CN114520327B - Preparation method and application of mesoporous molybdenum disulfide/carbon composite material - Google Patents
Preparation method and application of mesoporous molybdenum disulfide/carbon composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 78
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 4
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 26
- 239000012298 atmosphere Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 6
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 229960001031 glucose Drugs 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229940091868 melamine Drugs 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 229940032147 starch Drugs 0.000 claims description 2
- 229960004793 sucrose Drugs 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000001132 ultrasonic dispersion Methods 0.000 description 17
- 239000012300 argon atmosphere Substances 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 239000011149 active material Substances 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 230000001351 cycling effect Effects 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of a mesoporous molybdenum disulfide/carbon composite material and application of the mesoporous molybdenum disulfide/carbon composite material serving as a negative electrode active material in a sodium ion battery system. And simultaneously depositing molybdenum salt, a sulfur source and a carbon source on the surface of SBA-15 based on a coprecipitation and high-temperature solid phase reaction method, and removing an SBA-15 template by using a hydrofluoric acid solution after high-temperature treatment to obtain a target product. The method is a universal method for preparing the molybdenum disulfide/carbon composite material, and has the characteristics of simple operation and mass preparation. The prepared molybdenum disulfide/carbon composite material maintains the original pore canal structure of SBA-15, and the molybdenum disulfide and carbon are excellently compounded together, so that the molybdenum disulfide/carbon composite material has excellent performance and wide application prospect in serving as a negative electrode material of a sodium ion battery.
Description
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to a preparation method and application of a mesoporous molybdenum disulfide/carbon composite material.
Background
Since the first commercial lithium ion battery was proposed by sony corporation of japan in 1991, lithium batteries have been rapidly developed (Journal of Power sources.100.101 (2001)). With the continuous development of society, the living standard of people is increasingly improved, and the demand of lithium ion batteries is also increasingly increased. In recent years, the expansion and development of lithium batteries from portable electronic devices (mobile phones, watches, computers, etc.) to large-scale energy storage fields typified by electric automobiles has put serious efforts on the supply of lithium batteries (ionics.20.1651 (2014)). However, the lack of natural lithium resources and the non-uniformity of the global lithium source distribution cannot meet the requirement of large-scale development of future lithium batteries (Nature chemistry.2.510 (2010)). Sodium in the same period of the periodic table as lithium has very similar physicochemical properties as lithium, while sodium is very abundant in its reserves on earth and its distribution is widespread, and both battery systems also have a high degree of similarity in working principle (Advanced Energy materials.2.710 (2012)). As one of the most potential secondary battery replacement systems for lithium ion batteries, the development of high-performance sodium ion batteries is of great importance in meeting the needs of large-scale energy storage in the future.
Electrode materials are important components of sodium ion batteries and play a critical role in determining battery performance. The electrode material includes a positive electrode material and a negative electrode material. In terms of positive electrode materials, many positive electrode materials in sodium ion battery systems can be derived from lithium battery systems, and these positive electrode materials tend to exhibit similar electrochemical properties as the positive electrode materials in lithium battery systems. In the case of the negative electrode material, however, since the ionic radius of sodium is larger than that of lithium, many negative electrode materials for lithium battery systems cannot be directly used for sodium battery systems, which seriously hinders the progress of commercialization of sodium battery systems (Journal of Power sources.243.585 (2013)). Molybdenum disulfide is used as one of the most promising anode materials in a sodium ion battery system, and the unique S-Mo-S two-dimensional layered structure and the interlayer spacing of 0.62nm ensure the effective transmission of sodium ions in the charge and discharge process when the molybdenum disulfide is used as the sodium ion anode material (Nano energy.20.1 (2016)). The molybdenum disulfide stores sodium through an intercalation-transformation mechanism, and has a purity of 670 mAh.g -1 Is a theoretical specific capacity of (c). However, molybdenum disulfide has poor conductivity, and causes a large volume expansion effect in the charge and discharge process, so that the molybdenum disulfide has short cycle life and poor rate capability when used as a sodium-electricity negative electrode material (Nano energy.41.66 (2017)). One possible solution is to combine molybdenum disulfide with carbon materials to enhance the properties of the materials, and related studies have also shown that the introduction of carbon does enhance the conductivity and stability of the materials (Advanced Functional materials.27.1702116 (2017)). However, the preparation of the composite materials often uses a carbon skeleton as a template to grow molybdenum disulfide, the practical requirements on capacity and cycle performance can not be met, and the method for preparing the composite of carbon and molybdenum disulfide in situ is still a difficulty in research. Thus, there is still a need for further exploration of molybdenum disulfide/carbon composites with higher capacities and long-term cycling stability.
