CN117895190A - Lithium-sulfur battery interlayer material and preparation method and application thereof - Google Patents
Lithium-sulfur battery interlayer material and preparation method and application thereof Download PDFInfo
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- CN117895190A CN117895190A CN202410277787.XA CN202410277787A CN117895190A CN 117895190 A CN117895190 A CN 117895190A CN 202410277787 A CN202410277787 A CN 202410277787A CN 117895190 A CN117895190 A CN 117895190A
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- 239000000463 material Substances 0.000 title claims abstract description 62
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011229 interlayer Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 35
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 27
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000003763 carbonization Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 238000009987 spinning Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000005077 polysulfide Substances 0.000 abstract description 12
- 229920001021 polysulfide Polymers 0.000 abstract description 12
- 150000008117 polysulfides Polymers 0.000 abstract description 12
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000014233 sulfur utilization Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof
- H01M50/48—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof characterised by the material
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof
- H01M50/474—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof characterised by their position inside the cells
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium sulfur battery interlayer material and a preparation method and application thereof, wherein the lithium sulfur battery interlayer material is formed by coating carbon nanofibers with molybdenum trisulfide sheets and cobaltosic oxide particles, the thickness of the molybdenum trisulfide sheets is 6-12 nm, the equivalent diameter of the cobaltosic oxide particles is 80-400 nm, the diameter of the carbon nanofibers is 0.9-1.2 mu m, the mass of the molybdenum trisulfide sheets is 30.7-76.3% of the mass of the cobaltosic oxide particles, and the mass of the carbon nanofibers is 42.7-85.2% of the mass of the lithium sulfur battery interlayer material. The invention prepares the composite fiber membrane through electrostatic spinning, carbonization, hydrothermal and calcination to prepare the sandwich material composed of molybdenum trisulfide sheets and cobaltosic oxide particles coated with carbon nanofibers, so as to adsorb polysulfide and ensure rapid electrochemical redox reaction kinetics. The electrochemical performance and the cycling stability of the battery are optimized when the lithium-sulfur battery is sandwiched.
Description
Technical Field
The invention belongs to the field of lithium-sulfur batteries, and particularly relates to a lithium-sulfur battery interlayer material, and a preparation method and application thereof.
Background
With the increasing severity of energy crisis and environmental pollution problems, lithium sulfur batteries are receiving increasing attention and are considered one of the most promising batteries. It has a remarkably high energy density (2600 Wh/kg), is nontoxic, low in cost and high in theoretical specific capacity (1675 mAh/g). However, lithium sulfur batteries face the following challenges in practical applications: sulfur electron/ion inertness, notoriously "shuttling" and lithium dendrites resulting from non-uniform lithium ion deposition. Among them, the "shuttle effect" caused by polysulfide intermediates (LiPS, li 2Sx, 3.ltoreq.x.ltoreq.8) is particularly serious, which leads to problems of irreversible loss of active materials in batteries, reduction of sulfur utilization, acceleration of capacity decay, reduction of coulomb efficiency, reduction of cycling stability, and the like.
To address these issues, a number of strategies have been adopted, including a variety of strategies for designing sulfur hosts, introducing interlayers, and adding new additives. Among them, the construction of a functional interlayer between a separator and an active electrode is considered to be a reliable and simple method of suppressing polysulfide shuttling. For example, chinese patent document publication No. CN115602909a discloses a lithium sulfur battery, an interlayer, a preparation method and use, comprising: a sheet-like carrier having a plurality of network channels; the network channel is used for realizing the adsorption of polysulfide ions in the electrolyte and the guiding action of electrons or metal ions through supporting a load material; and loading slurry, coating on the surface of the flaky carrier. In addition, the Chinese patent document with publication number CN114068932B discloses a flexible self-doping material for a lithium-sulfur battery, a preparation method and application thereof, and the flexible self-doping material is prepared from fibrillated PBO fibers and has a three-dimensional structure. However, the existing interlayer material has poor barrier effect on polysulfide, so that the loss of active substances in the battery is serious, the battery cycle performance is poor, and the battery cycle life is reduced.
Disclosure of Invention
The invention aims to provide a lithium-sulfur battery interlayer material, and a preparation method and application thereof. The sandwich material can effectively avoid the shuttle effect, thereby improving the electrochemical performance and the cycle stability of the battery.
In order to solve the technical problems, the invention provides the following technical scheme:
In a first aspect, the invention provides a lithium sulfur battery interlayer material, which consists of molybdenum trisulfide sheets and cobaltosic oxide particles coated with carbon nanofibers, wherein the thickness of the molybdenum trisulfide sheets is 6-12 nm, the equivalent diameter of the cobaltosic oxide particles is 80-400 nm, the diameter of the carbon nanofibers is 0.9-1.2 mu m, the mass of the molybdenum trisulfide sheets is 30.7-76.3% of the mass of the cobaltosic oxide particles, and the mass of the carbon nanofibers is 42.7-85.2% of the mass of the lithium sulfur battery interlayer material.
In a second aspect, the invention also provides a preparation method of the lithium-sulfur battery interlayer material, which comprises the following steps:
(1) Dissolving a carbon source, ammonium tetrathiomolybdate and a pore-forming agent in N, N-dimethylformamide to obtain a spinning solution, and preparing a composite fiber membrane by an electrostatic spinning technology; wherein the mass ratio of the carbon source to the ammonium tetrathiomolybdate to the pore-forming agent is 0.6-2.0: 1:0.5 to 1.0;
(2) The composite fiber membrane is placed in a protective atmosphere for carbonization heat treatment, and a molybdenum trisulfide sheet coated carbon nanofiber material is prepared;
(3) Sequentially dissolving a cobalt source and thiourea in deionized water under stirring to obtain a precursor solution; then adding the molybdenum trisulfide sheet coated carbon nanofiber material into the solution for hydrothermal treatment, taking out the treated material, washing with deionized water or ethanol, and drying to obtain a precursor;
(4) Calcining the precursor in the air atmosphere at 200-500 deg.c to obtain the sandwich material of lithium-sulfur cell.
Preferably, in the step (1), the carbon source is at least one of polyacrylonitrile or polyvinylpyrrolidone, the pore-forming agent is at least one of polymethyl methacrylate or polystyrene, and the mass ratio of the carbon source to the ammonium tetrathiomolybdate to the pore-forming agent is 0.8-1.6: 1:0.5 to 0.8.
Preferably, in the step (1), the process parameters of the electrospinning are as follows: the high voltage of the electrostatic spinning is 10-20 kV, the pushing speed of the spinning solution is 0.5-2 ml/min, and the receiving distance is 10-20 cm.
Preferably, in the step (2), the heat treatment temperature is 500-900 ℃, the heating rate of the heat treatment is controlled to be 2-5 ℃/min, and the time is 6-12 h.
Preferably, in the step (3), the cobalt source is one of cobalt acetate, cobalt nitrate or cobalt oxalate, the molar concentration of the cobalt source in the precursor solution is 0.05-0.5 mol/L, and the molar ratio of thiourea to the cobalt source is 1-5: 1, a step of; the hydrothermal treatment temperature is 120-200 ℃ and the time is 6-12 h; the drying temperature is 60-80 ℃ and the drying time is 4-8 h.
Preferably, in the step (4), the temperature rising rate is controlled to be 2-5 ℃/min, and the calcination time is 6-18 h.
In a third aspect, the invention also provides an application of the lithium sulfur battery interlayer material in a lithium sulfur battery interlayer, wherein the lithium sulfur battery interlayer material can be directly used as a lithium sulfur battery interlayer, and is clamped between a diaphragm and a positive plate in the lithium sulfur battery assembly process.
The beneficial effects of the invention are as follows:
1. The synergistic effect of the carbon nanofiber network, large surface area MoS 3 nanoplatelets, and Co 3O4 particles has a key role in preventing polysulfide shuttling effects.
2. In the lithium-sulfur battery interlayer material prepared by the invention, highly dispersed MoS 3 nano sheets and Co 3O4 particles are uniformly coated on the carbon nano fibers, and the lithium-sulfur battery interlayer material has the structural advantage of different functional components. The MoS 3 nano sheet structure has large surface area, stronger affinity with polysulfide, and low lithium ion diffusion resistance, so that rapid ion transmission is realized. Meanwhile, nearby Co 3O4 particles provide immediate electron conduction channels for polysulfide adsorption to adsorb polysulfide, ensuring rapid electrochemical redox reaction kinetics.
3. The continuous network of carbon nanofibers provides robust interlayer integrity and excellent electrical conductivity. In addition, it can facilitate ion transport due to the three-dimensional open frame with high porosity and minimize volume changes of the interlayer material during long-term cycling.
4. In summary, the lithium-sulfur battery interlayer material prepared by the method of the invention is prominent in lithium-sulfur battery applications. The initial specific capacity is up to 1220.1-1223.6 mAh/g at 0.5C, and the capacity retention rate is 80.6-83.8% in 500 cycle tests.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a lithium sulfur battery interlayer material prepared in example 1;
FIG. 2 is an SEM magnification of a lithium sulfur battery interlayer material prepared according to example 1;
FIG. 3 is an X-ray diffraction (XRD) pattern of the lithium sulfur battery interlayer material prepared in example 1;
Fig. 4 is a graph showing the cycling stability at 0.5C of the lithium sulfur battery interlayer material prepared in example 1.
Detailed Description
The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited thereto.
Example 1
(1) 0.6G of polyacrylonitrile, 0.6g of polyvinylpyrrolidone, 1g of ammonium tetrathiomolybdate, 0.2g of polymethyl methacrylate and 0.4g of polystyrene are dissolved in 20ml of N, N-dimethylformamide to obtain a spinning solution, and then a composite fiber film is prepared by an electrostatic spinning method, wherein the electrostatic spinning process comprises the following steps: the voltage is 10kV, the spinning solution pushing speed is 0.5ml/min, and the receiving distance is 20cm; wherein, the mass ratio of polyacrylonitrile to polyvinylpyrrolidone, ammonium tetrathiomolybdate, polymethyl methacrylate to polystyrene is 1.2:1:0.5;
(2) Placing the composite fiber membrane in an argon atmosphere, and heating to 600 ℃ at a heating rate of 3 ℃/min for 8 hours to obtain molybdenum trisulfide sheet coated carbon nanofibers (MoS 3 -CNFs);
(3) Putting MoS 3 -CNFs into a reaction kettle of a precursor solution, performing hydrothermal treatment in an oven at 120 ℃ for 6 hours, taking out a sample from the reaction kettle, cleaning with deionized water, and drying in a drying oven at 60 ℃ for 4 hours to obtain a precursor; wherein the cobalt source is cobalt nitrate, the molar concentration of the cobalt nitrate in the precursor solution is 0.1mol/L, and the molar ratio of thiourea to the cobalt nitrate is 2:1, a step of;
(4) And (3) heating the precursor to 350 ℃ at a heating rate of 5 ℃/min in an air atmosphere, and preserving heat for 6 hours to calcine the precursor to obtain the molybdenum trisulfide sheet and the cobaltosic oxide particle coated carbon nanofiber lithium sulfur battery interlayer material (MoS 3-Co3O4 @CNFs).
The lithium sulfur battery interlayer material is obtained in the embodiment, the molybdenum trisulfide sheet is 65.1% of the mass of the cobaltosic oxide particles as measured by inductively coupled atomic emission spectrometry (ICP-AES), and the carbon nanofiber is 60.5% of the mass of the lithium sulfur battery interlayer material.
Example 2
(1) 0.6G of polyacrylonitrile, 1g of ammonium tetrathiomolybdate and 0.8g of polymethyl methacrylate are dissolved in 20ml of N, N-dimethylformamide to obtain a spinning solution, and then a composite fiber film is prepared by an electrostatic spinning method, wherein the process parameters of electrostatic spinning are as follows: the voltage is 20kV, the spinning solution pushing speed is 1.5ml/min, and the receiving distance is 10cm; wherein, the mass ratio of polyacrylonitrile to ammonium tetrathiomolybdate to polymethyl methacrylate is 0.6:1:0.8;
(2) Placing the composite fiber membrane in an argon atmosphere, and heating to 900 ℃ at a heating rate of 2 ℃/min for 12 hours to obtain MoS 3 -CNFs;
(3) Putting MoS 3 -CNFs into a reaction kettle of a precursor solution, performing hydrothermal treatment in an oven at 150 ℃ for 12 hours, taking out a sample from the reaction kettle, washing with ethanol, and drying in a drying oven at 80 ℃ for 6 hours to obtain a precursor; wherein the cobalt source is cobalt oxalate, the molar concentration of the cobalt oxalate in the precursor solution is 0.05mol/L, and the molar ratio of thiourea to the cobalt oxalate is 1:1, a step of;
(4) And (3) heating the precursor to 200 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and preserving heat for 12 hours to calcine to obtain MoS 3-Co3O4 @CNFs.
