CN115417465A - Nickel disulfide electrode material, preparation method and application - Google Patents
Nickel disulfide electrode material, preparation method and application Download PDFInfo
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- CN115417465A CN115417465A CN202211281960.0A CN202211281960A CN115417465A CN 115417465 A CN115417465 A CN 115417465A CN 202211281960 A CN202211281960 A CN 202211281960A CN 115417465 A CN115417465 A CN 115417465A
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- C01G53/11—Sulfides
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention belongs to the field of electrode materials of magnesium ion batteries, and relates to a nickel disulfide electrode material, and a preparation method and application thereof. The method successfully synthesizes cotton-shaped NiS by a simple one-step low-temperature molten salt method by taking molten eutectic salt nickel nitrate hexahydrate-NaCl as a reaction supply liquid medium and nickel nitrate hexahydrate and sodium thiosulfate pentahydrate as raw materials 2 . The preparation method of the nickel disulfide electrode material provided by the invention has the advantages of low cost, environmental protection, low temperature, easiness in realization of large-scale industrial production and the like. NiS is prepared by 2 Is used as a positive electrode material to assemble a magnesium battery,by controlling the voltage window and testing the electrochemical performance of the nickel disulfide electrode material, the nickel disulfide electrode material has excellent electrochemical performance at 100 mA g ‑1 Discharge capacity at the time of discharge was 261 mAh g ‑1 At 200 mA g ‑1 The capacity retention after 288 weeks of lower cycle was 44%.
Description
Technical Field
The invention belongs to the field of electrode materials of magnesium ion batteries, and relates to a nickel disulfide electrode material, and a preparation method and application thereof.
Background
Energy storage is one of important support technologies for realizing the aim of 'double carbon', and with the proposal of the aim of double carbon, the advantages of new energy are gradually highlighted. The power battery is taken as the most important framework in the new energy industry, and is greatly supported by China in recent years, wherein the secondary battery and the lithium ion battery are the most representative storage batteries so far. Although lithium ion batteries are widely used in mobile devices or electric automobiles, their use in large batteries (e.g., stationary energy storage batteries) is not suitable from the viewpoint of safety, abundance of elements, and cost. Therefore, it is very necessary to develop an environment-friendly polyvalent metal battery using magnesium, zinc and calcium.
Magnesium rechargeable batteries have a relatively low redox potential, tend to be electrodeposited without forming dendritic structures, and can be safely used as anodes, compared to lithium metal anode batteries, and thus magnesium ion batteries are one of the most promising large energy storage systems in practical applications other than lithium ion batteries. However, the development of magnesium ion batteries is still immature at present, and suitable cathode materials and electrolytes are not available to achieve excellent electrochemical performance. The study shows that Mg 2+ Is a divalent ion, mg due to its high charge, strong interaction with other ions 2+ The diffusion kinetics are poor. Therefore, it is very urgent to improve the diffusion kinetics of magnesium ions in the electrode to obtain a high performance magnesium ion battery.
Transition Metal Dihalides (TMDs) are of great interest because of their unique electronic structure, high electrical conductivity, and abundant redox chemistry. Nickel disulfide (NiS) 2 ) The method has the advantages of high theoretical capacity, low cost, environmental friendliness and the like, and has great advantages in the aspect of actual energy storage. However, as tested, niS 2 The electrochemical performance of the nickel disulfide electrode is poor, so an intelligent strategy is urgently needed to develop a high-performance nickel disulfide electrode.
Researchers in the prior art have successfully adopted a variety of methods for the production of nickel disulfide. For example: hydrothermal method, solid phase method, molten salt method, etc. These methods have their own advantages but still have some problems. For example, the product prepared by the traditional molten salt method has low purity, relatively high reaction temperature, complex process and expensive raw materials; the hydrothermal method has complex preparation process, generates hazardous wastewater and is not easy to treat. And the methods are not suitable for mass production due to low safety and long production period. Therefore, an effective preparation method for preparing high-purity nickel disulfide electrode material simply, rapidly and in large quantities must be found.
