CN108878907B - Carbon/sulfur nano composite material and preparation method and application thereof - Google Patents

Carbon/sulfur nano composite material and preparation method and application thereof Download PDF

Info

Publication number
CN108878907B
CN108878907B CN201810699711.0A CN201810699711A CN108878907B CN 108878907 B CN108878907 B CN 108878907B CN 201810699711 A CN201810699711 A CN 201810699711A CN 108878907 B CN108878907 B CN 108878907B
Authority
CN
China
Prior art keywords
carbon
sulfur
composite material
crystal
oxygen reduction
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.)
Active
Application number
CN201810699711.0A
Other languages
Chinese (zh)
Other versions
CN108878907A (en
Inventor
车仁超
陈冠宇
张捷
余雪锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fudan University
Original Assignee
Fudan University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fudan University filed Critical Fudan University
Priority to CN201810699711.0A priority Critical patent/CN108878907B/en
Publication of CN108878907A publication Critical patent/CN108878907A/en
Application granted granted Critical
Publication of CN108878907B publication Critical patent/CN108878907B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the technical field of nano functional materials, and particularly relates to a carbon/sulfur nano composite material and a preparation method and application thereof. The invention obtains the carbon sphere material with spherical morphology through the controllable synthesis of adding the surfactant, and sulfur nanocrystalline particles grow on the surface of the carbon sphere after the carbon sphere material is compounded with sulfur. The carbon/sulfur composite material has better electrocatalytic performance, the initial potential of oxygen reduction reaction is-0.18V, and the limiting diffusion current is 3.5mA/cm‑2. In addition, the composite material has low preparation cost and high efficiency, is easier to industrially amplify so as to solve the problem of practical application, is used as a catalytic material for effective oxygen reduction reaction with a novel structure, and has wide application prospect.

