CN113353918A - Mesoporous hollow carbon sphere with adjustable morphology prepared by metal ion catalytic induction and application thereof - Google Patents
Mesoporous hollow carbon sphere with adjustable morphology prepared by metal ion catalytic induction and application thereof Download PDFInfo
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- CN113353918A CN113353918A CN202110816643.3A CN202110816643A CN113353918A CN 113353918 A CN113353918 A CN 113353918A CN 202110816643 A CN202110816643 A CN 202110816643A CN 113353918 A CN113353918 A CN 113353918A
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- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a mesoporous hollow carbon sphere with adjustable morphology prepared by metal ion catalytic induction and application thereof, wherein CTAB, PDA and nitrate metal salt are dissolved in a mixture of ethanol and deionized water, then the mixture is vigorously stirred for 1-2 h, then concentrated ammonia water is added, the mixture is stirred for 12h at room temperature to obtain a spherical colloid precursor, then the spherical colloid precursor is calcined in an argon atmosphere of a tube furnace to obtain a hollow silicon carbon sphere, and then redundant silicon dioxide is removed by using a sodium hydroxide solution at the temperature of 50-80 ℃ to obtain the mesoporous hollow carbon sphere.
Description
Technical Field
The invention belongs to the field of preparation of sodium metal battery cathode materials, and particularly relates to mesoporous hollow carbon spheres with adjustable morphology prepared by metal ion catalytic induction and application thereof.
Background
The current generation of intelligent electronic devices, mobile devices and energy storage markets is rapidly increasing, creating a huge demand for mobile power sources. Lithium Ion Batteries (LIBs) have the advantages of high energy density and long cycle life and are widely used in the field of secondary batteries. However, with the continuous use of LIB in recent years, the price of lithium has rapidly increased and the content of lithium in the earth crust has also been reduced. Sodium-based batteries are receiving much attention as potential replacements for currently commercialized lithium-ion batteries due to their electrochemical properties similar to that of lithium and abundant sodium reserves. However, the practical application of the sodium ion battery is restricted due to the lack of matching of a proper negative electrode material, and the carbon-based negative electrode material is a sodium storage negative electrode material with a great application prospect. Due to the unique advantages of regular small diameter, hollow space, thin shell, high surface area and the like, the mesoporous hollow carbon sphere can provide enough active sites, spaces and transmission channels for charge retention and high-energy storage.
Disclosure of Invention
The invention aims to provide a method for preparing mesoporous hollow carbon spheres with adjustable morphology and composition by utilizing metal ion catalytic induction, which can synthesize a large specific surface area and effectively adjust a carbon material structure so as to obtain a sodium-storage carbon cathode with ultrahigh multiplying power and ultra-long cycle life. Tetraethoxysilane TEOS is selected as a silicon source template, PDA is selected as a condensing agent, metal atoms are used as metal doping to synthesize hollow silicon carbon spheres in situ, different metal ratios are adjusted, and mesoporous hollow carbon spheres (MHCS-metal ions) with different shapes are synthesized through alkali treatment.
In order to realize the technical scheme, the invention adopts the following technical scheme:
a method for preparing mesoporous hollow carbon spheres with adjustable morphology and composition by utilizing metal ion catalytic induction comprises the following steps:
dissolving 200-500mg CTAB, 0.001-0.005mol PDA and 1-10mmol nitrate (Cu, Zn, Fe, Bi, Ni and the like) in a mixture of ethanol (10-50 ml) and deionized water (60-80 ml), then violently stirring for 1-2 h, adding 1-2ml concentrated ammonia water, stirring for 12h at room temperature to obtain a spherical colloid precursor, then keeping at 900 ℃ for 8-12h in an argon atmosphere of a tubular furnace at 700-900 ℃ to obtain hollow silicon carbon spheres, and then removing redundant silicon dioxide by using 0.5-3 mol/L sodium hydroxide solution at 50-80 ℃ to obtain the Mesoporous Hollow Carbon Spheres (MHCS).