Disclosure of Invention
Aiming at the technical problems, the invention provides a nickel disulfide electrode material, a preparation method and application thereof. Compared with the traditional molten salt method, the low-temperature molten salt method used in the experiment finally overcomes the defects of low product purity, relatively high reaction temperature, complex process, expensive raw materials, complicated preparation process and the like in the traditional method by adjusting the proportion of molten salt. In the reaction, the recrystallization effect of NaCl can promote the generation of nickel disulfide, so that the nickel disulfide electrode material with high purity and small particle size is finally obtained in a short time in the reaction, which is beneficial to improving the specific area of a sample, thereby increasing the discharge specific capacity. And finally, taking the material as a positive electrode material of a magnesium ion battery, investigating the electrochemical performance of the material and exploring a magnesium storage mechanism of the material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a process for preparing nickel disulfide electrode material by one-step low-temp molten-salt method to melt eutectic salt nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O) -NaCl is used as a liquid medium for reaction, and nickel nitrate hexahydrate and sodium thiosulfate pentahydrate are used as raw materials to prepare the nickel disulfide electrode material.
Further, the preparation method of the nickel disulfide electrode material comprises the following steps:
(1) Preparing an electrode material: uniformly grinding nickel nitrate hexahydrate, sodium thiosulfate pentahydrate and NaCl, and then carrying out constant-temperature reaction to obtain a nickel disulfide turbid electrode material;
(2) Preparing a finished product of the electrode material: and (2) cooling the nickel disulfide turbid electrode material obtained in the step (1) to room temperature. Adding deionized water for ultrasonic treatment, and after uniform mixing, separating, cleaning and drying to obtain the nickel disulfide electrode material.
Further, the mass ratio of nickel nitrate hexahydrate, sodium thiosulfate pentahydrate and NaCl in the step (1) is (8-10): (18-20): 1-2.
Further, the mixture ground by adding NaCl in the step (1) is in a flowing state, and due to moisture absorption of NaCl, crystal water in nickel nitrate hexahydrate and sodium thiosulfate pentahydrate is released in the air, so that a liquid-phase medium is provided for the reaction.
Further, the temperature of the constant temperature reaction in the step (1) is 160 to 180 ℃.
Further, the constant-temperature reaction time in the step (1) is 10 to 14h.
Further, in the step (2), washing for 3 to 5 times by using deionized water, and then washing for 3 to 5 times by using ethanol, wherein the drying temperature is 60 ℃, and the drying time is 6 to 20h.
Further, the nickel disulfide electrode material prepared by the preparation method consists of nickel disulfide nanoparticles with the particle diameter of 10 to 110nm, the morphology structure of the nickel disulfide electrode material is cotton-shaped, and the molecular formula is NiS 2 。
Furthermore, the nickel disulfide electrode material is applied to the field of preparing magnesium ion batteries as a positive electrode material.
Further, the magnesium ion battery consists of a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the positive electrode comprises a nickel disulfide electrode material, a conductive agent, a positive adhesive and a positive current collector; the preparation method of the anode comprises the following steps: adding the nickel disulfide material, the conductive agent and the anode adhesive into a mortar, grinding, adding the organic solvent, uniformly stirring, coating on the copper foil, and drying.
Further, in the preparation method of the positive electrode, the conductive agent is acetylene black or carbon black, and the positive electrode adhesive is polyvinylidene fluoride or polytetrafluoroethylene.
Further, the mass ratio of the nickel disulfide electrode material to the conductive agent to the positive electrode adhesive is (8-A-B): (1 + A): (1 + B), wherein A is more than or equal to 0 and less than or equal to 2, B is more than or equal to 0 and less than or equal to 1, the mass of the positive electrode is 30 to 60 mg, the organic solvent is N-methylpyrrolidone, the coating mode is any one of blade coating, spin coating or drop coating, and the thickness of the copper foil is 14 to 21 mu m.
Further, the diameter of the copper foil wafer is 8 mm, the loaded active mass of each copper foil is 0.48-0.64 mg, the drying temperature after coating is 60 ℃, and the drying time is 6-12 h.