Disclosure of Invention
The method is characterized in that molybdenum disulfide and a carbon precursor are co-deposited on the surface of SBA-15, after high-temperature solid-phase reaction, a hydrofluoric acid solution is used for removing the SBA-15 template to obtain the molybdenum disulfide/carbon composite material, and the method has the characteristics of simple operation and mass preparation. The prepared molybdenum disulfide/carbon composite material maintains the original pore canal structure of SBA-15, and the molybdenum disulfide and carbon are excellently compounded together in structure, so that the molybdenum disulfide/carbon composite material as a negative electrode material of a sodium ion battery shows excellent electrochemical performance.
The invention adopts the following technical means:
a preparation method of a molybdenum disulfide/carbon composite material comprises the following steps:
(1) Depositing molybdenum salt, a sulfur source and a carbon source on the surface of SBA-15 by using a coprecipitation method to obtain a precursor mixture;
(2) Heating the precursor mixture to the end temperature by adopting temperature programming treatment under inert atmosphere, and then keeping the temperature constant; the molybdenum salt reacts with a sulfur source to generate molybdenum disulfide, and a carbon source is carbonized to carbon;
(3) Heating the product obtained in the step (2) to the end temperature by adopting temperature programming treatment under the reducing atmosphere, and then keeping the temperature constant; the end point temperature is higher than that of the step (2);
(4) And (3) carrying out acid treatment on the product obtained in the step (3), and carrying out acid etching to remove SBA-15 to obtain the molybdenum disulfide/carbon composite material.
Further, in the step (1), the mass ratio of the molybdenum salt, the sulfur source and the carbon source is 1:1-3:0.1-2.
Further, the molybdenum salt is one of ammonium tetrathiomolybdate, ammonium molybdate, ammonium phosphomolybdate, sodium phosphomolybdate or sodium molybdate; the sulfur source is one of thiourea, sodium sulfide, potassium sulfide, ammonium sulfide or thioacetamide; the carbon source is one of soluble starch, sucrose, anhydrous glucose, dopamine hydrochloride, melamine or dicyandiamide.
Further, the co-deposition temperature is 60-100 ℃ and the time is 12-24 hours.
Further, in the step (2), the inert atmosphere is one of argon, nitrogen or helium; the temperature programming treatment is to heat at the temperature rising rate of 1-10 ℃/min to the end point temperature of 400-550 ℃ and then to keep the temperature for 2-5 h.
Further, in the step (3), the reducing atmosphere is a mixed atmosphere of hydrogen and inert atmosphere, and the hydrogen accounts for 5-20% of the mixed atmosphere; the temperature programming treatment is to heat up to the end temperature of 700-900 ℃ at the temperature rising rate of 5-15 ℃/min, and keep the temperature for 0.5-2.5 h.
Further, in the step (4), the acid in the acid treatment is hydrofluoric acid solution with the concentration of 5% -20%, and the acid treatment time is 6-12 hours; the drying temperature is 60-80 ℃ and the drying time is 12-24 h after washing.
The invention also provides a molybdenum disulfide/carbon composite material obtained by the preparation method.
Further, the molybdenum disulfide/carbon composite material has mesoporous structure characteristics similar to SBA-15.
The invention also provides application of the molybdenum disulfide/carbon composite material in a sodium ion battery system as a negative electrode material.
Compared with the prior art, the invention has the following advantages:
1. the reaction process can synchronously generate molybdenum disulfide and carbon, and compared with a molybdenum disulfide/carbon composite prepared by a simple carbon coating method, the molybdenum disulfide/carbon composite prepared by the method has a more stable structure.
