CN116177531A - Phosphorus-sulfur co-doped antimony-based carbon nanomaterial and preparation method and application thereof - Google Patents
Phosphorus-sulfur co-doped antimony-based carbon nanomaterial and preparation method and application thereof Download PDFInfo
- Publication number
- CN116177531A CN116177531A CN202211617601.8A CN202211617601A CN116177531A CN 116177531 A CN116177531 A CN 116177531A CN 202211617601 A CN202211617601 A CN 202211617601A CN 116177531 A CN116177531 A CN 116177531A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- phosphorus
- based carbon
- antimony
- doped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 22
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 20
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000004146 energy storage Methods 0.000 claims abstract description 5
- 239000011232 storage material Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 7
- 239000002082 metal nanoparticle Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 9
- 229910001415 sodium ion Inorganic materials 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
Images
Classifications
-
- 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
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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 belongs to the technical field of nano materials, and particularly relates to a phosphorus-sulfur co-doped antimony-based carbon nano material, and a preparation method and application thereof. Adding antimony sulfide and sulfur powder into a triethylamine solution for hydrothermal reaction; drying to obtain a precursor; and placing the precursor in a porcelain boat, placing sodium dihydrogen hypophosphite in another porcelain boat, coating the two porcelain boats together, calcining, and cooling after the end. According to the invention, the antimony metal nano particles are loaded on the phosphorus-sulfur co-doped carbon nano material, so that the cost is low, and theoretical support and technical support are provided for the industrialized application of the porous carbon material in the electrochemical energy fields of energy storage materials and the like.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a phosphorus-sulfur co-doped antimony-based carbon nano material, and a preparation method and application thereof.
Background
With the continuous consumption of fossil fuels and the increase of environmental pollution, the search for clean and renewable energy sources that can replace fossil fuels is a trend. As a representative of the chemical energy storage system, lithium ion batteries have achieved widespread use. However, lithium ion batteries have problems of poor safety, low recovery rate, resource shortage, high price and serious environmental pollution, and become a bottleneck for development of new energy industry and a resistance for sustainable development. Under the market demand of a large number of batteries, the sodium is environment-friendly, low-cost and rich, so that the sodium ion battery anode material becomes a research hot spot.
Currently, the negative electrode materials of sodium ion batteries mainly comprise: carbon material, oxide/phosphate material, p-block element, and oxide/sulfate. Among them, the porous carbon material stands out in the negative electrode material of the sodium ion battery. Therefore, selecting a suitable negative electrode material for a sodium ion battery is a highly desirable problem. Research shows that Na is realized by utilizing porous carbon material + Has positive promotion effects on structural stability, conductivity and environmental friendliness, but the porous carbon material can limit the specific capacity performance of the sodium ion battery. As a typical transition metal sulfide, antimony sulfide has excellent physicochemical properties, and can accommodate a large Na due to its laminar flow properties + High power and long service life of the sodium ion battery are realized. Therefore, the development of the phosphorus-sulfur co-doped antimony-based carbon nanomaterial with low cost and excellent performance has good economic and social benefits.
Disclosure of Invention
In order to obtain a porous carbon material which can be applied to a negative electrode of a sodium ion battery and realize high power and long service life of the sodium ion battery, the invention provides a phosphorus-sulfur co-doped antimony-based carbon nanomaterial.
The invention also provides a preparation method of the phosphorus-sulfur co-doped antimony-based carbon nanomaterial, which is obtained by carrying out hydrothermal reaction on antimony sulfide and sulfur powder in triethylamine solution and carrying out phosphorylation on a cleaned and dried sample by utilizing sodium dihydrogen hypophosphite.
