersant and nano SnO2Hollow micro-meterPlacing the reaction bottle in an ultrasonic dispersion instrument, heating to 60-70 ℃, carrying out ultrasonic dispersion treatment for 1-2 h, heating the solution again to 100 ℃ and carrying out reflux reaction for 10-12 h, carrying out reduced pressure distillation on the solution to remove the solvent, washing the solid product by using a proper amount of distilled water, placing the solid product in an air-blast drier, fully drying at 70-80 ℃, placing the solid product in a resistance furnace, heating to 420 ℃ and 440 ℃ at the heating rate of 2-4 ℃/min, and calcining for 4-6h, wherein the calcined product is FeCo alloy modified nano SnO2Hollow microspheres.
Preferably, the SnCl4The mass molar ratio of the urea to the substance is 1: 6.5-7.
Preferably, the FeCl3、CoCl2Urotropin, citric acid and nano SnO2The weight molar ratio of the five substances is 1:1.2-1.5:1-1.2:0.2-0.4: 0.4-0.5.
Preferably, the carbon-coated FeCo alloy modified SnO2The preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
(1) adding a proper amount of mixed solvent of ethylene glycol and distilled water into a reaction bottle, wherein the volume ratio of the ethylene glycol to the distilled water is 3-4:1, and then sequentially adding 18-22 parts of 3-aminophenol, 20-25 parts of phytic acid and 12-30 parts of FeCo alloy modified nano SnO2Hollow microsphere, placing reaction bottle in ultrasonic disperser, heating to 70-80 deg.C, ultrasonic frequency is 20-25 KHz, ultrasonic dispersing for 1-2 hr, adding 20-24 parts of potassium persulfate, placing reaction bottle in low-temperature cooler, stirring at-5-0 deg.C and uniform speed for 5-8 hr, adding 1-2 parts of phosphoric esterification catalyst p-methyl benzenesulfonic acid and 11-15 parts of condensing agentN,NPutting the solution into an oil bath, heating to 120-140 ℃, uniformly stirring for reaction for 20-25 h, cooling the solution to room temperature, adding excessive distilled water until a large amount of solid is separated out, passing the solution through a high-speed centrifuge, removing the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the nano SnO modified by the phosphoric acid esterified polyaniline coated FeCo alloy2Hollow microspheres.
(2) Phosphoric acid esterified polyaniline coated FeCo alloy modified nano SnO2Placing the hollow microspheres in an atmosphere resistance furnace, heating to 820-850 ℃ at the heating rate of 3-5 ℃/min2Calcining for 6-8 h in the atmosphere, wherein the calcined product is SnO modified by carbon-coated FeCo alloy2The negative electrode material of the sodium ion battery.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the carbon-coated FeCo alloy modified SnO2Sodium ion battery negative electrode material and preparation method thereof, and nano SnO2The hollow microsphere has an ultra-large specific surface area, and Fe-Co prepared by an in-situ growth method is in SnO2The surface of the hollow microsphere forms an alloy with Sn, the metal property of the alloy enhances the conductivity of the negative electrode material, improves the diffusion and transmission rate of Na + and electrons between the negative electrode material and the electrolyte, and promotes the forward proceeding of electrochemical reaction, thereby enhancing the rate capability of the negative electrode material, and the Fe-Co-Sn alloy inhibits the nano SnO2Agglomerate into particles and shorten Na+While increasing the active sites of the anode material.