Further, the preparation method of the negative electrode comprises the following steps: polishing the magnesium sheet by using abrasive paper until two surfaces are smooth, and then cleaning the polished magnesium sheet by using a dilute hydrochloric acid solution; washing the magnesium sheet by using distilled water and absolute ethyl alcohol respectively to obtain a magnesium cathode with a smooth surface, and cutting the magnesium sheet into a circular sheet by using a punching machine; the concentration of the dilute hydrochloric acid is 0.1 to 0.5M, and the diameter of the magnesium wafer is 8 to 13 mm.
Further, the assembly method of the magnesium ion battery comprises the following steps: in a glove box, a coin-type battery CR2032 is used, an anode, a diaphragm, a cathode and fillers are respectively compounded together in a lamination mode, meanwhile, electrolyte is dripped, and finally, a sealing machine is used for packaging the battery to obtain a magnesium ion battery; the glass fiber diaphragm is used as the diaphragm, and the electrolyte is 0.4M 2PhMgCl/THF-AlCl 3 (APC for short) electrolyte.
The invention has the following beneficial effects:
1. the nickel disulfide electrode material provided by the invention is prepared from nickel nitrate hexahydrate, sodium chloride and sodium thiosulfate pentahydrate serving as raw materials by adopting a low-temperature molten salt method. The participation of NaCl can accelerate the separation of crystal water in reactants, and provides a good liquid medium for the reaction; in the case of not adding NaCl, the mixture was brown mixed viscous substance during the grinding process, and the fluidity was not good. The combination of nickel nitrate hexahydrate and NaCl can lower the melting point of the nickel nitrate, thereby lowering the reaction temperature. In general, the reaction avoids the addition of a solvent, reduces the conditions required by the reaction, is convenient to operate, causes less pollution and has good application prospect.
2. The nickel disulfide constructed by the method is similar to cotton flocculent in appearance, so that the ionic conductivity of the electrode material can be improved, the integral conductivity of the electrode is further improved, and the rate capability of the battery is improved. The existence of a molten salt system in the reaction process enables the reaction to be carried out on an atomic scale, the dissolution of NaCl is beneficial to the uniformity of raw material mixing, and the space limitation effect of NaCl in a molten state can promote high-purity flocculent NiS 2 The electrode is generated quickly, and has good electronic and ionic conductivity and structural stability, the utilization efficiency of the active material is improved, and the purpose of optimizing electrochemical performance is realized.
3. The presence of NaCl in the present invention also carries a dual role: firstly, a molten salt system can be formed with nickel nitrate hexahydrate to provide a liquid medium for reaction, so that the reaction is completed at a lower temperature (160 to 180 ℃) within a shorter time (10 to 14h); secondly, the NiS is used as a template to synthesize granular NiS with smaller grain diameter 2 (consists of nickel disulfide nano-particles with the particle diameter of 10 to 110nm), relieves NiS to a certain extent 2 Irregular development and size.
4. When the magnesium ion battery is assembled by the nickel disulfide material prepared by the method, the diaphragm is made of glass fiber, and the electrolyte is APC (ammonium nitrate), excellent synergistic effect and good stability are shown. Through tests, the nickel disulfide electrode material is 100 mA g -1 The discharge capacity can reach 261 mAh g -1 . Also shows excellent long-cycle performance at 200 mA g -1 The capacity retention after the following cycles was 44%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows scanning electron micrographs (a) (b) of a nickel disulfide electrode material prepared in stainless steel autoclave I of example 1 of the present invention and (c) (d) of a nickel disulfide electrode material prepared in stainless steel autoclave II of the comparative example (without NaCl addition).
FIG. 2 is a diagram showing the state that three kinds of raw materials are reacted at a constant temperature of 60 ℃ and then transformed into a hard mass in example 1 of the present invention.
FIG. 3 is an X-ray diffraction (XRD) spectrum of a nickel disulfide electrode material prepared by stainless steel autoclave I in example 1 of the present invention.
FIG. 4 is an X-ray diffraction (XRD) spectrum of a material prepared from stainless steel autoclave II (without NaCl addition) in a comparative example of the present invention.
Fig. 5 is an energy dispersion spectrum of the nickel disulfide electrode material prepared in example 1 of the present invention.
Fig. 6 is a charge-discharge curve of a magnesium ion battery prepared by using a nickel disulfide electrode material as a positive electrode in example 1 of the present invention under different current densities.
