CN110247030B - Method for preparing three-dimensional porous microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with metal/carbon yolk shell structures - Google Patents
Method for preparing three-dimensional porous microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with metal/carbon yolk shell structures Download PDFInfo
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Abstract
The invention provides a method for preparing a three-dimensional porous microsphere surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with a metal/carbon yolk shell structure, which comprises the following steps: preparing a precursor: selecting antimony acetate, ammonium citrate and sodium chloride as raw materials, mixing and dissolving in deionized water, and spraying the obtained uniform mixed solution into balls by using a spray dryer to prepare a precursor; preparing a three-dimensional porous microsphere composite material formed by enclosing nitrogen/sulfur co-doped carbon nanosheets embedded with antimony/carbon yolk shell structures: and (3) placing the precursor prepared in the step (1) in the midstream of a tubular furnace, placing thiourea in the upstream, and obtaining the three-dimensional porous microsphere composite material formed by the nitrogen/sulfur co-doped carbon nanosheets embedded with the antimony/carbon yolk shell structure in a multi-step manner in one pot. The prepared three-dimensional porous microsphere composite material formed by surrounding nitrogen/sulfur co-doped carbon nanosheets embedded with antimony/carbon yolk shell structures is used as a negative electrode of a sodium ion battery.
Description
Technical Field
The invention relates to a method for preparing a three-dimensional porous microsphere surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with a metal/carbon yolk shell structure by using a spray drying method, can show ultrahigh performance in a sodium ion battery negative electrode test, and belongs to the technical field of nano composite material preparation technology and battery application.
Background
With the high concern of renewable energy utilization, the development and application of lithium/sodium ion batteries are in need. At present, the preparation process of the lithium/sodium ion battery anode material is increasingly perfect, and the performance basically meets the industrial requirement. However, the development and application of the negative electrode material mostly stay in the basic research stage, and the industrial production is difficult due to the low yield of the preparation process (hydrothermal process, solvent thermal process, electrostatic spinning and the like), complex process and high cost. Another key problem is that it is difficult to obtain stable cycling performance under high current when the product obtained by various preparation schemes is used as a negative electrode of a lithium/sodium ion battery, which greatly limits the possibility of industrial application. Therefore, the large-scale and high-efficiency preparation of the electrode material with the large-rate and long-cycle performance in the lithium/sodium ion battery cathode is still a difficult problem.
The nitrogen/sulfur-codoped three-dimensional porous carbon microsphere has large specific surface area, high mechanical strength and excellent conductivity, so that the nitrogen/sulfur-codoped three-dimensional porous carbon microsphere can be applied to the field of battery cathodes such as lithium, sodium and potassium, and other metal-based nano materials can be embedded into the porous carbon microsphere as a load matrix due to the abundant pore structures and the doped nitrogen and sulfur atoms. The yolk shell structure is proved to be capable of effectively relieving the metal volume expansion and increasing the cycle stability in the battery charging and discharging processes. The yolk shell structure combined with the nitrogen/sulfur co-doped three-dimensional porous carbon microsphere composite material can be used as a positive electrode material and a negative electrode material of a high-performance sodium ion battery and a lithium ion battery, and is even expected to show excellent performance in the fields of super-capacitors, lithium-sulfur batteries, lithium metal batteries, electro-catalysis hydrogen evolution and the like.
Disclosure of Invention
The invention aims to provide a method for industrially preparing three-dimensional porous microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with metal/carbon yolk shell structures; the method has the advantages of simple and efficient process, low cost and good repeatability, the obtained three-dimensional porous microsphere composite material formed by the nitrogen/sulfur co-doped carbon nanosheets embedded with the antimony/carbon yolk shell structures is uniform in shape and large in yield, and when the material is applied to the negative electrode of the sodium-ion battery, the super-long cycle life can be displayed even under the condition of large current. The technical scheme is as follows:
a method for preparing three-dimensional porous microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with metal/carbon yolk shell structures comprises the following steps:
1) preparation of the precursor
Antimony acetate, ammonium citrate and sodium chloride are selected as raw materials, mixed and dissolved in deionized water, and the obtained uniform mixed solution is sprayed into balls by a spray dryer, so that the precursor is prepared.
