CN109713256B - High-performance monodisperse carbon sphere negative electrode material with special structure and preparation method and application thereof - Google Patents
High-performance monodisperse carbon sphere negative electrode material with special structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-performance monodisperse carbon sphere with a special structure and a preparation method and application thereof, wherein the preparation method comprises the steps of adding phytic acid, P123 and ferric sulfate salt into a solution of pyrrole or aniline monomer, carrying out ice bath magnetic stirring, adding an ammonium persulfate aqueous solution to initiate copolymerization reaction, and finally preparing an iron-doped special spherical carbon structure material with monodisperse characteristics in one step through high-temperature carbonization. The invention has the advantages of cheap preparation raw materials, simple operation process, high yield, excellent charge and discharge performance of the material and convenient industrial production.
Description
Technical Field
The invention relates to the technical field of negative electrode materials of sodium-ion batteries, in particular to a high-performance monodisperse carbon sphere negative electrode material with a special structure and a preparation method and application thereof.
Background
In the seventh and eighty years of the twentieth century, research on sodium ion batteries and lithium ion batteries is almost on the same level, however, the successful application of graphite cathodes in lithium ion batteries directly promotes the commercialization process of the lithium ion batteries, the sodium ion batteries still do not realize industrial breakthrough so far, and one of the bottlenecks is lack of suitable practical cathode materials. In recent years, research on sodium ion batteries has been advanced, and research on negative electrode materials has been focused mainly on carbon materials and some non-carbon materials (metals and oxide materials, alloy materials, phosphorus, and the like). The non-carbon material exhibits high storage capacity for both lithium and sodium, but has not been applied on a large scale even in a lithium ion battery with a high degree of commercialization due to problems of low conductivity, large volume change, and easy pulverization. The problems also exist in the sodium ion battery, and the carbon-based material not only has a lower sodium-embedded platform, higher capacity and good cycling stability, but also has the advantages of abundant resources, simple preparation and the like. Therefore, the carbon material is still the key anode material which is hopefully to promote the industrialization of sodium ions.
The main sodium-storing carbon materials with application prospect at present comprise: (1) the soft carbon material mainly refers to a graphite-like carbon material with a layered structure, and mainly stores sodium in an interlayer intercalation mode, so that the conductivity is good, but the specific capacity is low; (2) hard carbon materials, which have complex and various structures, usually have various forms for storing sodium ions, although the capacity is high, the initial coulombic efficiency is low; (3) nanocarbon materials such as graphene, carbon nanotubes, and the like generally rely on surface adsorption to store sodium, and can realize rapid charge and discharge, but problems such as low coulombic efficiency and poor cyclicity make them difficult to be practically used in a short time (zhangwei, zhang, wu si da, and the like. Therefore, the development of a novel carbon-based negative electrode material of the sodium-ion battery is extremely urgent. In addition, the research on the influence relationship of the carbon material structure on the sodium storage performance is still insufficient. Furthermore, carbon materials of the Zhao-shi carbon (Chaoite carbon) structure are currently found only widely in meteorites and the like, and are rare in nature. At present, no method for preparing the Chaoite carbon on a large scale is available.
Disclosure of Invention
Aiming at the defects of the prior problems, the first object of the invention is to provide a preparation method of a high-performance monodisperse carbon sphere negative electrode material with a special structure;
the second purpose of the invention is to provide a high-performance monodisperse carbon sphere negative electrode material with a special structure;
the third purpose of the invention is to provide the application of the high-performance special-structure monodisperse carbon sphere negative electrode material in the preparation of the sodium battery electrode.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a high-performance monodisperse carbon sphere negative electrode material with a special structure comprises the steps of adding phytic acid, P123 and ferric sulfate salt into a solution of pyrrole or aniline monomer, carrying out ice bath magnetic stirring, adding an ammonium persulfate aqueous solution to initiate copolymerization reaction, and finally preparing the iron-doped spherical Chaoite carbon structure material with the monodisperse characteristic in one step through high-temperature carbonization.
