CN110137465B - Carbon @ Fe2O3@ carbon microsphere composite material and application thereof - Google Patents

Carbon @ Fe2O3@ carbon microsphere composite material and application thereof Download PDF

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CN110137465B
CN110137465B CN201910394308.1A CN201910394308A CN110137465B CN 110137465 B CN110137465 B CN 110137465B CN 201910394308 A CN201910394308 A CN 201910394308A CN 110137465 B CN110137465 B CN 110137465B
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carbon
microsphere
composite material
hollow
lithium ion
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CN110137465A (en
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王震康
杨宏训
刘永闵
曹宗林
张翔
王伟
袁爱华
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Jiangsu University of Science and Technology
Marine Equipment and Technology Institute Jiangsu University of Science and Technology
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Jiangsu University of Science and Technology
Marine Equipment and Technology Institute Jiangsu University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to carbon @ Fe2O3@ carbon microsphere composite material and application thereof, and carbon @ Fe2O3The @ carbon microsphere composite material is prepared from tetraethyl orthosilicate, ammonia water, resorcinol, formaldehyde, iron salt and dopamine, the diameter of the prepared carbon @ Fe2O3@ carbon microsphere is 200-300 nm, the thickness of the microsphere carbon inner shell is about 15-30 nm, and Fe2O3The thickness of the middle layer is 30-60 nm, and the thickness of the carbon shell is 3-7 nm; said carbon @ Fe2O3The @ carbon microsphere nanocomposite is used as a negative electrode material of a lithium ion battery. The invention has the advantages that: carbon @ Fe of the invention2O3The @ carbon microsphere material is applied to the lithium ion battery, so that the capacity retention rate of the lithium battery is greatly improved, and the process is simple, good in reproducibility and easy to implement.

Description

Carbon @ Fe2O3@ carbon microsphere composite material and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to carbon @ Fe2O3The @ carbon microsphere composite material and the application thereof.
Background
The lithium ion battery has the advantages of high voltage, high capacity, small volume, light weight, no memory effect, small self-discharge, long cycle life and the like, so that the lithium ion battery becomes a novel chemical power supply with great potential in the 21 st century. The theoretical capacity of the negative electrode material graphite in the current commercial lithium battery is only 372mAh/g, and the application requirement of a high-performance battery cannot be met. Therefore, the development of a negative electrode material having a higher capacity, a long cycle life and a high rate performance has been a pursued goal of researchers at home and abroad.
To increase Fe2O3The electrochemical performance of (a) is mainly considered from the following aspects: (1) preparation of nanoscale Fe2O3The hollow structure of the hollow nano material is beneficial to the permeation of electrolyte and the transmission of lithium ions on one hand, and can relieve the change of the volume of the material in the charging and discharging process on the other hand; (2) mixing Fe2O3The presence of carbon, in combination with carbon, not only improves the inherent low conductivity characteristics of iron oxide, but also acts as a buffer layer to mitigate Fe2O3Stress generated by volume change during charge and discharge; the electrochemical performance of ferric oxide as a cathode material can be obviously improved by combining the design, and the carbon @ Fe is prepared by simple treatment methods such as low-temperature inorganic precipitation, subsequent calcination annealing and the like2O3@ carbon microsphere composite materials. The hierarchical composite structure has unique structural advantages, and on one hand, the hierarchical composite structure has a large hollow structure formed by internal carbon spheres and a small hollow structure inside iron oxide, so that the bearing degree of the material to volume change stress can be obviously enhanced; on the other hand, due to the simultaneous existence of the inner carbon layer and the outer carbon layer, the volume change of the ferric oxide can be better relieved by using the inner carbon layer and the outer carbon layer as buffer layers, and the conductivity of the electrode material can be greatly increased, so that the rate capability of the electrode material is improved. The carbon @ Fe2O3The @ carbon microsphere negative electrode material is applied to a lithium battery, the cycle life of the lithium battery can be remarkably prolonged (after the lithium battery is cycled for 100 times under the current density of 0.2C, the charging capacity of about 1163mAh/g is obtained, and the coulombic efficiency is 98.06%), and relevant reports of the material are not reported at home and abroad at present.