The invention also provides application of the phosphorus-sulfur co-doped antimony-based carbon nanomaterial. The technical scheme adopted by the invention for achieving the purpose is as follows:
the invention provides a preparation method of a phosphorus-sulfur co-doped antimony-based carbon nanomaterial, which comprises the following steps:
(1) Adding antimony sulfide and sulfur powder into triethylamine solution, performing hydrothermal reaction, cleaning and drying to obtain a precursor;
(2) And (3) placing the precursor obtained in the step (1) in a porcelain boat, placing sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to an air inlet, coating the two porcelain boats together, placing the two porcelain boats in a tube furnace for calcination, and cooling to room temperature after the process is finished to obtain the phosphorus-sulfur co-doped stibium-based carbon nanomaterial. In the process of cooling,
preferably, in the step (1), the mass volume ratio of the antimony sulfide, the sulfur powder and the triethylamine is (3-5) g (0.5-1.5) g:10mL.
Preferably, in step (1), the hydrothermal reaction is carried out at a temperature of 120 ℃ for 6 hours.
Preferably, in the step (2), the mass ratio of the precursor to the sodium dihydrogen phosphate is 0.02-0.04:1.
preferably, the calcination is carried out in an argon atmosphere, and the temperature is raised to 420-470 ℃ at a heating rate of 4-6 ℃/min, and the calcination is kept for 1.5-3h; most preferably, the inlet speed of the argon is 140-160mL/min.
The invention also provides the phosphorus-sulfur co-doped antimony-based carbon nanomaterial prepared by the preparation method.
The invention also aims to provide an application of the phosphorus-sulfur co-doped antimony-based carbon nanomaterial prepared by the preparation method or the phosphorus-sulfur co-doped antimony-based carbon nanomaterial in an energy storage material in the electrochemical field.
The beneficial effects of the invention are as follows: according to the invention, the antimony metal nano particles are loaded on the phosphorus-sulfur co-doped carbon nano material by using a simple hydrothermal synthesis method, so that the cost is low, and theoretical support and technical support are provided for the industrialized application of the porous carbon material in the electrochemical energy fields of energy storage materials and the like.
Drawings
Fig. 1 is SEM and TEM images of example 1 of the present invention.
Figure 2 is an XRD pattern of example 1 of the present invention.
FIG. 3 is a FTIR chart of example 1 of the present invention;
fig. 4 is a cycle number-specific capacity diagram.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings, in order to provide a more thorough understanding of the present disclosure, and to fully convey the scope of the disclosure to those skilled in the art. While the drawings illustrate exemplary embodiments of the present disclosure, it should be understood that the invention is not limited to the embodiments set forth herein.
Example 1
(1): 0.68g of antimony sulfide and 0.16g of sulfur powder were added to 10mL of triethylamine solution, and then the solution was transferred to a 25mL reaction vessel with a stainless steel substrate and kept in a forced air drying oven at 120℃for 6 days; naturally cooling, cleaning with ethanol, and drying in a vacuum drying oven at 60deg.C for 30min to obtain precursor;
(2): and (2) placing 0.03g of the precursor obtained in the step (1) into a porcelain boat, placing 1g of sodium dihydrogen hypophosphite into another porcelain boat, keeping the sodium dihydrogen hypophosphite close to an air inlet, coating the two porcelain boats by using tin foil, placing the two porcelain boats into a tube furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under an argon atmosphere of 150mL/min, keeping the temperature for 2 hours, and cooling to room temperature to obtain the phosphorus-sulfur co-doped stibium-based carbon nanomaterial.
Fig. 1 is a scanning electron microscope and a transmission electron microscope of the phosphorus-sulfur co-doped antimony-based carbon nanomaterial prepared in example 1, and it can be seen from the graph that the material has a porous structure and uniform gaps. Figure 2 is an XRD pattern of the material. Fig. 3 is a FTIR diagram.
