CN113044814A - Molybdenum selenide nano-microspheres and preparation method thereof, electrode and aluminum ion battery - Google Patents
Molybdenum selenide nano-microspheres and preparation method thereof, electrode and aluminum ion battery Download PDFInfo
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- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000004005 microsphere Substances 0.000 title claims abstract description 78
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011229 interlayer Substances 0.000 claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 58
- -1 aluminum ion Chemical class 0.000 claims description 51
- 229910052711 selenium Inorganic materials 0.000 claims description 51
- 239000011669 selenium Substances 0.000 claims description 51
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 49
- 229910052750 molybdenum Inorganic materials 0.000 claims description 43
- 239000011733 molybdenum Substances 0.000 claims description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 22
- 238000004729 solvothermal method Methods 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical group O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002077 nanosphere Substances 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- RCMWGBKVFBTLCW-UHFFFAOYSA-N barium(2+);dioxido(dioxo)molybdenum Chemical compound [Ba+2].[O-][Mo]([O-])(=O)=O RCMWGBKVFBTLCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000009830 intercalation Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 18
- 238000003756 stirring Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000012300 argon atmosphere Substances 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 239000006258 conductive agent Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000002608 ionic liquid Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- DORQJBTVNDGTEY-UHFFFAOYSA-N selanylidenemolybdenum Chemical group [Se].[Mo] DORQJBTVNDGTEY-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/32—Spheres
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2006/40—Electric properties
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- 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
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Abstract
The invention provides a molybdenum selenide nano microsphere, a preparation method thereof, an electrode and an aluminum ion battery, and relates to the technical field of aluminum ion batteries. The molybdenum selenide nano microsphere provided by the invention is a microsphere formed by stacking nano sheets, and the interlayer spacing is 0.60-0.67 nm. In the invention, the molybdenum selenide nano-microspheres have larger interlayer spacing and weaker acting force between layers, so that Al is ensured3+Can realize better reversible de-intercalation and obtain better electrochemical performance.
Description
Technical Field
The invention relates to the technical field of aluminum ion batteries, in particular to a molybdenum selenide nano microsphere, a preparation method thereof, an electrode and an aluminum ion battery.
Background
Currently, lithium ion batteries are in extremely widespread commercial use. However, the shortage of lithium resources cannot satisfy the future application of large-scale energy storage equipment, and the defects of flammability and toxicity of lithium metal and volatility of lithium ion battery electrolyte cause the lithium ion battery to be combinedIs not a sustainable energy storage direction. In recent years, other rechargeable metal ion batteries, such as sodium, potassium, calcium, magnesium and aluminum plasma batteries, have been considered as viable alternatives to lithium ions. Among them, aluminum is the most abundant element in earth crust and is widely distributed in the world. Aluminum ion batteries have a high volumetric capacity (8040mAh cm) compared to lithium ion batteries-3) And gravimetric capacity (2980mAh g-1) And the cost is low, so that the aluminum ion battery becomes the next generation energy storage device with great development potential. In addition, the ionic liquid serving as the electrolyte of the aluminum ion battery has the advantages of being difficult to volatilize, low in flammability, low in toxicity and the like, so that the safety performance of the aluminum ion battery is obviously improved.
Aluminum Ion Batteries (AIBs) are of great interest for their unique and excellent electrochemical properties. The research on the positive electrode material of the aluminum ion battery is mainly focused on graphite materials, transition metal compounds, non-stoichiometric compounds, and the like. Compared with the lithium ion battery, the battery reaction of the aluminum ion battery mainly comprises intercalation reaction (graphite material, the ion participating in the reaction is AlCl4 -) And intercalation/phase transition reaction (transition metal compound, the ion participating in the reaction being Al3+)。Al3+With AlCl4 -Al with the same number of ions inserted than with more charge3+The theoretical specific capacity produced by intercalation is AlCl4 -Three times that of the original. Therefore, as a positive electrode material of an aluminum ion battery, the transition metal compound has a higher specific discharge capacity than a graphite material, and is considered as a novel material of an aluminum ion battery with potential energy storage.