Disclosure of Invention
The invention aims to provide carbon @ Fe2O3@ carbon microsphere composite material and application thereof to solve the problem that the existing ferric oxide is taken as a lithium ion battery cathode materialThe technical problem of poor cycle life.
In order to solve the technical problems, the technical scheme of the invention is as follows: carbon @ Fe2O3The @ carbon microsphere composite material has the innovation points that: said carbon @ Fe2O3The @ carbon microsphere composite material is prepared from tetraethyl orthosilicate, ammonia water, resorcinol, formaldehyde, iron salt and dopamine, and prepared carbon @ Fe2O3The diameter of the @ carbon microsphere is 200-300 nm, the thickness of the microsphere carbon inner shell is about 15-30 nm, and the thickness of Fe2O3The thickness of the middle layer is 30-60 nm, and the thickness of the carbon shell is 3-7 nm;
said carbon @ Fe2O3The @ carbon microsphere composite material is prepared by the following steps:
step 1: preparation of silica @ phenolic resin microspheres: adding tetraethyl orthosilicate and ammonia water into ethanol/water solution, stirring for 1-2 h, adding resorcinol and formaldehyde, and continuously stirring for 12-24 h; in the ethanol/water solution system, the volume fraction of ethanol is 72-85%, each liter of reaction solution contains 50-80 ml of TEOs, the concentration of ammonia water is 120-180 ml, 12-18 g of resorcinol and 18-25 ml of formaldehyde; then transferring the reaction solution into a high-pressure reaction kettle and carrying out hydrothermal reaction for 12-24 h; after naturally cooling to room temperature, centrifugally washing and collecting a product to obtain the silicon dioxide @ phenolic resin microspheres;
step 2: preparation of functionalized hollow carbon spheres: putting silicon dioxide @ phenolic resin into a tube furnace, heating to 400-500 ℃ at a speed of 4-6 ℃/min under the atmosphere of nitrogen or argon or a nitrogen-argon mixed gas with any ratio, then heating to 550-750 ℃ at a speed of 1-2.5 ℃/min to prevent a material structure from being broken, keeping for 2-4 hours, fully carbonizing the phenolic resin, and naturally cooling to room temperature to obtain SiO2@ carbon microsphere materials; then SiO2Soaking the @ carbon microspheres in 15-25 wt% of hydrofluoric acid solution for 12-24 hours, then carrying out centrifugal separation, and washing with deionized water to obtain hollow carbon spheres; then, the obtained hollow carbon spheres are firstly placed in concentrated nitric acid with the mass fraction of 60-70% at the temperature of 25-35 ℃ and stirred for 2 hours to be fully soaked and preliminarily functionalized, and then the temperature is raised toContinuously stirring for 8-10 h at 50-80 ℃ for functionalization; then washing with water and drying to obtain functionalized hollow carbon spheres;
and step 3: carbon @ Fe2O3Preparing a microsphere material: adding the functionalized hollow carbon spheres obtained in the step 2 into deionized water to obtain a hollow carbon sphere dispersion liquid; then adding iron salt into the hollow carbon sphere dispersion liquid, and stirring at the temperature of 60-80 ℃ at the speed of 600-900 rpm/min for 4-6 h to obtain carbon @ FeOOH; the concentration of the hollow carbon sphere dispersion liquid is 0.5-1 g/L, and the concentration of the ferric salt is 0.2-1 mol/L; collecting a product through centrifugation, and washing the product for 2-3 times by using deionized water to obtain the hollow carbon microsphere composite material carbon @ FeOOH wrapped by the hydroxyl iron oxide; then placing the carbon @ FeOOH in a tube furnace, heating to 350-450 ℃ at the speed of 1-6 ℃/min in the atmosphere of nitrogen or argon or a nitrogen-argon mixed gas with any ratio, keeping the temperature for 2-6 h, and naturally cooling to room temperature to obtain the carbon @ Fe2O3A microsphere nanomaterial;
and 4, step 4: the carbon @ Fe in the step 32O3Dispersing the microsphere nano material in a trihydroxymethyl aminomethane solution, adding dopamine, and stirring at normal temperature for 4-6 h; said carbon @ Fe2O3The dispersion concentration of the microsphere nano material is 0.5-1 g/L; the concentration of the dopamine is 0.4-1 g/L; the concentration of the tris (hydroxymethyl) aminomethane is 1-1.2 g/L; after the reaction is finished, collecting a product through centrifugation, and washing the product for 2-3 times by using deionized water; placing the dried product in a tubular furnace, heating to 250-300 ℃ at the speed of 2-4 ℃/min under the atmosphere of nitrogen or argon or a nitrogen-argon mixed gas with any ratio, keeping the temperature for 0.5-1 h, heating to 350-450 ℃ at the speed of 0.5-1 ℃/min to stabilize the material structure, keeping the carbonized dopamine layer for 2-4 h, and naturally cooling to room temperature to obtain carbon @ Fe2O3@ carbon microsphere composite materials.
