[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN107460725B - Sulfur-doped cobalt phosphide-carbon nanofiber composite material and preparation method thereof - Google Patents

Sulfur-doped cobalt phosphide-carbon nanofiber composite material and preparation method thereof Download PDF

Info

Publication number
CN107460725B
CN107460725B CN201710572425.3A CN201710572425A CN107460725B CN 107460725 B CN107460725 B CN 107460725B CN 201710572425 A CN201710572425 A CN 201710572425A CN 107460725 B CN107460725 B CN 107460725B
Authority
CN
China
Prior art keywords
carbon nanofiber
composite material
sulfur
cobalt
nanofiber composite
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.)
Expired - Fee Related
Application number
CN201710572425.3A
Other languages
Chinese (zh)
Other versions
CN107460725A (en
Inventor
刘天西
孙振
樊玮
张祎
晁国杰
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.)
Donghua University
Original Assignee
Donghua 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 Donghua University filed Critical Donghua University
Priority to CN201710572425.3A priority Critical patent/CN107460725B/en
Publication of CN107460725A publication Critical patent/CN107460725A/en
Application granted granted Critical
Publication of CN107460725B publication Critical patent/CN107460725B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/5805—Phosphides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • General Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Textile Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Toxicology (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Inorganic Fibers (AREA)

Abstract

本发明公开了一种硫掺杂的磷化钴/碳纳米纤维复合材料及其制备方法。所述制备方法为：将聚丙烯腈分散液进行静电纺丝，得到聚丙烯腈纳米纤维膜；将聚丙烯腈纳米纤维膜预氧化后进行升温碳化，得到碳纳米纤维膜，将其进行表面亲水处理，得到碳纳米纤维预处理膜；将钴盐与硫脲按比例分散于有机溶剂中，然后将该分散液与碳纳米纤维预处理膜通过溶剂热反应，得到一硫化钴/碳纳米纤维复合材料，将其与次亚磷酸钠发生磷化反应，制得硫掺杂的磷化钴/碳纳米纤维复合材料。本发明制备的复合材料形貌可控，具有较高的比表面积和优良的导电性，可作为一种理想的高性能电催化材料，以及超级电容器和锂离子电池等新能源器件的电极材料。The invention discloses a sulfur-doped cobalt phosphide/carbon nanofiber composite material and a preparation method thereof. The preparation method is as follows: electrospinning the polyacrylonitrile dispersion liquid to obtain a polyacrylonitrile nanofiber film; pre-oxidizing the polyacrylonitrile nanofiber film, then performing heating and carbonization to obtain a carbon nanofiber film, and subjecting the film to surface affinity Water treatment to obtain a carbon nanofiber pretreatment film; disperse cobalt salt and thiourea in an organic solvent in proportion, and then react the dispersion with the carbon nanofiber pretreatment film through solvothermal reaction to obtain cobalt monosulfide/carbon nanofiber The composite material is subjected to a phosphating reaction with sodium hypophosphite to obtain a sulfur-doped cobalt phosphide/carbon nanofiber composite material. The composite material prepared by the invention has controllable morphology, high specific surface area and excellent electrical conductivity, and can be used as an ideal high-performance electrocatalytic material and an electrode material for new energy devices such as supercapacitors and lithium ion batteries.