Example 2
Step (1) adding 0.68g of antimony sulfide and 0.16g of sulfur powder into 10mL of triethylamine solution, transferring the solution into a 25mL reaction kettle with a stainless steel substrate, and maintaining the solution in a blast drying oven at 120 ℃ for 6 days; naturally cooling, cleaning with ethanol, and drying in a vacuum drying oven at 60deg.C for 30min to obtain precursor;
and (2) placing 0.03g of the precursor obtained in the step (1) into a porcelain boat, placing 1g of sodium dihydrogen hypophosphite into another porcelain boat, keeping the sodium dihydrogen hypophosphite close to an air inlet, coating the two porcelain boats with tin foil, placing the two porcelain boats into a tube furnace, heating to 420 ℃ at a heating rate of 5 ℃/min under an argon atmosphere of 150mL/min, keeping the temperature for 2h, and cooling to room temperature to obtain the phosphorus-sulfur co-doped stibium-based carbon nanomaterial.
Example 3
Step (1) adding 0.68g of antimony sulfide and 0.16g of sulfur powder into 10mL of triethylamine solution, transferring the solution into a 25mL reaction kettle with a stainless steel substrate, and maintaining the solution in a blast drying oven at 120 ℃ for 6 days; naturally cooling, cleaning with ethanol, and drying in a vacuum drying oven at 60deg.C for 30min to obtain precursor;
and (2) placing 0.03g of the precursor obtained in the step (1) into a porcelain boat, placing 1g of sodium dihydrogen hypophosphite into another porcelain boat, keeping the sodium dihydrogen hypophosphite close to an air inlet, coating the two porcelain boats with tin foil, placing the two porcelain boats into a tube furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under an argon atmosphere of 150mL/min, keeping the temperature for 1h, and cooling to room temperature to obtain the phosphorus-sulfur co-doped stibium-based carbon nanomaterial.
Example 4
Step (1) adding 0.68g of antimony sulfide and 0.34g of sulfur powder into 10mL of triethylamine solution, transferring the solution into a 25mL reaction kettle with a stainless steel substrate, and maintaining the solution in a blast drying oven at 120 ℃ for 6 days; naturally cooling, cleaning with ethanol, and drying in a vacuum drying oven at 60deg.C for 30min to obtain precursor;
and (2) placing 0.03g of the precursor obtained in the step (1) into a porcelain boat, placing 1g of sodium dihydrogen hypophosphite into another porcelain boat, keeping the sodium dihydrogen hypophosphite close to an air inlet, coating the two porcelain boats by using tin foil, placing the two porcelain boats into a tube furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under an argon atmosphere of 150mL/min, keeping the temperature for 2h, and cooling to room temperature to obtain the phosphorus-sulfur co-doped stibium-based carbon nanomaterial.
Example 5
Step (1) adding 0.68g of antimony sulfide and 0.16g of sulfur powder into 10mL of triethylamine solution, transferring the solution into a 25mL reaction kettle with a stainless steel substrate, and maintaining the solution in a blast drying oven at 120 ℃ for 6 days; naturally cooling, cleaning with ethanol, and drying in a vacuum drying oven at 60deg.C for 30min to obtain precursor;
and (2) placing 0.03g of the precursor obtained in the step (1) into a porcelain boat, placing 1g of sodium dihydrogen hypophosphite into another porcelain boat, keeping the sodium dihydrogen hypophosphite close to an air inlet, coating the two porcelain boats with tin foil, placing the two porcelain boats into a tube furnace, heating to 470 ℃ at a heating rate of 5 ℃/min under an argon atmosphere of 150mL/min, keeping the temperature for 2h, and cooling to room temperature to obtain the phosphorus-sulfur co-doped stibium-based carbon nanomaterial.
Comparative example 1
Step (1) adding 0.68g of antimony sulfide and 0.16g of sulfur powder into 10mL of triethylamine solution, transferring the solution into a 25mL reaction kettle with a stainless steel substrate, and maintaining the solution in a blast drying oven at 120 ℃ for 6 days; and naturally cooling, cleaning with ethanol, and drying in a vacuum drying oven at 60 ℃ for 30min to obtain the sulfur-doped antimony-based carbon nanomaterial.