Fig. 7 is a specific capacity curve of a magnesium ion battery prepared by using a nickel disulfide electrode material as a positive electrode in example 1 of the present invention at different discharge rates.
FIG. 8 shows that 200 mA g of the Mg-ion battery prepared by using the nickel disulfide electrode material as the positive electrode in the embodiment 1 of the invention -1 Lower cycle stability curve.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1
The embodiment is a preparation method and application of a nickel disulfide electrode material, and the steps are as follows:
(1) 3 g of nickel nitrate hexahydrate, 6.39 g of sodium thiosulfate pentahydrate and 0.333 g of sodium chloride are weighed, uniformly ground and transferred into a polytetrafluoroethylene lined stainless steel autoclave I with the capacity of 25 mL. The reaction is carried out for 12 hours in a constant temperature air-blast drying oven at 180 ℃. After the reaction is finished, cooling to room temperature, and adding deionized water for ultrasonic treatment for 30 min to form a uniform solution. And after the ultrasonic treatment is finished, repeatedly washing and cleaning with deionized water and ethanol, centrifuging for 3-5 times, and drying overnight in a constant-temperature air-blowing drying box at 60 ℃ to obtain the nickel disulfide electrode material.
(2) The preparation method of the magnesium ion battery comprises the following steps:
preparation of the positive electrode: weighing a total of 30 mg of the prepared nickel disulfide electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 8. Then the obtained product is placed in a vacuum drying oven at 60 ℃ for 12 hours and is cut into round copper sheets with the diameter of 8 mm by a punching machine, and the mass of each copper sheet loaded with nickel disulfide is about 0.49 mg.
Preparing a negative electrode: and (4) polishing the magnesium sheet by using 400-mesh sand paper until two surfaces are smooth. And then cleaning the polished magnesium sheet by using 0.1M dilute hydrochloric acid solution, and then washing the magnesium sheet by using distilled water and absolute ethyl alcohol respectively to obtain the magnesium cathode with a smooth surface. Finally, the magnesium sheet was cut into a disc 13 mm in diameter using a punch.
Assembling: in a glove box, a coin-type battery CR2032 is used, an anode, a diaphragm, a cathode and fillers are respectively compounded together in a lamination mode, meanwhile, electrolyte is dripped, and finally, a sealing machine is used for packaging the battery to obtain a magnesium ion battery; the glass fiber diaphragm is used as the diaphragm, and the electrolyte is 0.4M 2PhMgCl/THF-AlCl 3 (abbreviated as APC) electrolyte.
FIGS. 1 (a) and (b) are scanning electron microscopes of the nickel disulfide electrode material obtained from the stainless steel autoclave I in this example, which show that the nickel disulfide electrode material is a cotton-like active material and has a particle diameter of 10 to 110nm.
FIG. 2 is a diagram showing the state of conversion of three raw materials into a hard mass after isothermal reaction in the stainless steel autoclave I of this example. As can be seen from the figure, the three raw materials are converted into a hard block state instead of powder after being reacted at the constant temperature of 60 ℃, and a melting region exists between NaCl and nickel nitrate hexahydrate.
FIG. 3 is an XRD pattern of nickel disulfide material obtained from stainless steel autoclave I of this example, which is consistent with a pattern reported in the literature, indicating successful production of nickel disulfide material.
Fig. 5 is a spectrum diagram of the nickel disulfide electrode material obtained in this example, which shows that the material mainly contains Ni and S elements.
Comparative example
The comparative example is a preparation method (without NaCl) and application of a nickel disulfide electrode material, and comprises the following steps:
(1) 3 g of nickel nitrate hexahydrate and 6.39 g of sodium thiosulfate pentahydrate are weighed, uniformly ground and transferred to a polytetrafluoroethylene-lined stainless steel autoclave II (without adding NaCl) with the capacity of 25 mL. The reaction is carried out for 12 hours in a constant temperature air-blast drying oven at 180 ℃. After the reaction is finished, cooling to room temperature, and adding deionized water for ultrasonic treatment for 30 min to form a uniform solution. And after the ultrasonic treatment is finished, repeatedly washing and cleaning with deionized water and ethanol, centrifuging for 3-5 times, and drying overnight in a constant-temperature air-blast drying oven at the temperature of 60 ℃ to obtain the nickel disulfide electrode material.
