CN111293297A - Carbon-coated MoSe2Black phosphorus composite material and preparation method thereof - Google Patents
Carbon-coated MoSe2Black phosphorus composite material and preparation method thereof Download PDFInfo
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- CN111293297A CN111293297A CN202010118881.2A CN202010118881A CN111293297A CN 111293297 A CN111293297 A CN 111293297A CN 202010118881 A CN202010118881 A CN 202010118881A CN 111293297 A CN111293297 A CN 111293297A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052698 phosphorus Inorganic materials 0.000 title description 2
- 239000011574 phosphorus Substances 0.000 title description 2
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract 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 abstract description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 239000010453 quartz Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 8
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 229910016001 MoSe Inorganic materials 0.000 claims description 40
- 229910001414 potassium ion Inorganic materials 0.000 claims description 20
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 235000015393 sodium molybdate Nutrition 0.000 claims description 8
- 239000011684 sodium molybdate Substances 0.000 claims description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- 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
- 235000007686 potassium Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 2
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000000047 product Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 boron sodium selenide Chemical compound 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/36—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides carbon-coated MoSe2The black phosphorus composite material and the preparation method thereof, the preparation method comprises the following steps: uniformly mixing sodium borohydride and selenium powder and dissolving in deionized water to obtain a sodium boroselenide solution; dissolving a molybdenum source in deionized water to obtain a molybdenum source solution; adding a molybdenum source solution into a sodium boroselenide solution, and then uniformly stirring and mixing to obtain a mixed solution; adding an organic carbon source into the mixed solution, and uniformly mixing to obtain a mixture; adding the mixture into a high-pressure reaction kettle for heat preservation reaction, cooling, centrifuging, washing, and drying in vacuum overnight to obtain a product; putting the product into a quartz tube, vacuumizing to a set vacuum degree, and then emptying the quartz tubeCalcining in gas and heating to a third preset temperature at a set speed to obtain a precursor MoSe2C; the precursor MoSe2Ball milling the mixture of the/C and the black phosphorus in an inert atmosphere to obtain carbon-coated MoSe2A black phosphorus composite material; the carbon-coated MoSe2The black phosphorus composite material is prepared by the preparation method.
Description
Technical Field
The invention belongs to the technical field of electrochemistry and batteries, relates to a potassium ion battery cathode material, and particularly relates to carbon-coated MoSe2A black phosphorus composite material and a preparation method thereof.
Background
Energy and environment are two major topics involved in the sustainable development of human society. In the face of energy and environmental issues, new clean energy technologies, particularly energy storage technologies, are considered to be one of the effective approaches. Compared with the traditional nickel-hydrogen battery and lead-acid battery, the alkali metal ion (Li)+/Na+/K+) The battery has higher energy density and environmental friendliness, and has wide application prospect in the field of clean energy storage, wherein the lithium ion battery is widely applied to the fields of communication equipment, electronic equipment, electric automobiles and the like due to the advantages of safety, high energy density, long service life and the like. However, the lithium resources are not distributed uniformly, the storage capacity is small, the price is high, and the application of the lithium resources in the field of large-scale energy storage is limited. In comparison, the sodium and potassium resources are abundant, widely exist in the crust and the ocean and are cheaper. And sodium, potassium and lithium belong to the same main group element, the chemical properties are close, and the working principle is similar. Therefore, sodium ion and potassium ion batteries are considered as the most promising alternative energy storage technologies besides lithium ion batteries, especially in the large-scale energy storage field with high requirements on cost and resource abundance.