2. The mesoporous molybdenum disulfide/carbon composite material prepared by the invention well maintains the mesoporous characteristics of the original template SBA-15. When the porous structures are used as the negative electrode material of the sodium ion battery, the porous structures not only increase the contact area of the material and electrolyte, are beneficial to the rapid transmission of sodium ions in the charge and discharge process, but also enhance the structural stability of the material in the long-time charge and discharge process, and show excellent electrochemical performance when being used as the negative electrode material of the sodium ion battery.
3. The preparation method disclosed by the invention is simple and wide in application range, and the obtained mesoporous molybdenum disulfide/carbon composite material has potential application prospects in the field of energy storage.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to the drawings without inventive effort to a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the molybdenum disulfide/carbon composite material of example 1.
Fig. 2 is a transmission electron microscopy image of molybdenum disulfide/carbon composite of example 1.
FIG. 3 is a graph showing that the molybdenum disulfide/carbon composite material of example 1 has a current density of 100 mA.g in a test voltage range of 0.4 to 3V -1 Performance graph at time.
FIG. 4 shows that the molybdenum disulfide/carbon composite material of example 2 has a current density of 500 mA.g in the test voltage range of 0.01 to 3V -1 Performance graph at time.
FIG. 5 is a graph showing that the molybdenum disulfide/carbon composite material of example 2 has a current density of 1 A.g in a test voltage range of 0.01 to 3V -1 Performance graph at time.
Fig. 6 is a high resolution scanning electron microscope image of the molybdenum disulfide/carbon composite material of example 3.
FIG. 7 is a graph showing that the molybdenum disulfide/carbon composite material of example 3 has a current density of 200mA.g in a test voltage range of 0.01 to 3V -1 Performance graph at time.
FIG. 8 is a graph of the rate capability of the molybdenum disulfide/carbon composite of example 3 over a test voltage range of 0.01 to 3V.
FIG. 9 is a graph showing that the molybdenum disulfide/carbon composite material of example 3 has a current density of 1 A.g in a test voltage range of 0.01 to 3V -1 Performance graph at time.
FIG. 10 is a graph showing that the molybdenum disulfide/carbon composite material of example 3 has a current density of 2A.g in a test voltage range of 0.01 to 3V -1 Performance graph at time.
FIG. 11 is a graph showing the comparison of the performance of the molybdenum disulfide/carbon composites of examples 3, 4 and 5 at a measured voltage range of 0.01 to 3V and a current density of 1 A.g-1.
FIG. 12 is a graph showing that the molybdenum disulfide/carbon composite material of comparative example 1 has a current density of 500 mA.g in a test voltage range of 0.01 to 3V -1 Performance graph at time.
Detailed Description
The entire material preparation process is described in detail by way of examples below, the starting materials used in the examples below being conventional products which are commercially available.
(1) Sequentially adding a molybdenum salt, a sulfur source and a carbon source into deionized water, stirring and dissolving completely, adding SBA-15, and performing ultrasonic dispersion to form a uniform dispersion.
(2) The dispersion in (1) was placed on a magnetic stirrer, stirred at room temperature until the solvent was sufficiently evaporated, and then the resulting sample was placed in a forced air drying oven for further drying.
(3) And (3) placing the dried sample in the step (2) in a tube furnace, programming to be at 400-550 ℃ under the protection of argon atmosphere, and keeping the temperature for 2-5 h.
(4) After the constant temperature in the step (3) is finished, replacing the argon atmosphere with hydrogen-argon mixed gas, further programming to heat to 700-900 ℃, and keeping the constant temperature for 0.5-2.5 h.
(5) The sample obtained in (4) is treated by hydrofluoric acid solution for 6 to 12 hours to remove SBA-15, and then is filtered by suction and washed by water and ethanol for a plurality of times until the filtrate is neutral.
(6) And (3) drying the sample in the step (5) to obtain the mesoporous molybdenum disulfide/carbon composite material.
The ultrasonic dispersion time after adding SBA-15 in the step (1) is preferably 30-60 min.
The drying temperature in the step (2) is preferably 80-100 ℃.
The flow rate of the argon atmosphere in the step (3) is preferably 50-80 mL/min; the temperature programming rate is preferably 2 to 6 ℃/min.
The hydrogen in the step (4) accounts for 5-10% of the volume of the hydrogen-argon mixed atmosphere; the temperature programming rate is preferably 10 to 15 ℃/min.