(2) The preparation method of the magnesium ion battery comprises the following steps:
preparation of the positive electrode: weighing a total of 30 mg of the prepared nickel disulfide electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 8. Then the obtained product is placed in a vacuum drying oven at 60 ℃ for 12 hours and cut into round copper sheets with the diameter of 8 mm by a punch, and the mass of nickel disulfide loaded on each copper sheet is about 0.49 mg.
Preparation of a negative electrode: and (5) polishing the magnesium sheet by using 400-mesh sand paper until two sides are smooth. And then cleaning the polished magnesium sheet by using 0.1M dilute hydrochloric acid solution, and then washing the magnesium sheet by using distilled water and absolute ethyl alcohol respectively to obtain the magnesium cathode with a smooth surface. Finally, the magnesium sheet was cut into a disc having a diameter of 13 mm using a punch.
Assembling: in a glove box, a coin-type battery CR2032 is used, an anode, a diaphragm, a cathode and a filler are respectively compounded together in a lamination mode, meanwhile, electrolyte is dripped, and finally, a sealing machine is used for packaging the battery to obtain a magnesium ion battery; the glass fiber membrane is used as a membrane, and the electrolyte is 0.4M 2PhMgCl/THF-AlCl 3 (abbreviated as APC) electrolyte.
The effect of NaCl on the course of the reaction can be determined by comparing example 1 autoclave I with comparative example autoclave II.
Fig. 1 (c) (d) is a scanning electron microscope of the nickel disulfide electrode material obtained in the stainless steel autoclave ii of the present comparative example, and the particle diameter of the nickel disulfide electrode material formed without NaCl is larger than that of the nickel disulfide electrode material prepared in the stainless steel autoclave i of the example 1, which may reduce the ionic conductivity of the electrode material, and further reduce the overall conductive capability of the electrode; and the larger the particle, the longer the channel for magnesium ion intercalation and deintercalation, which directly affects the deintercalation of magnesium ions, thereby affecting the battery performance.
FIG. 4 is an XRD pattern of the material obtained in the stainless steel autoclave II of this comparative example, and it is found by comparison that the purity of the material can be increased by the participation of NaCl.
Example 2
The embodiment is a preparation method and application of a nickel disulfide electrode material, and the steps are as follows:
(1) Weighing 2.831 g of nickel nitrate hexahydrate, 6.094 g of sodium thiosulfate pentahydrate and 0.353 g of sodium chloride, uniformly grinding, transferring into a polytetrafluoroethylene lined stainless steel autoclave with the capacity of 25 mL, and reacting in a constant-temperature forced air drying oven at 180 ℃ for 12 hours. After the reaction is finished, cooling to room temperature, and adding deionized water for ultrasonic treatment for 30 min to form a uniform solution. And after the ultrasonic treatment is finished, repeatedly washing and cleaning with deionized water and ethanol, centrifuging for 3-5 times, and drying overnight in a constant-temperature air-blowing drying box at 60 ℃ to obtain the nickel disulfide electrode material.
(2) The preparation method of the magnesium ion battery comprises the following steps:
preparation of the positive electrode: weighing a total of 30 mg of the prepared nickel disulfide electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 8. Then the obtained product is placed in a vacuum drying oven at 60 ℃ for 12 hours and cut into round copper sheets with the diameter of 8 mm by a punch, and the mass of nickel disulfide loaded on each copper sheet is about 0.49 mg.
Preparation of a negative electrode: and (4) polishing the magnesium sheet by using 400-mesh sand paper until two surfaces are smooth. And then cleaning the polished magnesium sheet by using 0.1M dilute hydrochloric acid solution, and then washing the magnesium sheet by using distilled water and absolute ethyl alcohol respectively to obtain the magnesium cathode with a smooth surface. Finally, the magnesium sheet was cut into a disc 13 mm in diameter using a punch.