At present, negative electrode materials such as carbon materials, metal oxides, organic materials and the like for potassium ion batteries have potential safety hazards, or the problems of irreversible capacity loss, poor electrochemical cycle and rate capability, low charging and discharging coulombic efficiency and the like caused by volume expansion and pulverization in the circulation process of the electrode materials due to too large radius of potassium ions; these problems severely limit the practical application of these negative electrode materials in potassium ion batteries. Therefore, a method with long cycle life, excellent rate capability, high coulombic efficiency and high coulombic efficiency is developedThe stable and high-safety cathode material becomes one of the key points in the development of the current potassium ion battery. Carbon-coated MoSe of the invention2The black phosphorus composite material is used as a negative electrode material of a potassium ion battery, and the negative electrode material shows small volume expansion in the process of potassium intercalation/deintercalation cycle, and shows excellent cycle and rate capability and high charge-discharge coulombic efficiency.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide carbon-coated MoSe2A black phosphorus composite material and a preparation method thereof.
The invention provides carbon-coated MoSe2The preparation method of the black phosphorus composite material is characterized by comprising the following steps: step 1, uniformly mixing sodium borohydride and selenium powder and dissolving in deionized water to obtain a sodium boroselenide solution; step 2, dissolving a molybdenum source in deionized water to obtain a molybdenum source solution; step 3, adding a molybdenum source solution into the sodium boroselenide solution, stirring at a first preset temperature, and uniformly mixing to obtain a mixed solution; step 4, adding an organic carbon source into the mixed solution, and uniformly mixing to obtain a mixture; step 5, adding the mixture into a high-pressure reaction kettle, carrying out heat preservation reaction at a second preset temperature, naturally cooling to room temperature, centrifuging, washing for 3 times by using deionized water and ethanol respectively, and then drying overnight in vacuum to obtain a product; step 6, placing the product in a quartz tube, vacuumizing to a set vacuum degree, calcining the quartz tube in air, and heating to a third preset temperature at a set speed to obtain a precursor MoSe2C; step 7, adding a precursor MoSe2Ball milling the mixture of the/C and the black phosphorus in an inert atmosphere to obtain carbon-coated MoSe2A black phosphorus composite material.
The carbon-coated MoSe provided by the invention2The preparation method of the black phosphorus composite material can also have the following characteristics: in the step 1, the molar ratio of selenium powder to sodium borohydride is 2-8: 1 to 4.
The carbon-coated MoSe provided by the invention2The preparation method of the black phosphorus composite material can also have the following characteristics: it is composed ofIn step 2, the molybdenum source is one or more of ammonium molybdate, sodium molybdate and potassium molybdate.
The carbon-coated MoSe provided by the invention2The preparation method of the black phosphorus composite material can also have the following characteristics: wherein the molar ratio of the molybdenum source solution in the step 3 to the selenium powder in the boron sodium selenide solution is 1-4: 2-8, the first preset temperature is 50-80 ℃, the stirring speed is 20-60 rpm, and the stirring time is 0.5-2 h.
The carbon-coated MoSe provided by the invention2The preparation method of the black phosphorus composite material can also have the following characteristics: the organic carbon source in the step 4 is one or a mixture of two of citric acid and glucose, and the mass ratio of the organic carbon source to the selenium powder in the mixed solution is 1-10: 1-10 ℃, the second preset temperature is 60-80 ℃, and the stirring speed is 20-30 rpm.
The carbon-coated MoSe provided by the invention2The preparation method of the black phosphorus composite material can also have the following characteristics: wherein the third preset temperature in the step 5 is 100-300 ℃, the time is 5-24 h, and the vacuum temperature is 60 ℃.
The carbon-coated MoSe provided by the invention2The preparation method of the black phosphorus composite material can also have the following characteristics: wherein the vacuum degree of the quartz tube in the step 6 is 10-2-10-4Pa, the heating rate during calcination is 1-5 ℃/min, the fourth predetermined temperature is 500-700 ℃, and the calcination time is 3-24 h.
The carbon-coated MoSe provided by the invention2The preparation method of the black phosphorus composite material can also have the following characteristics: wherein the black phosphorus in the step 7 is one or a mixture of two of ball-milled black phosphorus and calcined black phosphorus, the ball-milling rotating speed is 10-60 Hz, and the ball-milling time is 0.5-2 h.