The concentration of the hydrofluoric acid solution used in the step (5) is preferably 10% to 15%.
In the step (6), the preferable drying temperature is 60-80 ℃; the drying time is 12-24 hours.
The products of examples 1-5 of the present invention were tested by the following apparatus and method:
characterization of the product morphology in example 1 using Scanning Electron Microscopy (SEM);
characterization of the product morphology in example 1 by Transmission Electron Microscopy (TEM);
characterizing the morphology of the product in example 3 with High Resolution Scanning Electron Microscopy (HRSEM);
the electrochemical properties of the products of examples 1-5 were measured in a sodium ion battery system.
Example 1
The molybdenum disulfide/carbon composite material was prepared as follows.
(1) 300mg of sodium molybdate, 600mg of thiourea and 600mg of sucrose are sequentially stirred and dissolved in 20mL of deionized water, 400mg of template SBA-15 is added, and ultrasonic dispersion is uniform.
(2) The ultrasonic dispersion liquid in the step (1) is placed on a magnetic stirrer to be stirred, and after the solvent is completely volatilized, the ultrasonic dispersion liquid is transferred into a blast drying box to be dried for 24 hours at 60 ℃.
(3) And (3) placing the completely dried sample in the step (2) in a tube furnace, programming to 400 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, and keeping the temperature for 4 hours.
(4) After the constant temperature in the step (3) is finished, the argon atmosphere is replaced by a hydrogen-argon mixed atmosphere containing 10% of hydrogen, and the temperature is increased from 400 ℃ to 900 ℃ at a programmed temperature increasing rate of 10 ℃/min, and the temperature is kept constant for 2 hours.
(5) The sample obtained in (4) was treated with a 10% strength hydrofluoric acid solution for 6 hours. After the treatment is finished, the solution is filtered by suction, and is washed with water and ethanol for a plurality of times until the filtrate is neutral.
(6) And (3) placing the washed sample in the step (5) in a blast drying oven for drying for 12 hours to obtain the molybdenum disulfide/carbon composite material.
The scanning electron microscope of the material shows that the material well maintains the structure of the template SBA-15, and the mesoporous structure existing inside the material can be observed through the cross section of the material (see figure 1). The transmission electron microscope chart of the material shows that obvious molybdenum disulfide lattice stripes exist in the mesoporous molybdenum disulfide/carbon composite material (see figure 2).
Example 2
The molybdenum disulfide/carbon composite material was prepared as follows.
(1) 300mg of sodium molybdate, 600mg of thiourea and 200mg of sucrose are sequentially stirred and dissolved in 20mL of deionized water, 1g of template SBA-15 is added, and ultrasonic dispersion is uniform.
(2) The ultrasonic dispersion liquid in the step (1) is placed on a magnetic stirrer to be stirred, and after the solvent is completely volatilized, the ultrasonic dispersion liquid is transferred into a blast drying box to be dried for 24 hours at 60 ℃.
(3) And (3) placing the completely dried sample in the step (2) in a tube furnace, programming to 400 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, and keeping the temperature for 4 hours.
(4) After the constant temperature in the step (3) is finished, the argon atmosphere is replaced by a hydrogen-argon mixed atmosphere containing 10% of hydrogen, and the temperature is increased from 400 ℃ to 900 ℃ at a programmed temperature increasing rate of 10 ℃/min, and the temperature is kept constant for 2 hours.
(5) The sample obtained in (4) was treated with a 10% strength hydrofluoric acid solution for 6 hours. After the treatment is finished, the solution is filtered by suction, and is washed with water and ethanol for a plurality of times until the filtrate is neutral.
(6) And (3) placing the washed sample in the step (5) in a blast drying oven for drying for 12 hours to obtain the molybdenum disulfide/carbon composite material.
Example 3
The molybdenum disulfide/carbon composite material was prepared as follows.
(1) 250mg of sodium molybdate, 350mg of thiourea and 125mg of dopamine hydrochloride are sequentially stirred and dissolved in 20mL of deionized water, 1.5g of template SBA-15 is added, and ultrasonic dispersion is uniform.
(2) The ultrasonic dispersion liquid in the step (1) is placed on a magnetic stirrer to be stirred, and after the solvent is completely volatilized, the ultrasonic dispersion liquid is transferred into a blast drying box to be dried for 24 hours at 60 ℃.