The lithium sulfur battery interlayer material is obtained in the embodiment, the mass of the molybdenum trisulfide sheet is 30.7% of the mass of the cobaltosic oxide particles measured by ICP-AES, and the mass of the carbon nanofiber is 42.7% of the mass of the lithium sulfur battery interlayer material.
Example 3
(1) 2G of polyvinylpyrrolidone, 1g of ammonium tetrathiomolybdate and 1g of polystyrene are dissolved in 20ml of N, N-dimethylformamide to obtain a spinning solution, and then a composite fiber film is prepared by an electrostatic spinning method, wherein the electrostatic spinning process comprises the following steps: the voltage is 15kV, the spinning solution pushing speed is 2ml/min, and the receiving distance is 12cm; wherein, the mass ratio of polyvinylpyrrolidone, ammonium tetrathiomolybdate and polystyrene is 2:1:1, a step of;
(2) Placing the composite fiber membrane in an argon atmosphere, and heating to 500 ℃ at a heating rate of 5 ℃/min for 6 hours to obtain MoS 3 -CNFs;
(3) Putting MoS 3 -CNFs into a reaction kettle of a precursor solution, performing hydrothermal treatment in an oven at 200 ℃ for 10 hours, taking out a sample from the reaction kettle, washing with ethanol, and drying in a drying oven at 75 ℃ for 8 hours to obtain a precursor; wherein the cobalt source is cobalt acetate, the molar concentration of the cobalt acetate in the precursor solution is 0.5mol/L, and the molar ratio of thiourea to the cobalt acetate is 5:1, a step of;
(4) And (3) heating the precursor to 500 ℃ at a heating rate of 4 ℃/min in an air atmosphere, and preserving heat for 18 hours to calcine to obtain MoS 3-Co3O4 @CNFs.
The lithium sulfur battery interlayer material is obtained in the embodiment, the mass of the molybdenum trisulfide sheet is 76.3% of the mass of the cobaltosic oxide particles measured by ICP-AES, and the mass of the carbon nanofiber is 85.2% of the mass of the lithium sulfur battery interlayer material.
Example 4
(1) 0.8G of polyacrylonitrile, 0.7g of polyvinylpyrrolidone, 1g of ammonium tetrathiomolybdate and 0.2g of polymethyl methacrylate are dissolved in 20ml of N, N-dimethylformamide to obtain a spinning solution, and then a composite fiber membrane is prepared by an electrostatic spinning method, and the process parameters of electrostatic spinning are as follows: the voltage is 12kV, the spinning solution pushing speed is 0.9ml/min, and the receiving distance is 15cm; wherein the mass ratio of the polyacrylonitrile to the polyvinylpyrrolidone, the ammonium tetrathiomolybdate and the polymethyl methacrylate is 1.5:1:0.8;
(2) Placing the composite fiber membrane in a nitrogen atmosphere, and heating to 750 ℃ at a heating rate of 3 ℃/min, wherein the calcination time is 10 hours, so as to obtain MoS 3 -CNFs;
(3) Putting MoS 3 -CNFs into a reaction kettle of a precursor solution, performing hydrothermal treatment in an oven at 120 ℃ for 8 hours, taking out a sample from the reaction kettle, cleaning with deionized water, and drying in a drying oven at 65 ℃ for 8 hours to obtain a precursor; wherein the cobalt source is cobalt nitrate, the molar concentration of the cobalt nitrate in the precursor solution is 0.25mol/L, and the molar ratio of thiourea to the cobalt nitrate is 5:1, a step of;
(4) And (3) heating the precursor to 300 ℃ at a heating rate of 3 ℃/min in an air atmosphere, and preserving heat for 15 hours to calcine the precursor to obtain MoS 3-Co3O4 @CNFs.
The lithium sulfur battery interlayer material is obtained in the embodiment, the molybdenum trisulfide sheet is 48.5% of the mass of the cobaltosic oxide particles measured by ICP-AES, and the carbon nanofiber is 71.0% of the mass of the lithium sulfur battery interlayer material.