The carbon-coated MoSe provided by the invention2The preparation method of the black phosphorus composite material can also have the following characteristics: wherein the carbon-coated MoSe in the step 72MoSe in black phosphorus composite material2The nano-sheets are stacked into a nano-flower structure, and the MoSe is coated with carbon2Nanosheet surface。
The invention also provides carbon-coated MoSe2The black phosphorus composite material is used as a negative electrode material of a potassium ion battery and has the following characteristics: coating of MoSe with the above carbon2The black phosphorus composite material is prepared by the preparation method.
Action and Effect of the invention
The carbon-coated MoSe of the invention is adopted2The composite material prepared by the preparation method of the black phosphorus composite material can be used as a potassium ion battery cathode material, has good conductivity, higher specific capacity and stable charge and discharge performance, has the advantages of small volume expansion after potassium insertion, high structural stability, stable cycle performance, good rate capability, high charge and discharge coulombic efficiency and safety and the like, is moderate in potassium insertion/removal potential, has better cycle performance and rate capability in the current potassium ion battery cathode material, and can be directly used in the fields of potassium ion secondary batteries and the like.
Further, the carbon-coated MoSe of the present invention2Because the adopted molybdenum diselenide material has good structural stability, and the characteristics of the layered structure endow the molybdenum diselenide material with good electronic and ionic conduction performance, the molybdenum diselenide material is coated with a carbon layer, and then the black phosphorus is compounded, the cycle stability of the composite material is improved, so that the battery shows excellent rate capability, high charging and discharging coulombic efficiency and high safety.
Drawings
FIG. 1 is MoSe in example 1 of the present invention2XRD pattern of the material;
FIG. 2 is carbon-coated MoSe in example 1 of the present invention2A cycle performance test chart of the black phosphorus composite material;
FIG. 3 is carbon-coated MoSe in example 2 of the present invention2A cycle performance test chart of the black phosphorus composite material;
FIG. 4 is carbon-coated MoSe in example 3 of the present invention2The cycle performance test chart of the black phosphorus composite material.
Detailed Description
In order to make the technical means and functions of the present invention easy to understand, the present invention is specifically described below with reference to the embodiments and the accompanying drawings.
< example 1>
Step 1, weighing 0.3g of selenium powder and 0.35g of sodium borohydride, dissolving in deionized water, and stirring at 35 ℃ for 30min at a stirring speed of 20rpm to obtain a sodium boroselenide solution.
And 2, weighing 0.3g of sodium molybdate, and dissolving the sodium molybdate in deionized water to prepare a sodium molybdate aqueous solution.
And 3, adding the mixed solution into a sodium molybdate aqueous solution, and stirring at the temperature of 30 ℃ for 40min at the stirring speed of 20rpm to obtain the mixed solution.
And 4, adding 1g of glucose into the mixed solution, and stirring at the temperature of 30 ℃ for 30min at the stirring speed of 20rpm to obtain a mixture.
And 5, adding the mixture into a high-pressure reaction kettle, preserving heat for 20 hours at the temperature of 210 ℃, centrifuging the reaction solution after the reaction kettle is naturally cooled to room temperature, washing the reaction solution for 3 times by using deionized water and ethanol respectively, and then carrying out vacuum drying on the black powder product at the temperature of 60 ℃ overnight to obtain the product.
Step 6, placing the product in a quartz tube and vacuumizing to 10 DEG-3Pa, heating to 750 ℃ at the heating rate of 3 ℃/min in the air and calcining for 3h to obtain a precursor MoSe2/C。
Step 7, adding the precursor MoSe2Placing the/C and the calcined black phosphorus in an inert gas atmosphere for ball milling with the ball milling speed of 55Hz and the ball milling time of 1h to obtain the carbon-coated MoSe2The black phosphorus composite material A.