2) Preparation of three-dimensional porous microsphere composite material formed by enclosing nitrogen/sulfur co-doped carbon nanosheets embedded with antimony/carbon yolk shell structures
Placing the precursor prepared in the step 1) in a midstream of a tube furnace, placing thiourea in the upstream, and carrying out a 1 st step of one-pot multistep: heating to 280 ℃ at a speed of 1 ℃/min under the atmosphere of high-purity argon, and preserving heat for 2 hours to obtain the Sb-containing alloy2S3Intermediate (b) of (1), denoted NaCl @ N, S-carbon/Sb2S3(ii) a Step 2: heating to 450 ℃ under the atmosphere of high-purity argon, switching to hydrogen-argon mixed gas, and keeping the temperature for 2h, wherein the currently obtained intermediate product is converted into Sb which is recorded as NaCl @ N, S-carbon/Sb; and 3, step 3: heating to 600 ℃ in a high-purity argon atmosphere, preserving heat for 2 hours by using argon as carrier gas, cooling to room temperature to obtain a calcined product, marking as NaCl @ Sb @ NS-3DPCMSS-120, and constructing an egg yolk shell structure by using the physical property that Sb is severely sublimated at the temperature of more than 500 ℃ due to the characteristic of low melting point in the heat preservation process; and then NaCl is removed from NaCl @ Sb @ NS-3DPCMSs-120, and Sb @ NS-3DPCMSs-120 is obtained by vacuum drying, thus obtaining the three-dimensional porous microsphere composite material surrounded by the nitrogen/sulfur co-doped carbon nanosheets embedded with the antimony/carbon yolk shell structure.
1) In accordance with Sb3+C and C Na+The material weight ratio of (1), (12-18) and (25-30) to 100.
The prepared three-dimensional porous microsphere composite material formed by surrounding nitrogen/sulfur co-doped carbon nanosheets embedded with antimony/carbon yolk shell structures is used as a negative electrode of a sodium ion battery.
Compared with the prior art, the method and the device of the inventionHas the following advantages: (1) NaCl (recyclable) is used as a template, and inexpensive (CH) is used3COO)3Sb、C6H5O7(NH4)3And CH4N2S is used as a raw material, so that the cost is greatly saved; (2) the process continuity of the prepared three-dimensional porous microsphere composite material formed by enclosing of the nitrogen/sulfur co-doped carbon nanosheets embedded with the antimony/carbon yolk shell structures is high; (3) the product has high purity, high yield and good controllability, and is expected to promote the practical application of large-scale industrial preparation of other composite materials with similar structures in the future.
Drawings
FIG. 1 shows the N, S-carbon/Sb after NaCl removal by water washing prepared according to the present invention2S3XRD spectra of N, S-carbon/Sb, Sb @ NS-3 DPCMSs-120;
FIG. 2 shows the precursor NaCl @ (CH) prepared by the present invention3COOH)3Sb-C6H5O7(NH4)3SEM image of (a);
FIG. 3 is an SEM image of Sb @ NS-3DPCMSs-120 prepared by the present invention after NaCl is removed by washing;
FIG. 4 is a TEM image of Sb @ NS-3DPCMSs-120 after NaCl is removed by washing prepared by the present invention;
FIG. 5 is an HRTEM image of Sb @ NS-3DPCMSs-120 after NaCl removal by water washing prepared according to the present invention;
FIG. 6 shows the multiplying power and 100mAg of Sb @ NS-3DPCMSs-120 composite material prepared by the present invention, its carbon skeleton (denoted as NS-3DPCMSs) and commercial Sb microparticles (Pure-Sb)-1Cycling performance at current density;
FIG. 7 shows Sb @ NS-3DPCMSs-120 composite material prepared by the present invention in 17Ag-1Long term cycling performance at current density
FIG. 8 shows Sb @ NS-3DPCMSs-120 composite material prepared by the present invention in 20Ag-1Long term cycling performance at current density
Nothing in this specification is said to apply to the prior art.
Detailed Description
Specific examples of the production method of the present invention are given below. These examples are only intended to illustrate the preparation process of the present invention in detail and do not limit the scope of protection of the claims of the present application.
The technical scheme for solving the problems is to design a method for preparing three-dimensional porous microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with antimony/carbon yolk shell structures through spray drying and subsequent one-pot multi-step calcining treatment, wherein the preparation method adopts the following process route:
1) preparation of the precursor
Antimony acetate ((CH) is selected3COO)3Sb), ammonium citrate (C)6H5O7(NH4)3) And sodium chloride (NaCl) as raw materials, mixing and dissolving in deionized water, stirring with a magnetic stirrer at room temperature for 9h, and spray drying the obtained uniform mixed solution at 175 deg.C to obtain precursor (marked as NaCl @ (CH)3COOH)3Sb-C6H5O7(NH4)3). The white powder obtained was collected for use.