Comparative example 1
This comparative example did not incorporate a cobalt source, and all other things were consistent with the procedure of example 1.
Comparative example 2
In this comparative example, ammonium tetrathiomolybdate was not added, and the procedure of example 1 was otherwise identical.
Performance test:
The MoS 3-Co3O4 @cnfs prepared in example 1 was used as a lithium-sulfur battery interlayer material, a polypropylene porous membrane (Celgard 2300) was used as a battery separator, a C/S composite material was used as a positive electrode, metallic lithium was used as a counter electrode, and an electrolyte was 1.0mol/LLiTFSI and 0.2mol/LLiN0 3 mixed solution with 1, 3-dioxolane and 1, 2-dimethoxyethane (w/w, 1/1), and a CR2025 button cell was assembled in a glove box filled with argon. The cells were cycled at different current densities over a fixed potential range (1.7-2.8 Vvs. Li +/Li) on a CT-4008-5A6V system. The test current density was 0.5C, the test voltage range was 1.7-2.8V, and the test results are shown in table 1:
Fig. 1 and 2 are SEM images of the lithium sulfur battery interlayer material prepared in example 1. From the figure, it can be observed that the interlayer material consists of molybdenum trisulfide sheets and cobaltosic oxide particles coated with carbon nanofibers, wherein the thickness of the molybdenum trisulfide sheets is 6-12 nm, the equivalent diameter of the cobaltosic oxide particles is 80-400 nm, and the diameter of the carbon nanofibers is 0.9-1.2 μm. The MoS 3 nanoplatelets and Co 3O4 particles with large surface areas have strong affinity to polysulfides and ensure rapid electrochemical redox kinetics; in addition, the continuous network of carbon nanofibers provides robust interlayer integrity and excellent electrical conductivity. Thus, the synergistic effect of the carbon nanofiber network, large surface area MoS 3 nanoplatelets, and Co 3O4 particles has a key role in preventing polysulfide shuttling.
XRD testing was performed on the lithium sulfur battery interlayer material obtained in example 1, as shown in fig. 3. As can be seen from fig. 3, the sharp peaks shown are consistent with PDF standard card numbers, indicating that the synthesized material contains Co 3O4, and in addition, the inclusion peak at around 15 o shows the presence of amorphous MoS 3.
The prepared lithium sulfur battery interlayer material was assembled into a lithium sulfur battery in a glove box, and subjected to electrochemical testing at a current density of 0.5C under a condition of 1.7-2.8V, as shown in fig. 4. The initial specific capacity of the lithium sulfur battery interlayer material is 1223.6mAh/g, the capacity retention rate reaches 83.8% after 500 times of circulation, and the lithium sulfur battery interlayer material has excellent charge and discharge performance and circulation stability. The same test was conducted on the materials of examples 2 to 4, and the results were similar to those of example 1 (Table 1), in that the difference in specific discharge capacity at a current density of 0.5C was not more than 3.5mAh/g, and the difference in capacity retention was not more than 3.2%.
Compared with the comparative sample, the example has better performance under the condition of 0.5C, which shows that the synergistic effect of MoS 3 and Co 3O4 has great barrier effect on polysulfide, thereby realizing better specific discharge capacity and cycle stability.
The invention has been described in further detail in the foregoing description of the embodiments, but such description is not to be construed as limiting the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The lithium sulfur battery interlayer material is characterized by comprising molybdenum trisulfide sheets and cobaltosic oxide particles coated with carbon nanofibers, wherein the thickness of the molybdenum trisulfide sheets is 6-12 nm, the equivalent diameter of the cobaltosic oxide particles is 80-400 nm, the diameter of the carbon nanofibers is 0.9-1.2 mu m, the mass of the molybdenum trisulfide sheets is 30.7-76.3% of the mass of the cobaltosic oxide particles, and the mass of the carbon nanofibers is 42.7-85.2% of the mass of the lithium sulfur battery interlayer material.