Further, the preparation method specifically comprises the following steps:
(1) adding P123 into deionized water, ultrasonically stirring and dispersing until the P123 is completely dissolved, and then adding Fe2(SO4)3.7H2O, ultrasonically stirring for 15 min; then starting ice bath and magnetic stirring for 20 min;
(2) dispersing pyrrole or aniline in deionized water, ultrasonically stirring and dispersing uniformly (without oil drops), adding P123 and phytic acid, ultrasonically stirring and dispersing until completely dissolved; then starting ice bath and magnetic stirring for 20 min;
(3) dispersing the solution in the step (1) in the solution in the step (2), and magnetically stirring for 20min in ice bath;
(4) additionally preparing an ammonium persulfate aqueous solution, pouring the ammonium persulfate aqueous solution into the mixed solution obtained in the step (3), and carrying out ice bath for 12 hours; after the reaction is finished, carrying out suction filtration, washing for 3-5 times by using deionized water, and carrying out vacuum drying for 3-5 h at 70 ℃ to prepare a precursor monodisperse ball;
(5) and (4) carbonizing the material obtained in the step (4) at high temperature under protective gas to prepare the high-performance material with the special structure and the monodisperse carbon spheres.
Further, the pyrrole or aniline is dispersed in deionized water, and the molar concentration of the pyrrole or aniline is 0.05-0.5M/L; adding P123 and phytic acid, wherein the total mass ratio of the P123 to water is 1: 70-700, wherein the mass ratio of the phytic acid to the water is 1: 5-150; said addition of Fe2(SO4)3.7H2O，Fe2(SO4)3.7H2The mass ratio of O to water is 1: 10-500.
Further, the carbon materials prepared by the special structure all show a Chaoite carbon phase structure.
Further, the iron is doped, and the doping amount atomic ratio of the final iron is 1-4%.
Further, the adding amount of the ammonium persulfate is 1-3 times of the mass of the aniline or pyrrole monomer.
Further, the high-temperature treatment comprises the following steps: at Ar, Ar/H2Heat treatment is carried out for 1-12h at 500-800 ℃ under the atmosphere of mixed gas or He.
The high-performance monodisperse carbon sphere negative electrode material with the special structure is prepared by the preparation method.
The high-performance monodisperse carbon sphere negative electrode material with the special structure is applied to the preparation of sodium battery electrodes.
Advantageous effects
(1) According to the characteristics of the sodium battery negative electrode material in charge-discharge circulation, the iron-doped spherical Chaoite carbon structural material with the monodispersity is prepared by a one-step liquid phase method, the effective lattice spacing of the carbon material with the structural characteristics can greatly improve the sodium storage capacity of the carbon material, and the monodispersity can effectively solve the problem that the electrode material is polarized under high-rate operation, so that the circulation performance of the material is improved and prolonged.
(2) The invention has the advantages of cheap preparation raw materials, simple operation process, high yield, excellent charge and discharge performance of the material and convenient industrial production. The invention obviously improves the long cycle performance and rate performance of the active substance. In addition, the solvent used in the invention is water, and is environment-friendly.
Drawings
FIG. 1 is an XRD pattern of a sample obtained in examples 1 to 3, and a to c are XRD patterns of samples corresponding to examples 1 to 3; d is comparative example with no Fe addition2(SO4)3.7H2An XRD spectrum of the O sample;
FIG. 2 shows example 2 and comparative example without addition of Fe2(SO4)3.7H2XPS spectra of O samples;
FIG. 3 is SEM images of samples of examples and comparative examples; wherein a is a comparative example with no Fe added2(SO4)3.7H2SEM spectra of O samples; b to d are SEM images of samples corresponding to examples 1 to 3;
FIG. 4 is TEM spectra of examples and comparative examples; wherein a is a comparative example with no Fe added2(SO4)3.7H2A TEM spectrum of the O sample; b to d are TEM images of samples corresponding to examples 1 to 3;
FIG. 5 is TEM spectra of examples and comparative examples; wherein a is a comparative example with no Fe added2(SO4)3.7H2A TEM spectrum of the O sample; b to d are high-resolution TEM images of the samples corresponding to examples 1 to 3;
FIG. 6 shows samples corresponding to examples 1 to 3 and comparative examples in which Fe was not added2(SO4)3.7H2A graph of the cycling performance of the O (0g Fe-rated C) sample at 5A/g current density;
FIG. 7 shows samples corresponding to examples 1 to 3 and comparative examples in which Fe was not added2(SO4)3.7H2O (0g Fe-coped C)) sample rate performance plot;
FIG. 8 shows a sample corresponding to example 2 and a comparative example in which Fe was not added2(SO4)3.7H2O (0g Fe-coped C)) samples.