Mixing the composite material A prepared by the above steps with acetylene black and a binder according to the weight ratio of 7: 2: 1 into slurry, drawing the slurry on a copper foil, and drying the slurry in vacuum at 80 ℃ overnight. And cutting the dried electrode material into pole pieces, selecting 2016 battery case to assemble in a glove box, standing the assembled battery overnight, and carrying out electrochemical performance test by using a blue battery test system.
FIG. 1 is MoSe in example 1 of the present invention2XRD pattern of material with X-ray incidence on the abscissaTwice the angle, the ordinate is the diffraction intensity.
As can be seen from FIG. 1, the synthesized material was pure MoSe after alignment with the standard alignment card2。
FIG. 2 is carbon-coated MoSe in example 1 of the present invention2The cycle performance test chart of the black phosphorus composite material.
Coating the obtained carbon with MoSe2The black phosphorus composite material is applied to the negative electrode of the potassium ion battery, and as can be seen from figure 2, the capacity of the battery is 315.6mAh/g after 150 circles of charging and discharging at 0.5A/g, and the carbon-coated MoSe2The black phosphorus composite material obviously improves the capacity, the cycle life and the cycle stability of the battery.
< example 2>
Step 1, weighing 0.4g of selenium powder and 0.45g of sodium borohydride, dissolving in deionized water, and stirring at 65 ℃ for 1h at a stirring speed of 40rpm to obtain a sodium boroselenide solution.
Step 2, weighing 0.4g of potassium molybdate, and dissolving the potassium molybdate in deionized water to prepare a potassium molybdate aqueous solution;
and 3, adding the boron sodium selenide solution into the sodium molybdate aqueous solution, and stirring at the temperature of 60 ℃ for 1.5h at the stirring speed of 30rpm to obtain a mixed solution.
And 4, stirring 2g of citric acid mixed solution at 60 ℃ for 1h at the stirring speed of 30rpm to obtain a mixture.
And 5, adding the mixture into a high-pressure reaction kettle, preserving heat for 10 hours at the temperature of 300 ℃, centrifuging the reaction solution after the reaction kettle is naturally cooled to room temperature, washing the reaction solution for 3 times by using deionized water and ethanol respectively, and then carrying out vacuum drying on the black powder product at the temperature of 60 ℃ overnight to obtain the product.
Step 6, placing the product in a quartz tube and vacuumizing to 10 DEG-4Pa, heating to 600 ℃ at the heating rate of 3 ℃/min in the air and calcining for 6h to obtain a precursor MoSe2/C。
Step 7, adding the precursor MoSe2Ball-milling the/C and the black phosphorus obtained by ball milling in an inert gas atmosphere at a ball-milling rate of 45Hz for 2h to obtain carbon-coated MoSe2A black phosphorus composite material B.
Mixing the composite material B prepared by the method with acetylene black and a binder according to the weight ratio of 7: 2: 1 into slurry, drawing the slurry on a copper foil, and drying the slurry in vacuum at 80 ℃ overnight. And cutting the dried electrode material into pole pieces, selecting 2016 battery case to assemble in a glove box, standing the assembled battery overnight, and carrying out electrochemical performance test by using a blue battery test system.
FIG. 3 is carbon-coated MoSe in example 2 of the present invention2The cycle performance test chart of the black phosphorus composite material.
Coating the obtained carbon with MoSe2The black phosphorus composite material is applied to the negative electrode of the potassium ion battery, and as can be seen from figure 3, the capacity of the battery after 150 circles under the charge and discharge of 0.5A/g is also 275.5mAh/g, and the MoSe is coated by carbon2The black phosphorus composite material obviously improves the capacity, the cycle life and the cycle stability of the battery.
< example 3>
Step 1, weighing 0.5g of selenium powder and 0.55g of sodium borohydride, dissolving in deionized water, and stirring at 85 ℃ for 2h at the stirring speed of 30rpm to obtain a sodium boroselenide solution.
And 2, weighing 0.5g of ammonium molybdate, and dissolving in deionized water to prepare an ammonium molybdate aqueous solution.