Description

Carbon/sulfur nano composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano functional materials, and particularly relates to a carbon/sulfur nano composite material, a preparation method thereof and application thereof in electrical catalysis of oxygen reduction reaction.
Background
The novel power supply technology, such as metal air battery, proton exchange membrane fuel cell and the like, has the outstanding advantages of high energy conversion efficiency, strong cruising ability, cleanness, environmental protection and the like, and is expected to have wide application in important fields of portable electronic equipment, new energy automobiles, decentralized fixed power stations and the like[1]. However, the problems of less available material range, high price and the like still exist, and the large-scale application of the technologies still faces challenges. The Oxygen Reduction Reaction (ORR) is a critical step in metal air batteries, fuel cells, and the like. However, the reaction is complicated and has a high energy barrier, and thus a large overpotential is generally required for driving[2]. Thus, redox reactions generally require catalysisThe agent catalyzes. At present, the Pt catalyst is generally used as the ORR catalyst with higher catalytic activity, however, the Pt catalyst still has inherent disadvantages, such as easy generation of CO poisoning deactivation, and the Pt catalyst is expensive and difficult to be applied on a large scale. Although modification of Pt catalysts is still of interest to researchers, the most fundamental solution is still to use non-Pt catalysts.
Due to the unique structure on molecular and nano-scale, the nano-carbon material has unique application prospect in many aspects[3]. By means of doping, the structure of the carbon nano material is changed to a certain degree, so that the physical and chemical properties such as pH value, catalytic performance, conductivity and the like of the carbon nano material are influenced[4-6]. Non-noble metal element doped carbon-based materials have shown superior oxygen reduction catalytic performance than pure nanocarbon materials, and have attracted attention. In recent years, the main method for synthesizing carbon-based materials doped with non-noble metal elements is the in-situ synthesis method[6]CVD growth[7]In comparison with these methods, hydrothermal synthesis is generally carried out at a relatively low temperature, is simple and easy to operate, and many different materials have been reported to be successfully prepared by this method[8-9]. The synthesis of the sulfur nanocrystals is reported rarely in the literature and has certain research value.
The invention obtains the carbon sphere material with spherical morphology through the controllable synthesis of adding the surfactant, and sulfur nanocrystalline particles are grown on the surface of the carbon sphere after the carbon sphere material is compounded with sulfur. The composite material has more active sites, can improve the oxygen reduction performance of the material, and improves the electrocatalytic activity of the material.
Disclosure of Invention
The invention aims to provide a carbon/sulfur nano composite material with excellent oxygen reduction performance, a preparation method thereof and application in the field of oxygen reduction catalysis.
The nano material provided by the invention is a carbon/sulfur nano composite material, is spherical, and has different particle size along with different reaction temperatures. The initial potential of the composite material in the oxygen reduction reaction is-0.18V, and the limiting current density is 3.5mA/cm2Have a better ideaGood electrocatalytic performance. Can be used in fuel cells or metal air cells as an effective oxygen reduction catalyst.
The invention provides a preparation method of the carbon/sulfur nano composite material, which comprises the following specific steps:
(1) hydrothermal synthesis of carbon spheres
Adding 0.02-0.06 g of sodium dodecyl sulfate and 0.05-0.10 g of polypropylene glycol/ethylene oxide addition polymer into 20 +/-0.5 mL of deionized water, and stirring for 25-40 min at normal temperature until the sodium dodecyl sulfate and the polypropylene glycol/ethylene oxide addition polymer are completely dissolved;
adding 3.0-3.5g xylose into 40 + -0.5 mL deionized water, stirring at normal temperature (such as-105 min) until completely dissolving;
and then, mixing the two solutions, and continuously stirring for 25-30 min to obtain a stable and uniform colorless transparent solution. Pouring the solution into a hydrothermal kettle (with the volume of about 50 mL), heating to 160-200 ℃, and reacting for 12 +/-0.5 h; obtaining a carbon sphere material;
(2) purification and work-up of the product
After the hydrothermal kettle is cooled, centrifugally separating the black product, washing the black product for a plurality of times by using deionized water and absolute ethyl alcohol, and drying the black product in a vacuum oven at the temperature of 55-65 ℃;
(3) synthesis of carbon/sulfur nanocomposites
Mixing and grinding 0.08-0.15 g of the synthesized carbon sphere material and 0.50-0.80 g of sublimed sulfur (S) until the powder is gray, then roasting in a tubular furnace under the nitrogen atmosphere, and roasting at 550-700 ℃ for 5-8h to obtain the carbon/sulfur nano composite material.
The carbon/Sulfur nano composite material prepared by the invention has the carbon sphere size of 600-800nm, small Sulfur nano crystal particles with obvious crystal characteristics grow on the surface of the carbon sphere, the Sulfur nano crystal particle diameter is about 5-8nm, and the Sulfur nano crystal particle has a sulfurur crystal structure.
The carbon/sulfur nano composite material prepared by the invention can be used for testing oxygen reduction reaction. The method comprises the following specific steps:
dispersing 1.5mg of carbon/sulfur composite material in 1mL of ethanol/water solution, then adding 40 muL of thiophene serving as a dispersing agent, then dropwise adding 10 muL of thiophene on an electrode, and then placing the electrode in an electrochemical workstation to measure the oxygen reduction performance of a sample.
The carbon/sulfur composite material is used in fuel cell or metal air cell, and has high catalytic effect and low cost.