(3) And (3) placing the completely dried sample in the step (2) in a tube furnace, programming to 500 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, and keeping the temperature for 2 hours.
(4) After the constant temperature in the step (3) is finished, the argon atmosphere is replaced by a hydrogen-argon mixed atmosphere containing 10% of hydrogen, and the temperature is increased from 500 ℃ to 800 ℃ at a programmed temperature increasing rate of 10 ℃/min, and the temperature is kept constant for 2 hours.
(5) The sample obtained in (4) was treated with a 10% strength hydrofluoric acid solution for 6 hours. After the treatment is finished, the solution is filtered by suction, and is washed with water and ethanol for a plurality of times until the filtrate is neutral.
(6) And (3) placing the washed sample in the step (5) in a blast drying oven for drying for 12 hours to obtain the molybdenum disulfide/carbon composite material.
The high resolution scanning electron microscopy image of the material shows that the material well replicates the tunnel structure of SBA-15 (see figure 6).
Example 4
The molybdenum disulfide/carbon composite material was prepared as follows.
(1) 250mg of sodium molybdate, 350mg of thiourea and 250mg of dopamine hydrochloride are sequentially stirred and dissolved in 20mL of deionized water, 1.5g of template SBA-15 is added, and ultrasonic dispersion is uniform.
(2) The ultrasonic dispersion liquid in the step (1) is placed on a magnetic stirrer to be stirred, and after the solvent is completely volatilized, the ultrasonic dispersion liquid is transferred into a blast drying box to be dried for 24 hours at 60 ℃.
(3) And (3) placing the completely dried sample in the step (2) in a tube furnace, programming to be at the temperature of 500 ℃ at the temperature rising rate of 5 ℃ for 2 hours under the argon atmosphere, and keeping the temperature constant.
(4) After the constant temperature in the step (3) is finished, the argon atmosphere is replaced by a hydrogen-argon mixed atmosphere containing 10% of hydrogen, and the temperature is increased from 500 ℃ to 800 ℃ at a programmed temperature increasing rate of 10 ℃/min, and the temperature is kept constant for 2 hours.
(5) The sample obtained in (4) was treated with a 10% strength hydrofluoric acid solution for 6 hours. After the treatment is finished, the solution is filtered by suction, and is washed with water and ethanol for a plurality of times until the filtrate is neutral.
(6) And (3) placing the washed sample in the step (5) in a blast drying oven for drying for 12 hours to obtain the molybdenum disulfide/carbon composite material.
Example 5
The molybdenum disulfide/carbon composite material was prepared as follows.
(1) 250mg of sodium molybdate, 350mg of thiourea and 375mg of dopamine hydrochloride are sequentially stirred and dissolved in 20mL of deionized water, 1.5g of template SBA-15 is added, and ultrasonic dispersion is uniform.
(2) The ultrasonic dispersion liquid in the step (1) is placed on a magnetic stirrer to be stirred, and after the solvent is completely volatilized, the ultrasonic dispersion liquid is transferred into a blast drying box to be dried for 24 hours at 60 ℃.
(3) And (3) placing the completely dried sample in the step (2) in a tube furnace, programming to 500 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, and keeping the temperature for 2 hours.
(4) After the constant temperature in the step (3) is finished, the argon atmosphere is replaced by a hydrogen-argon mixed atmosphere containing 10% of hydrogen, and the temperature is increased from 500 ℃ to 800 ℃ at a programmed temperature increasing rate of 10 ℃/min, and the temperature is kept constant for 2 hours.
(5) The sample obtained in (4) was treated with a 10% strength hydrofluoric acid solution for 6 hours. After the treatment is finished, the solution is filtered by suction, and is washed with water and ethanol for a plurality of times until the filtrate is neutral.
(6) And (3) placing the washed sample in the step (5) in a blast drying oven for drying for 12 hours to obtain the molybdenum disulfide/carbon composite material.
Comparative example 1
The molybdenum disulfide/carbon composite material was prepared as follows.