The carbon-coated FeCo alloy modified SnO2Sodium ion battery cathode material and preparation method thereof, and nanometer SnO coated with phosphated polyaniline2Calcining the hollow microspheres to form N-P-O co-doped porous carbon-coated nano SnO2The hollow microspheres are doped with N to form graphite nitrogen and pyridine nitrogen structures in porous carbon, the graphite nitrogen structures enhance the conductivity of the porous carbon material and promote the transmission and diffusion of electrons, and the pyridine nitrogen structures reduce Na+Overpotential of a de-intercalation interface between the cathode material and the electrolyte promotes forward progress of electrode redox reaction, the radius of P atoms is much larger than that of C atoms, and the interlayer spacing of porous carbon is enlarged through P doping, so that a richer pore structure is formed, and the porous carbon material is better coated with nano SnO2Hollow microspheres with a pore structure of Na-in-removed from a tin-based negative electrode material+In the process, expansion buffering is improved, the volume expansion and contraction effects of the negative electrode material are reduced, the electrochemical cycle stability of the negative electrode material is improved, and O doping is provided for the porous carbon materialA large number of surface oxygen functional groups are formed, rich active defect sites are formed, and the sodium storage capacity of the cathode material is greatly improved, so that the specific capacitance and the electrochemical activity of the cathode material are improved.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: SnO modified by carbon-coated FeCo alloy2The negative electrode material of the sodium-ion battery and the preparation method thereof comprise the following formula raw materials in parts by weight: 12-30 parts of FeCo alloy modified nano SnO2Hollow microspheres, 18-22 parts of 3-aminophenol, 20-25 parts of phytic acid, 20-24 parts of potassium persulfate, 1-2 parts of a phosphorylation catalyst and 11-15 parts of a condensing agent, wherein the phosphorylation catalyst is p-toluenesulfonic acid, and the condensing agent is p-toluenesulfonic acidN,N"-diisopropylcarbodiimide.
FeCo alloy modified nano SnO2The preparation method of the hollow microsphere comprises the following steps:
(1) addition of SnCl to distilled water in reaction flask4And urea, the mass molar ratio of the two substances is 1:6.5-7, the reaction bottle is placed in an ultrasonic dispersion instrument and heated to 70-80 ℃, the ultrasonic frequency is 20-25 KHz, ultrasonic dispersion treatment is carried out for 1-2 h, then ethanol solvent is added, the volume ratio of the ethanol solvent to distilled water is 2-2.5:1, the solution is transferred into a hydrothermal synthesis reaction kettle and placed in a reaction kettle heating box, the heating is carried out to 220 ℃ and 240 ℃, the reaction is carried out for 18-20 h, the solution is decompressed and distilled to remove the solvent, a proper amount of distilled water is used for washing a solid product, and the solid product is fully dried to prepare the nano SnO2Hollow microspheres.
(2) Adding a proper amount of distilled water solvent into a reaction bottle, and then sequentially adding FeCl3、CoCl2Urotropin, citric acid dispersant and nano SnO2Hollow microspheres with the weight molar ratio of 1:1.2-1.5:1-1.2:0.2-0.4:0.4-0.5, placing a reaction bottle in an ultrasonic dispersion instrument, heating to 60-70 ℃, carrying out ultrasonic dispersion treatment for 1-2 h, heating the solution to 110 ℃, carrying out reflux reaction for 10-12 h, carrying out reduced pressure distillation on the solution to remove the solvent, washing the solid product with a proper amount of distilled water, placing the solid product in a blast drier, and fully drying at 70-80 DEG CDrying, namely placing the solid product in a resistance furnace, heating to 420-4 ℃/min, calcining for 4-6h, wherein the temperature rise rate is 2-4 ℃/min, and the calcined product is FeCo alloy modified nano SnO2Hollow microspheres.
SnO modified by carbon-coated FeCo alloy2The preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
(1) adding a proper amount of mixed solvent of ethylene glycol and distilled water into a reaction bottle, wherein the volume ratio of the ethylene glycol to the distilled water is 3-4:1, and then sequentially adding 18-22 parts of 3-aminophenol, 20-25 parts of phytic acid and 12-30 parts of FeCo alloy modified nano SnO2Hollow microsphere, placing reaction bottle in ultrasonic disperser, heating to 70-80 deg.C, ultrasonic frequency is 20-25 KHz, ultrasonic dispersing for 1-2 hr, adding 20-24 parts of potassium persulfate, placing reaction bottle in low-temperature cooler, stirring at-5-0 deg.C and uniform speed for 5-8 hr, adding 1-2 parts of phosphoric esterification catalyst p-methyl benzenesulfonic acid and 11-15 parts of condensing agentN,NPutting the solution into an oil bath, heating to 120-140 ℃, uniformly stirring for reaction for 20-25 h, cooling the solution to room temperature, adding excessive distilled water until a large amount of solid is separated out, passing the solution through a high-speed centrifuge, removing the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the nano SnO modified by the phosphoric acid esterified polyaniline coated FeCo alloy2Hollow microspheres.