Comparative example 2
Step (1) adding 0.68g of antimony sulfide and 0.16g of sulfur powder into 10mL of triethylamine solution, transferring the solution into a 25mL reaction kettle with a stainless steel substrate, and maintaining the solution in a blast drying oven at 120 ℃ for 6 days; naturally cooling, cleaning with ethanol, and drying in a vacuum drying oven at 60deg.C for 30min to obtain precursor;
and (2) placing 0.03g of the precursor obtained in the step (1) into a porcelain boat, placing 0.5g of sodium dihydrogen hypophosphite into another porcelain boat, keeping the sodium dihydrogen hypophosphite close to an air inlet, coating the two porcelain boats with tin foil, placing the two porcelain boats into a tubular furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under an argon atmosphere of 150mL/min, keeping the temperature for 2h, and cooling to room temperature to obtain the phosphorus-sulfur co-doped antimony-based carbon nanomaterial.
Effect data
Sodium ion battery performance tests were performed on example 1, comparative example 1 and comparative example 2 using a blue electric battery test system, and a cycle number-specific capacity chart was drawn, and the results are shown in fig. 4. The result shows that the phosphorus-sulfur co-doped antimony-based carbon nanomaterial prepared in the embodiment 1 has high specific capacity and good cycle stability, and meets the effect expectation.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention are clearly and completely described above in conjunction with the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Accordingly, the above detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (8)
1. The preparation method of the phosphorus-sulfur co-doped antimony-based carbon nanomaterial is characterized by comprising the following steps of:
(1) Adding antimony sulfide and sulfur powder into triethylamine solution, performing hydrothermal reaction, cleaning and drying to obtain a precursor;
(2) And (3) placing the precursor obtained in the step (1) in a porcelain boat, placing sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to an air inlet, coating the two porcelain boats together, placing the two porcelain boats in a tube furnace for calcination, and cooling to room temperature after the process is finished to obtain the phosphorus-sulfur co-doped stibium-based carbon nanomaterial.
2. The preparation method according to claim 1, wherein in the step (1), the mass-volume ratio of the antimony sulfide, the sulfur powder and the triethylamine is (3-5) g (0.5-1.5) g:10mL.
3. The method according to claim 1 or 2, wherein in the step (1), the hydrothermal reaction is a reaction at a temperature of 120 ℃ for 6 hours.
4. The method according to claim 1, wherein in the step (2), the mass ratio of the precursor to the sodium dihydrogen phosphate is 0.02 to 0.04:1.
5. the method according to claim 1 or 4, wherein the calcination is carried out by heating to 420 to 470 ℃ at a heating rate of 4 to 6 ℃/min under an argon atmosphere for 1.5 to 3 hours.
6. The method according to claim 5, wherein the argon gas is introduced at a rate of 140-160mL/min.
7. A phosphorus-sulfur co-doped antimony-based carbon nanomaterial prepared by the preparation method of any one of claims 1-6.
8. Use of the phosphorus-sulfur co-doped antimony-based carbon nanomaterial prepared by the preparation method of any one of claims 1-6 or the phosphorus-sulfur co-doped antimony-based carbon nanomaterial of claim 7 in an energy storage material in the electrochemical field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211617601.8A CN116177531A (en) | 2022-12-15 | 2022-12-15 | Phosphorus-sulfur co-doped antimony-based carbon nanomaterial and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211617601.8A CN116177531A (en) | 2022-12-15 | 2022-12-15 | Phosphorus-sulfur co-doped antimony-based carbon nanomaterial and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116177531A true CN116177531A (en) | 2023-05-30 |
Family
ID=86435439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211617601.8A Pending CN116177531A (en) | 2022-12-15 | 2022-12-15 | Phosphorus-sulfur co-doped antimony-based carbon nanomaterial and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116177531A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4722774A (en) * | 1987-02-25 | 1988-02-02 | Chemical & Metal Industries, Inc. | Recovery or arsenic and antimony from spent antimony catalyst |