Disclosure of Invention
The invention aims to provide a molybdenum selenide nano microsphere, a preparation method thereof, an electrode and an aluminum ion battery.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a molybdenum selenide nano microsphere, which is a microsphere formed by stacking nano sheets, and the interlayer spacing is 0.60-0.67 nm.
Preferably, the particle size of the molybdenum selenide nano-microspheres is 300-500 nm.
The invention provides a preparation method of molybdenum selenide nano microspheres in the technical scheme, which comprises the following steps:
mixing a selenium source and a reducing agent to obtain a selenium source solution;
mixing a molybdenum source and dimethylformamide to obtain a molybdenum source solution;
mixing the selenium source solution and the molybdenum source solution, and carrying out solvothermal reaction to obtain molybdenum selenide powder;
and carrying out heat treatment on the molybdenum selenide powder to obtain the molybdenum selenide nano-microspheres.
Preferably, the selenium source is selenium dioxide and/or elemental selenium; the reducing agent comprises sodium borohydride and/or hydrazine hydrate; the molar ratio of the reducing agent to selenium in the selenium source is 40-125: 1.
Preferably, the molybdenum source comprises one or more of ammonium molybdate, sodium molybdate and barium molybdate; the molar ratio of the dimethyl formamide to the molybdenum element in the molybdenum source is 0.5-5: 1.
Preferably, the molar ratio of the selenium element in the selenium source to the molybdenum element in the molybdenum source is 1.5-3.0: 1.
Preferably, the temperature of the solvothermal reaction is 140-220 ℃ and the time is 6-16 h.
Preferably, the temperature of the heat treatment is 300-800 ℃ and the time is 2-8 h.
The invention provides an electrode, which comprises the molybdenum selenide nano-microspheres or the molybdenum selenide nano-microspheres prepared by the preparation method in the technical scheme.
The invention provides an aluminum ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the positive electrode is the electrode in the technical scheme.
The invention provides a molybdenum selenide nano microsphere, which is a microsphere formed by stacking nano sheets, and the interlayer spacing is 0.60-0.67 nm. In the invention, the molybdenum selenide nano-microspheres have larger sizesThe layer spacing of (1) and the acting force between layers is weak, so that Al3+Can realize better reversible de-intercalation and obtain better electrochemical performance.
The invention also provides a preparation method of the molybdenum selenide nano microsphere, which is simple, low in cost and suitable for industrial production.
The aluminum ion battery assembled by taking the molybdenum selenide nano microspheres as the active components of the anode material has higher specific capacity and good cycling stability. The embodiment result shows that under the voltage range of 0.1-2.0V and the multiplying power of 0.1C, the first discharge specific capacity is up to 241.3mAh/g, the first charge specific capacity is up to 267.9mAh/g, under the current density of 50mA/g (0.25C), the discharge specific capacity is still up to 43.3mAh/g after 500 cycles, and the good cycle stability is shown.
Drawings
FIG. 1 is an XRD diffractogram of the molybdenum selenide nanospheres prepared in example 1;
FIG. 2 is an SEM image of the molybdenum selenide nanospheres prepared in example 1;
FIG. 3 is a TEM image of the molybdenum selenide nanospheres prepared in example 1;
FIG. 4 is a charge-discharge curve diagram of an aluminum ion battery assembled by the molybdenum selenide nano-microspheres obtained in example 1;
fig. 5 is a graph of the cycle performance of an aluminum ion battery assembled by the molybdenum selenide nano-microspheres obtained in example 1.
Detailed Description
The invention provides a molybdenum selenide nano microsphere, which is a microsphere formed by stacking nano sheets, and the interlayer spacing is 0.60-0.67 nm. In the invention, the interlayer spacing of the molybdenum selenide nano microspheres is preferably 0.62-0.65 nm; the thickness of the nano-flake for forming the microsphere is preferably 0.03-0.15 nm.