Further, the iron salt is any one of ferric chloride, ferric nitrate or ferric sulfate.
Carbon @ Fe as described above2O3The application of the @ carbon microsphere composite material has the innovation points that: said carbon @ Fe2O3The @ carbon microsphere nanocomposite is used as a negative electrode material of a lithium ion battery.
Further, said carbon @ Fe2O3The @ carbon microsphere nanocomposite is applied to a CR2032 button type lithium ion battery and comprises the following specific steps:
step A: carbon @ Fe according to a mass ratio of 70:20:102O3@ carbon microsphere nanocomposite: conductive agent Super P: uniformly mixing the binder sodium carboxymethyl cellulose to obtain a solid mixture;
and B: and B, mixing the solid mixture obtained in the step A and ultrapure water according to a mass ratio of 18: 82-25: 75, mixing and uniformly stirring to prepare slurry;
and C: coating the slurry obtained in the step B on copper foil, and drying and rolling to obtain a lithium ion battery electrode plate with the thickness of 13-23 mu m;
step D: taking the lithium ion battery electrode plate obtained in the step C as a battery negative plate, adopting a microporous polypropylene membrane as a diaphragm, and adopting a solvent of 1mol/L LiPF6The electrolyte is prepared by assembling dimethyl carbonate and dipropyl carbonate which are equal in volume into a CR2032 button type lithium ion battery in a glove box filled with argon.
The invention has the advantages that:
(1) carbon @ Fe of the invention2O3The existence of the @ carbon microsphere composite material can relieve the volume change of the ferric oxide in the charging and discharging process on one hand, and is favorable for the permeation of electrolyte and the transmission of lithium ions on the other hand, so that the cycle life of the composite material can be obviously improved; the carbon layer can improve the characteristic of low conductivity of the ferric oxide on one hand, and can also be used as a buffer layer to relieve the volume change of the ferric oxide in the charging and discharging processes, so that the cycle stability of the ferric oxide is effectively improved;
(2) carbon @ Fe of the invention2O3The preparation method of the @ carbon microsphere composite material comprises the steps of carbonizing SiO2@ phenolic resin by adopting stage gradient temperature rise, infiltrating the SiO2@ phenolic resin by using concentrated nitric acid in the subsequent functionalization stage of the hollow carbon spheres in advance, and the like, so that the structural integrity of the material is maintained, and the material is also capable of being used for preparing the hollow carbon spheresThe ideal functionalization effect is achieved; then finally synthesizing the carbon @ Fe with a complete structure and a hierarchical hollow structure through a series of steps of inorganic precipitation → annealing phase transformation → polymer wrapping → stage heating carbonization and the like2O3@ carbon microsphere materials;
(3) carbon @ Fe of the invention2O3The @ carbon microsphere composite material can be used as a lithium ion battery cathode material with excellent performance, has high capacity, can remarkably prolong the cycle life of a lithium battery, (1163 mAh/g of charging capacity is obtained after 100 times of circulation at 0.2 ℃, and the discharging capacity is still 758.8mAh/g after 1000 times of circulation at 1 ℃), and has the advantages of simple process, good reproducibility, easy implementation and suitability for large-scale production.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a scanning electron micrograph of a hollow carbon sphere prepared in example 1 of the present invention.
FIG. 2 is carbon @ Fe prepared in example 1 of the present invention2O3X-ray diffraction results of @ carbon microspheres.
FIG. 3 is carbon @ Fe prepared in example 1 of the present invention2O3TEM image of @ carbon microsphere.