Description

Sulfur-doped cobalt phosphide-carbon nanofiber composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of transition metal phosphide-carbon materials, and particularly relates to a sulfur-doped cobalt phosphide/carbon nanofiber composite material and a preparation method thereof.
Background
The catalytic performance of an electrochemical catalyst is greatly dependent on the electrocatalytic activity of the catalyst. Among the first row transition metal compounds, the cobalt-based transition metal compound has very superior electrochemical catalytic performance. The cobalt-based transition metal compound is a potential electro-catalytic hydrogen evolution catalyst because of the low free energy barrier required for forming adsorbed hydrogen atoms on the surface of cobalt atoms. A large number of researches show that the cobalt phosphide nano material has very excellent catalytic capability, but is easy to form agglomeration so that the catalytic active point of the cobalt phosphide nano material cannot be fully exposed, and the catalytic hydrogen evolution rate of the cobalt phosphide nano material is inhibited.
Carbon materials are widely used as support substrates for electrocatalytically active substances due to their high mechanical strength and good electrical conductivity. High molecular polymers are often selected as precursors for carbon materials due to their high carbon content and high designability of structure and composition. The Carbon Nanofiber (CNF) which is the most common carbon nanofiber can be obtained after the electrostatic spinning Polyacrylonitrile (PAN) nanofiber membrane is carbonized at high temperature. The sulfur-doped cobalt phosphide nanosheets grow on the surface of the carbon fiber in situ, so that not only can agglomeration of the nanosheets be inhibited and catalytic active points of the nanosheets be exposed to the maximum extent, but also the carbon fibers which are crosslinked with one another can provide a three-dimensional conductive path for transmission of electrons. In addition, the open multi-stage structure also effectively shortens the mass transfer process, so that the catalytic active points can be fully contacted with the electrolyte, and the catalytic performance of the composite material is effectively improved.
Disclosure of Invention
The invention aims to solve the problems that: provides a sulfur-doped cobalt phosphide/carbon nanofiber composite material with excellent electrochemical performance and a preparation method thereof.
In order to solve the problems, the invention provides a preparation method of a sulfur-doped cobalt phosphide/carbon nanofiber composite material, which is characterized by comprising the following steps of:
step 1): adding polyacrylonitrile powder into N, N-dimethylformamide solvent, and continuously stirring to obtain uniform viscous dark yellow polyacrylonitrile dispersion liquid;
step 2): performing electrostatic spinning on the polyacrylonitrile dispersion liquid to obtain a polyacrylonitrile nanofiber membrane;
step 3): pre-oxidizing the polyacrylonitrile nano-fiber membrane in an air atmosphere to obtain a pre-oxidized polyacrylonitrile nano-fiber membrane;
step 4): heating and carbonizing the pre-oxidized polyacrylonitrile nano-fiber membrane under the protection of inert gas to obtain a carbon nano-fiber membrane;
step 5): cutting the carbon nanofiber membrane into small pieces, soaking the small pieces in a nitric acid/concentrated sulfuric acid mixed solution, and performing surface hydrophilic treatment to obtain a carbon nanofiber pretreatment membrane;
step 6): dispersing cobalt salt and thiourea in an organic solvent in proportion, and then carrying out solvothermal reaction on the dispersion liquid and a carbon nanofiber pretreatment film to obtain a cobalt sulfide/carbon nanofiber composite material;
step 7): and carrying out a phosphating reaction on the cobalt monosulfide/carbon nanofiber composite material and sodium hypophosphite under the protection of inert gas to prepare the sulfur-doped cobalt phosphide/carbon nanofiber composite material.
Preferably, the electrostatic spinning process parameters in step 2) are as follows: the electrostatic field voltage is 15-25 kV, the spinning speed is 0.15-0.3 mm/min, and the receiving distance is 20-30 cm.