The composite material has low preparation cost and high efficiency, is easy to industrially amplify so as to solve the problem of practical application, and has wide application prospect as a catalytic material for effective oxygen reduction reaction with a novel structure.
Drawings
FIG. 1 is a scanning electron micrograph of the carbon/sulfur composite structure.
FIG. 2 is a transmission electron micrograph of a carbon/sulfur composite. Wherein (a) is the overall morphology of the carbon/sulfur composite material, and (b) is a high-resolution transmission electron microscope (HRTEM) image.
FIG. 3 is a high resolution TEM image of the carbon/sulfur composite structure.
FIG. 4 is a graph demonstrating the presence of sulfur in the carbon/sulfur composite. Wherein a is an energy spectrum, wherein the peak of Cu in the spectrum is caused by the interference existing in a copper mesh in a test; b is a STEM photograph demonstrating the presence of sulfur atoms on the carbon substrate.
FIG. 5 is a cyclic voltammetric performance test with carbon/sulfur complexes.
FIG. 6 shows the performance of linear sweep voltammetry tests for different carbon/sulfur composites with different sulfur loadings.
Detailed Description
Example 1:
(1) hydrothermal synthesis of carbon spheres
Adding 0.02g of sodium dodecyl sulfate and 0.05g of polypropylene glycol/ethylene oxide addition polymer into 20mL of deionized water, and stirring for 25min at normal temperature until the sodium dodecyl sulfate and the propylene glycol/ethylene oxide addition polymer are completely dissolved;
adding another 3.0g of xylose into 40mL of deionized water, and stirring for 5min at normal temperature until the xylose is completely dissolved;
then, the two solutions were mixed and stirred for 25min to obtain a stable and uniform colorless transparent solution. Pouring the solution into a hydrothermal kettle with the volume of 50mL, heating to 160 ℃, and reacting for 12 h; obtaining a carbon sphere material, wherein the shape of the carbon sphere material is ellipsoidal, and the particle size of the carbon sphere material is about 600 nm;
(2) purification and work-up of the product
After the hydrothermal kettle is cooled, centrifugally separating the black product, washing the black product for a plurality of times by using deionized water and absolute ethyl alcohol, centrifugally separating the black product, and drying the black product in a vacuum oven at the temperature of 55 ℃;
(3) synthesis of carbon/sulfur composite materials
0.08g of the obtained carbon sphere material was mixed and ground with 0.50g of sublimed sulfur (S) until the powder became gray, followed by firing in a tube furnace under a nitrogen atmosphere at 550 ℃ for 8 hours to obtain a carbon/sulfur composite material in which sulfur nanocrystals were not found to be present.
Example 2:
(1) hydrothermal synthesis of carbon spheres
Adding 0.04g of sodium dodecyl sulfate and 0.075g of polypropylene glycol/ethylene oxide addition polymer into 20mL of deionized water, and stirring for 30min at normal temperature until the sodium dodecyl sulfate and the propylene glycol/ethylene oxide addition polymer are completely dissolved;
adding another 3.2g of xylose into 39.5mL of deionized water, and stirring for 5min at normal temperature until the xylose is completely dissolved;
then, the two solutions were mixed and stirred for 30min to obtain a stable and uniform colorless transparent solution. Pouring the solution into a hydrothermal kettle with the volume of 50mL, heating to 180 ℃, and reacting for 12 h; obtaining a carbon sphere material, wherein the shape of the carbon sphere material is relatively intact spherical, and the particle size of the carbon sphere material is about 800 nm;
(2) purification and work-up of the product
After the hydrothermal kettle is cooled, centrifugally separating the black product, washing the black product for a plurality of times by using deionized water and absolute ethyl alcohol, centrifugally separating the black product, and drying the black product in a vacuum oven at the temperature of 60 ℃;
(3) synthesis of carbon/sulfur composite materials
0.10g of the obtained carbon sphere material and 0.60g of sublimed Sulfur (S) are mixed and ground until the powder is gray, then the powder is roasted in a tubular furnace in the nitrogen atmosphere and roasted at 600 ℃ for 6 hours to obtain the carbon/Sulfur composite material, and Sulfur nano crystals exist, have the particle size of about 5nm, have a sulfurer crystal structure and are compounded uniformly.
Example 3:
(1) hydrothermal synthesis of carbon spheres
Adding 0.06g of sodium dodecyl sulfate and 0.10g of polypropylene glycol/ethylene oxide addition polymer into 20mL of deionized water, and stirring for 40min at normal temperature until the sodium dodecyl sulfate and the propylene glycol/ethylene oxide addition polymer are completely dissolved;
adding another 3.5g of xylose into 40mL of deionized water, and stirring for 5min at normal temperature until the xylose is completely dissolved;
then, the two solutions were mixed and stirred for 40min to obtain a stable and uniform colorless transparent solution. Pouring the solution into a hydrothermal kettle with the volume of 50mL, heating to 200 ℃, and reacting for 12.5 h; and obtaining the C material, wherein the shape of the C material is spherical, and the particle size is about 1.5 mu m. The particle size distribution is uneven and is distributed at 600 nm-3 mu m;
(2) purification and work-up of the product
After the hydrothermal kettle is cooled, centrifugally separating the black product, washing the black product for a plurality of times by using deionized water and absolute ethyl alcohol, centrifugally separating the black product, and drying the black product in a vacuum oven at the temperature of 70 ℃;
(3) synthesis of carbon/sulfur composite materials
Mixing and grinding 0.15g of the obtained carbon sphere material and 0.80g of sublimed Sulfur (S) until the powder is gray, then roasting in a tubular furnace in a nitrogen atmosphere at 700 ℃ for 5 hours to obtain the carbon/Sulfur composite material, and finding that Sulfur nanocrystals exist, have the particle size of about 5nm, have a sulfurur crystal structure and have serious agglomeration phenomenon.