And 3, adding the mixed solution into a sodium molybdate aqueous solution, and stirring at the temperature of 80 ℃ for 2 hours at the stirring speed of 30rpm to obtain the mixed solution.
And 4, adding 4g of glucose into the mixed solution, and stirring at the temperature of 80 ℃ for 2h at the stirring speed of 30rpm to obtain a mixture.
And 5, adding the mixture into a high-pressure reaction kettle, preserving heat for 6 hours at 300 ℃, centrifuging the reaction solution after the reaction kettle is naturally cooled to room temperature, washing the reaction solution for 3 times by using deionized water and ethanol respectively, and then carrying out vacuum drying on the black powder product at 60 ℃ overnight to obtain the product.
Step 6, placing the product in a quartz tube and vacuumizing to 10 DEG-2Pa, heating to 600 ℃ at the heating rate of 3 ℃/min in the air and calcining for 6h to obtain a precursor MoSe2/C。
Step 7, adding the precursor MoSe2C product andplacing the calcined black phosphorus in an inert gas atmosphere for ball milling at a ball milling speed of 45Hz for 0.5h to obtain the final product of carbon-coated MoSe2A black phosphorus composite material C.
Mixing the composite material C prepared by the above steps with acetylene black and a binder according to the weight ratio of 7: 2: 1 into slurry, drawing the slurry on a copper foil, and drying the slurry in vacuum at 80 ℃ overnight. And cutting the dried electrode material into pole pieces, selecting 2016 battery case to assemble in a glove box, standing the assembled battery overnight, and carrying out electrochemical performance test by using a blue battery test system.
FIG. 4 is carbon-coated MoSe in example 3 of the present invention2The cycle performance test chart of the black phosphorus composite material.
Coating the obtained carbon with MoSe2The black phosphorus composite material is applied to the negative electrode of the potassium ion battery, and as can be seen from figure 4, the capacity of the battery is 252.6mAh/g after 150 circles under the charge and discharge of 0.5A/g, and the MoSe is coated by carbon2The black phosphorus composite material obviously improves the capacity, the cycle life and the cycle stability of the battery.
Effects and effects of the embodiments
From examples 1 to 3, it can be seen that the prepared carbon-coated MoSe2The black phosphorus composite material is applied to the negative electrode of the potassium ion battery, and the vacuum degree is 10-3Pa, heating to 750 ℃, calcining for 3h, and preparing the obtained carbon-coated MoSe2When the black phosphorus composite material is applied to a potassium ion battery cathode, the capacity is 315.6mAh/g after the black phosphorus composite material is circulated for 150 circles under the current density of 0.5A/g, and a better effect can be achieved, namely the capacity, the cycle life and the cycle stability of the battery are obviously improved.
In conclusion, the carbon-coated MoSe of the invention is adopted2The composite material prepared by the preparation method of the black phosphorus composite material can be used as a potassium ion battery cathode material, has good conductivity, higher specific capacity and stable charge and discharge performance, has the advantages of small volume expansion after potassium insertion, high structural stability, stable cycle performance, good rate capability, high charge and discharge coulombic efficiency, high safety and the like, and is suitable for potassium insertion/removal potentialIn addition, the cycle performance and the rate performance are in a good level in the current potassium ion battery cathode material, and the lithium ion battery cathode material can be directly used in the fields of potassium ion secondary batteries and the like.