2) Method for preparing three-dimensional porous microsphere composite material formed by enclosing nitrogen/sulfur co-doped carbon nanosheets embedded with antimony/carbon yolk shell structures
The precursor prepared in the step 1 is placed in a tube furnace in the midstream, and thiourea (CH)4N2S, a source of sulfur to provide reaction and doping) is placed upstream. 1, a multi-step of one pot: heating to 280 ℃ at a speed of 1 ℃/min under the atmosphere of high-purity argon, and preserving heat for 2 hours to obtain the Sb-containing alloy2S3Intermediate (denoted as NaCl @ N, S-carbon/Sb)2S3) (ii) a Step 2: heating to 450 ℃ under the atmosphere of high-purity argon, switching to hydrogen-argon mixed gas, and preserving heat for 2h, wherein the currently obtained intermediate product is converted into Sb (recorded as NaCl @ N, S-carbon/Sb); and 3, step 3: heating to 600 ℃ in the high-purity argon atmosphere, preserving the heat for 2 hours by using argon as carrier gas, cooling to room temperature to obtain a calcined product (marked as NaCl @ Sb @ NS-3DPCMSs-120), and constructing an egg yolk shell structure by using the physical property that Sb is low in melting point (630 ℃) and is severely sublimated at the temperature of more than 500 ℃ in the heat preservation process. Washing NaCl @ Sb @ NS-3DPCMSs-120 with deionized water for more than 3 times to remove NaCl, and vacuum drying at 60 ℃ for 24 hours to obtain Sb @ NS-3DPCMSs-120, namely obtaining the three-dimensional porous microsphere composite material surrounded by the nitrogen/sulfur co-doped carbon nanosheets embedded with the antimony/carbon yolk shell structure.
Example 1
According to Sb3+C and C Na+In a mass ratio of 1:15 and 28:100, 0.95g of (CH)3COO)3Sb, 1.94g of C6H5O7(NH4)3And 10g NaCl in 80mL deionized water and stirred at room temperature for 9h to ensure C6H5O7(NH4)3Fully complexing with metal salt. And (3) carrying out spray drying on the obtained uniform solution by a spray dryer, wherein the inlet and outlet air temperatures of the spray dryer are respectively 175 ℃ and 90 ℃. In this process, the reaction is carried out by (CH)3COO)3Sb、C6H5O7(NH4)3And NaCl is self-assembled to form hollow spheres, and the sizes of the spheres are normally distributed. Because the water on the surface of the liquid drop is volatilized rapidly at high temperature, the water in the liquid drop carries NaCl to migrate to the surface, and the self-assembly of the liquid drop is caused to form a hollow sphere precursor NaCl @ (CH) in a very short time3COOH)3Sb-C6H5O7(NH4)3. The precursor was placed in the midstream of a tube furnace and excess thiourea was placed upstream (thermal decomposition produced H)2S), introducing argon to remove air, heating to 280 ℃ at a speed of 1 ℃/min, and keeping the temperature for 2 hours; heating to 450 ℃ at the speed of 8 ℃/min, and then changing into 20% hydrogen-argon mixed gas for heat preservation for 2 h; then the carrier gas is changed into pure argon, the temperature is raised to 600 ℃ at the speed of 8 ℃/min, the temperature is kept for 2h and then the temperature is cooled to room temperature, and the calcined product NaCl @ Sb @ NS-3DPCMSs-120 is obtained. The product was washed three times with deionized water and ethanol and dried in vacuo at 60 ℃ for 24h to give sample Sb @ NS-3 DPCMSs-120.
Example 2
According to Sb3+C and C Na+In a mass ratio of 1:15 and 28:100, 4.3g of (CH)3COO)3Sb, 8.74g of C6H5O7(NH4)3And 45g NaCl in 355mL deionized water, stirred at room temperature for 6h to ensure C6H5O7(NH4)3Fully complexing with metal salt. And (3) carrying out spray drying on the obtained uniform solution by a spray dryer, wherein the air inlet temperature and the air outlet temperature of the spray dryer are respectively 180 ℃ and 90 ℃. Placing the precursor in the midstream of a tube furnace, placing excessive thiourea in the upstream, introducing argon to remove air, heating to 280 ℃ at the speed of 1 ℃/min, and preserving heat for 100 min; heating to 450 ℃ at the speed of 5 ℃/min, and then changing into 15% hydrogen-argon mixed gas to preserve heat for 2 h; then the carrier gas is changed into pure argon, the temperature is raised to 600 ℃ at the speed of 5 ℃/min, the temperature is kept for 2h and then the temperature is cooled to room temperature, and the calcined product NaCl @ Sb @ NS-3DPCMSs-120 is obtained. The product is washed by deionized water for more than three times, and is dried in vacuum at 70 ℃ for 12h to obtain a sample Sb @ NS-3 DPCMSs-120.