Detailed Description
The present invention will be described in further detail with reference to examples. The reagents or instruments used are not indicated by manufacturers, and are regarded as conventional products which can be purchased in the market.
Example 1
0.1g of P123 is dispersed in a certain amount of deionized water and stirred and dispersed by ultrasound till being completely dissolved, and then 0.05g of Fe is added2(SO4)3.7H2O, ultrasonically stirring for 15 min; magnetic stirring was then started in an ice bath for 20 min. Additionally, 0.1mL of aniline is dispersed in a certain amount of deionized water, stirred and dispersed evenly (without oil drops) by ultrasonic, and added with 0.1g P123 and 0.08mL of phytic acid, stirred and dispersed by ultrasonic till being dissolved completely; magnetic stirring was then started in an ice bath for 20 min. Mixing the two solutions, and magnetically stirring for 20min under ice bath condition; 6mL of an aqueous ammonium persulfate solution (containing 0.5g of ammonium persulfate) was prepared, and the mixture was poured into the above mixed solution and cooled in ice for 12 hours. And after the reaction is finished, carrying out suction filtration, washing for 3-5 times by using deionized water, and carrying out vacuum drying for 3-5 h at 70 ℃ to prepare the precursor monodisperse ball. And carrying out heat treatment on the obtained material for 12h at 500 ℃ in Ar atmosphere to prepare the high-performance iron-doped monodisperse carbon sphere material. The atomic proportion of Fe in the sample of example 1 was 1.04%.
And fully grinding the sintered material, uniformly mixing the material with carbon black and carboxymethyl cellulose according to the proportion of 70: 15, coating, and performing vacuum drying at 70 ℃ for 24 hours to prepare the composite electrode. The electrode was placed in a 2025 cell can, with a sodium sheet as the counter electrode, a polyethylene film as the separator, and 1M NaClO4The constant current charge and discharge test was carried out on an assembled battery using EC: EMC: DMC (1/1/1 vol.) + 5% FEC as an electrolyte.
Example 2
Dispersing 0.2g of P123 in deionized water, ultrasonically stirring and dispersing until the P123 is completely dissolved, and then adding 0.3g of Fe2(SO4)3.7H2O, ultrasonically stirring for 15 min; magnetic stirring was then started in an ice bath for 20 min. Additionally, 0.229mL of aniline is dispersed in a certain amount of deionized water, stirred and dispersed evenly (without oil drops) by ultrasonic, and added with 0.2g P123 and 0.46mL of phytic acid, stirred and dispersed by ultrasonic till being dissolved completely; magnetic stirring was then started in an ice bath for 20 min. Mixing the two solutions, and magnetically stirring for 20min under ice bath condition; 6mL of an aqueous ammonium persulfate solution (containing 0.5g of ammonium persulfate) was prepared, and the mixture was poured into the above mixed solution and cooled in ice for 12 hours. After the reaction is finished, carrying out suction filtration, washing for 3-5 times by using deionized water, and carrying out vacuum drying for 3-5 h at 70 ℃ to obtain the catalystAnd (4) precursor monodisperse spheres. And carrying out heat treatment on the obtained material for 6h at 600 ℃ in Ar atmosphere to prepare the high-performance iron-doped monodisperse carbon sphere material. The atomic proportion of Fe in the sample of example 2 was 2.74%.
And fully grinding the sintered material, uniformly mixing the material with carbon black and carboxymethyl cellulose according to the proportion of 70: 15, coating, and performing vacuum drying at 70 ℃ for 24 hours to prepare the composite electrode. The electrode was placed in a 2025 cell can, with a sodium sheet as the counter electrode, a polyethylene film as the separator, and 1M NaClO4The constant current charge and discharge test was carried out on an assembled battery using EC: EMC: DMC (1/1/1 vol.) + 5% FEC as an electrolyte.