(2) Phosphoric acid esterified polyaniline coated FeCo alloy modified nano SnO2Placing the hollow microspheres in an atmosphere resistance furnace, heating to 820-850 ℃ at the heating rate of 3-5 ℃/min2Calcining for 6-8 h in the atmosphere, wherein the calcined product is SnO modified by carbon-coated FeCo alloy2The negative electrode material of the sodium ion battery.
Example 1:
(1) preparation of Nano SnO2Hollow microsphere component 1: addition of SnCl to distilled water in reaction flask4And urea with the mass molar ratio of 1:6.5, placing the reaction bottle in an ultrasonic disperser, heating to 80 deg.C, performing ultrasonic dispersion treatment for 1 h at ultrasonic frequency of 25KHz, adding ethanol solvent with volume ratio of 2.5:1 to distilled water, transferring the solution into a hydrothermal synthesis reactionPlacing the kettle in a reaction kettle heating box, heating to 240 ℃, reacting for 20 h, distilling the solution under reduced pressure to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the nano SnO2Hollow microsphere component 1.
(2) Preparation of FeCo alloy modified nano SnO2Hollow microsphere component 1: adding a proper amount of distilled water solvent into a reaction bottle, and then sequentially adding FeCl3、CoCl2Urotropin, citric acid dispersant and nano SnO2The method comprises the following steps of putting a reaction bottle in an ultrasonic dispersion instrument, heating to 70 ℃, carrying out ultrasonic dispersion treatment for 2 hours at an ultrasonic frequency of 25KHz, heating the solution to 110 ℃, carrying out reflux reaction for 12 hours, carrying out reduced pressure distillation on the solution to remove a solvent, washing a solid product with a proper amount of distilled water, putting the solid product in a blast drier, fully drying at 80 ℃, putting the solid product in a resistance furnace, heating to 440 ℃, calcining for 6 hours, wherein the calcined product is FeCo alloy modified nano SnO, and the molar ratio of the hollow microsphere component 1 to the hollow microsphere component 1 is 1:1.5:1.2:0.4:0.52Hollow microsphere component 1.
(3) Preparation of nano SnO modified by phosphated polyaniline-coated FeCo alloy2Hollow microsphere component 1: adding a proper amount of mixed solvent of ethylene glycol and distilled water into a reaction bottle, wherein the volume ratio of the ethylene glycol to the distilled water is 4:1, and then sequentially adding 22 parts of 3-aminophenol, 25 parts of phytic acid and 12 parts of FeCo alloy modified nano SnO2Placing a reaction bottle in an ultrasonic disperser, heating to 80 ℃, carrying out ultrasonic dispersion treatment for 2 h, adding 24 parts of potassium persulfate, placing the reaction bottle in a low-temperature cooler, carrying out uniform stirring reaction for 8 h at-5 ℃, adding 2 parts of phosphoric esterification catalyst p-toluenesulfonic acid and 15 parts of condensing agent to obtain a hollow microsphere component 1, placing the reaction bottle in the ultrasonic disperser, heating to the temperature of 25KHz, carrying out ultrasonic dispersion treatment for 2 h, adding 24 parts of potassium persulfate, placing the reaction bottle in the low-temperature cooler, carrying outN,NPutting the solution into an oil bath pot, heating to 140 ℃, uniformly stirring for reaction for 25 hours, cooling the solution to room temperature, adding excessive distilled water until a large amount of solid is separated out, passing the solution into a high-speed centrifuge, removing the solvent, washing the solid product with an appropriate amount of distilled water, and fully drying to prepare the nano SnO modified by the phosphated polyaniline-coated FeCo alloy2Hollow coreMicrosphere component 1.
(4) Preparation of carbon-coated FeCo alloy modified SnO2Negative electrode material 1 for sodium ion battery: phosphoric acid esterified polyaniline coated FeCo alloy modified nano SnO2The hollow microsphere component 1 is placed in an atmosphere resistance furnace, the heating rate is 5 ℃/min, the temperature is increased to 850 ℃, and the temperature is controlled to be N2Calcining for 8 h in the atmosphere, wherein the calcined product is SnO modified by carbon-coated FeCo alloy2A sodium ion battery negative electrode material 1.
Example 2:
(1) preparation of Nano SnO2Hollow microsphere component 2: addition of SnCl to distilled water in reaction flask4And urea, the mass molar ratio of the two substances is 1:6.5, a reaction bottle is placed in an ultrasonic dispersion instrument and heated to 70 ℃, the ultrasonic frequency is 20KHz, ultrasonic dispersion treatment is carried out for 2 hours, then an ethanol solvent is added, the volume ratio of the ethanol solvent to distilled water is 2.5:1, the solution is transferred into a hydrothermal synthesis reaction kettle and placed in a reaction kettle heating box, the temperature is heated to 240 ℃, the reaction is carried out for 18 hours, the solution is decompressed and distilled to remove the solvent, a proper amount of distilled water is used for washing a solid product, the solid product is fully dried, and the nano SnO is prepared2Hollow microsphere component 2.
(2) Preparation of FeCo alloy modified nano SnO2Hollow microsphere component 2: adding a proper amount of distilled water solvent into a reaction bottle, and then sequentially adding FeCl3、CoCl2Urotropin, citric acid dispersant and nano SnO2Placing a reaction bottle in an ultrasonic dispersion instrument, heating to 60 ℃, carrying out ultrasonic dispersion treatment for 2 hours, heating the solution to 100 ℃, carrying out reflux reaction for 10 hours, carrying out reduced pressure distillation on the solution to remove the solvent, washing the solid product with a proper amount of distilled water, placing the washed solid product in a blast drier, fully drying at 80 ℃, placing the solid product in a resistance furnace, heating to 420 ℃, calcining for 6 hours, wherein the calcined product is FeCo alloy modified nano SnO, and the mass molar ratio of the hollow microsphere component 2 to the hollow microsphere component 1.2:1.2:0.2: 0.0.52Hollow microsphere component, 2.
(3) Preparation of nano SnO modified by phosphated polyaniline-coated FeCo alloy2Hollow microsphere component 2: adding proper amount of the mixture into a reaction bottleMixing a solvent of ethylene glycol and distilled water in a volume ratio of 3:1, and sequentially adding 21 parts of 3-aminophenol, 24 parts of phytic acid and 16 parts of FeCo alloy modified nano SnO2Placing a reaction bottle in an ultrasonic disperser, heating to 80 ℃, carrying out ultrasonic dispersion treatment for 2 h, adding 23 parts of potassium persulfate, placing the reaction bottle in a low-temperature cooler, carrying out uniform stirring reaction for 5 h at-5 ℃, adding 1.8 phosphoric acid esterification catalyst p-toluenesulfonic acid and 14.2 condensing agent to obtain the component 2N,NPutting the solution into an oil bath pot, heating to 140 ℃, uniformly stirring for reaction for 20 hours, cooling the solution to room temperature, adding excessive distilled water until a large amount of solid is separated out, passing the solution into a high-speed centrifuge, removing the solvent, washing the solid product with an appropriate amount of distilled water, and fully drying to prepare the nano SnO modified by the phosphated polyaniline-coated FeCo alloy2Hollow microsphere component 2.
(4) Preparation of carbon-coated FeCo alloy modified SnO2Sodium-ion battery negative electrode material 2: phosphoric acid esterified polyaniline coated FeCo alloy modified nano SnO2The hollow microsphere component 2 is placed in an atmosphere resistance furnace, the heating rate is 3 ℃/min, the temperature is increased to 850 ℃, and the temperature is controlled to be N2Calcining for 8 h in the atmosphere, wherein the calcined product is SnO modified by carbon-coated FeCo alloy2And 2, a sodium-ion battery negative electrode material.
Example 3:
(1) preparation of Nano SnO2Hollow microsphere component 3: addition of SnCl to distilled water in reaction flask4And urea, the molar ratio of the two substances is 1:6.8, the reaction bottle is placed in an ultrasonic dispersion instrument and heated to 75 ℃, the ultrasonic frequency is 22 KHz, ultrasonic dispersion treatment is carried out for 1.5 h, then ethanol solvent is added, the volume ratio of the ethanol solvent to distilled water is 2.2:1, the solution is transferred into a hydrothermal synthesis reaction kettle and placed in a reaction kettle heating box, the temperature is increased to 230 ℃, the reaction is carried out for 19 h, the solution is decompressed and distilled to remove the solvent, a proper amount of distilled water is used for washing a solid product, the solid product is fully dried, and the nano SnO is prepared2Hollow microsphere component 3.