In the invention, the particle size of the molybdenum selenide nano-microspheres is preferably 300-500 nm. In the invention, the molybdenum selenide nano-microspheres are pure phases.
The invention also provides a preparation method of the molybdenum selenide nano microsphere in the technical scheme, which comprises the following steps:
mixing a selenium source and a reducing agent to obtain a selenium source solution;
mixing a molybdenum source and dimethylformamide to obtain a molybdenum source solution;
mixing the selenium source solution and the molybdenum source solution, and carrying out solvothermal reaction to obtain molybdenum selenide powder;
and carrying out heat treatment on the molybdenum selenide powder to obtain the molybdenum selenide nano-microspheres.
The invention mixes the selenium source and the reducing agent to obtain the selenium source solution. In the invention, the selenium source is preferably selenium dioxide and/or elemental selenium; the reducing agent preferably comprises sodium borohydride and/or hydrazine hydrate; the molar ratio of the reducing agent to the selenium element in the selenium source is preferably 40-125: 1, and more preferably 60-110: 1. In the present invention, the mixing is preferably performed under sealed conditions; the mixing temperature is preferably 30-65 ℃, and more preferably 50-60 ℃; the mixing is preferably carried out under stirring. In the invention, the reducing agent can fully reduce the selenium source into elemental selenium, and pure-phase molybdenum selenide is obtained by combining with subsequent reaction.
In a specific embodiment of the present invention, when the reducing agent is sodium borohydride, preferably, the sodium borohydride is dissolved in water first to obtain a sodium borohydride aqueous solution; and then mixing the selenium source with the sodium borohydride aqueous solution to obtain a selenium source solution. In the present invention, the concentration of the aqueous sodium borohydride solution is preferably 5 mol/L.
In a specific embodiment of the present invention, the mass concentration of hydrazine hydrate is preferably 80%.
In the invention, a molybdenum source and dimethylformamide are mixed to obtain a molybdenum source solution. In the present invention, the molybdenum source preferably includes one or more of ammonium molybdate, sodium molybdate and barium molybdate; the molar ratio of the dimethylformamide to the molybdenum element in the molybdenum source is preferably 1: 2-5: 1, and more preferably 3: 2-4: 1. The invention takes the dimethylformamide as the solvent to dissolve the molybdenum source, is safe and low in toxicity, and is easy to be mutually dissolved with other organic solvents. In the invention, the mixing is preferably carried out under the ultrasonic condition, and the power of the ultrasonic is preferably 100-600W, more preferably 200-500W; the time of the ultrasonic treatment is preferably 0.3-4 h, and more preferably 1-3 h. Under the ultrasonic condition, the invention is more beneficial to fully dispersing the molybdenum source to form uniform molybdenum source solution.
After the selenium source solution and the molybdenum source solution are obtained, the selenium source solution and the molybdenum source solution are mixed for solvothermal reaction to obtain molybdenum selenide powder. In the invention, the molar ratio of the selenium element in the selenium source to the molybdenum element in the molybdenum source is preferably 2: 3-3: 1, and more preferably 1: 1-5: 2. The molybdenum selenide nano microspheres prepared according to the proportion have optimal performance, and molybdenum selenide with different shapes can be obtained by adjusting the proportion of the selenium source and the molybdenum source; if the ratio of the selenium source to the molybdenum source is too large or too small, lamellar petal-shaped microspheres with well dispersed morphology are difficult to obtain.
In the present invention, the method of mixing the selenium source solution and the molybdenum source solution preferably includes: and dropwise adding the selenium source solution into the molybdenum source solution, and heating and stirring. The invention has no special requirement on the specific dropping speed and can be added dropwise. In the invention, the heating and stirring temperature is preferably 30-80 ℃, and more preferably 45-60 ℃; the heating and stirring time is preferably 30-40 min.
In the invention, the temperature of the solvothermal reaction is preferably 140-220 ℃, and more preferably 180-200 ℃; the solvothermal reaction time is preferably 6-16 h, and more preferably 12-14 h. In the invention, the selenium source and the molybdenum source are subjected to oxidation-reduction reaction in the process of solvothermal reaction to obtain molybdenum selenide; the invention controls the temperature and time of the solvothermal reaction, is more beneficial to the formation and growth of molybdenum selenide cores, and prepares the molybdenum selenide nano-microspheres with excellent electrochemical performance.
According to the invention, preferably, after the solvothermal reaction, the obtained solid product is sequentially washed and dried to obtain molybdenum selenide powder. In the invention, the washing mode is preferably that deionized water and ethanol are alternately washed; the number of washing is preferably 2 or more. In the invention, the drying temperature is preferably 60-100 ℃, and more preferably 70-80 ℃; the drying time is preferably 6-16 h, and more preferably 8-14 h. The invention removes water-soluble impurities by washing.
In the invention, the molybdenum selenide powder is black powder.
After molybdenum selenide powder is obtained, the molybdenum selenide powder is subjected to heat treatment to obtain the molybdenum selenide nano-microspheres. In the invention, the temperature of the heat treatment is preferably 300-800 ℃, and more preferably 500-700 ℃; the time of the heat treatment is preferably 2-8 h, and more preferably 3-6 h. In the present invention, the heat treatment is preferably performed in a protective atmosphere, and particularly preferably in a nitrogen atmosphere or an argon atmosphere. In the heat treatment process, the crystallinity of the molybdenum selenide can be improved.
The invention also provides an electrode which comprises the molybdenum selenide nano-microspheres or the molybdenum selenide nano-microspheres prepared by the preparation method in the technical scheme. In the present invention, the electrode preferably comprises a current collector, and a conductive agent, a binder and molybdenum selenide nano microspheres coated on the surface of the current collector. In the present invention, the current collector preferably includes molybdenum foil, tantalum foil, or carbon paper; the thickness of the current collector is preferably 20 μm; the conductive agent preferably includes acetylene black; the binder preferably comprises polytetrafluoroethylene. In the invention, based on the total mass of the conductive agent, the binder and the molybdenum selenide nano microspheres, the addition amount of the conductive agent is preferably 5-15%, the addition amount of the binder is preferably 15-45%, and the addition amount of the molybdenum selenide nano microspheres is preferably 60-80%.
In a specific embodiment of the present invention, the method for preparing the electrode preferably comprises the steps of: fully grinding the molybdenum selenide nano microspheres, the conductive agent and the binder, and then dispersing in absolute ethyl alcohol to obtain slurry; and (3) carrying out slurry drawing on the surface of the current collector by using the slurry to prepare the electrode. In the invention, the concentration of the slurry is preferably 10-25 mol/L, and more preferably 15-20 mol/L.
The invention also provides an aluminum ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the positive electrode is the electrode in the technical scheme. In the present invention, the anode preferably includes a simple substance of aluminum or an aluminum alloy; the membrane preferably comprises a glass fiber membrane, a polyethylene membrane or a polypropylene membrane; the glass fiber membrane is preferably Whatman GF/D glass fiber; the electrolyte preferably comprises an ionic liquid consisting of anhydrous aluminum chloride and 1-ethyl-3-methylimidazole hydrochloride. In the present invention, the molar ratio of anhydrous aluminum chloride to 1-ethyl-3-methylimidazole hydrochloride in the electrolyte is preferably 1.3: 1; the total concentration of anhydrous aluminum chloride and 1-ethyl-3-methylimidazole hydrochloride in the electrolyte is preferably 1.0 mol/L. In the invention, the ionic liquid used as the electrolyte of the aluminum ion battery has the advantages of non-flammability, non-volatility, no pollution and the like, and compared with the traditional lithium ion battery, the safety performance is obviously improved.