| GB201517661D0 (en) * | 2015-10-06 | 2015-11-18 | Faradion Ltd | Process for preparing hard carbon composite materials |
| CN112264065A (en) * | 2020-10-12 | 2021-01-26 | 齐鲁工业大学 | Iron/antimony-based heteroatom co-doped carbon nano material and preparation method and application thereof |
| CN113735181A (en) * | 2021-09-06 | 2021-12-03 | 安徽工业大学 | Antimony-cobalt sulfide-carbon composite nanorod and preparation method and application thereof |
-
2022
- 2022-12-15 CN CN202211617601.8A patent/CN116177531A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4722774A (en) * | 1987-02-25 | 1988-02-02 | Chemical & Metal Industries, Inc. | Recovery or arsenic and antimony from spent antimony catalyst |
| GB201517661D0 (en) * | 2015-10-06 | 2015-11-18 | Faradion Ltd | Process for preparing hard carbon composite materials |
| CN112264065A (en) * | 2020-10-12 | 2021-01-26 | 齐鲁工业大学 | Iron/antimony-based heteroatom co-doped carbon nano material and preparation method and application thereof |
| CN113735181A (en) * | 2021-09-06 | 2021-12-03 | 安徽工业大学 | Antimony-cobalt sulfide-carbon composite nanorod and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11634332B2 (en) | Selenium-doped MXene composite nano-material, and preparation method and use thereof | |
| CN107146915B (en) | A kind of preparation method of porous bismuth-carbon composite | |
| CN109786743B (en) | Tellurium-doped MXene material and preparation method and application thereof | |
| CN107601501A (en) | A kind of preparation method and applications of biomass-based porous carbon | |
| CN109786742B (en) | Se-doped MXene battery negative electrode material and preparation method and application thereof | |
| CN112072101A (en) | Boron-doped MXene material and preparation method thereof | |
| CN111354952A (en) | Graphite felt composite electrode and preparation method thereof | |
| CN109888280B (en) | Sulfur-doped MXene negative electrode material of potassium ion battery and preparation method thereof | |
| CN113809286B (en) | Metal Organic Framework (MOF) catalyzed growth carbon nanotube coated nickel-tin alloy electrode material and preparation method and application thereof | |
| CN116177531A (en) | Phosphorus-sulfur co-doped antimony-based carbon nanomaterial and preparation method and application thereof | |
| CN111313025A (en) | Nitrogen-doped carbon-coated flaky titanium oxide material and preparation method and application thereof | |
| CN113346070B (en) | Preparation method of lantern-shaped metal-oxygen-carbon composite material and application of lantern-shaped metal-oxygen-carbon composite material in non-aqueous potassium ion battery | |
| CN112072100B (en) | Iron-based dianion carbonized carbon composite material and preparation method and application thereof | |
| CN113223871B (en) | Preparation and application of NiO/C composite electrode material with foam nickel sheet as substrate | |
| CN109671923A (en) | A kind of preparation method and lithium-sulfur cell of ordered nano array nitrogen sulphur codope carbon sulphur composite carbon bar material | |
| CN113097467B (en) | Preparation method of lithium ion battery composite material with double-layer shell structure | |
| CN115148946A (en) | Preparation method of positive pole piece of lithium-sulfur battery and lithium-sulfur battery | |
| CN110828796B (en) | Yolk shell structure potassium ion battery negative electrode material and preparation method thereof | |
| CN109592676B (en) | Preparation method of carbon nano composite material derived from carbon nanosheet matrix grown on graphene oxide | |
| CN112908716A (en) | Zinc oxide-graphene composite electrode material with diatomite as carrier and preparation method thereof | |
| CN113130905A (en) | Ultra-small cobalt sulfide nanosheet/carbon cloth composite material and preparation method thereof | |
| CN108455685A (en) | A kind of N/Co3O4Composite porous preparation method | |
| CN115110112B (en) | Industrial preparation method of nickel-molybdenum electrode and nickel-molybdenum electrode | |
| CN114804204B (en) | V is prepared by solvothermal-carbon reduction method 6 O 13 Method for preparing nanometer flower ball material | |
| CN117543038B (en) | Modification preparation process of bipolar plate of proton exchange membrane fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |