CN110707307A - Hollow nanofiber Co3O4/S composite material, preparation method and application - Google Patents
Hollow nanofiber Co3O4/S composite material, preparation method and application Download PDFInfo
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- CN110707307A CN110707307A CN201911008418.6A CN201911008418A CN110707307A CN 110707307 A CN110707307 A CN 110707307A CN 201911008418 A CN201911008418 A CN 201911008418A CN 110707307 A CN110707307 A CN 110707307A
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- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 239000002121 nanofiber Substances 0.000 title claims abstract description 35
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000001523 electrospinning Methods 0.000 claims abstract description 11
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 9
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 229920001021 polysulfide Polymers 0.000 abstract description 5
- 239000005077 polysulfide Substances 0.000 abstract description 5
- 150000008117 polysulfides Polymers 0.000 abstract description 5
- 239000011888 foil Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- 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
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a hollow nanofiber Co3O4The preparation method and the application of the/S composite material comprise the following steps: (1) dissolving cobalt acetate, polyacrylonitrile and polyvinylpyrrolidone in an organic solvent, stirring at room temperature, and standing to obtain an electrospinning solution; (2) extracting the electrospinning liquid, carrying out electrostatic spinning, and collecting a sample by using carbon paper, wherein the voltage is 15kV, the distance between a needle head of the electrostatic spinning and the carbon paper is 12-15 cm, the injection flow rate is 60 mu L/min, and the temperature isPreparing the nano fiber at 21-25 ℃ and relative humidity of 80%; (3) oxidizing the nano-fiber in air at 300 ℃ to obtain an HCON material; (4) mixing sulfur and HCON material, and keeping the temperature at 155 ℃ to prepare hollow nanofiber Co3O4a/S composite material. The composite material can inhibit the shuttle effect of polysulfide, improve specific capacity and have good rate capability.
Description
Technical Field
The invention relates to a hollow nanofiber composite material, in particular to a hollow nanofiber Co3O4a/S composite material, a preparation method and application thereof.
Background
The lithium-sulfur battery is an energy storage system with high specific capacity (1675mAh/g) and high energy density (2600Wh/Kg), and the sulfur element in the positive electrode of the lithium-sulfur battery has no pollution to the environment. However, the lithium sulfur battery has several problems as follows:
(1) poor conductivity of sulfur results in low utilization thereof;
(2) the specific capacity is reduced by the decomposition and shuttling effects of polar polysulfides;
(3) the specific capacity retention rate after multiple cycles is low, resulting in short service life.
In recent decades, many advances have been made in the research of positive electrode materials in lithium sulfur batteries, and the development of long-cycle-stability lithium sulfur batteries has been a hot spot of research in various countries around the world. However, lithium sulfur batteries suffer from severe capacity fade during electrochemical reactions due to the decomposition and shuttling effects of polar polysulfides.
Disclosure of Invention
The invention aims to provide a hollow nanofiber Co3O4the/S composite material, the preparation method and the application solve the problems of poor conductivity and low specific capacity of the anode of the conventional lithium battery, can improve the specific capacity and has good rate capability.
In order to achieve the aim, the invention provides a hollow nanofiber Co3O4A method for preparing an/S composite, the method comprising:
(1) dissolving cobalt acetate, polyacrylonitrile and polyvinylpyrrolidone in an organic solvent, stirring at room temperature, and standing to obtain an electrospinning solution; wherein the mass ratio of the cobalt acetate to the polyacrylonitrile to the polyvinylpyrrolidone is 0.75-0.90: 0.5: 0.1;
(2) extracting the electrospinning liquid, carrying out electrostatic spinning, collecting a sample by using carbon paper, wherein the voltage is 15kV, the distance between a needle head of the electrostatic spinning and the carbon paper is 12-15 cm, the injection flow rate is 60 mu L/min, the temperature is 21-25 ℃, the relative humidity is 80%, and preparing the nano fiber;
(3) oxidizing the nano-fiber in air at 300 ℃ to obtain an HCON material;
(4) mixing sulfur and the HCON material, and preserving heat at 155 ℃ to prepare hollow nanofiber Co3O4a/S composite material.
Preferably, in step (1), the organic solvent comprises: n, N-dimethylformamide.
Preferably, in step (1), the cobalt acetate is cobalt acetate tetrahydrate; the mass ratio of the cobalt acetate tetrahydrate to the polyacrylonitrile to the polyvinylpyrrolidone is 1.2: 0.5: 0.1.
preferably, in the step (1), the stirring time is 15-18 h; the standing time is 12-15 h.
Preferably, in the step (2), the inner diameter of the needle of the syringe used for the electrospinning is 1.2 mm.
Preferably, in step (3), the oxidation time is 2 h.
Preferably, in step (3), the incubation time is 12 h.
The invention also provides a hollow nanofiber Co3O4a/S composite material having hollow nanotube-shaped fibers Co3O4And in the hollow nano tubular fiber Co3O4Has sulfur particles adhered to the surface thereof; wherein the sulfur particle content is 76%.
Preferably, the composite material is obtained by the production method according to any one of claims 1 to 7.
The invention also provides the hollow nanofiber Co3O4Use of/S composite materials as positive electrode active materials for lithium-sulphur batteries.
Hollow nanofiber Co of the invention3O4The preparation method and the application of the/S composite material solve the problems of the prior artThe sulfide has the problems of decomposition and shuttle effect, and has the following advantages:
(1) the composite material of the invention is hollow Co3O4Nano fiber (HCON for short) is used as a carrier material of sulfur to prepare Co3O4(ii) a/S composite material (HCON-S for short), using Co3O4The function of chemical affinity with polysulfide, the electronic conductivity of the material is enhanced, and the shuttle effect of polysulfide is inhibited;
(2) the composite material has high sulfur content, and has high specific capacity and good rate capability when being applied to the positive electrode of a lithium battery;
(3) the composite material provided by the invention is used as the positive electrode of the lithium-sulfur battery, has a high specific capacity retention rate after multiple cycles, and is good in cycling stability.
Drawings
FIG. 1 is an SEM topography of HCON prepared in example 1 of the present invention.
FIG. 2 is an SEM topography of the HCON-S composite material prepared in example 1 of the invention.
FIG. 3 is a TEM morphology of the HCON-S composite prepared in example 1 of the present invention.
FIG. 4 is an XRD pattern of HCON-S composite and HCON with elemental sulfur prepared in example 1 of the present invention.
FIG. 5 is a thermogravimetric analysis of the HCON-S composite prepared in example 1 of the present invention.
FIG. 6 is a graph showing the rate capability results for HCON-S composites prepared in example 1 of the present invention.
FIG. 7 is a graph of the long term cycling performance of the HCON-S composite prepared in example 1 of the present invention.
FIG. 8 is an ESI spectrum of HCON-S as an electrode and an S electrode prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) 1.2g of Co (CH)3COO)2·4H2Dissolving O (cobalt acetate tetrahydrate), 0.5g of PAN (polyacrylonitrile) and 0.1g of PVP (polyvinylpyrrolidone) in 15ml of DMF (N, N-dimethylformamide), electromagnetically stirring for 15-18 h at room temperature, and standing for 12-15 h to obtain an electrospinning solution;
(2) extracting the electrospinning liquid prepared in the step (1) by using an injector (the inner diameter of a needle head is 1.2mm), fixing the electrospinning liquid on a high-voltage electrostatic spinning machine for electrostatic spinning, and collecting the electrospinning liquid by using carbon paper as a receiving device, wherein the voltage is 15kV, the distance between the needle head and the carbon paper is 12-15 cm, the injection flow rate is 60 mu L/min, the temperature is 21-25 ℃, and the relative humidity is 80%, so that the nanofiber is prepared;
(3) placing the nanofiber prepared in the step (2) in air at 300 ℃ for oxidation for 2h, so as to prepare an HCON material;
(4) and (4) mixing sulfur and the HCON material prepared in the step (3), and then placing at 155 ℃ for heat preservation for 12 hours to prepare the HCON-S composite material.
The morphology of the prepared sample of the HCON material and the HCON-S composite material prepared in the embodiment 1 of the invention is observed through a scanning electron microscope and a transmission electron microscope, and the result is as follows:
as shown in fig. 1, which is an SEM topography of the HCON prepared in example 1 of the present invention, the outer diameter of the hollow tube is 60nm, and the surface of the hollow tube is rough, which is beneficial to carrying more elemental sulfur. As shown in FIG. 2, the SEM topography of the HCON-S composite material prepared in example 1 of the present invention shows a structure similar to that of HCON, and the outer surface of the HCON-S composite material is smoother than that of HCON. As shown in FIG. 3, a TEM morphology of the HCON-S composite material prepared in example 1 of the present invention shows that the HCON-S composite material is a hollow nanofiber structure, and the black shadow in the hollow nanofiber is elemental sulfur.
XRD analysis was performed on the HCON material and the HCON-S composite material prepared in example 1 of the present invention, and the results were as follows:
as shown in FIG. 4, the HCON-S composite material prepared in example 1 of the present inventionAnd XRD patterns of HCON and elemental sulfur, the HCON prepared showing Co3O4Has typical diffraction peaks, and confirms that Co is successfully prepared3O4And sulfur is immersed in the hollow nanofiber structure of HCON, the XRD pattern of the prepared HCON-S composite material is identical to the characteristic peak of original elemental sulfur, the difference is that the diffraction peak intensity of the HCON-S composite material is weaker than that of the original sulfur, and the fact that the sulfur element is immersed in the hollow nanofiber structure is confirmed.
Thermogravimetric analysis was performed on the HCON-S composite material prepared in example 1 of the present invention, and the results were as follows:
as shown in FIG. 5, a thermogravimetric analysis of the HCON-S composite prepared in example 1 of the present invention shows that the HCON-S composite has a sulfur content of about 76% (sulfur as a percentage of the total mass of the HCON-S composite) and better electrochemical performance.
The HCON material and the HCON-S composite material prepared in the embodiment 1 of the invention are subjected to electrochemical performance test, and the electrochemical performance test is carried out by assembling a 2032 button half-cell, which comprises the following specific steps:
the HCON material or HCON-S composite material prepared in example 1, the conductive agent SuperP and the binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 8:1:1, and the mixture was added to an appropriate amount of N-methylpyrrolidone (NMP) solvent and stirred for 1 hour to prepare an electrode slurry. Then the prepared plasma is evenly coated on the surface of the aluminum foil, then the aluminum foil is kept at 60 ℃ for 24 hours, and the aluminum foil is cooled to room temperature and then used as a positive electrode. The prepared aluminum foil sheet was used as a battery positive electrode with a disk punched out to a diameter of 11mm, a lithium foil was used as a negative electrode and a counter electrode, and the separator was a Clegard2300 polypropylene film. The electrolyte contains 1mol/L LiTFSI and 1mol/LLINO3And a volume ratio of 1:1, 3-Dioxolane (DOL) and 1, 2-Dimethoxyethane (DME).
The charge-discharge cycle performance test of the battery is carried out on a LANDCT2001A type battery tester, and the test voltage is between 1.5 and 3.0V. The cells were tested for electrochemical impedance (ESI) testing on a model CHI660E electrochemical workstation.
The electrochemical performance test results are as follows:
as shown in FIG. 6, which is a graph showing the rate capacity results of the HCON-S composite material prepared in example 1 of the present invention, the capacities of the HCON-S composite material as an electrode at 0.05C, 0.1C, 0.2C and 0.5C were 1406mAh/g, 1368mAh/g, 1216mAh/g and 1163mAh/g, respectively. When the current density was increased to 1C, the specific capacity of the HCON-S electrode remained 965 mAh/g. Finally, when the current density is restored to 0.1C, the capacity is restored, which indicates excellent rate capability. For pure sulfur electrodes, the specific capacity decays rapidly with increasing current density. Therefore, the HCON-S composite material prepared in the embodiment 1 of the invention has excellent conductive performance and shows good rate performance.