The morphology and size of the carbon/sulfur composite was characterized by scanning electron microscopy (SEM, Hitachi FE-SEM S-4800 operated at 1 kV) and was prepared by directly spraying the oven dried sample powder onto a conductive gel. High resolution photographs (HRTEM), energy loss spectra (EDS) and microstructure information of the carbon/sulfur composite material are represented by a transmission electron microscope (TEM, JEOL JEM-2100F operated at 200 kV), and a sample of the transmission electron microscope is prepared by dispersing the carbon/sulfur composite material in an ethanol solution and then dropwise adding 6 mu L of the solution onto a carbon-supported copper net.
The electrocatalytic properties of the carbon/sulfur composite are characterized by the electrochemical workstation. Dispersing 1.5mg of carbon/sulfur composite material in 1mL of ethanol/water solution, then adding 40 muL of dispersing agent thiophene, then dropwise adding 10 muL on an electrode, and then placing the electrode in an electrochemical workstation to measure the oxygen reduction performance of a sample.
The carbon/sulfur composite material prepared by the invention is analyzed and researched in appearance, characteristics and the like through a scanning electron microscope, a transmission electron microscope and the like.
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a carbon/sulfur composite. The carbon/sulfur composite material obtained by synthesis is observed to be in a typical spherical shape, and the average diameter is 600-800 nm.
FIG. 2 is a transmission electron micrograph of a carbon/sulfur composite. Wherein (a) is the overall morphology of the carbon/sulfur composite material, and as can be seen from the figure, the synthesized carbon spheres are solid spheres. (b) The High Resolution Transmission Electron Microscopy (HRTEM) image shows that the sulfur nanocrystals have a particle size of about 5 nm.
Fig. 3 is an enlarged High Resolution Transmission Electron Microscope (HRTEM) image with interplanar spacings of 3.25 a and 3.78 a corresponding to the (222) and (212) crystal planes of S, respectively, confirming that this method does allow for the synthesis of carbon/sulfur composites with sulfur nanocrystals.
In fig. 4, (a) is an EDS spectrum of the carbon/sulfur composite, and it is evident from the graph that the synthesis by the method has a distinct sulfur peak in the product, which is mutually confirmed by HRTEM, thus proving the presence of sulfur nanocrystals. (b) The figure is a STEM figure of the carbon/sulfur compound, and can be seen that sulfur atoms are relatively uniformly dispersed on the surface of carbon to form a carbon/sulfur compound structure, and the existence of sulfur changes the charge distribution of the carbon, so that adjacent carbon atoms carry a small amount of positive charges, thereby increasing the active sites for oxygen adsorption and improving the oxygen reduction performance of the material.
In order to investigate the oxygen reduction catalytic performance of the carbon/sulfur composite, CV curves and lsv curves of the carbon/sulfur composite were measured, and the results are shown in fig. 5 and 6. The reduction peaks of the carbon/sulfur composite materials with different sulfur loads are all shown at the position of about-0.3V relative to an Ag/AgCl reference electrode, and the oxygen reduction performance of the carbon/sulfur composite obtained after sulfur loading is obviousThe initial potential is about-0.18V relative to the Ag/AgCl reference electrode, the half-wave potential is about-0.36V relative to the Ag/AgCl reference electrode, and the limiting current density is about 3.5mA/cm2. By contrast, the initial potential and half-wave potential of the carbon sphere material were only-0.3V and-0.47V relative to the Ag/AgCl reference electrode, and the limiting current density was about 2.8mA/cm2. Therefore, the carbon/sulfur composite material prepared by the method has good oxygen reduction performance and can be applied to fuel cells. Metal air batteries, and the like.
The melting point of sulfur is about 120 c and then a large amount of vaporization is started, so that it is difficult to produce sulfur nanocrystals by the conventional method. Compared with the traditional sulfur atom cluster, the sulfur nanocrystal has stronger oxygen adsorption capacity, thereby increasing the oxygen reduction performance of the material. Meanwhile, the carbon/sulfur composite material synthesized by the method has a large number of defects, and the sulfur nanocrystal has obvious atomic steps and excellent electrochemical activity, so that the carbon/sulfur composite material synthesized by the method has obviously more excellent electrochemical activity and electrocatalysis performance compared with a common carbon sphere material.
Reference to the literature
[1]Liu J, Mooney H, Hull V, et al. Systems integration for globalsustainability[J]. Science, 2015, 347(6225): 1258832.
[2] Xia W,MahmoodA, Liang Z, et al. Earth-abundant nanomaterials for oxygen reduction[J].AngewandteChemieInternational Edition, 2016, 55(8): 2650-2676
[3]Nie Y, Li L, Wei Z. Recent advancements in Pt and Pt-free catalystsfor oxygen reduction reaction[J]. Chemical Society Reviews, 2015,44(8):2168-2201.
[4] Higgins D, Zamani P, Yi J A, et al. The application of grapheneand its composites in oxygen reduction electrocatalysis: a perspectiveand reviewof recent progress[J]. Energy&Environmental Science,2016, 9(2): 357-390.
[5] Wood K N, O'Hayre R, Pylypenilo S. Recent progress onnitrogen/carbon structuresdesigned for use in energy andsustainability applications[J]. Energy&Environmental Science, 20147(4): 1212-1249.
[6] Duan J, Chen S, Jaroniec M, et al. Heteroatom-dopedgraphene-based materials for energy-relevant electrocatalyticprocesses[J]. ACS Catalysis, 20155(9): 5207-5234
[7] Zhu C, Li H, Fu S, et al. Highly efficient nonprecious metalcatalysts towards oxygen reduction reaction based on three-dimensional porous carbon nanostructures[J]. Chem. Soc. Rev.,2016, 45(3): 517-531.
[8] Zhou M, Wang H L, Guo S. Towards high-efficiencynanoelectrocatalysts for oxygenreduction through engineeringadvanced carbon nanomaterials.[J]. Chemical Society Reviews, 2016,45(5):1273-1307.
[9] He W, Wang Y, Jiang C, et al. Structural effects of a carbonmatrix in non-precious metal O2-reduction electrocatalysts[J].Chemical Society Reviews, 2016, 45(9): 2396-2409.。

