CN107732166B - Preparation of nano Ni3S2-C composite material method and application thereof - Google Patents
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Abstract
The invention relates to a method for preparing nano Ni3S2-C composite material process and its use, comprising the following steps: s01: preparation of precursor Ni3(BTC)2DMF; s02: subjecting the precursor Ni obtained in the step S01 to a protective gas atmosphere3(BTC)2Pre-carbonizing for 1 to 6 hours with DMF to obtain pre-carbonized precursor Ni3(BTC)2DMF; s03: subjecting the pre-carbonized precursor Ni to a protective gas atmosphere3(BTC)2Mixing DMF and sulfur powder, then carrying out high-temperature vulcanization for 1 to 10 hours, and cooling to obtain Ni3S2-a C composite material. The invention has the beneficial effects that: the preparation method of the precursor is simple, has high yield and can be used for large-scale preparation and production; ni3S2the-C composite material has excellent cycling stability and rate capability, huge specific surface area, high utilization rate of electrode materials and excellent specific capacity.
Description
Technical Field
The invention relates to the technical field of preparation methods of battery electrode materials, in particular to a method for preparing nano Ni3S2-C composite material and its use.
Background
The zinc-nickel battery belongs to a secondary water system zinc-based battery, and is hopeful to replace a lithium ion battery due to ultrahigh power and energy density, lower production cost and non-combustible and non-explosive high safety, so that the zinc-nickel battery occupies a large-scale energy storage market in the future. Particularly, with a series of breakthrough progress recently made on the protection work of zinc dendrite on the negative electrode, the secondary alkaline zinc-nickel battery has been developed in a breakthrough way.
In a traditional alkaline nickel-zinc battery, a mixture of metal zinc and activated carbon is used as a negative electrode, nickel hydroxide is used as a positive electrode, and a mixed solution of potassium hydroxide, lithium hydroxide, zinc acetate and zinc oxide is used as an electrolyte. Due to the low electrochemical potential (-0.763V) and the high theoretical capacity (820mAh/g) of the metal zinc, the alkaline nickel-zinc battery has the energy density as high as 80Wh/kg, and the power density can also reach 12 KW/kg. Although already superior to most water-based batteries, there is still a gap in performance compared to ion batteries. The performance of the current alkaline nickel-zinc battery is mainly limited by the capacity of the positive electrode: the positive electrode of the alkaline nickel-zinc battery mainly depends on surface oxidation-reduction reaction to provide capacity, although nickel hydroxide has the advantages of easy preparation and high theoretical specific capacity, the nickel hydroxide is superior to nickel hydroxide and difficult to nanocrystallize, so that the material utilization rate of the nickel hydroxide in electrode reaction is low, and the expressed capacity is far lower than the theoretical capacity. Therefore, in order to further improve the performance of the secondary alkaline nickel-zinc battery, the secondary alkaline nickel-zinc battery needs to be redesigned and the anode material needs to be reselected.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing nano Ni aiming at the defects of the prior art3S2-C composite material and its use.
The technical scheme for solving the technical problems is as follows:
according to one aspect of the invention, the preparation of nano Ni is provided3S2-C composite material process comprising the steps of:
s01: preparation of precursor Ni3(BTC)2·DMF；
S02: subjecting the precursor Ni obtained in the step S01 to a protective gas atmosphere3(BTC)2Pre-carbonizing for 1 to 6 hours with DMF to obtain pre-carbonized precursor Ni3(BTC)2·DMF；
S03: subjecting the pre-carbonized precursor Ni to a protective gas atmosphere3(BTC)2Mixing DMF and sulfur powder, then carrying out high-temperature vulcanization for 1 to 10 hours, and cooling to obtain Ni3S2-a C composite material.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the precursor Ni in the step S013(BTC)2The DMF is obtained by the solvothermal reaction of a nickel source and BTC, namely adding the nickel source and trimesic acid into a solvent for dissolving to obtain a clear solution, transferring the clear solution into a reaction kettle, sealing the reaction kettle, preserving the temperature for 1 to 20 hours, cooling to room temperature, and obtaining a productSeparating, cleaning and drying to obtain precursor Ni3(BTC)2·DMF。
Further, the nickel source is one or more of nitrate of nickel, acetate of nickel, sulfate of nickel, oxide of nickel, chloride of nickel and fluoride of nickel.
Further, the solvent used in the solvent thermal reaction is one or a mixture of water, N-N dimethylformamide, methanol and ethanol.
Further, the reaction temperature of the solvothermal reaction is 80 ℃ to 250 ℃.
Further, the step S02 is to process the precursor Ni3(BTC)2The temperature at which DMF is pre-carbonized is from 250 ℃ to 350 ℃.
Further, the pre-carbonized precursor Ni is treated in the step S033(BTC)2The temperature at which DMF undergoes sulfidation is at least 50 ℃ above the boiling temperature of S.