In the present invention, the assembly of the aluminum ion battery is preferably performed in an argon atmosphere glove box, and the present invention has no special requirement on the specific method of the assembly, and the assembly method known to those skilled in the art can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 300mg of elemental selenium into 67.5mL of hydrazine hydrate, sealing, heating and stirring at 50 ℃ until a selenium source is dissolved to obtain a selenium source solution;
adding 46mg of sodium molybdate into 10mL of dimethylformamide, and ultrasonically dispersing for 40min at 400W to obtain a molybdenum source solution;
dropwise adding 10mL of the selenium source solution into the molybdenum source solution, continuously stirring for 40min at 30 ℃, and then carrying out solvothermal reaction for 12h at 180 ℃; respectively and alternately washing the obtained solid product with deionized water and ethanol for 3 times, and drying at 80 ℃ for 14h to obtain black molybdenum selenide powder;
and carrying out heat treatment on the molybdenum selenide powder for 2 hours at 600 ℃ in an argon atmosphere to obtain the molybdenum selenide nano-microspheres.
The XRD diffractogram of the molybdenum selenide nano-microspheres prepared in this example is shown in fig. 1, and as can be seen from fig. 1, the molybdenum selenide nano-microspheres are pure phases.
An SEM image of the molybdenum selenide nano-microspheres prepared in this embodiment is shown in fig. 2, and as can be seen from fig. 2, the molybdenum selenide nano-microspheres are microspheres formed by stacking nano-sheets, and have a particle size of 300 to 500 nm.
A TEM image of the molybdenum selenide nano microsphere prepared in this example is shown in fig. 3, and as can be seen from fig. 3, the interlayer distance of the molybdenum selenide nano microsphere is 0.65 nm.
Assembling the battery: weighing 0.06g of the molybdenum selenide nano-microspheres prepared in the embodiment, adding 0.03g of acetylene black (SP) as a conductive agent and 0.01g of Polytetrafluoroethylene (PTFE) as a binder, fully grinding, adding 1.5mL of absolute ethanol for dispersing and mixing, uniformly mixing, pulling slurry on a molybdenum foil with the thickness of 20 mu m to prepare a positive plate, taking an aluminum sheet as a negative electrode, taking Whatman GF/D glass fiber as a diaphragm and 1.0mol/L of anhydrous aluminum chloride (AlCl) in an argon atmosphere glove box3) And 1-ethyl-3-methylimidazole hydrochloride ([ EMIm)]Cl) in a molar ratio of 1.3:1, assembling the soft package battery by taking the prepared ionic liquid as electrolyte; and testing the charging and discharging performance of the assembled aluminum ion battery under the voltage range of 0.01-2.0V.
The charge-discharge curve diagram of the aluminum ion battery assembled by the molybdenum selenide nano-microspheres prepared in the embodiment is shown in fig. 4, and the cycle performance diagram is shown in fig. 5.
Through detection, under the multiplying power of 0.1C (1C is 200mAh/g), the first discharge specific capacity of the assembled aluminum ion battery is up to 241.3mAh/g, the first charge specific capacity is up to 267.9mAh/g, and under the multiplying power of 0.25C (1C is 200mAh/g), the discharge specific capacity of the assembled aluminum ion battery is still 43.3mAh/g after circulating for 500 circles, which shows that the aluminum ion battery assembled by the molybdenum selenide nano microspheres provided by the invention has higher specific capacity and better circulation stability.
Example 2
Adding 350mg of elemental selenium into 75.6mL of 5mol/L sodium borohydride aqueous solution, sealing, heating and stirring at 60 ℃ until a selenium source is dissolved to obtain a selenium source solution;
adding 64mg of ammonium molybdate into 30mL of dimethylformamide, and ultrasonically dispersing for 50min at 600W to obtain a molybdenum source solution;
dropwise adding 30mL of the selenium source solution into the molybdenum source solution, continuously stirring for 40min at 50 ℃, and then carrying out solvothermal reaction for 14h at 180 ℃; respectively and alternately washing the obtained solid product with deionized water and ethanol for 3 times, and drying at 70 ℃ for 14h to obtain black molybdenum selenide powder;
and carrying out heat treatment on the molybdenum selenide powder for 3 hours at the temperature of 500 ℃ in the argon atmosphere to obtain the molybdenum selenide nano-microspheres.