Preferably, the process parameters of the pre-oxidation in the step 3) are as follows: the pre-oxidation temperature is 250-300 ℃, the heating rate is 1-2 ℃/min, and the pre-oxidation time is 1-2 h.
Preferably, the process parameters of the temperature-rising carbonization in the step 4) are as follows: the inert gas is high-purity argon or high-purity nitrogen, the carbonization temperature is 800-1500 ℃, the carbonization time is 1-3 h, and the heating rate is 5-10 ℃/min.
Preferably, the process parameters of the surface hydrophilic treatment in the step 5) are as follows: the volume ratio of the nitric acid to the concentrated sulfuric acid is 1: 1-3: 1, and the soaking time is 10-60 min.
Preferably, the cobalt salt in step 6) is any one or more of cobalt nitrate, cobalt acetate and cobalt chloride; the concentration of the cobalt salt in the obtained dispersion liquid is 10-30 mg/mL; the mol ratio of sulfur atoms in the thiourea to cobalt atoms in the cobalt salt is 1: 1; the organic solvent is ethanol, N-dimethylformamide or a mixed solution of the ethanol and the N, N-dimethylformamide.
Preferably, the process parameters of the solvothermal reaction in the step 6) are as follows: the reaction temperature is 180-240 ℃, and the reaction time is 10-24 h.
Preferably, the process parameters of the phosphating reaction in the step 7) are as follows: the reaction temperature is 300-600 ℃, and the reaction time is 1-2 h.
The invention also provides a sulfur-doped cobalt phosphide/carbon nanofiber composite material prepared by the preparation method of the sulfur-doped cobalt phosphide/carbon nanofiber composite material.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation process is simple, the operation is easy, and the preparation method is convenient and effective;
2. in the preparation process, firstly, cobalt sulfide nanosheet/carbon nanofiber is prepared, on one hand, the cobalt sulfide nanosheet/carbon nanofiber can be used as a template for preparing a phosphated strand nanosheet later, on the other hand, most of S elements are replaced by using a phosphine phosphating process to generate cobalt phosphide, and a small amount of residual S is used as a doping element, so that the catalytic activity of the cobalt phosphide is further improved;
3. the substrate of choice is the simple carbon nanofiber membrane that is prepared. The carbon nanofiber has high conductivity and is more favorable for electron transfer. The carbon nanofiber has high specific surface area, and can provide more sites for the growth of a cobalt sulfide nanosheet template;
4. the prepared sulfur-doped cobalt phosphide/carbon nanofiber composite material has better flexibility. The carbon nanofiber and the sulfur-doped cobalt phosphide nanosheet are effectively compounded, so that the advantages of the carbon nanofiber, the sulfur-doped cobalt phosphide nanosheet and the carbon nanofiber can be fully exerted, and the composite material with the multilevel structure is successfully constructed.
The sulfur-doped cobalt phosphide/carbon nanofiber composite material prepared by the method can be used as a high-performance catalyst material and an ideal electrode material of new energy devices such as lithium ion batteries and the like.
Drawings
FIG. 1 is a comparison of SEM images of two composites made according to example 1; wherein a and b are cobalt monosulfide/carbon nanofiber composite materials; c. d is a sulfur-doped cobalt phosphide/carbon nanofiber composite material;
FIG. 2 is an XRD pattern of the cobalt monosulfide/carbon nanofiber composite and the sulfur-doped cobalt phosphide/carbon nanofiber composite prepared in example 1;
FIG. 3 is a graph comparing the electrochemical catalytic hydrogen evolution performance plots for sulfur-doped cobalt phosphide/carbon nanofiber composites prepared in example 1 and sulfur-doped cobalt phosphide nanosheets; wherein, a is a linear sweep voltammetry curve (LSV), and b is a Tafel curve.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
A preparation method of a sulfur-doped cobalt phosphide/carbon nanofiber composite material comprises the following steps:
(1) adding 1g of polyacrylonitrile powder into 10mLN, N-Dimethylformamide (DMF), and continuously stirring to prepare a uniform viscous dispersion liquid;
(2) carrying out electrostatic spinning on the obtained polyacrylonitrile dispersion liquid, wherein the adjusting process parameters are as follows: electrostatic field voltage is 20kV, spinning speed is 0.3mm/min, receiving distance is 20cm, and polyacrylonitrile nano fiber membrane is prepared;