FIG. 4 is carbon @ Fe prepared in example 1 of the present invention2O3@ carbon microsphere high power TEM image.
FIG. 5 is carbon @ Fe prepared in example 1 of the present invention2O3The cycle performance curve of the lithium ion battery taking the @ carbon microspheres as the negative electrode material at 0.2 ℃.
FIG. 6 is carbon @ Fe prepared in example 1 of the present invention2O3The cycle performance curve of the lithium ion battery with the @ carbon microspheres as the negative electrode material at 1C.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the scope of the embodiments described herein.
Example 1
(1) Adding 1.7ml TEOS, 4ml ammonia water into 15ml ethanol and 6ml water simultaneouslyThe resulting mixed solution was stirred for 1 hour. Subsequently, 0.4g of resorcinol and 0.56ml of formaldehyde are added and stirring is continued for 24 h. The reaction solution was then hydrothermally reacted at 100 ℃ for 24 hours, and the product was collected by centrifugation and washed 4 times with ethanol. To obtain SiO2@ phenolic resin.
(2) Drying the SiO obtained in the step (1)2@ phenolic resin is placed in a tube furnace, nitrogen protective gas is introduced at the air inflow of 0.5L/min, the temperature is increased to 400 ℃ at the speed of 6 ℃/min and is kept for half an hour, then the temperature is increased to 700 ℃ at the speed of 1 ℃/min and is kept for 2 hours, and SiO is obtained2@ carbon microsphere, SiO2And (3) soaking the @ carbon in 15 wt% hydrofluoric acid solution for 12h, centrifuging and collecting a product, and washing the product to be neutral by using water to obtain the hollow carbon ball.
(3) And ultrasonically dispersing 300mg of hollow carbon spheres in 20ml of concentrated nitric acid (68 wt%), stirring at room temperature for 1h, heating to 80 ℃, refluxing and stirring for 10h, centrifugally collecting products at the rotating speed of 8000r/min after the reaction is finished, and washing the products with ultrapure water for 5 times to obtain the functionalized hollow carbon spheres.
(4) And (2) carrying out ultrasonic treatment on 50mg of hollow carbon spheres for 40min to uniformly disperse the hollow carbon spheres in 100ml of deionized water, adding 0.541g of ferric chloride hexahydrate, stirring in a water bath at the temperature of 75 ℃ for 5h, after the reaction is finished, centrifugally collecting a product at the rotating speed of 8000r/min, and washing with ultrapure water for 4 times to obtain carbon @ FeOOH.
(5) Placing the carbon @ FeOOH dried in the step (4) into a tube furnace, introducing nitrogen at the air inflow of 0.5L/min, raising the temperature to 350 ℃ at the heating rate of 2 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain carbon @ Fe2O3A microsphere nanocomposite.
(6) 150mg of carbon @ Fe2O3The microsphere composite material is subjected to ultrasonic treatment for 20min to be uniformly dispersed in 250ml of deionized water, and 0.1g of dopamine and 1g of tris (hydroxymethyl) aminomethane are added. Stir at room temperature for 4 h. After the reaction is finished, centrifugally collecting the product at the rotating speed of 5000r/min, washing the product for 4 times by using ultrapure water, and drying the obtained sample at 60 ℃ overnight; placing the dried sample in a tube furnace, heating to 300 ℃ at the speed of 4 ℃/min and keeping for 0.5h, then heating to 450 ℃ at the speed of 1 ℃/min and keeping for 2h to completely carbonize the dopamine layer, and finally obtaining carbon@Fe2O3@ carbon microsphere nanocomposites.
(7) Assembling and testing performance of the lithium ion battery, namely, carbon @ Fe is added according to the mass ratio of 70:20:102O3Mixing the @ carbon microsphere, the conductive agent Super P and the binder sodium carboxymethylcellulose uniformly; and then according to the mass ratio of 20: 80, mixing the solid mixture after being uniformly mixed with ultrapure water and uniformly stirring to prepare slurry; and then coating the slurry on a copper foil, and drying and rolling to obtain the lithium ion battery electrode plate. Then taking a lithium plate as an electrode positive plate, taking a microporous polypropylene film as a diaphragm, and taking 1mol/LLIPF6(the solvent is dimethyl carbonate and dipropyl carbonate with equal volume) as electrolyte, and the electrolyte and the electrode slice are assembled into a CR2032 button type lithium ion battery in a glove box filled with argon. And standing the lithium ion battery for 24 hours, and then performing charge and discharge tests under the current densities of 0.2C and 1C respectively, wherein the charge and discharge voltage is between 0.01 and 3.0V.