Claims (2)

1. A preparation method of a carbon/sulfur compound is characterized by comprising the following specific steps:
(1) hydrothermal synthesis of carbon spheres:
adding 0.02-0.06 g of sodium dodecyl sulfate and 0.05-0.10 g of polypropylene glycol/ethylene oxide addition polymer into 20 +/-0.5 mL of deionized water, and stirring for 25-40 min at normal temperature until the sodium dodecyl sulfate and the polypropylene glycol/ethylene oxide addition polymer are completely dissolved;
adding 3.0-3.5g of xylose into 40 +/-0.5 mL of deionized water, and stirring at normal temperature until the xylose is completely dissolved;
then, mixing the two solutions, and continuously stirring for 25-30 min to obtain a stable and uniform colorless transparent solution; pouring the colorless transparent solution into a hydrothermal kettle, heating to 160-200 ℃, and reacting for 12 +/-0.5 h; obtaining a carbon sphere material;
(2) purification and work-up of the product:
after the hydrothermal kettle is cooled, centrifugally separating a product, washing the product for a plurality of times by using deionized water and absolute ethyl alcohol, and drying the product in a vacuum oven at the temperature of 55-65 ℃;
(3) synthesis of carbon/sulfur nanocomposites
Mixing and grinding 0.08-0.15 g of the synthesized carbon sphere material and 0.50-0.80 g of sublimed sulfur (S) until the powder is gray, then roasting in a tubular furnace under the nitrogen atmosphere, and roasting at 550-700 ℃ for 5-8 hours to obtain a carbon/sulfur nano composite material; the obtained carbon/Sulfur nano composite material is spherical, the size of the carbon sphere is 600-800nm, small Sulfur nano-crystal particles with obvious crystal characteristics grow on the surface of the carbon sphere, the particle size of the Sulfur nano-crystal is 5-8nm, the carbon/Sulfur nano composite material has a Sulfur crystal structure, and the crystal spacing 3.25A and 3.78A are respectively corresponding to the (222) crystal face and the (212) crystal face of S; the material has different particle size depending on the reaction temperature.
2. The use of the carbon/sulfur nanocomposite coated with sulfur nanocrystalline particles prepared according to the preparation method of claim 1 in electrocatalysis of oxygen reduction reaction.
CN201810699711.0A 2018-06-29 2018-06-29 Carbon/sulfur nano composite material and preparation method and application thereof Active CN108878907B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810699711.0A CN108878907B (en) 2018-06-29 2018-06-29 Carbon/sulfur nano composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810699711.0A CN108878907B (en) 2018-06-29 2018-06-29 Carbon/sulfur nano composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108878907A CN108878907A (en) 2018-11-23
CN108878907B true CN108878907B (en) 2021-02-26