(3) pre-oxidizing the obtained polyacrylonitrile spinning membrane in an air atmosphere, wherein the pre-oxidation temperature is 250 ℃, the heating rate is 1 ℃/min, and the pre-oxidation time is 1h, so as to prepare the pre-oxidized polyacrylonitrile nanofiber membrane;
(4) carrying out high-temperature carbonization on the polyacrylonitrile nano-fiber membrane in high-purity nitrogen at the temperature of 800 ℃ for 2h to prepare a carbon nano-fiber composite membrane;
(5) cutting the prepared carbon fiber membrane into small pieces, soaking the small pieces in a nitric acid/concentrated sulfuric acid mixed solution for surface hydrophilic treatment, wherein the volume ratio of nitric acid to concentrated sulfuric acid is 1:1, and the soaking time is 10 min;
(6) 247.37mg of cobalt nitrate hexahydrate and 64.7mg of thiourea are dissolved in 10mL of a solvent (DMF) without N, N-dimethylformamide and subjected to ultrasonic treatment for 5min to prepare a uniform salt solution;
(7) mixing the prepared salt solution with 2 × 2cm2The carbon nanofiber composite membrane is put into a hydrothermal kettle, reacts for 12 hours at the temperature of 200 ℃, after the natural cooling, the fiber membrane is taken out, repeatedly washed by deionized water and ethanol for many times and dried, and the cobalt sulfide/carbon nanofiber composite material is prepared and is marked as CoS @ CNF-1;
(8) and carrying out a phosphating reaction on the cobalt monosulfide/carbon nanofiber composite material and 100mg of sodium hypophosphite under the protection of inert gas to prepare the sulfur-doped cobalt phosphide/carbon nanofiber composite material S-CoP @ CNF-1.
The structural morphology of the sulfur-doped cobalt phosphide/carbon nanofiber composite material obtained by the invention was characterized by using a Scanning Electron Microscope (SEM), an X-ray diffractometer (XRD) and an electrochemical workstation, and the results are as follows:
(1) the SEM test results show that: in the cobalt monosulfide/carbon nanofiber composite material, cobalt monosulfide nanosheets uniformly grow on carbon nanofibers with high specific surface area and high conductivity, agglomeration of the cobalt monosulfide is effectively inhibited, and full exposure of electrochemical active edges is guaranteed; in the sulfur-doped cobalt phosphide/carbon nanofiber composite material, the cobalt phosphide presents an obvious nanosheet shape, and the effectiveness of the template design of the cobalt monosulfide nanosheet is shown. See fig. 1.
(2) An XRD test result shows that the prepared graphene/carbon nanofiber composite membrane has a wider diffraction peak at a 2 theta (26 degrees) position, and the diffraction peak corresponds to a (002) crystal face of the carbon nanofiber. The prepared cobalt monosulfide/carbon nanofiber composite material simultaneously shows a diffraction peak of carbon and a characteristic peak of CoS, and the successful coincidence of the two is shown. After the phosphorization reaction, the XRD diffraction pattern of the sulfur-doped cobalt phosphide/carbon nanofiber composite material shows a characteristic peak of CoP. See fig. 2.
(3) Electrochemical tests show that the prepared sulfur-doped cobalt phosphide/carbon nanofiber composite material has excellent electrochemical catalytic hydrogen evolution performance, when the current density reaches 10mA/cm, the required voltage is only 53.6mV, the Tafel slope is 46mV/decade, and the performance of the sulfur-doped cobalt phosphide is far better than that of pure sulfur-doped cobalt phosphide.
Example 2
The cobalt salt and thiourea in example 1 were replaced with 494.75mg of cobalt nitrate hexahydrate and 129.41mg of thiourea, respectively, and the rest was the same as in example 1, and the finally obtained composite material was designated as S-CoP @ CNF-2.
Example 3
The amount of sodium hypophosphite used in example 1 was changed to 200mg in example 1, and the composite material obtained in the end was recorded as S-CoP @ CNF-3 in the same manner as in example 1.
Example 4
The hydrothermal reaction temperature in example 1 was changed to 180 ℃ in example 1, and the composite material obtained finally was designated as S-CoP @ CNF-4 in the same manner as in example 1.