(2) Preparation of FeCo alloy modified nano SnO2Hollow microsphere component3: adding a proper amount of distilled water solvent into a reaction bottle, and then sequentially adding FeCl3、CoCl2Urotropin, citric acid dispersant and nano SnO2The weight molar ratio of the hollow microsphere component 3 to the five substances is 1:1.35:1.1:0.3:0.45, a reaction bottle is placed in an ultrasonic dispersion instrument and heated to 65 ℃, the ultrasonic frequency is 22 KHz, ultrasonic dispersion treatment is carried out for 1.5 h, the solution is heated to 105 ℃, reflux reaction is carried out for 11 h, the solution is decompressed and distilled to remove the solvent, a proper amount of distilled water is used to wash the solid product, the solid product is placed in a blast drier and fully dried at 75 ℃, the solid product is placed in a resistance furnace, the temperature rise rate is 3 ℃/min, the solid product is heated to 430 ℃ and calcined for 5 h, and the calcined product is FeCo alloy modified nano SnO2Hollow microsphere component 3.
(3) Preparation of nano SnO modified by phosphated polyaniline-coated FeCo alloy2Hollow microsphere component 3: adding a proper amount of mixed solvent of ethylene glycol and distilled water into a reaction bottle, wherein the volume ratio of the ethylene glycol to the distilled water is 3.5:1, and then sequentially adding 20 parts of 3-aminophenol, 23 parts of phytic acid and 20 parts of FeCo alloy modified nano SnO2Placing a reaction bottle in an ultrasonic disperser, heating to 75 ℃, carrying out ultrasonic dispersion treatment for 1.5 h at the ultrasonic frequency of 22 KHz, adding 22 parts of potassium persulfate, placing the reaction bottle in a low-temperature cooler, carrying out uniform stirring reaction for 6.5 h at the temperature of-3 ℃, adding 1.5 parts of a phosphorylation catalyst p-toluenesulfonic acid and 13.5 parts of a condensing agentN,NPutting the solution into an oil bath pot, heating to 130 ℃, uniformly stirring for reaction for 22 hours, cooling the solution to room temperature, adding excessive distilled water until a large amount of solid is separated out, passing the solution into a high-speed centrifuge, removing the solvent, washing the solid product with an appropriate amount of distilled water, and fully drying to prepare the nano SnO modified by the phosphated polyaniline-coated FeCo alloy2Hollow microsphere component 3.
(4) Preparation of carbon-coated FeCo alloy modified SnO2Negative electrode material 3 of sodium ion battery: phosphoric acid esterified polyaniline coated FeCo alloy modified nano SnO2The hollow microsphere component 3 is placed in an atmosphere resistance furnace, the heating rate is 4 ℃/min, the temperature is increased to 835 ℃, and the temperature is increased to N2In the atmosphereCalcining for 7 h, wherein the calcined product is SnO modified by carbon-coated FeCo alloy2And 3, a sodium-ion battery negative electrode material.
Example 4:
(1) preparation of Nano SnO2Hollow microsphere component 4: addition of SnCl to distilled water in reaction flask4And urea, the mass molar ratio of the two substances is 1:6.5, a reaction bottle is placed in an ultrasonic dispersion instrument and heated to 70 ℃, the ultrasonic frequency is 25KHz, ultrasonic dispersion treatment is carried out for 2 hours, then an ethanol solvent is added, the volume ratio of the ethanol solvent to distilled water is 2.5:1, the solution is transferred into a hydrothermal synthesis reaction kettle and placed in a reaction kettle heating box, the temperature is heated to 220 ℃, the reaction is carried out for 20 hours, the solution is decompressed and distilled to remove the solvent, a proper amount of distilled water is used for washing a solid product, the solid product is fully dried, and the nano SnO is prepared2A hollow microsphere component 4.