2. The preparation method of the lithium-sulfur battery interlayer material is characterized by comprising the following steps of:
(1) Dissolving a carbon source, ammonium tetrathiomolybdate and a pore-forming agent in N, N-dimethylformamide to obtain a spinning solution, and preparing a composite fiber membrane by an electrostatic spinning technology; wherein the mass ratio of the carbon source to the ammonium tetrathiomolybdate to the pore-forming agent is 0.6-2.0: 1:0.5 to 1.0;
(2) The composite fiber membrane is placed in a protective atmosphere for carbonization heat treatment, and a molybdenum trisulfide sheet coated carbon nanofiber material is prepared;
(3) Sequentially dissolving a cobalt source and thiourea in deionized water under stirring to obtain a precursor solution; then adding the molybdenum trisulfide sheet coated carbon nanofiber material into the solution for hydrothermal treatment, taking out the treated material, washing with deionized water or ethanol, and drying to obtain a precursor;
(4) Calcining the precursor in the air atmosphere at 200-500 deg.c to obtain the sandwich material of lithium-sulfur cell.
3. The method for preparing a lithium-sulfur battery interlayer material according to claim 2, wherein in the step (1), the carbon source is at least one of polyacrylonitrile or polyvinylpyrrolidone, the pore-forming agent is at least one of polymethyl methacrylate or polystyrene, and the mass ratio of the carbon source, the ammonium tetrathiomolybdate and the pore-forming agent is 0.8-1.6: 1:0.5 to 0.8.
4. The method for preparing a lithium-sulfur battery interlayer material according to claim 2, wherein in the step (1), the process parameters of electrospinning are as follows: the high voltage of the electrostatic spinning is 10-20 kV, the pushing speed of the spinning solution is 0.5-2 ml/min, and the receiving distance is 10-20 cm.
5. The method for preparing a lithium-sulfur battery interlayer material according to claim 2, wherein in the step (2), the protective atmosphere is nitrogen or argon, the heat treatment temperature is 500-900 ℃, the heat treatment control temperature rise rate is 2-5 ℃/min, and the time is 6-12 h.
6. The method for preparing a lithium-sulfur battery interlayer material according to claim 2, wherein in the step (3), the cobalt source is one of cobalt acetate, cobalt nitrate and cobalt oxalate, the molar concentration of the cobalt source in the precursor solution is 0.05-0.5 mol/L, and the molar ratio of thiourea to the cobalt source is 1-5: 1, a step of; the hydrothermal treatment temperature is 120-200 ℃ and the time is 6-12 h; the drying temperature is 60-80 ℃ and the drying time is 4-8 h.
7. The method for preparing a lithium-sulfur battery interlayer material according to claim 2, wherein in the step (4), the temperature rise rate is controlled to be 2-5 ℃/min, and the calcination time is 6-18 h.
8. Use of the lithium sulfur battery interlayer material according to claim 1, wherein the lithium sulfur battery interlayer material is used in a lithium sulfur battery interlayer.
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| CN109065808A (en) * | 2018-08-07 | 2018-12-21 | 河北工业大学 | A kind of preparation method of the functional interlayer for lithium-sulfur cell |
| CN114204218A (en) * | 2021-11-22 | 2022-03-18 | 大连理工大学 | Loaded hollow Co3O4Preparation method of positive electrode side interlayer for cubic lithium-sulfur battery |
| CN116936965A (en) * | 2023-06-12 | 2023-10-24 | 浙江地坤键新能源科技有限公司 | Diaphragm with slow release function for high-energy-density secondary battery |
| KR20230153108A (en) * | 2022-04-28 | 2023-11-06 | 충북대학교 산학협력단 | HYBRID NANOFIBERS FOR Li-S BATTERIES, Li-S BATTERIES COMPRISING THE SAME AND MANUFACTURING METHOD THEREFOR |
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| CN109065808A (en) * | 2018-08-07 | 2018-12-21 | 河北工业大学 | A kind of preparation method of the functional interlayer for lithium-sulfur cell |
| CN114204218A (en) * | 2021-11-22 | 2022-03-18 | 大连理工大学 | Loaded hollow Co3O4Preparation method of positive electrode side interlayer for cubic lithium-sulfur battery |
| KR20230153108A (en) * | 2022-04-28 | 2023-11-06 | 충북대학교 산학협력단 | HYBRID NANOFIBERS FOR Li-S BATTERIES, Li-S BATTERIES COMPRISING THE SAME AND MANUFACTURING METHOD THEREFOR |
| CN116936965A (en) * | 2023-06-12 | 2023-10-24 | 浙江地坤键新能源科技有限公司 | Diaphragm with slow release function for high-energy-density secondary battery |
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