Claims (7)

1. A preparation method of a sulfur-doped cobalt phosphide/carbon nanofiber composite material is characterized by comprising the following steps of:
step 1): adding polyacrylonitrile powder into N, N-dimethylformamide solvent, and continuously stirring to obtain uniform viscous dark yellow polyacrylonitrile dispersion liquid;
step 2): performing electrostatic spinning on the polyacrylonitrile dispersion liquid to obtain a polyacrylonitrile nanofiber membrane;
step 3): pre-oxidizing the polyacrylonitrile nano-fiber membrane in an air atmosphere to obtain a pre-oxidized polyacrylonitrile nano-fiber membrane;
step 4): heating and carbonizing the pre-oxidized polyacrylonitrile nano-fiber membrane under the protection of inert gas to obtain a carbon nano-fiber membrane;
step 5): cutting the carbon nanofiber membrane into small pieces, soaking the small pieces in a nitric acid/concentrated sulfuric acid mixed solution, and performing surface hydrophilic treatment to obtain a carbon nanofiber pretreatment membrane;
step 6): dispersing cobalt salt and thiourea in an organic solvent in proportion, and then carrying out solvothermal reaction on the dispersion liquid and a carbon nanofiber pretreatment film to obtain a cobalt sulfide/carbon nanofiber composite material;
step 7): carrying out a phosphating reaction on the cobalt monosulfide/carbon nanofiber composite material and sodium hypophosphite under the protection of inert gas to prepare a sulfur-doped cobalt phosphide/carbon nanofiber composite material;
in the step 6), the cobalt salt is any one or more of cobalt nitrate, cobalt acetate and cobalt chloride; the concentration of the cobalt salt in the obtained dispersion liquid is 10-30 mg/mL; the molar ratio of sulfur atoms in the thiourea to cobalt atoms in the cobalt salt is 1: 1; the organic solvent adopts ethanol, N-dimethylformamide or a mixed solution of the ethanol and the N, N-dimethylformamide;
the process parameters of the solvothermal reaction in the step 6) are as follows: the reaction temperature is 180-240 ℃, and the reaction time is 10-24 h.
2. The method for preparing the sulfur-doped cobalt phosphide/carbon nanofiber composite material according to claim 1, wherein the electrostatic spinning in the step 2) has the following process parameters: the electrostatic field voltage is 15-25 kV, the spinning speed is 0.15-0.3 mm/min, and the receiving distance is 20-30 cm.
3. The method for preparing the sulfur-doped cobalt phosphide/carbon nanofiber composite material according to claim 1, wherein the pre-oxidation process parameters in the step 3) are as follows: the pre-oxidation temperature is 250-300 ℃, the heating rate is 1-2 ℃/min, and the pre-oxidation time is 1-2 h.
4. The method for preparing the sulfur-doped cobalt phosphide/carbon nanofiber composite material according to claim 1, wherein the process parameters of the temperature-rising carbonization in the step 4) are as follows: the inert gas is high-purity argon or high-purity nitrogen, the carbonization temperature is 800-1500 ℃, the carbonization time is 1-3 h, and the heating rate is 5-10 ℃/min.
5. The method for preparing the sulfur-doped cobalt phosphide/carbon nanofiber composite material as claimed in claim 1, wherein the process parameters of the surface hydrophilic treatment in the step 5) are as follows: the volume ratio of the nitric acid to the concentrated sulfuric acid is 1: 1-3: 1, and the soaking time is 10-60 min.
6. The method for preparing the sulfur-doped cobalt phosphide/carbon nanofiber composite material according to claim 1, wherein the process parameters of the phosphating reaction in the step 7) are as follows: the reaction temperature is 300-600 ℃, and the reaction time is 1-2 h.
7. A sulfur-doped cobalt phosphide/carbon nanofiber composite prepared by the method for preparing a sulfur-doped cobalt phosphide/carbon nanofiber composite as set forth in any one of claims 1 to 6.
CN201710572425.3A 2017-07-13 2017-07-13 Sulfur-doped cobalt phosphide-carbon nanofiber composite material and preparation method thereof Expired - Fee Related CN107460725B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710572425.3A CN107460725B (en) 2017-07-13 2017-07-13 Sulfur-doped cobalt phosphide-carbon nanofiber composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710572425.3A CN107460725B (en) 2017-07-13 2017-07-13 Sulfur-doped cobalt phosphide-carbon nanofiber composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107460725A CN107460725A (en) 2017-12-12
CN107460725B true CN107460725B (en) 2020-05-05

