CN108091874B - Preparation method of nano nickel-cobalt-sulfur particles used as lithium-sulfur battery positive electrode - Google Patents
Preparation method of nano nickel-cobalt-sulfur particles used as lithium-sulfur battery positive electrode Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 33
- 239000011593 sulfur Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 10
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 10
- 239000001632 sodium acetate Substances 0.000 claims abstract description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims abstract description 8
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims abstract description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229920001021 polysulfide Polymers 0.000 abstract description 3
- 239000005077 polysulfide Substances 0.000 abstract description 3
- 150000008117 polysulfides Polymers 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000004763 sulfides Chemical class 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011858 nanopowder Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910003003 Li-S Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
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Abstract
The invention relates to a preparation method of nano nickel-cobalt-sulfur particles used as a positive electrode of a lithium-sulfur battery, which comprises the following steps: dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and sodium acetate in a solvent, adding potassium persulfate or ammonium persulfate, stirring, pouring into a reaction kettle for reaction, cooling, washing, centrifuging, drying, dissolving in the solvent, ultrasonically treating, adding sodium sulfide nonahydrate, pouring into the reaction kettle for reaction, cooling, washing, centrifuging and drying to obtain the catalyst. The method is simple and easy to implement, safe and environment-friendly, has easily available raw materials and low cost, and is suitable for large-scale production; the prepared nano nickel-cobalt-sulfur particles are small in size, the specific surface area is increased, the nano nickel-cobalt-sulfur particles have a good fixing effect on polysulfide, and the shuttle effect of the battery is obviously weakened. In addition, nickel cobalt sulfide has good conductivity compared with oxides and binary sulfides which are generally used for sulfur fixation. The cycling stability of the battery is improved under the condition of ensuring a certain specific capacity, and the lithium-sulfur battery has great potential on the aspect of solving the existing problems of the lithium-sulfur battery.
Description
Technical Field
The invention belongs to the field of preparation of electrode materials of ion batteries, and particularly relates to a preparation method of nano nickel-cobalt-sulfur particles used as a positive electrode of a lithium-sulfur battery.
Background
The efficient utilization and storage of energy has been a major technological problem in the advance of energy development. During this period, lithium ion batteries enter people's lives as high-load and portable devices, and lithium sulfur batteries have very high theoretical specific capacity (1675mAh/g) which is far higher than that of the current lithium ion batteries using graphite as a negative electrode (372mAh/g), so that the lithium sulfur batteries become promising next-generation energy storage devices. However, lithium-sulfur batteries have more serious problems than the disadvantages of conventional lithium-ion batteries: lithium metal can gradually generate lithium dendrite in the charging and discharging process, and finally the battery is short-circuited due to the fact that a diaphragm is pierced; because the metal lithium is used, the requirement on the sealing performance of the battery is high; lithium polysulfide as a discharge intermediate product can be dissolved in electrolyte, and reacts with metal lithium along with the arrival of the electrolyte at a negative electrode in the charge-discharge process, so that the performance of the battery is seriously attenuated; the elemental sulfur is an insulator, and the internal resistance of the battery is high; the density of the final product lithium sulfide is lower than that of elemental sulfur, so that the volume of the positive electrode expands, and the structure of the battery is damaged. The current solution is mainly to coat sulfur in a nano material with a sulfur fixing effect; modifying the diaphragm; modifying the electrolyte; a solid electrolyte is used.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of nano nickel cobalt sulfur particles used as the positive electrode of a lithium sulfur battery, the method is simple and easy to implement, safe and environment-friendly, the raw materials are easy to obtain, the cost is low, and the method is suitable for large-scale production.
The invention relates to a preparation method of nano nickel-cobalt-sulfur particles used as a lithium-sulfur battery anode, which comprises the following specific steps:
(1) dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and sodium acetate in a solvent in a mass ratio of 1-2:1-2:20-60 to form a mixed solution, adding potassium persulfate or ammonium persulfate, and stirring to obtain a solution, wherein the concentration of sodium acetate in the mixed solution is 0.025-0.075g/mL, and the mass ratio of the sodium acetate to the potassium persulfate or the ammonium persulfate is 10-30: 1-2;
(2) pouring the solution obtained in the step (1) into a reaction kettle for reaction, cooling, washing, centrifuging and drying to obtain nano nickel cobaltate;
(3) dissolving the nano nickel cobaltate in the step (2) in a solvent to form a nano nickel cobaltate solution, performing ultrasonic treatment, adding sodium sulfide nonahydrate, pouring into a reaction kettle for reaction, cooling, washing, centrifuging and drying to obtain nano nickel cobalt sulfur particles, wherein the concentration of the nano nickel cobaltate solution is 0.75-2.25mg/mL, and the mass ratio of the nano nickel cobaltate to the sodium sulfide nonahydrate is 1-3: 24-32.