The synthesis mechanism of the invention is as follows: mesoporous Hollow Carbon Spheres (MHCS) with different shapes and adjustable components are prepared through the synergistic effect of dopamine hydrochloride (PDA) and a metal framework. PDA can be used as an additional carbon source in the self-assembly process during the simultaneous polycondensation process of tetraethyl orthosilicate (TEOS). Under the catalytic action of metal, PDA is easy to shrink in the carbonization process, which is beneficial to the formation of a hollow carbon structure (see the attached figures 2 g-i). But only with the aid of PDA the resulting silicon-oxygen-carbide composite has a very thick shell. The metal is introduced to be complexed with the PDA and sintered, and the formation of hollow structures with different shapes can be regulated and promoted through different coordination and catalytic actions. The additives PDA and metal ions can promote the secondary polycondensation yield of ethyl orthosilicate, suggesting that they participate in the bottom-up self-assembly and polycondensation processes. In addition, the hollow spheres are sintered and then silicon oxide is removed by using alkaline water, so that a mesoporous structure is generated. The XPS general spectrum of mesoporous hollow carbon spheres has been listed to include C, N, O, metal ions (carbon as the main component).
The application of the mesoporous hollow carbon spheres in the sodium metal battery is as follows: assembling a sodium metal battery: MHCS: CMC: the mass ratio of the carbon black is 80-85: 5-10: 10-15 parts by weight of the mixture are uniformly coated on a copper foil with the thickness of 1.2 cm2 to be used as a negative electrode, the positive electrode is metallic sodium, and the electrolyte is 1.0M NaPF6DEGDME solution of (a). The battery was packed in a glove box under argon (oxygen and moisture content below 1 ppm).
The invention has the beneficial effects that:
according to the mesoporous hollow carbon sphere with adjustable morphology prepared by metal ion catalytic induction, due to the large gaps and the large specific surface, rapid ion and electron transmission is realized, so that good rate performance and excellent cycle stability are shown. The material has low cost, excellent performance and stable material structure, and has good application prospect in a high-performance sodium ion battery system.
Drawings
FIG. 1 is an XRD pattern of MHCS-Zn, MHCS-Bi and pure MHCS materials;
FIG. 2 is high low magnification Scanning Electron Microscope (SEM) images of MHCS-Bi (a, b), MHCS-Zn (d, e) and pure MHCS (g, h) images of MHCS-Bi (c), MHCS-Zn (f) and pure MHCS (i) Transmission Electron Microscope (TEM) images;
FIG. 3 is (a) a BET diagram of MHCS-Bi and MHCS-Zn, and (b) a BJH diagram of MHCS-Bi and MHCS-Zn;
FIG. 4 is a graph showing charge and discharge curves and multiplying power curves of MHCS-Zn (a, b) and MHCS-Bi (c, d) with materials;
FIG. 5 is a graph of the long term cycling of MHCS-Zn (a) and MHCS-Bi (b) materials;
FIG. 6 is an XPS plot of MHCS-Zn and MHCS-Bi materials.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
200mg of CTAB, 0.005mol of PDA and 3 mmol of Zn (NO)3)2Or 3 mmol of Bi (NO)3)2Dissolving the mixture in a mixture of ethanol (30 ml) and deionized water (70 ml), then violently stirring for 2h, adding 1ml of concentrated ammonia water, stirring for 12h at room temperature, collecting and drying to obtain a spherical colloid precursor, then keeping the temperature of 850 ℃ for 8 h in an argon atmosphere of a tube furnace to obtain hollow silicon carbon spheres, and then removing redundant silicon dioxide by using 1 mol/L sodium hydroxide solution at the temperature of 50 ℃ for 12h to obtain the mesoporous hollow carbon spheres (Zn-MHCS or Bi-MHCS).