Family

ID=64297276

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810699711.0A Active CN108878907B (en) 2018-06-29 2018-06-29 Carbon/sulfur nano composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108878907B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013078605A1 (en) * 2011-11-29 2013-06-06 Institute Of Chemistry, Chinese Academy Of Sciences Sulfur-carbon composite for lithium-sulfur battery, the method for preparing said composite, and the electrode material and lithium-sulfur battery comprising said composite
CN104272504A (en) * 2012-05-03 2015-01-07 汉阳大学校产学协力团 Method for manufacturing carbon-sulfur composite, carbon sulfur composite manufactured thereby, and electrochemical device including same
CN107746056A (en) * 2017-11-06 2018-03-02 江苏森森炭业科技有限公司 A kind of production method of spherical activated charcoal

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013078605A1 (en) * 2011-11-29 2013-06-06 Institute Of Chemistry, Chinese Academy Of Sciences Sulfur-carbon composite for lithium-sulfur battery, the method for preparing said composite, and the electrode material and lithium-sulfur battery comprising said composite
CN104272504A (en) * 2012-05-03 2015-01-07 汉阳大学校产学协力团 Method for manufacturing carbon-sulfur composite, carbon sulfur composite manufactured thereby, and electrochemical device including same
CN107746056A (en) * 2017-11-06 2018-03-02 江苏森森炭业科技有限公司 A kind of production method of spherical activated charcoal

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
High-efficiency oxygen reduction to hydrogen peroxide catalysed by oxidized carbon materials;Zhiyi Lu等;《Nature catalysis》;20180115;第1卷;第156-162页 *
溶剂热法合成碳纳米材料;朱永春等;《无机化学学报》;20080430;第24卷(第4期);第499-504页 *