The results of this example are shown in fig. 1 to 5; as can be seen from fig. 1, it has a uniform spherical morphology, which is seen from individual breakages as having a hollow structure with a diameter of about 220 nm; as can be seen from FIG. 2, the peaks correspond to the peaks of iron sesquioxide (JCPDS card: 33-0664), respectively, wherein the broad peak around 22 ° is attributed to the peak of carbon element in the material; as can be seen from FIG. 3, carbon @ Fe2O3The @ carbon microspheres have uniform shape distribution and Fe2O3Coated with a carbon layer having a thickness of about 5nm, and Fe2O3The nano-rod also has a hollow structure; as can be seen from FIG. 4, Fe2O3A carbon layer is wrapped outside the carbon layer, and the thickness of the carbon layer is about 5 nm; fe2O3Has a rod shape and a hollow structure.
Example 2
(1) 2.2ml of TEOS, 4ml of ammonia water were simultaneously added to a mixed solution composed of 19ml of ethanol and 8ml of water and stirred for 1 hour. Subsequently, 0.4g of resorcinol and 0.56ml of formaldehyde are added and stirring is continued for 24 h. The reaction solution was then hydrothermally reacted at 100 ℃ for 24 hours, and the product was collected by centrifugation and washed 4 times with ethanol. To obtain SiO2@ phenolic resin.
(2) Drying the SiO obtained in the step (1)2@ phenolic aldehyde treePutting the grease into a tube furnace, introducing nitrogen protective gas at the air inflow of 0.5L/min, heating to 400 ℃ at the speed of 6 ℃/min and keeping for half an hour, then heating to 700 ℃ at the speed of 1 ℃/min and keeping for 2 hours to obtain SiO2@ carbon microsphere, SiO2And (3) soaking the @ carbon in 15 wt% hydrofluoric acid solution for 12h, centrifuging and collecting a product, and washing the product to be neutral by using water to obtain the hollow carbon ball.
(3) And ultrasonically dispersing 300mg of hollow carbon spheres in 20ml of concentrated nitric acid (68 wt%), stirring at room temperature for 1h, heating to 80 ℃, refluxing and stirring for 10h, centrifugally collecting products at the rotating speed of 8000r/min after the reaction is finished, and washing the products with ultrapure water for 5 times to obtain the functionalized hollow carbon spheres.
(4) And (2) carrying out ultrasonic treatment on 100mg of hollow carbon spheres for 40min to uniformly disperse the hollow carbon spheres in 100ml of deionized water, adding 0.829g of ferric nitrate, stirring in a water bath at 75 ℃ for 5h, centrifugally collecting a product at a rotating speed of 8000r/min after the reaction is finished, and washing the product for 4 times by using ultrapure water to obtain @ carbon FeOOH.
The other steps are the same as in example 1.
Example 3
(1) 1.3ml of TEOS, 4ml of ammonia water were simultaneously added to a mixed solution composed of 12ml of ethanol and 4ml of water, and stirred for 1 hour. Subsequently, 0.4g of resorcinol and 0.56ml of formaldehyde are added and stirring is continued for 24 h. The reaction solution was then hydrothermally reacted at 100 ℃ for 24 hours, and the product was collected by centrifugation and washed 4 times with ethanol. To obtain SiO2@ phenolic resin.
(2) Drying the SiO obtained in the step (1)2@ phenolic resin is placed in a tube furnace, nitrogen protective gas is introduced at the air inflow of 0.5L/min, the temperature is increased to 400 ℃ at the speed of 6 ℃/min and is kept for half an hour, then the temperature is increased to 700 ℃ at the speed of 1 ℃/min and is kept for 2 hours, and SiO is obtained2@ carbon microsphere, SiO2And (3) soaking the @ carbon in 15 wt% hydrofluoric acid solution for 12h, centrifuging and collecting a product, and washing the product to be neutral by using water to obtain the hollow carbon ball.