(1) 600mg of sucrose is stirred and dissolved in 20mL of water, 375 mu L of concentrated sulfuric acid is added, after stirring uniformly, 400mg of SBA-15 is added into the solution and stirred to be uniform paste, the paste is placed in an oven, the temperature is raised to 100 ℃ at a programmed temperature rise rate of 10 ℃/min, the temperature is kept for 6 hours, after the temperature is kept constant, the temperature is kept at 160 ℃ and the temperature is kept for 2 hours, and a precursor mixture is obtained.
(2) Under the protection of inert atmosphere, heating the precursor mixture in the step (1) to 400 ℃ at a temperature programming rate of 5 ℃/min, then keeping the temperature for 4 hours, and further heating to 900 ℃ and keeping the temperature for 2 hours to obtain the composite of SBA-15 and carbon.
(3) 1.1g of ammonium molybdate tetrahydrate was dissolved in 20mL of water with stirring, and 600mg of the complex of (2) was added to the solution and dispersed uniformly by ultrasonic. Finally, the homogeneous dispersion is stirred to dryness at room temperature and further dried in an oven.
(4) Mixing the sample of (3) with 10mL of CS 2 Transferring the mixture into a reaction kettle, heating to 400 ℃ at a programmed heating rate of 5 ℃/min and keeping the temperature for 4 hours.
(5) And (3) treating the sample in the step (4) by using 10% hydrofluoric acid solution for 6 hours, after the treatment is finished, carrying out suction filtration, washing the filtrate to be neutral by using water and ethanol, and drying the filtrate at 80 ℃ for 12 hours to obtain a final product.
The comparative example prepares a molybdenum disulfide/carbon composite material by first synthesizing a carbon skeleton and then growing molybdenum disulfide on the carbon surface. Performance test data (see fig. 12) indicate that the composite material is not only low in reversible capacity but also exhibits poor cycling stability over long periods of time. This comparison demonstrates that preparing a composite by simple molybdenum disulfide growth on a carbon backbone does not improve the performance of the material well, and also demonstrates the importance of excellent in situ recombination of molybdenum disulfide and carbon.
Application example 1
The molybdenum disulfide/carbon composite material obtained in example 1 was used in a sodium ion battery system to examine the electrochemical performance of the material as a battery negative electrode material.
1. Preparation of a battery:
sequentially weighing an active material, acetylene black and a binder (PVDF) according to a mass ratio of 7:2:1, forming uniform active material slurry in 1-methyl-2-pyrrolidone with proper dosage, coating the active material slurry on a copper foil by using a coating machine, and then placing the copper foil in an oven to dry at 60 ℃ for 24 hours. In an argon filled glove box (ensuring that the water oxygen values are all below 0.1 ppm), sodium metal was used as the counter electrode, whatman glass fiber was used as the separator, 1.0M NaCF 3 SO 3 A CR2016 battery was assembled by dissolving diglyme as an electrolyte.
2. Electrochemical performance evaluation:
the constant-current charge and discharge performance test is carried out on the battery by using a Xinwei battery test system, the test voltage range is 0.4-3V, and the current density is 100 mA.g -1 The cyclic stability of the material. All cells were tested in an incubator at 30 ℃.
3. Discussion of results:
the molybdenum disulfide/carbon composite material in example 1 had a current density of 100 mA.g in the voltage range of 0.4 to 3V -1 Exhibits good cycle stability even after 120 cycles of charge and dischargeThe composite material still has 200 mAh.g -1 Is shown (see fig. 3).
Application example 2
The molybdenum disulfide/carbon composite material obtained in example 2 was used in a sodium ion battery system to examine the electrochemical performance of the material as a battery negative electrode material.
1. Preparation of a battery:
sequentially weighing an active material, acetylene black and a binder (PVDF) according to a mass ratio of 7:2:1, forming uniform active material slurry in 1-methyl-2-pyrrolidone with proper dosage, coating the active material slurry on a copper foil by using a coating machine, and then placing the copper foil in an oven to dry at 60 ℃ for 24 hours. In an argon filled glove box (ensuring that the water oxygen values are all below 0.1 ppm), metallic sodium was used as the counter electrode, whatman glass fiber was used as the separator, 1.0M NaClO 4 A CR2016 battery was assembled by dissolving a mixed solution of ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1 as an electrolyte.