The molybdenum selenide nano-microspheres prepared by the embodiment are pure phases; the morphology is microspheres formed by stacking nano sheets, and the particle size is 300-500 nm; the interlayer spacing of the molybdenum selenide nano microspheres is 0.63 nm.
Assembling the battery: weighing 0.06g of the molybdenum selenide nano-microspheres prepared in the embodiment, adding 0.03g of acetylene black (SP) as a conductive agent and 0.01g of Polytetrafluoroethylene (PTFE) as a binder, fully grinding, adding 1.5mL of anhydrous ethanol for dispersing and mixing, uniformly mixing, then pulling slurry on tantalum foil with the thickness of 20 mu m to prepare a positive plate, taking aluminum as a negative electrode, taking a polyethylene diaphragm as a diaphragm and 1.0mol/L of anhydrous AlCl in an argon atmosphere glove box3And [ EMIm]Cl in a molar ratio of 1.3:1, assembling the soft package battery by taking the prepared ionic liquid as electrolyte; and testing the charging and discharging performance of the assembled aluminum ion battery under the voltage range of 0.01-2.0V.
Through detection, under the multiplying power of 0.1C (1C is 200mAh/g), the first discharge specific capacity of the assembled aluminum ion battery is up to 212.4mAh/g, the first charge specific capacity is up to 247.7mAh/g, and under the multiplying power of 0.25C (1C is 200mAh/g), the discharge specific capacity of the assembled aluminum ion battery is still 40.6mAh/g after 200 cycles of circulation.
Example 3
Adding 450mg of selenium dioxide into 100mL of 5mol/L sodium borohydride aqueous solution, sealing, heating and stirring at 55 ℃ until a selenium source is dissolved to obtain a selenium source solution;
adding 79mg of ammonium molybdate into 40mL of dimethylformamide, and ultrasonically dispersing for 3h at 200W to obtain a molybdenum source solution;
dropwise adding 40mL of the selenium source solution into the molybdenum source solution, continuously stirring for 30min at 60 ℃, and then carrying out solvothermal reaction for 12h at 200 ℃; respectively washing the obtained solid product with deionized water and ethanol for 3 times in a crossed manner, and drying at 75 ℃ for 12h to obtain black molybdenum selenide powder;
and carrying out heat treatment on the molybdenum selenide powder for 2 hours at 700 ℃ in an argon atmosphere to obtain the molybdenum selenide nano-microspheres.
The molybdenum selenide nano-microspheres prepared by the embodiment are pure phases; the morphology is microspheres formed by stacking nano sheets, and the particle size is 300-500 nm; the interlayer spacing of the molybdenum selenide nano microspheres is 0.62 nm.
Assembling the battery: weighing 0.06g of the molybdenum selenide nano-microspheres prepared in the embodiment, adding 0.03g of acetylene black (SP) as a conductive agent and 0.01g of Polytetrafluoroethylene (PTFE) as a binder, fully grinding, adding 1.5mL of absolute ethanol for dispersion and mixing, uniformly mixing, then pulling slurry on a molybdenum foil with the thickness of 20 mu m to prepare a positive plate, taking an aluminum sheet as a negative electrode, taking a polypropylene diaphragm as a diaphragm and 1.0mol/L of absolute AlCl in an argon atmosphere glove box3And [ EMIm]Cl in a molar ratio of 1.3:1, assembling the soft package battery by taking the prepared ionic liquid as electrolyte; and testing the charging and discharging performance of the assembled aluminum ion battery under the voltage range of 0.01-2.0V.