The application of the mesoporous hollow carbon spheres in the sodium metal battery is as follows: assembling a sodium metal battery: Zn-MHCS or Bi-MHCS: CMC: the mass ratio of the carbon black is 80-85: 5-10: mixing 10-15, grinding, and uniformly coating on 1.2 cm2The copper foil is used as a negative electrode, the positive electrode is metallic sodium, and the electrolyte is 1.0DEGDME solution of M NaPF 6. The battery was packed in a glove box under argon (oxygen and moisture content below 1 ppm).
Comparative example 1
200mg of CTAB and 0.005mol of PDA are dissolved in a mixture of ethanol (30 ml) and deionized water (70 ml), then the mixture is vigorously stirred for 2h, 1ml of strong ammonia water is added, the mixture is stirred for 12h at room temperature, a spherical colloid precursor is obtained after collection and drying, then the spherical colloid precursor is kept for 8 h at 850 ℃ in an argon atmosphere of a tube furnace to obtain hollow silicon carbon spheres, and then 1 mol/L of sodium hydroxide solution is used for removing excessive silicon dioxide at 50 ℃ for 12h to obtain the mesoporous hollow carbon spheres (pure MHCS).
FIG. 1 shows XRD patterns of alkali-treated carbon materials MHCS-Bi, MHCS-Zn and pure MHCS after calcination, respectively, and it can be seen that both are amorphous as a whole after alkali treatment.
FIG. 2 is an SEM image and a TEM image of MHCS-Bi and MHCS-Zn, from which it can be seen that MHCS-Bi and MHCS-Zn both exhibit a thin-shell hollow carbon sphere of about 100 nm, and MHCS-Zn exhibits a hollow shrivelled sphere after alkali etching due to the adjustment of the distribution ratio of internal silicon oxide by the metal frame and the polycondensation of PDA, so that the specific surface areas are significantly increased, and from the BET image of FIG. 3a, the specific surface areas of MHCS-Bi and MHCS-Zn having excessively large specific surface areas are 1211.7 m/g and 1675.5 m/g, respectively, and the BJH aperture ratio is 1.42 cm3G and 2.09 cm3And/g, the fact that mesoporous hollow carbon sphere materials with ultrahigh specific surface area can be synthesized by different metal contents and the polymerization of PDA can be proved. From the BJH pore distribution plot of fig. 3b, it can be seen that the pore size of both hollow carbon spheres is mainly concentrated at 4 nm, but that MHCS-Zn clearly has a higher degree of porosity and more pores.
From the scanning and transmission electron micrographs (FIG. 2 g-i) of the comparative pure MHCS, it can be seen that the carbon spheres obtained in the case of PDA only, although they are also hollow, have extremely thick shells and small hollow spaces inside (FIG. 2 i), and no significant cracks or holes are observed in the spheres.
FIG. 4 shows the sodium storage performance of button cell composed of MHCS-Bi and MHCS-Zn and sodium metal respectivelyThe test of (1) shows that the initial discharge capacity of MHCS-Bi is 304.2 mA h g < -1 >, the initial charge capacity is 253.2mA h g < -1 >, and the first coulombic efficiency is 83.2%; MHCS-Zn initial discharge capacity is 220.2 mA h g < -1 >, initial charge capacity is 189.6 mA h g < -1 >, and first coulombic efficiency is 86.2%; MHCS-Bi and MHCS-Zn have excellent rate performance in the aspect of rate performance, and the capacity is stably increased after high current activation: at a current density of 20A/g, MHCS-Bi and MHCS-Zn still have a current density of 220.1mA h g-1And 200.6 mA h g-1Ultra high capacity.
FIG. 5 (a) MHCS-Zn capacity remains 171.9mA h g-1 with excellent sodium storage even after 2500 cycles at 5A current density while FIG. 5 (b) MHCS-Bi has a high initial capacity due to its excessive oxygen content, but this capacity is irreversible, gradually decays in subsequent cycles, and after 1500 cycles the capacity is only 160.7 mA h g-1Thus, the method comprises the following steps.