As shown in fig. 7, in order to obtain a long-term cycle performance curve of the HCON-S composite material prepared in example 1 of the present invention, the cycle performance of the HCON-S composite material as an electrode was tested 800 times at 1C, and it can be seen that the initial specific capacity of the HCON-SS composite material prepared in example 1 as an electrode at 1C was 965mAh/g, the specific capacity was 805mAh/g after 800 cycles, and the specific capacity retention rate was 83%.
As shown in FIG. 8, which is an ESI spectrum of HCON-S prepared in example 1 of the present invention as an electrode and an S electrode, an electrochemical impedance spectrum is shown which is composed of two parts, a low frequency part is a semicircle and a high frequency part is a straight line. The HCON-S electrode exhibited a smaller semicircle and showed more superior conductivity compared to the pure sulfur electrode.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. Hollow nanofiber Co3O4A method for preparing an/S composite, the method comprising:
(1) dissolving cobalt acetate, polyacrylonitrile and polyvinylpyrrolidone in an organic solvent, stirring at room temperature, and standing to obtain an electrospinning solution; wherein the mass ratio of the cobalt acetate to the polyacrylonitrile to the polyvinylpyrrolidone is 0.75-0.90: 0.5: 0.1;
(2) extracting the electrospinning liquid, carrying out electrostatic spinning, collecting a sample by using carbon paper, wherein the voltage is 15kV, the distance between a needle head of the electrostatic spinning and the carbon paper is 12-15 cm, the injection flow rate is 60 mu L/min, the temperature is 21-25 ℃, the relative humidity is 80%, and preparing the nano fiber;
(3) oxidizing the nano-fiber in air at 300 ℃ to obtain an HCON material;
(4) mixing sulfur and the HCON material, and preserving heat at 155 ℃ to prepare hollow nanofiber Co3O4a/S composite material.
2. The hollow nanofiber Co of claim 13O4A method for producing an/S composite material, characterized in that, in the step (1), the organic solvent contains: n, N-dimethylformamide.
3. The hollow nanofiber Co of claim 13O4The preparation method of the/S composite material is characterized in that in the step (1), cobalt acetate tetrahydrate is adopted; the mass ratio of the cobalt acetate tetrahydrate to the polyacrylonitrile to the polyvinylpyrrolidone is 1.2: 0.5: 0.1.
4. the hollow nanofiber Co of claim 13O4The preparation method of the/S composite material is characterized in that in the step (1), the stirring time is 15-18 h; the standing time is 12-15 h.
5. The hollow nanofiber Co of claim 13O4The preparation method of the/S composite material is characterized in that in the step (2), the inner diameter of the needle head of the syringe used for electrostatic spinning is 1.2 mm.
6. The hollow nanofiber Co of claim 13O4A method for producing an/S composite material, characterized in that, in the step (3),the oxidation time is 2 h.
7. The hollow nanofiber Co of any of claims 1 to 63O4The preparation method of the/S composite material is characterized in that in the step (3), the heat preservation time is 12 hours.
8. Hollow nanofiber Co3O4the/S composite material is characterized in that the composite material is provided with hollow nano tubular fibers Co3O4And in the hollow nano tubular fiber Co3O4Has sulfur particles adhered to the surface thereof; wherein the sulfur particle content is 76%.
9. The hollow nanofiber Co of claim 83O4A/S composite material, characterized in that it is obtained by the production process according to any one of claims 1 to 7.
10. Hollow nanofibrous Co as in claim 8 or 93O4Use of a/S composite material, characterized in that the composite material is used as a positive electrode active material for a lithium-sulfur battery.
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