2. Electrochemical performance evaluation:
the constant-current charge and discharge performance test is carried out on the battery by using a Xinwei battery test system, the test voltage range is 0.01-3V, and the current densities are respectively 500 mA.g -1 And 1 A.g -1 The cycling stability of the electrode material. All cells were tested in an incubator at 30 ℃.
3. Discussion of results:
the molybdenum disulfide/carbon composite material in example 2 had a current density of 500 mA.g in the voltage range of 0.01 to 3V -1 325 mAh.g still remains after up to 140 times of cyclic charge and discharge -1 Is shown (see fig. 4). Even at higher current densities of 1A g -1 Under the condition, the material still has 295 mAh.g -1 Is shown (see fig. 5).
Application example 3
The molybdenum disulfide/carbon composite material obtained in example 3 was used in a sodium ion battery system to examine the electrochemical performance of the material as a battery negative electrode material.
1. Preparation of a battery:
sequentially weighing active materials according to the mass ratio of 7:2:1The material, acetylene black and binder (PVDF) were formed into a uniform active material slurry in a proper dose of 1-methyl-2-pyrrolidone, and the active material slurry was coated on copper foil using a coater, and then dried in an oven at 60 ℃ for 24 hours. In an argon filled glove box (ensuring that the water oxygen values are all below 0.1 ppm), metallic sodium was used as the counter electrode, whatman glass fiber was used as the septum, 1.0M NaPF 6 A CR2016 battery was assembled by dissolving propylene carbonate and adding 5% fluoroethylene carbonate as an electrolyte.
2. Electrochemical performance evaluation:
the constant-current charge and discharge performance test is carried out on the battery by using a Xinwei battery test system, the test voltage range is 0.01-3V, and the current density is 200 mA.g respectively -1 ，1A·g -1 And 2 A.g -1 The cycling stability of the electrode material. And testing the multiplying power performance of the electrode material under the same voltage range. All cells were tested in an incubator at 30 ℃.
3. Discussion of results:
the molybdenum disulfide/carbon composite material in example 3 was found to be at 200 mA.g -1 Has a current density of up to 875 mAh.g -1 The material shows good cycle stability performance with an increase in cycle number, and even after 100 cycles of charge-discharge cycle, the material has a specific discharge capacity of about 480 mAh.g -1 Is shown (see fig. 7). The material also exhibits excellent rate performance when it is at 100 mA.g, respectively -1 、200mA·g -1 、500mA·g -1 、1000mA·g -1 And 2000 mA.g -1 After 10 cycles of current density of (2) the current density was returned to 100 mA.g -1 The material still has the temperature of 500 mAh.g -1 And maintains good cycling stability (see figure 8). At a high current density of 1 A.g -1 Under the test, the material still keeps up to 324 mAh.g after being charged and discharged for 1000 times -1 Is shown (see fig. 9). The material has higher current density of 2A.g -1 Still maintains good circulation stability, and after 1000 circles of circulation test, 262 mAh.g -1 Is shown (see fig. 10).
Application example 4
The molybdenum disulfide/carbon composite materials obtained in example 4 and example 5 were used in a sodium ion battery system to examine electrochemical properties when they were used as a battery negative electrode material.
1. Preparation of a battery:
sequentially weighing an active material, acetylene black and a binder (PVDF) according to a mass ratio of 7:2:1, forming uniform active material slurry in 1-methyl-2-pyrrolidone with proper dosage, coating the active material slurry on a copper foil by using a coating machine, and then placing the copper foil in an oven to dry at 60 ℃ for 24 hours. In an argon filled glove box (ensuring that the water oxygen values are all below 0.1 ppm), metallic sodium was used as the counter electrode, whatman glass fiber was used as the septum, 1.0M NaPF 6 A CR2016 battery was assembled by dissolving propylene carbonate and adding 5% fluoroethylene carbonate as an electrolyte.
2. Electrochemical performance evaluation:
the constant-current charge and discharge performance test is carried out on the battery by using a Xinwei battery test system, the test voltage range is 0.01-3V, and the current density is 1 A.g -1 The cycling stability of the electrode material. All cells were tested in an incubator at 30 ℃.