(2) Preparation of FeCo alloy modified nano SnO2Hollow microsphere component 4: adding a proper amount of distilled water solvent into a reaction bottle, and then sequentially adding FeCl3、CoCl2Urotropin, citric acid dispersant and nano SnO2The preparation method comprises the following steps of (1) putting a reaction bottle in an ultrasonic dispersion instrument, heating to 60 ℃, carrying out ultrasonic dispersion treatment for 1 h at the ultrasonic frequency of 25KHz, heating the solution again to 100 ℃, carrying out reflux reaction for 12 h, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with a proper amount of distilled water, putting the solid product in a blast drier, fully drying at 80 ℃, putting the solid product in a resistance furnace, heating to 420 ℃, calcining for 6h, wherein the calcined product is FeCo alloy modified nano SnO2A hollow microsphere component 4.
(3) Preparation of nano SnO modified by phosphated polyaniline-coated FeCo alloy2Hollow microsphere component 4: adding a proper amount of mixed solvent of ethylene glycol and distilled water into a reaction bottle, wherein the volume ratio of the ethylene glycol to the distilled water is 3.5:1, and then sequentially adding 19 parts of 3-aminophenol, 21 parts of phytic acid and 24 parts of FeCo alloy modified nano SnO2Placing the reaction flask in an ultrasonic disperser, heating to 70 deg.C and ultrasonic frequency of 25KHz, performing ultrasonic dispersion treatment for 2 hr, adding 21 parts of potassium persulfate, and reactingPlacing the reaction flask in a low-temperature cooling instrument, stirring at constant speed at-5 deg.C for 5 hr, adding 1.2 parts of phosphoric esterification catalyst p-toluenesulfonic acid and 11.8 condensing agentN,NPutting the solution into an oil bath pot, heating to 130 ℃, uniformly stirring for reaction for 20 hours, cooling the solution to room temperature, adding excessive distilled water until a large amount of solid is separated out, passing the solution into a high-speed centrifuge, removing the solvent, washing the solid product with an appropriate amount of distilled water, and fully drying to prepare the nano SnO modified by the phosphated polyaniline-coated FeCo alloy2A hollow microsphere component 4.
(4) Preparation of carbon-coated FeCo alloy modified SnO2Sodium-ion battery negative electrode material 4: phosphoric acid esterified polyaniline coated FeCo alloy modified nano SnO2The hollow microsphere component 4 is placed in an atmosphere resistance furnace, the heating rate is 5 ℃/min, the temperature is increased to 820 ℃, and the temperature is controlled to be N2Calcining for 6 hours in the atmosphere, wherein the calcined product is SnO modified by carbon-coated FeCo alloy2And 4, a negative electrode material 4 of the sodium-ion battery.
Example 5:
(1) preparation of Nano SnO2Hollow microsphere component 5: addition of SnCl to distilled water in reaction flask4And urea, the mass molar ratio of the two substances is 1:6.5, a reaction bottle is placed in an ultrasonic dispersion instrument and heated to 70 ℃, the ultrasonic frequency is 20KHz, ultrasonic dispersion treatment is carried out for 1 h, an ethanol solvent is added, the volume ratio of the ethanol solvent to distilled water is 2:1, the solution is transferred into a hydrothermal synthesis reaction kettle and placed in a reaction kettle heating box, the temperature is heated to 220 ℃, the reaction is carried out for 18 h, the solution is decompressed and distilled to remove the solvent, a proper amount of distilled water is used for washing a solid product, the solid product is fully dried, and the nano SnO is prepared2A hollow microsphere component 5.
(2) Preparation of FeCo alloy modified nano SnO2Hollow microsphere component 5: adding a proper amount of distilled water solvent into a reaction bottle, and then sequentially adding FeCl3、CoCl2Urotropin, citric acid dispersant and nano SnO25, the weight molar ratio of the five substances is 1:1.2:1:0.2:0.4, the reaction bottle is placed in an ultrasonic dispersion instrument, the temperature is increased to 60 ℃, the ultrasonic frequency is 20KHz, and the reaction is carried outPerforming ultrasonic dispersion treatment for 1 h, heating the solution to 100 ℃ again, performing reflux reaction for 10 h, distilling the solution under reduced pressure to remove the solvent, washing the solid product with a proper amount of distilled water, placing the solid product in a blast drier, fully drying at 70 ℃, placing the solid product in a resistance furnace, heating to 420 ℃ at the temperature rise rate of 2 ℃/min, and calcining for 4 h, wherein the calcined product is FeCo alloy modified nano SnO2A hollow microsphere component 5.