Further, in the step S03, the pre-carbonized precursor Ni3(BTC)2The mass ratio of DMF to sulfur powder is in the range of 10:1 to 1: 1.
Further, the shielding gas used in step S02 and step S03 is a mixed gas of any one or more of nitrogen, argon, hydrogen, and carbon monoxide.
According to another aspect of the present invention, there is provided a method for preparing nano Ni according to the above-mentioned one3S2Nano Ni prepared by method of-C composite material3S2Application of the-C composite material to a positive electrode material of a secondary nickel-zinc battery.
The invention has the beneficial effects that: precursor Ni of the invention3(BTC)2The preparation method of DMF is simple, has high yield and can be used for large-scale preparation and production; nanocomposite Ni3S2The structure of-C is completely duplicated in the precursor Ni3(BTC)2DMF, and carbonization of the carbon skeleton formed by BTC effectively limits Ni3S2Grow up of Ni3S2The nano particles are uniformly distributed in the carbon skeleton, and not only can be increasedAdding Ni3S2Electrical conductivity of-C composite material and prevention of Ni3S2The nano particles are agglomerated and pulverized in the charging and discharging processes, so that Ni3S2the-C composite material has excellent cycling stability; ni produced in addition3S2the-C composite material has rich pore structure, provides rich transmission channels for the electrolyte and has excellent rate performance; obtained Ni3S2-C composite material, Ni3S2The particle size is about 5nm, the specific surface area is huge, the utilization rate of the electrode material is high, and the specific capacity is excellent.
Drawings
FIG. 1 shows the nano Ni prepared in the first embodiment of the present invention3S2-TEM images of the C composite;
FIG. 2 shows the nano Ni prepared in the third embodiment of the present invention3S2-TEM images of the C composite;
FIG. 3 shows the nano Ni prepared in the fourth embodiment of the present invention3S2-a topography of the C composite;
FIG. 4 shows the nano Ni prepared in the fourth embodiment of the present invention3S2-a graph of electrochemical performance of the C composite;
FIG. 5 shows nano Ni particles prepared in the first to fourth embodiments of the present invention3S2-comparative plot of electrochemical performance of C composite.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
The following will provide a method for preparing nano Ni in the present embodiment with reference to the accompanying drawings3S2The method of the-C composite material and its application are described in detail.
Preparation of nano Ni3S2-C composite material process comprising the steps of:
s01: preparation of precursor Ni3(BTC)2·DMF；
S02: subjecting the step S0 to a protective gas atmosphere1 the precursor Ni is obtained3(BTC)2Pre-carbonizing for 1 to 6 hours with DMF to obtain pre-carbonized precursor Ni3(BTC)2·DMF；
S03: subjecting the pre-carbonized precursor Ni to a protective gas atmosphere3(BTC)2Mixing DMF and sulfur powder, then carrying out high-temperature vulcanization for 1 to 10 hours, and cooling to obtain Ni3S2-a C composite material.
Precursor Ni in the step S013(BTC)2The DMF is obtained by the solvothermal reaction of a nickel source and BTC, namely adding the nickel source and trimesic acid into a solvent for dissolving to obtain a clear solution, transferring the clear solution into a reaction kettle, sealing the reaction kettle, preserving the temperature for 1 to 20 hours, cooling to room temperature, separating a product, cleaning and drying to obtain a precursor Ni3(BTC)2·DMF。
The nickel source is one or a mixture of more of nitrate of nickel, acetate of nickel, sulfate of nickel, oxide of nickel, chloride of nickel and fluoride of nickel.
The solvent used in the solvent thermal reaction is one or a mixture of water, N-N dimethylformamide, methanol and ethanol.
The reaction temperature of the solvothermal reaction is 80 ℃ to 250 ℃, and in the present embodiment, is preferably 140 ℃.
The step S02 is to the precursor Ni3(BTC)2The temperature at which DMF is pre-carbonized is 250 ℃ to 350 ℃ and in this example is preferably 300 ℃.
Ni as the pre-carbonized precursor in the step S033(BTC)2The temperature at which DMF is subjected to sulfidation is at least 50 ℃ higher than the boiling temperature of the sulfur powder; for the pre-carbonized precursor Ni3(BTC)2The temperature at which DMF is sulfided is in the range of 450 ℃ to 850 ℃, in this example, preferably 650 ℃; and Ni as the pre-carbonized precursor3(BTC)2The temperature at which DMF undergoes vulcanization needs to be raised slowly, i.e., at a rate of 5 deg.C/min.
The protective gas used in the steps S02 and S03 is a mixture of one or more of nitrogen, argon, hydrogen and carbon monoxide.
In the step S03, the pre-carbonized precursor Ni3(BTC)2The mass ratio of DMF mixed with sulfur powder is in the range of 10:1 to 1:1, preferably 10:2 in this example.