Through detection, under the multiplying power of 0.1C (1C is 200mAh/g), the first discharge specific capacity of the assembled aluminum ion battery is up to 197.3mAh/g, the first charge specific capacity is up to 234.6mAh/g, and under the multiplying power of 0.25C (1C is 200mAh/g), the discharge specific capacity of the assembled aluminum ion battery is still 39.7mAh/g after 200 cycles of circulation.
Example 4
Adding 320mg of elemental selenium into 75mL of hydrazine hydrate, sealing, heating and stirring at 55 ℃ until a selenium source is dissolved to obtain a selenium source solution;
adding 46mg of barium molybdate into 10mL of dimethylformamide, and ultrasonically dispersing for 3 hours at 300W to obtain a molybdenum source solution;
dropwise adding 8mL of the selenium source solution into the molybdenum source solution, continuously stirring for 30min at 80 ℃, and then carrying out solvothermal reaction for 14h at 190 ℃; respectively and alternately washing the obtained solid product with deionized water and ethanol for 3 times, and drying at 65 ℃ for 16h to obtain black molybdenum selenide powder;
and carrying out heat treatment on the molybdenum selenide powder for 4 hours at the temperature of 650 ℃ in the argon atmosphere to obtain the molybdenum selenide nano microspheres.
The molybdenum selenide nano-microspheres prepared by the embodiment are pure phases; the morphology is microspheres formed by stacking nano sheets, and the particle size is 300-500 nm; the interlayer spacing of the molybdenum selenide nano microspheres is 0.64 nm.
Assembling the battery: weighing 0.06g of the molybdenum selenide nano-microspheres prepared in the embodiment, adding 0.03g of acetylene black (SP) as a conductive agent and 0.01g of Polytetrafluoroethylene (PTFE) as a binder, fully grinding, adding 1.5mL of absolute ethanol for dispersing and mixing, uniformly mixing, then pulling slurry on carbon paper with the thickness of 20 mu m to prepare a positive plate, taking aluminum as a negative electrode, taking a polypropylene diaphragm as a diaphragm and 1.0mol/L of absolute AlCl in an argon atmosphere glove box3And [ EMIm]Cl in a molar ratio of 1.3:1, assembling the soft package battery by taking the prepared ionic liquid as electrolyte; and testing the charging and discharging performance of the assembled aluminum ion battery under the voltage range of 0.01-2.0V.
Through detection, under the multiplying power of 0.1C (1C is 200mAh/g), the first discharge specific capacity of the assembled aluminum ion battery is up to 239.3mAh/g, the first charge specific capacity is up to 253.4mAh/g, and under the multiplying power of 0.25C (1C is 200mAh/g), the discharge specific capacity of the assembled aluminum ion battery is still 41.5mAh/g after circulating for 400 circles, which shows that the aluminum ion battery assembled by the molybdenum selenide nano microspheres provided by the invention has higher specific capacity and better circulation stability.
Example 5
Adding 70mg of selenium dioxide into 75mL of hydrazine hydrate, sealing, heating and stirring at 65 ℃ until a selenium source is dissolved to obtain a selenium source solution;
adding 23mg of sodium molybdate into 12mL of dimethylformamide, and ultrasonically dispersing for 50min at 500W to obtain a molybdenum source solution;
dropwise adding 12mL of the selenium source solution into the molybdenum source solution, continuously stirring for 30min at 45 ℃, and then carrying out solvothermal reaction for 6h at 220 ℃; respectively and alternately washing the obtained solid product with deionized water and ethanol for 2 times, and drying at 80 ℃ for 12 hours to obtain black molybdenum selenide powder;
and carrying out heat treatment on the molybdenum selenide powder for 6 hours at 800 ℃ in an argon atmosphere to obtain the molybdenum selenide nano-microspheres.
The molybdenum selenide nano-microspheres prepared by the embodiment are pure phases; the morphology is microspheres formed by stacking nano sheets, and the particle size is 300-500 nm; the interlayer spacing of the molybdenum selenide nano microspheres is 0.63 nm.