(3) Preparation of nano SnO modified by phosphated polyaniline-coated FeCo alloy2Hollow microsphere component 5: adding a proper amount of mixed solvent of ethylene glycol and distilled water into a reaction bottle, wherein the volume ratio of the ethylene glycol to the distilled water is 3:1, and then sequentially adding 18 parts of 3-aminophenol, 20 parts of phytic acid and 30 parts of FeCo alloy modified nano SnO2Placing a reaction bottle in an ultrasonic disperser, heating to 70 ℃, carrying out ultrasonic dispersion treatment for 1 h at the ultrasonic frequency of 20KHz, adding 20 parts of potassium persulfate, placing the reaction bottle in a low-temperature cooler, carrying out uniform stirring reaction for 5 h at the temperature of-5 ℃, adding 1 part of phosphoric esterification catalyst p-toluenesulfonic acid and 11 parts of condensing agentN,NPutting the solution into an oil bath pot, heating to 120 ℃, uniformly stirring for reaction for 20 hours, cooling the solution to room temperature, adding excessive distilled water until a large amount of solid is separated out, passing the solution into a high-speed centrifuge, removing the solvent, washing the solid product with an appropriate amount of distilled water, and fully drying to prepare the nano SnO modified by the phosphated polyaniline-coated FeCo alloy2A hollow microsphere component 5.
(4) Preparation of carbon-coated FeCo alloy modified SnO2Negative electrode material for sodium ion battery 5: phosphoric acid esterified polyaniline coated FeCo alloy modified nano SnO2The hollow microsphere component 5 is placed in an atmosphere resistance furnace, the heating rate is 3 ℃/min, the temperature is increased to 820 ℃, and the temperature is controlled to be N2Calcining for 6 hours in the atmosphere, wherein the calcined product is SnO modified by carbon-coated FeCo alloy2And 5, a sodium-ion battery negative electrode material.
In summary, the carbon-coated FeCo alloy modified SnO2Sodium ion battery negative electrode material and preparation method thereof, and nano SnO2The hollow microsphere has super large specific surface area, and Fe-Co prepared by in-situ growth methodSnO2The surface of the hollow microsphere forms an alloy with Sn, the metal property of the alloy enhances the conductivity of the negative electrode material, improves the diffusion and transmission rate of Na + and electrons between the negative electrode material and the electrolyte, and promotes the forward proceeding of electrochemical reaction, thereby enhancing the rate capability of the negative electrode material, and the Fe-Co-Sn alloy inhibits the nano SnO2Agglomerate into particles and shorten Na+While increasing the active sites of the anode material.
Coating nano SnO by using phosphated polyaniline2Calcining the hollow microspheres to form N-P-O co-doped porous carbon-coated nano SnO2The hollow microspheres are doped with N to form graphite nitrogen and pyridine nitrogen structures in porous carbon, the graphite nitrogen structures enhance the conductivity of the porous carbon material and promote the transmission and diffusion of electrons, and the pyridine nitrogen structures reduce Na+Overpotential of a de-intercalation interface between the cathode material and the electrolyte promotes forward progress of electrode redox reaction, the radius of P atoms is much larger than that of C atoms, and the interlayer spacing of porous carbon is enlarged through P doping, so that a richer pore structure is formed, and the porous carbon material is better coated with nano SnO2Hollow microspheres with a pore structure of Na-in-removed from a tin-based negative electrode material+In the process, the expansion buffer is improved, the volume expansion and contraction effects of the negative electrode material are reduced, the electrochemical cycle stability of the negative electrode material is improved, a large number of surface oxygen functional groups are provided for the porous carbon material by doping O, rich active defect sites are formed, the sodium storage capacity of the negative electrode material is greatly improved, and the specific capacitance and the electrochemical activity of the negative electrode material are improved.