(3) And ultrasonically dispersing 300mg of hollow carbon spheres in 20ml of concentrated nitric acid (68 wt%), stirring at room temperature for 1h, heating to 80 ℃, refluxing and stirring for 10h, centrifugally collecting products at the rotating speed of 8000r/min after the reaction is finished, and washing the products with ultrapure water for 5 times to obtain the functionalized hollow carbon spheres.
(4) And (2) carrying out ultrasonic treatment on 100mg of hollow carbon spheres for 40min to uniformly disperse the hollow carbon spheres in 100ml of deionized water, adding 1.021g of ferric sulfate, stirring in a 75 ℃ water bath for 5h, after the reaction is finished, centrifugally collecting a product at a rotating speed of 8000r/min, and washing the product for 4 times by using ultrapure water to obtain carbon @ FeOOH.
The other steps are the same as in example 1.
The lithium battery performance results of examples 1-3 are shown in tables 1 and 2.
Table 1 shows the capacities obtained in the first and 100 th cycles of the charge and discharge test of the lithium ion batteries of examples 1 to 3 at a current of 0.2C.
TABLE 1
Figure GDA0003372179780000071
As can be seen from Table 1, the carbon @ Fe of the present invention is used2O3The @ carbon microsphere is used as an electrode material and applied to a lithium ion battery, the charging capacity is more than 1000mAh/g after 100 cycles of circulation, the capacity retention rate is more than 70%, the carbon microsphere has good circulation performance, and the carbon microsphere is still far higher than that of a current commercialized graphite cathode material.
Table 2 shows the capacities obtained in the first and 1000 th cycles of the charge and discharge test of the lithium ion batteries of examples 1 to 3 at a current of 1C.
TABLE 2
Figure GDA0003372179780000081
As can be seen from Table 2, the carbon @ Fe of the present invention was used2O3The @ carbon microsphere is used as an electrode material and applied to a lithium ion battery, after 1000 cycles of circulation, the charging capacity is more than 723mAh/g, the capacity retention rate is more than 64.8%, and the @ carbon microsphere has good circulation performance and is still far higher than that of a current commercialized graphite cathode material.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (4)

1. Carbon @ Fe2O3The @ carbon microsphere composite material is characterized in that: said carbon @ Fe2O3The @ carbon microsphere composite material is prepared from tetraethyl orthosilicate, ammonia water, resorcinol, formaldehyde, iron salt and dopamine, and prepared carbon @ Fe2O3The diameter of the @ carbon microsphere is 200-300 nm, the thickness of the inner microsphere carbon shell is 15-30 nm, the thickness of the middle layer of Fe2O3 is 30-60 nm, and the thickness of the carbon shell is 3-7 nm;
said carbon @ Fe2O3The @ carbon microsphere composite material is prepared by the following steps:
step 1: preparation of silica @ phenolic resin microspheres: adding tetraethyl orthosilicate and ammonia water into ethanol/water solution, stirring for 1-2 h, adding resorcinol and formaldehyde, and continuously stirring for 12-24 h; in the ethanol/water solution system, the volume fraction of ethanol is 72-85%, each liter of reaction solution contains 50-80 ml of tetraethoxysilane, the concentration of ammonia water is 120-180 ml, 12-18 g of resorcinol and 18-25 ml of formaldehyde; then transferring the reaction solution into a high-pressure reaction kettle and carrying out hydrothermal reaction for 12-24 h; after naturally cooling to room temperature, centrifugally washing and collecting a product to obtain the silicon dioxide @ phenolic resin microspheres;
step 2: preparation of functionalized hollow carbon spheres: placing the silicon dioxide @ phenolic resin in a tube furnace, heating to 400-500 ℃ at a speed of 4-6 ℃/min under the atmosphere of nitrogen or argon or a nitrogen-argon mixture gas with any ratio, then heating to 550-750 ℃ at a speed of 1-2.5 ℃/min to prevent the material structure from being broken, keeping for 2-4 hours, fully carbonizing the phenolic resin, and then naturally cooling to room temperature to obtain the SiO2@ carbon microsphere material; then placing the SiO2@ carbon microspheres in 15-25 wt% of hydrofluoric acid solution to soak for 12-24 h, then carrying out centrifugal separation, and washing with deionized water to obtain hollow carbon spheres; then, the obtained hollow carbon spheres are firstly placed in concentrated nitric acid with the mass fraction of 60-70% at the temperature of 25-35 ℃ and stirred for 2 hours to be fully soaked and preliminarily functionalized, and then the temperature is increased to 50-80 ℃ and the mixture is continuously stirred for 8-10 hours to be functionalized; then washing with water and drying to obtain functionalized hollow carbon spheres;
