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 PDFInfo
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- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000010941 cobalt Substances 0.000 title claims abstract description 44
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000012528 membrane Substances 0.000 claims abstract description 30
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002121 nanofiber Substances 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 5
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 230000005686 electrostatic field Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000003990 capacitor Substances 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention discloses a sulfur-doped cobalt phosphide/carbon nanofiber composite material and a preparation method thereof. The preparation method comprises the following steps: performing electrostatic spinning on the polyacrylonitrile dispersion liquid to obtain a polyacrylonitrile nanofiber membrane; pre-oxidizing a polyacrylonitrile nanofiber membrane, then heating and carbonizing to obtain a carbon nanofiber membrane, and carrying out surface hydrophilic treatment on the carbon nanofiber membrane to obtain a carbon nanofiber pretreatment membrane; the cobalt salt and thiourea are dispersed in an organic solvent according to a certain proportion, then the dispersion liquid and a carbon nano fiber pretreatment film are subjected to solvothermal reaction to obtain a cobalt monosulfide/carbon nano fiber composite material, and the cobalt monosulfide/carbon nano fiber composite material and sodium hypophosphite are subjected to a phosphating reaction to obtain the sulfur-doped cobalt phosphide/carbon nano fiber composite material. The composite material prepared by the invention has controllable appearance, higher specific surface area and excellent conductivity, and can be used as an ideal high-performance electro-catalytic material and an electrode material of new energy devices such as a super capacitor, a lithium ion battery and the like.
Description
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.
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| 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 | Bimetal-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 |
| CN114715864B (en) * | 2022-05-06 | 2023-04-28 | 北京理工大学 | Transition metal phosphide with phosphorus vacancy filled by nonmetallic element, preparation method thereof and lithium-sulfur battery |
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