FIG. 6 is an XPS total spectrum of MHCS-Bi and MHCS-Zn, from which it is found that MHCS-Bi decreases in C/O ratio by 13.35 due to the combination of a part of the metal and oxygen, which results in a subsequent MHCS-Bi capacity fade compared to MHCS-Zn (C/O = 16.13).
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A method for preparing mesoporous hollow carbon spheres with adjustable morphology and composition by utilizing metal ion catalytic induction is characterized by comprising the following steps: the method comprises the following steps: dissolving CTAB, PDA and nitrate metal salt in a mixture of ethanol and deionized water, then violently stirring for 1-2 h, adding concentrated ammonia water, stirring at room temperature for 12h to obtain a spherical colloid precursor, then calcining in a tube furnace in argon atmosphere to obtain hollow silicon carbon spheres, and then removing redundant silicon dioxide by using sodium hydroxide solution at the temperature of 50-80 ℃ to obtain the mesoporous hollow carbon spheres.
2. The method for preparing mesoporous hollow carbon spheres with adjustable morphology and composition by utilizing metal ion catalysis and induction as claimed in claim 1, wherein the method comprises the following steps: the CTAB mass is 200-500mg, the PDA molar mass is 0.001-0.005mol, and the metal nitrate molar mass is 1-10 mmol.
3. The method for preparing mesoporous hollow carbon spheres with adjustable morphology and composition by utilizing metal ion catalysis and induction as claimed in claim 1, wherein the method comprises the following steps: the metal nitrate salt includes Cu, Zn, Fe, Bi or Ni.
4. The method for preparing mesoporous hollow carbon spheres with adjustable morphology and composition by utilizing metal ion catalysis and induction as claimed in claim 1, wherein the method comprises the following steps: the calcination is specifically as follows: calcining at the temperature of 700 ℃ and 900 ℃ for 8-12 h.
5. A mesoporous hollow carbon sphere prepared by the method of any one of claims 1 to 4.
6. The application of the mesoporous hollow carbon sphere of claim 5 in a sodium metal battery cathode, which is characterized in that: mixing mesoporous hollow carbon spheres, CMC and carbon black in a mass ratio of 80-85: 5-10: 10-15 are mixed and ground, and then are uniformly coated on a copper foil to be used as a negative electrode.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016150406A1 (en) * | 2015-03-26 | 2016-09-29 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere, and preparation and application thereof |
| CN109225131A (en) * | 2018-09-13 | 2019-01-18 | 华北电力大学 | A kind of preparation method of nitrogen-doped nanometer hollow carbon balls |
| CN110280290A (en) * | 2019-07-08 | 2019-09-27 | 华南理工大学 | One kind having flower-shaped type nitrogen-doped carbon-spinel-type microspherical catalyst of high-specific surface area and the preparation method and application thereof |
| CN112151814A (en) * | 2020-09-27 | 2020-12-29 | 安徽大学 | Catalyst with transition metal compound/hollow carbon sphere composite structure, preparation method and application |
| CN112331868A (en) * | 2020-11-06 | 2021-02-05 | 五邑大学 | Iron-nitrogen-doped core-shell carbon sphere material and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016150406A1 (en) * | 2015-03-26 | 2016-09-29 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere, and preparation and application thereof |
| CN109225131A (en) * | 2018-09-13 | 2019-01-18 | 华北电力大学 | A kind of preparation method of nitrogen-doped nanometer hollow carbon balls |
| CN110280290A (en) * | 2019-07-08 | 2019-09-27 | 华南理工大学 | One kind having flower-shaped type nitrogen-doped carbon-spinel-type microspherical catalyst of high-specific surface area and the preparation method and application thereof |
| CN112151814A (en) * | 2020-09-27 | 2020-12-29 | 安徽大学 | Catalyst with transition metal compound/hollow carbon sphere composite structure, preparation method and application |
| CN112331868A (en) * | 2020-11-06 | 2021-02-05 | 五邑大学 | Iron-nitrogen-doped core-shell carbon sphere material and preparation method thereof |
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