and step 3: carbon @ Fe2O3 Preparing a microsphere material: adding the functionalized hollow carbon spheres obtained in the step 2 into deionized water to obtain a hollow carbon sphere dispersion liquid; then adding iron salt into the hollow carbon sphere dispersion liquid, and stirring at the temperature of 60-80 ℃ at the speed of 600-900 rpm/min for 4-6 h to obtain carbon @ FeOOH; the concentration of the hollow carbon sphere dispersion liquid is 0.5-1 g/L, and the concentration of the ferric salt is 0.2-1 mol/L; collecting a product through centrifugation, and washing the product for 2-3 times by using deionized water to obtain the hollow carbon microsphere composite material carbon @ FeOOH wrapped by the hydroxyl iron oxide; then placing the carbon @ FeOOH in a tube furnace, heating to 350-450 ℃ at the speed of 1-6 ℃/min in the atmosphere of nitrogen or argon or a nitrogen-argon mixed gas with any ratio, keeping the temperature for 2-6 h, and naturally cooling to room temperature to obtain the carbon @ Fe2O3 A microsphere nanomaterial;
and 4, step 4: the carbon @ Fe in the step 32O3Dispersing the microsphere nano material in a trihydroxymethyl aminomethane solution, adding dopamine, and stirring at normal temperature for 4-6 h; said carbon @ Fe2O3The dispersion concentration of the microsphere nano material is 0.5-1 g/L; the concentration of the dopamine is 0.4-1 g/L; the concentration of the tris (hydroxymethyl) aminomethane is 1-1.2 g/L; after the reaction is finished, collecting a product through centrifugation, and washing the product for 2-3 times by using deionized water; placing the dried product in a tubular furnace, heating to 250-300 ℃ at the speed of 2-4 ℃/min under the atmosphere of nitrogen or argon or a nitrogen-argon mixed gas with any ratio, keeping the temperature for 0.5-1 h, heating to 350-450 ℃ at the speed of 0.5-1 ℃/min to stabilize the material structure, keeping the carbonized dopamine layer for 2-4 h, and naturally cooling to room temperature to obtain carbon @ Fe2O3@ carbon microsphere composite materials.
2. Carbon @ Fe as in claim 12O3The @ carbon microsphere composite material is characterized in that: the iron salt is any one of ferric chloride, ferric nitrate or ferric sulfate.
3. Carbon @ Fe as in claim 12O3The application of the @ carbon microsphere composite material is characterized in that: the carbon @ Fe2O3@ carbon microsphere nano composite material is used as a negative electrode material of a lithium ion battery.
4. Carbon @ Fe as in claim 32O3The application of the @ carbon microsphere composite material is characterized in that: said carbon @ Fe2O3The @ carbon microsphere nanocomposite is applied to a CR2032 button type lithium ion battery and comprises the following specific steps:
step A: carbon @ Fe according to a mass ratio of 70:20:102O3@ carbon microsphere nanocomposite: conductive agent Super P: uniformly mixing the binder sodium carboxymethyl cellulose to obtain a solid mixture;
and B: and B, mixing the solid mixture obtained in the step A and ultrapure water according to a mass ratio of 18: 82-25: 75, mixing and uniformly stirring to prepare slurry;
and C: coating the slurry obtained in the step B on copper foil, and drying and rolling to obtain a lithium ion battery electrode plate with the thickness of 13-23 mu m;
step D: and D, taking the lithium ion battery electrode plate obtained in the step C as a battery negative plate, taking a microporous polypropylene membrane as a diaphragm, taking a solvent of 1mol/L LiPF6 as an electrolyte, and filling the solvent of dimethyl carbonate and dipropyl carbonate with the same volume into a glove box filled with argon to prepare the CR2032 button type lithium ion battery.
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