The experimental results and the advantageous effects of the present invention will be specifically described below with reference to specific examples and the accompanying drawings.
The first embodiment is as follows: preparation of nano Ni3S2-C composite material process and its use, comprising the following steps:
firstly, adding nickel nitrate and trimesic acid into a mixed solution of DMF (dimethyl formamide), methanol and water for dissolving to obtain a clear solution;
secondly, transferring the clear solution obtained in the first step into a reaction kettle, sealing the reaction kettle, preserving heat for 1h at 80 ℃, separating the product after cooling to room temperature, and then cleaning and drying to obtain a precursor Ni3(BTC)2·DMF；
Thirdly, the precursor Ni prepared in the second step3(BTC)2DMF is put in a porcelain boat, and then the porcelain boat is filled with precursor Ni3(BTC)2Putting the porcelain boat of DMF into an atmosphere furnace, and then introducing protective gas argon into the atmosphere furnace until the furnace is O2Completely discharging;
fourthly, O in the furnace to be subjected to atmosphere2After exhausting, the temperature in the atmosphere furnace is increased to 250 ℃ to remove the precursor Ni3(BTC)2DMF is subjected to pre-carbonization for 1h to obtain pre-carbonized Ni3(BTC)2·DMF；
Fifthly, pre-carbonized Ni obtained in the fourth step3(BTC)2Mixing DMF and sulfur powder according to the mass ratio of 10:1, then placing the mixture into a porcelain boat, placing the porcelain boat into an atmosphere furnace, introducing protective gas argon into the atmosphere furnace for 30min in advance, slowly (slowly, 5 ℃/min) raising the temperature in the atmosphere furnace to 450 ℃, and carrying out pre-carbonization on the Ni prepared in the step SO43(BTC)2Introduction of DMFCarrying out vulcanization treatment for 1h, and cooling the obtained product to room temperature along with a furnace to obtain Ni3S2-a C composite material;
sixthly, using the Ni obtained in the fifth step3S2the-C composite material is made into an electrode plate and is used for a positive electrode of a secondary nickel-zinc battery.
FIG. 1 shows the nano Ni prepared in the first embodiment3S2TEM (Transmission Electron microscope) image of the-C composite, from which it can be seen that the Ni which is finally obtained3S2The particle size was about 0.5 μm.
Example two: preparation of nano Ni3S2-C composite material process and its use, comprising the following steps:
firstly, adding nickel nitrate and trimesic acid into a mixed solution of DMF (dimethyl formamide), methanol and water for dissolving to obtain a clear solution;
secondly, transferring the clear solution obtained in the first step into a reaction kettle, sealing the reaction kettle, preserving heat at 165 ℃ for 11.5 hours, cooling to room temperature, separating the product, cleaning and drying to obtain a precursor Ni3(BTC)2·DMF；
Thirdly, the precursor Ni prepared in the second step3(BTC)2DMF is put in a porcelain boat, and then the porcelain boat is filled with precursor Ni3(BTC)2Putting the porcelain boat of DMF into an atmosphere furnace, and then introducing protective gas argon into the atmosphere furnace until the furnace is O2Completely discharging;
fourthly, O in the furnace to be subjected to atmosphere2After exhausting, the temperature in the atmosphere furnace is raised to 300 ℃ to remove the precursor Ni3(BTC)2DMF is subjected to pre-carbonization for 3.5h to obtain pre-carbonized Ni3(BTC)2·DMF；
Fifthly, pre-carbonized Ni obtained in the fourth step3(BTC)2Mixing DMF and sulfur powder according to the mass ratio of 5:1, then placing the mixture into a porcelain boat, placing the porcelain boat into an atmosphere furnace, introducing protective gas argon into the atmosphere furnace for 30min in advance, and then introducing protective gas argon into the atmosphere furnaceThe temperature was slowly (slowly means 5 ℃/min) raised to 650 ℃ for the pre-carbonized Ni obtained in step SO43(BTC)2Carrying out vulcanization treatment on DMF for 5.5h, and cooling the obtained product to room temperature along with a furnace to obtain Ni3S2-a C composite material;
sixthly, using the Ni obtained in the fifth step3S2the-C composite material is made into an electrode plate and is used for a positive electrode of a secondary nickel-zinc battery.