Assembling: in a glove box, a coin-type battery CR2032 is used, an anode, a diaphragm, a cathode and fillers are respectively compounded together in a lamination mode, meanwhile, electrolyte is dripped, and finally, a sealing machine is used for packaging the battery to obtain a magnesium ion battery; the glass fiber diaphragm is used as the diaphragm, and the electrolyte is 0.4M 2PhMgCl/THF-AlCl 3 (abbreviated as APC) electrolyte.
Example 3
The embodiment is a preparation method and application of a nickel disulfide electrode material, and the steps are as follows:
(1) Weighing 3.064 g of nickel nitrate hexahydrate, 6.460 g of sodium thiosulfate pentahydrate and 0.346 g of sodium chloride, uniformly grinding, transferring into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 25 mL, and reacting in a constant-temperature forced air drying oven at 180 ℃ for 12 hours. After the reaction is finished, cooling to room temperature, and adding deionized water for ultrasonic treatment for 30 min to form a uniform solution. And after the ultrasonic treatment is finished, repeatedly washing and cleaning with deionized water and ethanol, centrifuging for 3-5 times, and drying overnight in a constant-temperature air-blowing drying box at 60 ℃ to obtain the nickel disulfide electrode material.
(2) The preparation method of the magnesium ion battery comprises the following steps:
preparation of the positive electrode: weighing a total of 30 mg of the prepared nickel disulfide electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 8. Then the obtained product is placed in a vacuum drying oven at 60 ℃ for 12 hours and cut into round copper sheets with the diameter of 8 mm by a punch, and the mass of nickel disulfide loaded on each copper sheet is about 0.49 mg.
Preparation of a negative electrode: and (5) polishing the magnesium sheet by using 400-mesh sand paper until two sides are smooth. And then cleaning the polished magnesium sheet by using 0.1M dilute hydrochloric acid solution, and washing the magnesium sheet by using distilled water and absolute ethyl alcohol respectively to obtain the magnesium cathode with a smooth surface. Finally, the magnesium sheet was cut into a disc 13 mm in diameter using a punch.
Assembling: in a glove box, a coin-type battery CR2032 is used, an anode, a diaphragm, a cathode and fillers are respectively compounded together in a lamination mode, meanwhile, electrolyte is dripped, and finally, a sealing machine is used for packaging the battery to obtain a magnesium ion battery; the glass fiber diaphragm is used as the diaphragm, and the electrolyte is 0.4M 2PhMgCl/THF-AlCl 3 (APC for short) electrolyte.
Example 4
The embodiment relates to a preparation method and application of a nickel disulfide electrode material, and the preparation method comprises the following steps:
(1) Weighing 2 g of nickel nitrate hexahydrate, 5 g of sodium thiosulfate pentahydrate and 0.5 g of sodium chloride, uniformly grinding, transferring into a polytetrafluoroethylene lined stainless steel autoclave with the capacity of 25 mL, and reacting for 12 hours in a constant-temperature air-blowing drying oven at 170 ℃. After the reaction is finished, cooling to room temperature, and adding deionized water for ultrasonic treatment for 30 min to form a uniform solution. And after the ultrasonic treatment is finished, repeatedly washing and cleaning with deionized water and ethanol, centrifuging for 3-5 times, and drying overnight in a constant-temperature air-blowing drying box at 60 ℃ to obtain the nickel disulfide electrode material.
(2) The preparation method of the magnesium ion battery comprises the following steps:
preparation of the positive electrode: weighing 40 mg of the prepared nickel disulfide electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 7. Then the obtained product is placed in a vacuum drying oven at 60 ℃ for 6 hours and cut into round copper sheets with the diameter of 8 mm by a punch, and the mass of nickel disulfide loaded on each copper sheet is about 0.64 mg.
Preparing a negative electrode: and (5) polishing the magnesium sheet by using 400-mesh sand paper until two sides are smooth. And then cleaning the polished magnesium sheet by using 0.2M dilute hydrochloric acid solution, and washing the magnesium sheet by using distilled water and absolute ethyl alcohol respectively to obtain the magnesium cathode with a smooth surface. Finally, the magnesium sheet was cut into a disk having a diameter of 8 mm by using a punch.