Further, the carbon-coated MoSe of the present invention2Because the adopted molybdenum diselenide material has good structural stability, and the characteristics of the layered structure endow the molybdenum diselenide material with good electronic and ionic conduction performance, the molybdenum diselenide material is coated with a carbon layer, and then the black phosphorus is compounded, the cycle stability of the composite material is improved, so that the battery shows excellent rate capability, high charging and discharging coulombic efficiency and high safety.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. Carbon-coated MoSe2The preparation method of the black phosphorus composite material is characterized by comprising the following steps:
step 1, uniformly mixing sodium borohydride and selenium powder and dissolving in deionized water to obtain a sodium boroselenide solution;
step 2, dissolving a molybdenum source in deionized water to obtain a molybdenum source solution;
step 3, adding the molybdenum source solution into the sodium boroselenide solution, stirring at a first preset temperature, and uniformly mixing to obtain a mixed solution;
step 4, adding an organic carbon source into the mixed solution, and stirring and mixing uniformly at a second preset temperature to obtain a mixture;
step 5, adding the mixture into a high-pressure reaction kettle, carrying out heat preservation reaction at a third preset temperature, naturally cooling to room temperature, centrifuging, washing for 3 times by using deionized water and ethanol respectively, and then drying overnight in vacuum to obtain a product;
step 6, placing the product in a quartz tube, vacuumizing to a set vacuum degree, calcining the quartz tube in air, and heating to a fourth preset temperature at a set speed to obtain a precursor MoSe2/C；
Step 7, the precursor MoSe is added2Ball milling the mixture of the/C and the black phosphorus in an inert atmosphere to obtain carbon-coated MoSe2A black phosphorus composite material.
2. The carbon-coated MoSe of claim 12The preparation method of the black phosphorus composite material is characterized by comprising the following steps:
wherein the molar ratio of the selenium powder to the sodium borohydride in the step 1 is 2-8: 1 to 4.
3. The carbon-coated MoSe of claim 12The preparation method of the black phosphorus composite material is characterized by comprising the following steps:
wherein, the molybdenum source in the step 2 is one or a mixture of ammonium molybdate, sodium molybdate and potassium molybdate.
4. The carbon-coated MoSe of claim 12The preparation method of the black phosphorus composite material is characterized by comprising the following steps:
wherein the molar ratio of the molybdenum source solution in the step 3 to the selenium powder in the sodium boroselenide solution is 1-4: 2 to 8 percent of a solvent, and a solvent,
the first preset temperature is 50-80 ℃, the stirring speed is 20-60 rpm, and the stirring time is 0.5-2 h.
5. The carbon-coated MoSe of claim 12The preparation method of the black phosphorus composite material is characterized by comprising the following steps:
wherein the organic carbon source in the step 4 is one or a mixture of two of citric acid and glucose,
the mass ratio of the organic carbon source to the selenium powder in the mixed solution is 1-10: 1 to 10 parts of a first resin,
the second preset temperature is 60-80 ℃, and the stirring speed is 20-30 rpm.
6. The carbon-coated MoSe of claim 12The preparation method of the black phosphorus composite material is characterized by comprising the following steps:
wherein the third preset temperature in the step 5 is 100-300 ℃, the time is 5-24 h, and the vacuum temperature is 60 ℃.
7. The carbon-coated MoSe of claim 12The preparation method of the black phosphorus composite material is characterized by comprising the following steps:
wherein the vacuum degree of the quartz tube in the step 6 is 10-2-10-4Pa, the heating rate during calcination is 1-5 ℃/min, the fourth predetermined temperature is 500-700 ℃, and the calcination time is 3-24 h.
8. The carbon-coated MoSe of claim 12The preparation method of the black phosphorus composite material is characterized by comprising the following steps:
wherein the black phosphorus in the step 7 is one or a mixture of two of ball-milled black phosphorus and calcined black phosphorus,
the ball milling speed is 10-60 Hz, and the ball milling time is 0.5-2 h.
9. The carbon-coated MoSe of claim 12The preparation method of the black phosphorus composite material is characterized by comprising the following steps:
wherein the carbon-coated MoSe in the step 72MoSe in black phosphorus composite material2The nano sheets are stacked into a nano flower-like structure, and carbon is coated on the MoSe2And (3) the surface of the nanosheet.
10. Carbon-coated MoSe2A/black phosphorus composite material used as a negative electrode material of a potassium ion battery and coated with carbon MoSe according to claims 1 to 92The black phosphorus composite material is prepared by the preparation method.
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