The stirring time in the step (1) is 30-60 min.
And (3) in the steps (1) and (3), the solvent is deionized water.
The step (2) of pouring into a reaction kettle for reaction specifically comprises the following steps: heating to 140 ℃ and 180 ℃ at the heating rate of 5-10 ℃/min for reaction for 6-8 h; the drying temperature is 60 ℃, and the drying time is 12 h.
The filling rates of the materials poured into the reaction kettle in the steps (2) and (3) are both 80%; washing is firstly washed by deionized water and then by ethanol.
The ultrasonic time in the step (3) is 15-30 min; pouring the mixture into a reaction kettle for reaction specifically: heating to 90-120 ℃ at the heating rate of 5-10 ℃/min and reacting for 6-14 h; the drying temperature is 60 ℃, and the drying time is 12-24 h.
The size of the nano nickel-cobalt-sulfur particles in the step (3) is about 5 nm.
The step (3) of using the nano nickel-cobalt-sulfur particles as the positive electrode of the lithium-sulfur battery specifically comprises the following steps:
(1) mixing nano nickel cobalt sulfur and sublimed sulfur according to the mass ratio of 1:2-5, reacting under the protection of inert gas, and cooling to obtain a sulfur/nickel cobalt sulfur composite material;
(2) and (2) mixing the sulfur/nickel-cobalt-sulfur composite material in the step (1) with polyvinylidene fluoride (PVDF) and acetylene black in a mass ratio of 6-7:1-2:2-3, grinding, dissolving in a solvent, and coating on a clean aluminum foil for treatment to obtain the positive pole piece of the lithium-sulfur battery.
The inert gas in the step (1) is nitrogen or argon; the reaction time is 15-24h, and the reaction temperature is 150-160 ℃.
The solvent in the step (2) is NMP; the treatment specifically comprises the following steps: placing in a constant temperature vacuum drying oven at 60 deg.C for 12-24 h.
And (3) in the step (2), the positive pole piece of the lithium-sulfur battery is placed in a glove box, the battery is assembled by taking metal lithium as a negative pole, and the cycle performance and the rate performance are tested.
The invention utilizes a simple hydrothermal method to prepare the nano nickel cobalt sulfur particles, and the nano nickel cobalt sulfur particles are used as a sulfur fixing material, so that the cycle performance of the lithium sulfur battery is improved.
Advantageous effects
(1) The method is simple and easy to implement, safe and environment-friendly, has easily available raw materials and low cost, and is suitable for large-scale production;
(2) the nano particles prepared by the method have small size, the specific surface area is correspondingly improved, and the nickel-cobalt-sulfur has good fixing effect on polysulfide, so that the shuttle effect of the battery can be obviously weakened. In addition, nickel cobalt sulfide has good conductivity compared with oxides and binary sulfides which are generally used for sulfur fixation. The cycling stability of the battery is improved under the condition of ensuring a certain specific capacity, and the lithium-sulfur battery has great potential on the aspect of solving the existing problems of the lithium-sulfur battery.
Drawings
FIG. 1 is a scanning electron microscope image of low power field emission of nano nickel cobalt sulfur particles prepared in example 1;
FIG. 2 is a transmission electron microscope image of high power field emission of nano nickel cobalt sulfur particles prepared in example 1;
FIG. 3 is a graph showing the rate capability test at 0.1C, 0.2C, 0.5C, 1C, 2C, 1C, 0.5C, 0.2C, and 0.1C, respectively, for the nano Ni-Co-S particles used as the positive electrode of the Li-S battery in example 4;
fig. 4 is a graph of cycle stability performance test at 1C when the nano nickel cobalt sulfur particles of example 4 were used as a positive electrode of a lithium sulfur battery.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) 75mg of cobalt nitrate hexahydrate, 75mg of nickel nitrate hexahydrate and 3g of sodium acetate were weighed and dissolved in 40mL of deionized water, and then 0.2g of potassium persulfate or ammonium persulfate was added and stirred for 30min to obtain a pink solution.
(2) Pouring the pink solution obtained in the step (1) into a lining of a 50mL polytetrafluoroethylene high-pressure reaction kettle, sealing, placing in a constant-temperature oven, heating to 180 ℃ at a heating rate of 10 ℃/min, reacting for 6h, washing with deionized water and ethanol respectively after natural cooling, centrifuging for multiple times until no impurity ions exist, and placing in a constant-temperature vacuum drying oven at 60 ℃ for 12h to obtain fluffy and dry black nickel cobaltate nano powder.
(3) Taking 30mg of the black nickel cobaltate nano powder obtained in the step (2), adding 40mL of deionized water, performing ultrasonic dispersion for 30min, adding 0.96g of sodium sulfide nonahydrate, pouring the mixed solution into a lining of a 50mL polytetrafluoroethylene high-pressure reaction kettle, sealing, and placing in a constant temperatureHeating to 120 deg.C at a heating rate of 10 deg.C/min in a warm oven, reacting for 6-14h, naturally cooling, washing with deionized water and ethanol, centrifuging for several times until no impurity ion is formed, and placing in a constant temperature vacuum drying oven at 60 deg.C for 24h to obtain black nanometer nickel cobalt sulfur particle powder (Ni)1.5Co1.5S4)。
Fig. 1 and 2 show that: the product nano nickel cobalt sulfur particles have uniform size, and the size is about 5 nanometers.
Example 2
(1) 100mg of cobalt nitrate hexahydrate, 50mg of nickel nitrate hexahydrate and 3g of sodium acetate were weighed and dissolved in 40mL of deionized water, and then 0.2g of potassium persulfate or ammonium persulfate was added and stirred for 60min to obtain a pink solution.
(2) Pouring the pink solution obtained in the step (1) into a lining of a 50mL polytetrafluoroethylene high-pressure reaction kettle, sealing, placing in a constant-temperature oven, heating to 180 ℃ at a heating rate of 10 ℃/min, reacting for 6h, washing with deionized water and ethanol respectively after natural cooling, centrifuging for multiple times until no impurity ions exist, and placing in a constant-temperature vacuum drying oven at 60 ℃ for 12h to obtain fluffy and dry black nickel cobaltate nano powder.
(3) Taking 30mg of the black nickel cobalt oxide nano powder obtained in the step (2), adding 40mL of deionized water, performing ultrasonic dispersion for 30min, adding 0.96g of sodium sulfide nonahydrate, pouring the mixed solution into a lining of a 50mL polytetrafluoroethylene high-pressure reaction kettle, sealing, placing in a constant-temperature oven, heating to 120 ℃ at the heating rate of 10 ℃/min, reacting for 6h, after natural cooling, respectively washing with deionized water and ethanol, centrifuging for many times until no foreign ions exist, and placing in a constant-temperature vacuum drying oven at 60 ℃ for 24h to obtain black nano nickel cobalt sulfur particle powder (NiCo)2S4)。
Example 3
(1) 50mg of cobalt nitrate hexahydrate, 100mg of nickel nitrate hexahydrate and 3g of sodium acetate were weighed and dissolved in 40mL of deionized water, and then 0.2g of potassium persulfate or ammonium persulfate was added and stirred for 60min to obtain a pink solution.
(2) Pouring the pink solution obtained in the step (1) into a lining of a 50mL polytetrafluoroethylene high-pressure reaction kettle, sealing, placing in a constant-temperature oven, heating to 180 ℃ at a heating rate of 10 ℃/min, reacting for 6h, washing with deionized water and ethanol respectively after natural cooling, centrifuging for multiple times until no impurity ions exist, and placing in a constant-temperature vacuum drying oven at 60 ℃ for 12h to obtain fluffy and dry black nickel cobaltate nano powder.
(3) Taking 30mg of the black nickel cobalt oxide nano powder obtained in the step (2), adding 40mL of deionized water, performing ultrasonic dispersion for 30min, adding 0.96g of sodium sulfide nonahydrate, pouring the mixed solution into a lining of a 50mL polytetrafluoroethylene high-pressure reaction kettle, sealing, placing in a constant-temperature oven, heating to 120 ℃ at the heating rate of 5-10 ℃/min, reacting for 6h, respectively washing with deionized water and ethanol after natural cooling, centrifuging for many times until no foreign ions exist, and placing in a constant-temperature vacuum drying oven at 60 ℃ for 24h to obtain black nano nickel cobalt sulfur particle powder (Ni, Co and S particles)2CoS4)。
Example 4
(1) And (3) mixing 40mg of the nano nickel cobalt sulfur particle powder and 80mg of sublimed sulfur in the embodiment 2, preserving the heat for 24 hours at the temperature of 155 ℃ under the protection of nitrogen, and naturally cooling to room temperature to obtain the sulfur/nickel cobalt sulfur composite material.
(2) And (2) mixing 42mg of the sulfur/nickel-cobalt-sulfur composite material in the step (1) with 6mg of polyvinylidene fluoride (PVDF) and 12mg of acetylene black, uniformly grinding, dissolving with NMP, coating on a clean aluminum foil, and then placing in a constant-temperature vacuum drying oven at 60 ℃ for 24 hours to obtain the lithium-sulfur battery positive pole piece.
(3) And (3) placing the pole piece in the step (2) in a glove box, assembling the battery by using metal lithium as a negative electrode, and testing the rate performance and the cycling stability. FIG. 3 shows: the battery has higher capacity when being charged and discharged under low multiplying power of 0.1C, 0.2C and 0.5C, and the capacity is kept stable by the charging and discharging energy under high multiplying power of 1C and 2C.
FIG. 4 shows that: after the battery is charged and discharged for 1000 circles at 1C, the specific capacity is reduced from 550mAh/g to 200mAh/g, which is equivalent to that the capacity of each charge and discharge cycle is attenuated by 0.064%, and the coulombic efficiency is about 97%, thus the battery has better cycle stability.
Claims (9)
1. A preparation method of nano nickel cobalt sulfur particles used as a lithium sulfur battery anode comprises the following specific steps:
(1) dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and sodium acetate in a solvent in a mass ratio of 1-2:1-2:20-60 to form a mixed solution, adding potassium persulfate or ammonium persulfate, and stirring to obtain a solution, wherein the concentration of sodium acetate in the mixed solution is 0.025-0.075g/mL, and the mass ratio of the sodium acetate to the potassium persulfate or the ammonium persulfate is 10-30: 1-2;
(2) pouring the solution obtained in the step (1) into a reaction kettle for reaction, cooling, washing, centrifuging and drying to obtain nano nickel cobaltate;
(3) dissolving the nano nickel cobaltate in the step (2) in a solvent to form a nano nickel cobaltate solution, performing ultrasonic treatment, adding sodium sulfide nonahydrate, pouring into a reaction kettle for reaction, cooling, washing, centrifuging and drying to obtain nano nickel cobalt sulfur particles, wherein the concentration of the nano nickel cobaltate solution is 0.75-2.25mg/mL, and the mass ratio of the nano nickel cobaltate to the sodium sulfide nonahydrate is 1-3: 24-32.
2. The method for preparing nano nickel-cobalt-sulfur particles for use as a positive electrode of a lithium-sulfur battery according to claim 1, wherein the stirring time in step (1) is 30-60 min.
3. The method for preparing nano nickel-cobalt-sulfur particles for use as a positive electrode of a lithium-sulfur battery according to claim 1, wherein the solvents in steps (1) and (3) are deionized water.
4. The method for preparing nano nickel-cobalt-sulfur particles for use as a positive electrode of a lithium-sulfur battery according to claim 1, wherein the step (2) of pouring into a reaction kettle comprises the following steps: heating to 140 ℃ and 180 ℃ at the heating rate of 5-10 ℃/min for reaction for 6-8 h; the drying temperature is 60 ℃, and the drying time is 12 h.
5. The method for preparing nano nickel-cobalt-sulfur particles for use as a positive electrode of a lithium-sulfur battery according to claim 1, wherein the filling rates of the nano nickel-cobalt-sulfur particles poured into the reaction kettle in the steps (2) and (3) are both 80%; washing is firstly washed by deionized water and then by ethanol.
6. The method for preparing nano nickel-cobalt-sulfur particles for use as a positive electrode of a lithium-sulfur battery according to claim 1, wherein the ultrasonic time in the step (3) is 15-30 min; pouring the mixture into a reaction kettle for reaction specifically: heating to 90-120 ℃ at the heating rate of 5-10 ℃/min and reacting for 6-14 h; the drying temperature is 60 ℃, and the drying time is 12-24 h.
7. The method for preparing nano nickel-cobalt-sulfur particles for use as a positive electrode of a lithium-sulfur battery according to claim 1, wherein the nano nickel-cobalt-sulfur particles in the step (3) are used as a positive electrode of a lithium-sulfur battery, and specifically comprise:
(A) mixing nano nickel cobalt sulfur and sublimed sulfur according to the mass ratio of 1:2-5, reacting under the protection of inert gas, and cooling to obtain a sulfur/nickel cobalt sulfur composite material;
(B) and (2) mixing the sulfur/nickel-cobalt-sulfur composite material in the step (A) with polyvinylidene fluoride (PVDF) and acetylene black in a mass ratio of 6-7:1-2:2-3, grinding, dissolving in a solvent, and coating on a clean aluminum foil for treatment to obtain the positive pole piece of the lithium-sulfur battery.
8. The method for preparing nano nickel-cobalt-sulfur particles for use as a positive electrode of a lithium-sulfur battery according to claim 7, wherein the inert gas in the step (1) is argon; the reaction time is 15-24h, and the reaction temperature is 150-160 ℃.
9. The method for preparing nano nickel-cobalt-sulfur particles for use as a positive electrode of a lithium-sulfur battery according to claim 7, wherein the solvent in the step (2) is NMP; the treatment specifically comprises the following steps: placing in a constant temperature vacuum drying oven at 60 deg.C for 12-24 h.
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