3. Discussion of results:
the materials prepared in example 4 and example 5 were found to be 1 A.g -1 Exhibits good cycling stability at all current densities. Wherein the material of example 4 has a specific value of about 245 mAh.g -1 The material of example 5 has a reversible specific capacity of about 150 mAh.g -1 Is a reversible specific capacity of (a). Comparing the performance of the materials of example 3, example 4 and example 5 under the same test conditions, it was found that the specific capacity of the materials showed regular changes with the change of the dopamine hydrochloride content in the precursor (see fig. 11). Therefore, the change of the carbon content in the molybdenum disulfide/carbon composite material has an important influence on the performance of the material, and the improvement of the performance of the material is significant by introducing the proper carbon content into the composite material.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. The preparation method of the molybdenum disulfide/carbon composite material is characterized by comprising the following steps of:
(1) Co-depositing molybdenum salt, a sulfur source and a carbon source on the surface of SBA-15 by using a co-precipitation method to obtain a precursor mixture;
(2) Heating the precursor mixture obtained in the step (1) to the end temperature of 400-550 ℃ by adopting a temperature programming treatment under an inert atmosphere, and then keeping the temperature constant;
(3) Heating the product obtained in the step (2) to the end temperature by adopting temperature programming treatment under the reducing atmosphere, and then keeping the temperature constant; the end point temperature is higher than that of the step (2); the reducing atmosphere is a mixed atmosphere of hydrogen and inert atmosphere, and the hydrogen accounts for 5-20% of the mixed atmosphere; the end point temperature is 700-900 ℃;
(4) And (3) carrying out acid treatment on the product obtained in the step (3), and washing and drying to obtain the molybdenum disulfide/carbon composite material.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the mass ratio of the molybdenum salt to the sulfur source to the carbon source is 1:1-3:0.1-2.
3. The method of manufacturing according to claim 1, characterized in that: in the step (1), the molybdenum salt is one of ammonium tetrathiomolybdate, ammonium molybdate, ammonium phosphomolybdate, sodium phosphomolybdate or sodium molybdate; the sulfur source is one of thiourea, sodium sulfide, potassium sulfide, ammonium sulfide or thioacetamide; the carbon source is one of soluble starch, sucrose, anhydrous glucose, dopamine hydrochloride, melamine or dicyandiamide.
4. The method of manufacturing according to claim 1, characterized in that: in the step (1), the codeposition temperature is 60-100 ℃ and the codeposition time is 12-24 h.
5. The method of manufacturing according to claim 1, wherein: in the step (2), the inert atmosphere is one of argon, nitrogen or helium, and the flow rate is 50-80 mL/min; the temperature programming treatment is to heat at a temperature rising rate of 1-10 ℃/min to a final point temperature of 400-550 ℃ and then to keep the constant temperature for 2-5 h.
6. The method of manufacturing according to claim 1, wherein: and (3) heating the temperature programming treatment in the step (3) at a heating rate of 5-15 ℃/min to a finishing temperature of 700-900 ℃ and then keeping the temperature for 0.5-2.5 h.
7. The method of manufacturing according to claim 1, wherein: in the step (4), the acid in the acid treatment is hydrofluoric acid solution with the concentration of 5-20%, and the acid treatment time is 6-12 h; the drying temperature is 60-80 ℃ and the drying time is 12-24 h.
8. A molybdenum disulfide/carbon composite material obtained by the preparation method according to any one of claims 1 to 7, which has a mesoporous structure.
9. Use of the molybdenum disulfide/carbon composite material of claim 8 as a negative electrode material in a sodium ion battery system.
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| CN106299304A (en) * | 2016-09-27 | 2017-01-04 | 华南理工大学 | A kind of carbon cladding molybdenum sulfide composite and preparation method and application and a kind of sodium-ion battery |
| CN106816602A (en) * | 2017-03-28 | 2017-06-09 | 中南大学 | A kind of two selenium（Sulphur）Change molybdenum（Tungsten）/ carbon composite and its preparation method and application |
| CN110137475A (en) * | 2019-05-24 | 2019-08-16 | 西南大学 | A kind of hollow carbon sphere/molybdenum disulfide bipolarity composite material and preparation method and application |
| CN110571436A (en) * | 2019-08-23 | 2019-12-13 | 天津大学 | Preparation method of three-dimensional porous carbon loaded flaky molybdenum disulfide current collector for lithium metal cathode |
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