Example 3
0.5g of P123 is dispersed in deionized water and stirred by ultrasound till being dissolved completely, and then 2g of Fe is added2(SO4)3.7H2O, ultrasonically stirring for 15 min; magnetic stirring was then started in an ice bath for 20 min. Additionally, 0.916mL of aniline is dispersed in a certain amount of deionized water, stirred and dispersed evenly (without oil drops) by ultrasonic, and added with 0.5g P123 and 1.35mL of phytic acid, stirred and dispersed by ultrasonic till being dissolved completely; magnetic stirring was then started in an ice bath for 20 min. Mixing the two solutions, and magnetically stirring for 20min under ice bath condition; 6mL of an aqueous ammonium persulfate solution (containing 1.5g of ammonium persulfate) was prepared, and the mixture was poured into the above mixed solution and cooled in ice for 12 hours. And after the reaction is finished, carrying out suction filtration, washing for 3-5 times by using deionized water, and carrying out vacuum drying for 3-5 h at 70 ℃ to prepare the precursor monodisperse ball. And carrying out heat treatment on the obtained material for 1h at 800 ℃ in Ar atmosphere to prepare the high-performance iron-doped monodisperse carbon sphere material. The atomic proportion of Fe in the sample of example 3 was 3.94%.
And fully grinding the sintered material, uniformly mixing the material with carbon black and carboxymethyl cellulose according to the proportion of 70: 15, coating, and performing vacuum drying at 70 ℃ for 24 hours to prepare the composite electrode. The electrode was placed in a 2025 cell can, with a sodium sheet as the counter electrode, a polyethylene film as the separator, and 1M NaClO4The constant current charge and discharge test was carried out on an assembled battery using EC: EMC: DMC (1/1/1 vol.) + 5% FEC as an electrolyte.
Comparative example
Except that Fe is not added2(SO4)3.7H2O, other reaction conditions and reagents were the same as in example 2.
Material characterization and electrochemical Performance testing
The morphology structure of the composite material and the electrochemical performance of the composite material prepared by the method are tested and characterized by phase tests and cycle performance tests.
1. Structural analysis
FIGS. 1 a-c are XRD patterns of samples corresponding to examples 1-3; d is comparative example with no Fe addition2(SO4)3.7H2XRD pattern of O sample. It can be seen from the graph that Fe is not added2(SO4)3.7H2The O sample has a broad steamed bread peak between 20-30 deg., which is typical of amorphous carbon structures. However, the XRD patterns of the samples corresponding to examples 1-3 all showed peaks, which correspond to the carbon structure of Chaoite (PDF # 22-1069). FIG. 2 shows example 2 and comparative example without addition of Fe2(SO4)3.7H2XPS spectra of O samples. XPS tests show that the sample of example 2 and no addition of Fe2(SO4)3.7H2The O samples all contain C, N, O, P, Fe four elements; without addition of Fe2(SO4)3.7H2The atomic ratio of Fe in the O sample was 0.08%, and the atomic ratio of Fe in the example 2 sample was 2.74%. Addition of Fe2(SO4)3.7H2After O, the carbon content of the sample decreased overall.
2. Topography analysis
FIG. 3 is an SEM image of samples prepared in examples 1 to 3 of the present invention. As can be seen from the pictures, the nano materials prepared in the embodiments 1 to 3 all have spherical structures, and the size range is between 100 and 200 nm. Without addition of Fe2(SO4)3.7H2The O sample has micron-sized agglomerated morphology. FIGS. 4 and 5 are comparative examples with no Fe addition2(SO4)3.7H2TEM images and high-resolution TEM images of O samples and samples corresponding to examples 1 to 3. TEM images show that all the samples prepared in examples 1-3 are solid spheres. And isWith increasing Fe doping content, significant lattice fringes were found in the TEM sample of example 3. Table 1 gives the comparative examples without addition of Fe2(SO4)3.7H2Specific surface area values of O samples and samples corresponding to examples 1 to 3. As can be seen from the table, the specific surface area of the example doped with Fe is increased significantly.