Also Published As

Publication number Publication date
CN108878907A (en) 2018-11-23

Similar Documents

Publication Publication Date Title
Song et al. Metal-organic framework derived Fe/Fe3C@ N-doped-carbon porous hierarchical polyhedrons as bifunctional electrocatalysts for hydrogen evolution and oxygen-reduction reactions
Lei et al. A general strategy for bimetallic Pt-based nano-branched structures as highly active and stable oxygen reduction and methanol oxidation bifunctional catalysts
Guo et al. Nanosized Rh grown on single-walled carbon nanohorns for efficient methanol oxidation reaction
Wu et al. Tailored architectures of FeNi alloy embedded in N-doped carbon as bifunctional oxygen electrocatalyst for rechargeable zinc-air battery
Liu et al. Facile synthesis based on novel carbon-supported cyanogel of structurally ordered Pd 3 Fe/C as electrocatalyst for formic acid oxidation
Liang et al. Rational fabrication of thin-layered NiCo2S4 loaded graphene as bifunctional non-oxide catalyst for rechargeable zinc-air batteries
CN110479340B (en) Nano cobalt/nitrogen doped graphene composite material and preparation method thereof
Li et al. Co/Ni dual-metal embedded in heteroatom doped porous carbon core-shell bifunctional electrocatalyst for rechargeable Zn-air batteries
Cheng et al. Fabricating Pt-decorated three dimensional N-doped carbon porous microspherical cavity catalyst for advanced oxygen reduction reaction
Zhang et al. FeCo alloy/N, S co-doped carbon aerogel derived from directional-casting cellulose nanofibers for rechargeable liquid flow and flexible Zn-air batteries
Song et al. Fabrication of titanium nitride nanoparticles onto carbon nanotubes by atomic layer deposition for utilization as Pt electrocatalyst supports
Zhou et al. Phase and composition controllable synthesis of nickel phosphide-based nanoparticles via a low-temperature process for efficient electrocatalytic hydrogen evolution
Li et al. A facile templating fabrication of porous CoP nanoparticles towards electrocatalytic oxygen evolution
Li et al. Nano-manufacturing of Co (OH) 2@ NC for efficient oxygen evolution/reduction reactions
Gao et al. Co/NC-Gr composite derived from ZIF-67: effects of preparation method on the structure and electrocatalytic performance for oxygen reduction reaction
He et al. Metal organic framework derived perovskite/spinel heterojunction as efficient bifunctional oxygen electrocatalyst for rechargeable and flexible Zn-air batteries
Cheng et al. Controllable synthesis and phase-dependent electrocatalytic oxygen evolution performance of CoNiFe sulfide nanocubes
He et al. PdMn and PdFe nanoparticles over a reduced graphene oxide carrier for methanol electro-oxidation under alkaline conditions
Zhang et al. Spatial construction of ultrasmall Pt-decorated 3D spinel oxide-modified N-doped graphene nanoarchitectures as high-efficiency methanol oxidation electrocatalysts
Yan et al. Interfacial electronic regulation on NiCo2O4 nanowires@ NiFe-LDH nanosheets heterostructure for efficient oxygen evolution
Li et al. A Co-MOF-derived Co 9 S 8@ NS-C electrocatalyst for efficient hydrogen evolution reaction
Fu et al. N-doped hollow carbon tubes derived N-HCTs@ NiCo2O4 as bifunctional oxygen electrocatalysts for rechargeable Zinc-air batteries
CN110993966A (en) Fuel cell electrocatalyst and preparation method thereof
Zhang et al. Prussian-blue-analogue derived FeNi2S4/NiS nanoframes supported by N-doped graphene for highly efficient methanol oxidation electrocatalysis
Zhou et al. Graphitic-nitrogen-enriched carbon skeleton with embedment of Fe3C for superior performance air cathode in zinc-air battery

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
GR01 Patent grant
GR01 Patent grant