Claims (3)
1. A method for preparing three-dimensional porous microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with metal/carbon yolk shell structures comprises the following steps:
1) preparation of the precursor
Selecting antimony acetate, ammonium citrate and sodium chloride as raw materials, mixing and dissolving in deionized water, and spraying the obtained uniform mixed solution into balls by using a spray dryer to prepare a precursor;
2) preparation of three-dimensional porous microsphere composite material formed by enclosing nitrogen/sulfur co-doped carbon nanosheets embedded with antimony/carbon yolk shell structures
Placing the precursor prepared in the step 1) in a midstream of a tube furnace, placing thiourea in the upstream, and carrying out a 1 st step of one-pot multistep: heating to 280 ℃ at a speed of 1 ℃/min under the atmosphere of high-purity argon, and preserving heat for 2 hours to obtain the Sb-containing alloy2S3Intermediate (b) of (1), denoted NaCl @ N, S-carbon/Sb2S3(ii) a Step 2: heating to 450 ℃ under the atmosphere of high-purity argon, switching to hydrogen-argon mixed gas, keeping the temperature for 2 hours, and keeping Sb in the intermediate product2S3Converting into Sb, and recording as NaCl @ N, S-carbon/Sb; and 3, step 3: heating to 600 ℃ in a high-purity argon atmosphere, preserving heat for 2 hours by using argon as carrier gas, cooling to room temperature to obtain a calcined product, recording as NaCl @ Sb @ NS-3DPCMSs-120, and constructing an egg yolk shell structure by using the physical property that Sb is severely sublimated at the temperature of more than 500 ℃ due to the characteristic of low melting point of Sb in the heat preservation process; then adding NaCl @ SbAnd removing NaCl from the @ NS-3DPCMSs-120, and drying in vacuum to obtain Sb @ NS-3DPCMSs-120, namely obtaining the three-dimensional porous microsphere composite material surrounded by the nitrogen/sulfur co-doped carbon nanosheets embedded with the antimony/carbon yolk shell structure.
2. The method according to claim 1, wherein 1) is performed according to Sb3+C and C Na+The material weight ratio of (1), (12-18) and (25-30) to 100.
3. The three-dimensional porous microsphere composite material formed by enclosing nitrogen/sulfur co-doped carbon nanosheets embedded with the antimony/carbon yolk shell structure, prepared by the method according to claim 1, is used as a negative electrode material of a sodium-ion battery.
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| CN110739449A (en) * | 2019-09-26 | 2020-01-31 | 天津大学 | Preparation of Embedded FeS2Method for preparing three-dimensional microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets of nanoparticles |
| CN111600032A (en) * | 2020-05-27 | 2020-08-28 | 新昌县品宏科技有限公司 | SnSb alloy-carbon nanofiber sodium ion battery negative electrode material and preparation method thereof |
| CN112479258B (en) * | 2020-12-17 | 2023-05-16 | 陕西科技大学 | Molybdenum disulfide-carbon hollow sphere and preparation method and application thereof |
| CN113130864B (en) * | 2021-03-23 | 2022-08-16 | 华南理工大学 | Chemical bond enhanced silver ear-shaped porous carbon sphere embedded with monodisperse nano alloy particles and preparation and application thereof |
| CN113130924B (en) * | 2021-04-20 | 2022-09-06 | 中国科学技术大学 | Metal-air battery catalyst, preparation method and application thereof |
| CN114530598A (en) * | 2022-01-10 | 2022-05-24 | 广东工业大学 | Nitrogen-oxygen-sulfur doped carbon negative electrode material and preparation method and application thereof |
| CN114464872B (en) * | 2022-01-24 | 2023-08-29 | 西安交通大学 | Application of antimony nanosheets doped with halogen on surface in lithium ion battery |
| CN114843459B (en) * | 2022-04-14 | 2023-12-15 | 中国科学院长春应用化学研究所 | Antimony pentasulfide-based material and preparation method and application thereof |
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