Assembling: in a glove box, a coin-type battery CR2032 is used, an anode, a diaphragm, a cathode and a filler are respectively compounded together in a lamination mode, meanwhile, electrolyte is dripped, and finally, a sealing machine is used for packaging the battery to obtain a magnesium ion battery; the glass fiber diaphragm is used as the diaphragm, and the electrolyte is 0.4M 2PhMgCl/THF-AlCl 3 (APC for short) electrolyte.
Example 5
The embodiment relates to a preparation method and application of a nickel disulfide electrode material, and the preparation method comprises the following steps:
(1) Weighing 2 g of nickel nitrate hexahydrate, 5 g of sodium thiosulfate pentahydrate and 0.5 g of sodium chloride, uniformly grinding, transferring into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 25 mL, and reacting for 10 hours in a constant-temperature forced air drying oven at 180 ℃. After the reaction is finished, cooling to room temperature, and adding deionized water for ultrasonic treatment for 30 min to form a uniform solution. And after the ultrasonic treatment is finished, repeatedly washing and cleaning with deionized water and ethanol, centrifuging for 3-5 times, and drying overnight in a constant-temperature air-blowing drying box at 60 ℃ to obtain the nickel disulfide electrode material.
(2) The preparation method of the magnesium ion battery comprises the following steps:
preparation of the positive electrode: weighing 50 mg of the prepared nickel disulfide electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 6.5. Then the obtained product is placed in a vacuum drying oven at 60 ℃ for 8 hours and cut into round copper sheets with the diameter of 8 mm by a punch, and the mass of nickel disulfide loaded on each copper sheet is about 0.53 mg.
Preparation of a negative electrode: and (5) polishing the magnesium sheet by using 400-mesh sand paper until two sides are smooth. And then cleaning the polished magnesium sheet by using 0.3M dilute hydrochloric acid solution, and washing the magnesium sheet by using distilled water and absolute ethyl alcohol respectively to obtain the magnesium cathode with a smooth surface. Finally, the magnesium sheet was cut into a disc having a diameter of 11 mm using a punch.
Assembling: in a glove box, a coin-type battery CR2032 is used, an anode, a diaphragm, a cathode and fillers are respectively compounded together in a lamination mode, meanwhile, electrolyte is dripped, and finally, a sealing machine is used for packaging the battery to obtain a magnesium ion battery; the glass fiber membrane is used as a membrane, and the electrolyte is 0.4M 2PhMgCl/THF-AlCl 3 (abbreviated as APC) electrolyte.
Example 6
The embodiment is a preparation method and application of a nickel disulfide electrode material, and the steps are as follows:
(1) Weighing 2 g of nickel nitrate hexahydrate, 4 g of sodium thiosulfate pentahydrate and 0.4 g of sodium chloride, uniformly grinding, transferring into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 25 mL, and reacting for 10 hours in a constant-temperature air-blowing drying oven at 160 ℃. After the reaction is finished, cooling to room temperature, and adding deionized water for ultrasonic treatment for 30 min to form a uniform solution. And after the ultrasonic treatment is finished, repeatedly washing and cleaning with deionized water and ethanol, centrifuging for 3-5 times, and drying overnight in a constant-temperature air-blowing drying box at 60 ℃ to obtain the nickel disulfide electrode material.
(2) The preparation method of the magnesium ion battery comprises the following steps:
preparation of the positive electrode: weighing a total of 45 mg of the prepared nickel disulfide electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 5. Then the obtained product is placed in a vacuum drying oven at 60 ℃ for 10 hours and is cut into round copper sheets with the diameter of 8 mm by a punch, and the mass of nickel disulfide loaded on each copper sheet is about 0.48 mg.
Preparation of a negative electrode: and (5) polishing the magnesium sheet by using 400-mesh sand paper until two sides are smooth. And then cleaning the polished magnesium sheet by using 0.5M dilute hydrochloric acid solution, and then washing the magnesium sheet by using distilled water and absolute ethyl alcohol respectively to obtain the magnesium cathode with a smooth surface. Finally, the magnesium sheet was cut into a disc 13 mm in diameter using a punch.