Table 1 shows the specific surface area values of the samples corresponding to examples 1 to 3
| Sample (I) | Specific surface area (m)2/g) | Total pore volume (ml/g) |
| 0g Fe-doped | 20.773 | 0.0897 |
| Example 1 | 44.438 | 0.184 |
| Example 2 | 100.87 | 0.160 |
| Example 3 | 32.602 | 0.1459 |
3. Cycle performance test
FIG. 6 shows examples 1 to 3 of the present embodimentProduct and comparative example without addition of Fe2(SO4)3.7H2Graph of the cycling performance of the O sample at 5A/g current density. As can be seen from the figure, the samples prepared in the examples are used as the negative electrode of the sodium battery and all show better cycle performance, and can maintain 200mAh g after 300 cycles under the current density of 5A/g-1The above reversible capacity. FIG. 7 shows samples corresponding to examples 1 to 3 and comparative examples in which Fe was not added2(SO4)3.7H2O sample rate performance plot. It can be seen from the graph that the samples prepared in the examples all have better rate discharge performance when used as the negative electrode of the sodium battery. FIG. 8 shows a sample corresponding to example 2 and a comparative example in which Fe was not added2(SO4)3.7H2Cyclic voltammogram of O samples. As can be seen from the figure, Fe was not added2(SO4)3.7H2The O sample exhibited typical irreversible reaction types; the cyclic voltammetry of the sample corresponding to example 2 shows a distinct redox couple peak, and shows a quasi-reversible or reversible reaction type.
In conclusion, in the high-performance monodisperse carbon sphere negative electrode material with the special structure prepared by the invention, the structure material has higher sodium storage specific capacity due to the fact that the structure of the material is a Chaoite (PDF #22-1069) carbon structure. In addition, due to the monodispersity, Fe doping and other reasons, the prepared carbon material has high conductivity, and the prepared electrode material can keep relatively excellent rate performance.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept and the scope of the appended claims is intended to be protected.
Claims (5)
1. A preparation method of a high-performance monodisperse carbon sphere negative electrode material with a special structure is characterized by comprising the following steps: adding phytic acid, P123 and ferric sulfate salt into a solution of pyrrole or aniline monomer, carrying out ice bath magnetic stirring, adding an ammonium persulfate aqueous solution to initiate copolymerization reaction, and finally preparing the iron-doped spherical Zhao carbon structure material with monodispersity through high-temperature carbonization treatment, wherein the method specifically comprises the following steps:
(1) adding P123 into deionized water, ultrasonically stirring and dispersing until the P123 is completely dissolved, and then adding Fe2(SO4)3·7H2O, ultrasonically stirring for 15 min; then starting ice bath and magnetic stirring for 20 min;
(2) dispersing pyrrole or aniline in deionized water, ultrasonically stirring and dispersing uniformly, adding P123 and phytic acid, ultrasonically stirring and dispersing until the materials are completely dissolved; then starting ice bath and magnetic stirring for 20 min;
(3) dispersing the solution in the step (1) in the solution in the step (2), and magnetically stirring for 20min in ice bath;
(4) preparing an ammonium persulfate aqueous solution, adding the ammonium persulfate aqueous solution into the mixed solution obtained in the step (3), and carrying out ice bath for 12 hours; after the reaction is finished, carrying out suction filtration, washing for 3-5 times by using deionized water, and carrying out vacuum drying for 3-5 h at 70 ℃ to prepare a precursor monodisperse ball;
(5) carrying out high-temperature carbonization treatment on the material obtained in the step (4) under protective gas to prepare a high-performance monodisperse carbon sphere negative electrode material with a special structure;
wherein the pyrrole or aniline is dispersed in deionized water, and the molar concentration of the pyrrole or aniline is 0.05-0.5M; adding P123 and phytic acid, wherein the total mass ratio of the P123 to the deionized water is 1: 70-700, wherein the mass ratio of the phytic acid to the deionized water is 1: 5-150; fe2(SO4)3·7H2The mass ratio of O to deionized water is 1: 10-500; the special structure is that the carbon structure belongs to a Zhao carbon phase structure; the final doping amount mole ratio of the iron is 1-4%.
2. The preparation method of the high-performance special-structure monodisperse carbon sphere negative electrode material as claimed in claim 1, is characterized in that: the adding amount of the ammonium persulfate is 1-3 times of the mass of the pyrrole or aniline monomer.
3. The preparation method of the high-performance special-structure monodisperse carbon sphere negative electrode material as claimed in claim 1, is characterized in that: the high-temperature carbonization treatment conditions are as follows: at Ar, Ar/H2Mixed gas orAnd carrying out heat treatment for 1-12h at 500-800 ℃ in He atmosphere.
4. The high-performance monodisperse carbon sphere negative electrode material with a special structure prepared by the preparation method of claim 1.
5. The application of the high-performance special-structure monodisperse carbon sphere negative electrode material disclosed by claim 4 in preparing sodium ion battery electrodes.
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