Family

ID=60544256

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710572425.3A Expired - Fee Related CN107460725B (en) 2017-07-13 2017-07-13 Sulfur-doped cobalt phosphide-carbon nanofiber composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107460725B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108400290B (en) * 2018-01-03 2021-09-17 浙江衡远新能源科技有限公司 Preparation method of high-rate lithium-sulfur battery positive electrode material
CN108589264A (en) * 2018-05-03 2018-09-28 东华大学 Bismuth sulfide nano particle/nitrogen-doped carbon nano-fiber hybrid material and its preparation
CN109056193A (en) * 2018-07-04 2018-12-21 东华大学 The preparation method and application of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film
CN110745801B (en) * 2019-11-08 2022-10-11 扬州大学 Surface sulfur-doped cobalt phosphide nano material and preparation method thereof
CN111099567B (en) * 2019-12-31 2021-11-16 武汉科技大学 Preparation method of nickel phosphide nanofiber
CN112877812B (en) * 2021-01-21 2022-04-19 西北大学 A kind of bimetallic doped metal phosphide nanofiber and preparation method thereof
CN114976042A (en) * 2021-02-18 2022-08-30 中国科学院福建物质结构研究所 Composite material and preparation method and application thereof
CN115679339B (en) * 2021-07-22 2025-01-17 中国科学院大连化学物理研究所 Sulfur-doped phosphide polymorphic heterojunction full-decomposition hydroelectric catalyst and preparation method thereof
CN114715864B (en) * 2022-05-06 2023-04-28 北京理工大学 Transition metal phosphides filling phosphorus vacancies with non-metallic elements, their preparation and lithium-sulfur batteries
CN115074756B (en) * 2022-05-11 2023-05-12 深圳大学 Bimetal doped porous carbon nanofiber catalyst and preparation method and application thereof
CN115621445B (en) * 2022-10-25 2024-11-12 湖北三峡实验室 A red phosphorus-carbon negative electrode material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103316594A (en) * 2013-07-01 2013-09-25 大连理工大学 Preparation method of carbon-nanotube hollow fiber membranes
CN105280896A (en) * 2015-09-12 2016-01-27 复旦大学 Cobalt-nickel sulfide/carbon nanofiber composite material and preparation method and application thereof
CN105600745A (en) * 2016-03-18 2016-05-25 复旦大学 Cobalt disulfide/carbon nanofiber composite material and preparation method thereof
CN106098404A (en) * 2016-08-23 2016-11-09 东华大学 A kind of cobalt sulfide nickel/nitrogen-doped carbon nano-fiber composite and preparation thereof and application
CN106076377A (en) * 2016-06-06 2016-11-09 复旦大学 A kind of cobalt sulfide nickel carbon nanotube carbon nano-fiber composite material of phosphorus doping and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103316594A (en) * 2013-07-01 2013-09-25 大连理工大学 Preparation method of carbon-nanotube hollow fiber membranes
CN105280896A (en) * 2015-09-12 2016-01-27 复旦大学 Cobalt-nickel sulfide/carbon nanofiber composite material and preparation method and application thereof
CN105600745A (en) * 2016-03-18 2016-05-25 复旦大学 Cobalt disulfide/carbon nanofiber composite material and preparation method thereof
CN106076377A (en) * 2016-06-06 2016-11-09 复旦大学 A kind of cobalt sulfide nickel carbon nanotube carbon nano-fiber composite material of phosphorus doping and preparation method thereof
CN106098404A (en) * 2016-08-23 2016-11-09 东华大学 A kind of cobalt sulfide nickel/nitrogen-doped carbon nano-fiber composite and preparation thereof and application