Assembling the battery: weighing 0.06g of the molybdenum selenide nano-microspheres prepared in the embodiment, adding 0.03g of acetylene black (SP) as a conductive agent and 0.01g of Polytetrafluoroethylene (PTFE) as a binder, fully grinding, adding 1.5mL of absolute ethanol for dispersing and mixing, uniformly mixing, then pulling slurry on tantalum foil with the thickness of 20 mu m to prepare a positive plate, taking an aluminum sheet as a negative electrode, taking Whatman GF/D glass fiber as a diaphragm and 1.0mol/L of absolute AlCl in an argon atmosphere glove box3And [ EMIm]Cl in a molar ratio of 1.3:1, assembling the soft package battery by taking the prepared ionic liquid as electrolyte; and testing the charging and discharging performance of the assembled aluminum ion battery under the voltage range of 0.01-2.0V.
Through detection, under the multiplying power of 0.1C (1C is 200mAh/g), the first discharge specific capacity of the assembled aluminum ion battery is up to 217.1mAh/g, the first charge specific capacity is up to 233.4mAh/g, and under the multiplying power of 0.25C (1C is 200mAh/g), the discharge specific capacity of the assembled aluminum ion battery is still 38.7mAh/g after circulating for 350 circles, which shows that the aluminum ion battery assembled by the molybdenum selenide nano-microspheres provided by the invention has higher specific capacity and better circulation stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The molybdenum selenide nano microsphere is characterized by being a microsphere formed by stacking nano sheets, and the interlayer spacing is 0.60-0.67 nm.
2. The molybdenum selenide nano-microspheres according to claim 1, wherein the particle size of the molybdenum selenide nano-microspheres is 300-500 nm.
3. The preparation method of the molybdenum selenide nanospheres as claimed in any one of claims 1 to 2, which is characterized by comprising the following steps:
mixing a selenium source and a reducing agent to obtain a selenium source solution;
mixing a molybdenum source and dimethylformamide to obtain a molybdenum source solution;
mixing the selenium source solution and the molybdenum source solution, and carrying out solvothermal reaction to obtain molybdenum selenide powder;
and carrying out heat treatment on the molybdenum selenide powder to obtain the molybdenum selenide nano-microspheres.
4. The method of claim 3, wherein the selenium source is selenium dioxide and/or elemental selenium; the reducing agent comprises sodium borohydride and/or hydrazine hydrate; the molar ratio of the reducing agent to selenium in the selenium source is 40-125: 1.
5. The method of claim 3, wherein the molybdenum source comprises one or more of ammonium molybdate, sodium molybdate and barium molybdate; the molar ratio of the dimethyl formamide to the molybdenum element in the molybdenum source is 0.5-5: 1.
6. The method according to claim 3, wherein the molar ratio of the selenium element in the selenium source to the molybdenum element in the molybdenum source is 1.5 to 3.0: 1.
7. The preparation method according to claim 3, wherein the temperature of the solvothermal reaction is 140-220 ℃ and the time is 6-16 h.
8. The method according to claim 3, wherein the heat treatment is carried out at a temperature of 300 to 800 ℃ for 2 to 8 hours.
9. An electrode, characterized in that, the electrode comprises the molybdenum selenide nanospheres as set forth in any one of claims 1 to 2 or the molybdenum selenide nanospheres prepared by the preparation method as set forth in any one of claims 3 to 8.
10. An aluminum ion battery is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte; the positive electrode is the electrode according to claim 9.
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| CN105006570A (en) * | 2015-06-10 | 2015-10-28 | 中南大学 | Molybdenum selenide based composite cathode material for sodium-ion battery and preparation method thereof |
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| CN105006570A (en) * | 2015-06-10 | 2015-10-28 | 中南大学 | Molybdenum selenide based composite cathode material for sodium-ion battery and preparation method thereof |
| CN105428622A (en) * | 2015-11-30 | 2016-03-23 | 中南大学 | Sulfur-doped molybdenum selenide negative composite material for sodium-ion battery and preparation method of sulfur-doped molybdenum selenide negative composite material |
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