Assembling: in a glove box, a coin-type battery CR2032 is used, an anode, a diaphragm, a cathode and a filler are respectively compounded together in a lamination mode, meanwhile, electrolyte is dripped, and finally, a sealing machine is used for packaging the battery to obtain a magnesium ion battery; the glass fiber diaphragm is used as the diaphragm, and the electrolyte is 0.4M 2PhMgCl/THF-AlCl 3 (abbreviated as APC) electrolyte.
Effects of the embodiment
The electrode sheet prepared in example 1 was prepared into a battery and then subjected to electrochemical performance testing.
Fig. 6 is a charge-discharge curve of the magnesium ion battery prepared by using the nickel disulfide electrode material as the positive electrode in example 1 of the present invention under different current densities, and the discharge and charge plateaus can be clearly observed, which shows the excellent structural stability.
FIG. 7 is a specific capacity curve of a magnesium ion battery prepared by using a nickel disulfide electrode material as a positive electrode in example 1 of the present invention at different discharge rates, wherein the specific capacity curve is 100 mA g -1 Discharge capacity at the time of discharge was 261 mAh g -1 。
As can be seen from FIGS. 6 and 7, the material has excellent rate capability at 100 mA g -1 Discharge capacity at 261 mAh g -1 。
FIG. 8 shows that the concentration of 200 mA g of Mg-ion battery prepared by using the nickel disulfide electrode material as the positive electrode in example 1 of the present invention -1 Lower cycle stability curve. As shown in fig. 8, the nickel disulfide material has a certain cycle stability, and after 288 cycles, the capacity retention rate is 44%. The structure of the material is more beneficial to the contact between the nickel disulfide nanoparticles and the electrolyte, and the electrochemical reaction kinetics is accelerated.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of a nickel disulfide electrode material is characterized by preparing the nickel disulfide electrode material by a one-step low-temperature molten salt method and taking molten eutectic salt nickel nitrate hexahydrate-NaCl as a reaction supply liquid medium and taking nickel nitrate hexahydrate and sodium thiosulfate pentahydrate as raw materials.
2. The method for preparing the nickel disulfide electrode material according to claim 1, comprising the following steps:
(1) Preparing an electrode material: uniformly grinding nickel nitrate hexahydrate, sodium thiosulfate pentahydrate and NaCl, and then carrying out constant-temperature reaction to obtain a nickel disulfide turbid electrode material;
(2) Preparing a finished product of the electrode material: and (2) cooling the nickel disulfide turbid electrode material obtained in the step (1) to room temperature, adding deionized water for ultrasonic treatment, and after uniform mixing, separating, cleaning and drying to obtain the nickel disulfide electrode material.
3. The method for preparing the nickel disulfide electrode material according to claim 2, wherein: the mass ratio of the nickel nitrate hexahydrate, the sodium thiosulfate pentahydrate and the NaCl in the step (1) is (8-10): (18-20): 1-2).
4. The method for preparing a nickel disulfide electrode material as set forth in claim 2, wherein: in the step (1), the mixture of nickel nitrate hexahydrate, sodium thiosulfate pentahydrate and NaCl after being uniformly ground is in a flowing state.
5. The method for preparing a nickel disulfide electrode material according to claim 2 or 3, wherein: the temperature of the constant-temperature reaction in the step (1) is 160-180 ℃.
6. The method for preparing the nickel disulfide electrode material according to claim 5, wherein: the constant-temperature reaction time in the step (1) is 10 to 14h.
7. The method for preparing a nickel disulfide electrode material according to claim 2 or 3, wherein: and (2) washing for 3-5 times by using deionized water, and then washing for 3-5 times by using ethanol, wherein the drying temperature is 60 ℃, and the drying time is 6-20h.
8. The nickel disulfide electrode material prepared by the preparation method according to any one of claims 1 to 4 or 6, wherein: the nickel disulfide electrode material is composed of nickel disulfide nanoparticles with the particle diameter of 10 to 110nm, and the morphology structure of the nickel disulfide electrode material is cotton-shaped.
9. The application of the nickel disulfide electrode material of claim 8 in the field of preparing magnesium ion batteries as a positive electrode material.
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| CN117431598A (en) * | 2023-12-20 | 2024-01-23 | 中石油深圳新能源研究院有限公司 | Protective coating, preparation method thereof, fuel cell and metal connector of fuel cell |
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