Also Published As

Publication number Publication date
CN107460725A (en) 2017-12-12

Similar Documents

Publication Publication Date Title
CN107460725B (en) Sulfur-doped cobalt phosphide-carbon nanofiber composite material and preparation method thereof
CN106076377B (en) A kind of cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of phosphorus doping and preparation method thereof
Yao et al. Electrospun three-dimensional cobalt decorated nitrogen doped carbon nanofibers network as freestanding electrode for lithium/sulfur batteries
Miao et al. ZIF-8/ZIF-67-derived 3D amorphous carbon-encapsulated CoS/NCNTs supported on CoS-coated carbon nanofibers as an advanced potassium-ion battery anode
Lin et al. A functionalized carbon surface for high‐performance sodium‐ion storage
CN105597791B (en) A kind of selenizing molybdenum/porous carbon nanofiber composite material and preparation method and application
Gong et al. Polarity-assisted formation of hollow-frame sheathed nitrogen-doped nanofibrous carbon for supercapacitors
CN105742074B (en) Selenizing molybdenum composite material of a kind of porous carbon fiber based on poly-dopamine/bis- and preparation method thereof
CN105056983B (en) A kind of molybdenum disulfide nano sheet/nitrogen-doped carbon fiber hybrid material and preparation method thereof
Huang et al. Lawn-like FeCo2S4 hollow nanoneedle arrays on flexible carbon nanofiber film as binder-free electrodes for high-performance asymmetric pseudocapacitors
CN110075872B (en) Method for electrocatalytic hydrogen evolution by electrochemically activating molybdenum disulfide/carbon composite material
CN109417171B (en) Adjustable and mass-producible synthesis of graded porous nanocarbon/sulfur composite cathodes
CN105463831B (en) A kind of molybdenum disulfide/graphene/carbon nano-fiber composite material and preparation method thereof
CN105322146B (en) A kind of selenizing molybdenum/carbon nano-fiber/graphene composite material and preparation method thereof
CN105600745A (en) Cobalt disulfide/carbon nanofiber composite material and preparation method thereof
JP6302878B2 (en) Method for producing carbon nanofiber electrode carrying metal oxide using electrodeposition method
CN106252616A (en) A kind of nickelous selenide/hollow carbon fiber composite and preparation method thereof
CN105384439B (en) A kind of cobalt oxide zinc/graphene/carbon nano-fiber composite material and preparation method thereof
CN105322147B (en) A kind of tungsten disulfide/carbon nano-fiber/graphene composite material and preparation method thereof
Gu et al. Graphene sheets wrapped carbon nanofibers as a highly conductive three-dimensional framework for perpendicularly anchoring of MoS2: advanced electrocatalysts for hydrogen evolution reaction
CN106057489A (en) Molybdenum carbide/ graphene/carbon nanofiber composite material, and preparation method thereof
Sun et al. Integration of desulfurization and lithium–sulfur batteries enabled by amino‐functionalized porous carbon nanofibers
CN108390072A (en) A kind of cobalt sulfide dopen Nano porous carbon elctro-catalyst and the preparation method and application thereof
CN105297405A (en) Cobalt zinc sulfide/graphene/carbon nanofiber composite material and preparing method thereof
Zhang et al. Mesoporous NiCo 2 O 4 networks with enhanced performance as counter electrodes for dye-sensitized solar cells

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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20200505

CF01 Termination of patent right due to non-payment of annual fee