Claims (7)
1. SnO modified by carbon-coated FeCo alloy2The sodium-ion battery negative electrode material comprises the following formula raw materials in parts by weight, and is characterized in that: 12-30 parts of FeCo alloy modified nano SnO2Hollow microspheres, 18-22 parts of 3-aminophenol, 20-25 parts of phytic acid, 20-24 parts of potassium persulfate, 1-2 parts of a phosphorylation catalyst and 11-15 parts of a condensing agent.
2. A method as claimed in claim 1SnO modified by carbon-coated FeCo alloy2The negative electrode material of the sodium-ion battery is characterized in that: the phosphorylation catalyst is p-toluenesulfonic acid.
3. The carbon-coated FeCo alloy modified SnO according to claim 12The negative electrode material of the sodium-ion battery is characterized in that: the condensing agent isN,N"-diisopropylcarbodiimide.
4. The carbon-coated FeCo alloy modified SnO according to claim 12The negative electrode material of the sodium-ion battery is characterized in that: the FeCo alloy modified nano SnO2The preparation method of the hollow microsphere comprises the following steps:
(1) adding SnCl into distilled water solvent4And urea, performing ultrasonic dispersion treatment on the solution at 70-80 ℃ for 1-2 h at the ultrasonic frequency of 20-25 KHz, adding an ethanol solvent in the volume ratio of 2-2.5:1 to distilled water, transferring the solution into a hydrothermal synthesis reaction kettle, heating to 240 ℃ for reaction for 18-20 h, removing the solvent from the solution, washing a solid product, and drying to prepare nano SnO2Hollow microspheres;
(2) adding FeCl into distilled water solvent3、CoCl2Urotropin, citric acid dispersant and nano SnO2Carrying out ultrasonic dispersion treatment on the solution at 60-70 ℃ for 1-2 h with ultrasonic frequency of 20-25 KHz, heating the solution to 110 ℃ again, reacting for 10-12 h, removing the solvent from the solution, washing the solid product, drying, placing the solid product in a resistance furnace with the temperature rise rate of 2-4 ℃/min, heating to 420 ℃ and 440 ℃, calcining for 4-6h, wherein the calcined product is FeCo alloy modified nano SnO2Hollow microspheres.
5. FeCo alloy modified nano SnO according to claim 42Hollow microspheres, characterized in that: the SnCl4The mass molar ratio of the urea to the substance is 1: 6.5-7.
6. FeCo alloy according to claim 4Gold-modified nano SnO2Hollow microspheres, characterized in that: the FeCl3、CoCl2Urotropin, citric acid and nano SnO2The weight molar ratio of the five substances is 1:1.2-1.5:1-1.2:0.2-0.4: 0.4-0.5.
7. The carbon-coated FeCo alloy modified SnO according to claim 12The negative electrode material of the sodium-ion battery is characterized in that: the carbon-coated FeCo alloy modified SnO2The preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
(1) adding 18-22 parts of 3-aminophenol, 20-25 parts of phytic acid and 12-30 parts of FeCo alloy modified nano SnO into a mixed solvent of ethylene glycol and distilled water with the volume ratio of 3-4:12Hollow microsphere, ultrasonic dispersing the solution at 70-80 deg.C for 1-2 hr at ultrasonic frequency of 20-25 KHz, adding 20-24 parts of potassium persulfate, reacting at-5-0 deg.C for 5-8 hr, adding 1-2 parts of phosphoric esterification catalyst p-toluenesulfonic acid and 11-15 parts of condensing agentN,NHeating the solution to 140 ℃ for reaction for 20-25 h, cooling the solution to room temperature, adding distilled water until a large amount of solid is separated out, removing the solvent from the solution, washing the solid product, and drying to prepare the nano SnO modified by the phosphoric acid esterified polyaniline coated FeCo alloy2Hollow microspheres;
(2) phosphoric acid esterified polyaniline coated FeCo alloy modified nano SnO2Placing the hollow microspheres in an atmosphere resistance furnace, heating to 820-850 ℃ at the heating rate of 3-5 ℃/min2Calcining for 6-8 h in the atmosphere, wherein the calcined product is SnO modified by carbon-coated FeCo alloy2The negative electrode material of the sodium ion battery.
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