Example three: preparation of nano Ni3S2-C composite material process and its use, comprising the following steps:
firstly, adding nickel nitrate and trimesic acid into a mixed solution of DMF (dimethyl formamide), methanol and water for dissolving to obtain a clear solution;
secondly, transferring the clear solution obtained in the first step into a reaction kettle, sealing the reaction kettle, preserving heat at 250 ℃ for 20 hours, cooling to room temperature, separating the product, cleaning and drying to obtain a precursor Ni3(BTC)2·DMF；
Thirdly, the precursor Ni prepared in the second step3(BTC)2DMF is put in a porcelain boat, and then the porcelain boat is filled with precursor Ni3(BTC)2Putting the porcelain boat of DMF into an atmosphere furnace, and then introducing protective gas argon into the atmosphere furnace until the furnace is O2Completely discharging;
fourthly, O in the furnace to be subjected to atmosphere2After exhausting, the temperature in the atmosphere furnace is raised to 350 ℃ to remove the precursor Ni3(BTC)2DMF is subjected to pre-carbonization for 6h to obtain pre-carbonized Ni3(BTC)2·DMF；
Fifthly, pre-carbonized Ni obtained in the fourth step3(BTC)2Mixing DMF and sulfur powder according to the mass ratio of 1:1, then placing the mixture into a porcelain boat, placing the porcelain boat into an atmosphere furnace, introducing protective gas argon into the atmosphere furnace for 30min in advance, slowly (slowly, 5 ℃/min) raising the temperature in the atmosphere furnace to 850 ℃, and carrying out pre-carbonization on the Ni prepared in the step SO43(BTC)2Vulcanization treatment with DMF when vulcanizedThe time is 10 hours, the obtained product is cooled to room temperature along with the furnace, and Ni can be obtained3S2-a C composite material;
sixthly, using the Ni obtained in the fifth step3S2the-C composite material is made into an electrode plate and is used for a positive electrode of a secondary nickel-zinc battery.
As shown in FIG. 2, the nano Ni prepared in the third embodiment3S2TEM (Transmission Electron microscope) image of the-C composite, from which it can be seen that the Ni which is finally obtained3S2The particle size was about 200 nm.
Example four: preparation of nano Ni3S2-C composite material process and its use, comprising the following steps:
firstly, adding nickel nitrate and trimesic acid into a mixed solution of DMF (dimethyl formamide), methanol and water for dissolving to obtain a clear solution;
secondly, transferring the clear solution obtained in the first step into a reaction kettle, sealing the reaction kettle, preserving heat for 8 hours at 140 ℃, separating the product after cooling to room temperature, and then cleaning and drying to obtain a precursor Ni3(BTC)2·DMF；
Thirdly, the precursor Ni prepared in the second step3(BTC)2DMF is put in a porcelain boat, and then the porcelain boat is filled with precursor Ni3(BTC)2Putting the porcelain boat of DMF into an atmosphere furnace, and then introducing protective gas argon into the atmosphere furnace until the furnace is O2Completely discharging;
fourthly, O in the furnace to be subjected to atmosphere2After exhausting, the temperature in the atmosphere furnace is raised to 300 ℃ to remove the precursor Ni3(BTC)2DMF is subjected to pre-carbonization for 5h to obtain pre-carbonized Ni3(BTC)2·DMF；
Fifthly, pre-carbonized Ni obtained in the fourth step3(BTC)2Mixing DMF and sulfur powder at a mass ratio of 10:2, placing the mixture in a porcelain boat, placing the porcelain boat in an atmosphere furnace, introducing protective gas argon into the atmosphere furnace for 30min in advance, and slowing the temperature in the atmosphere furnace (slowly means 5 ℃. sup. 4 ℃ -min) to 650 deg.C, pre-carbonized Ni prepared in said step SO43(BTC)2Carrying out vulcanization treatment on DMF for 5h, and cooling the obtained product to room temperature along with a furnace to obtain Ni3S2-a C composite material;
sixthly, using the Ni obtained in the fifth step3S2the-C composite material is made into an electrode plate and is used for a positive electrode of a secondary nickel-zinc battery.
FIG. 3 shows the nano Ni prepared in the fourth embodiment3S2Morphology of the-C composite material in different states, including SEM (Scanning electron microscope) image and TEM (transmission electron microscope) image, from which it can be seen that the Ni obtained finally3S2The particle size is about 5nm, the specific surface area is huge, the utilization rate of the electrode material is high, and the specific capacity is excellent.
FIG. 4 shows the nano Ni prepared in the fourth embodiment3S2-electrochemical performance diagram of the C composite.
Example five: preparation of nano Ni3S2-C composite material process and its use, comprising the following steps:
firstly, adding nickel acetate and trimesic acid into a mixed solution of DMF (dimethyl formamide), ethanol and water for dissolving to obtain a clear solution;
secondly, transferring the clear solution obtained in the first step into a reaction kettle, sealing the reaction kettle, preserving heat for 8 hours at 140 ℃, separating the product after cooling to room temperature, and then cleaning and drying to obtain a precursor Ni3(BTC)2·DMF；
Thirdly, the precursor Ni prepared in the second step3(BTC)2DMF is put in a porcelain boat, and then the porcelain boat is filled with precursor Ni3(BTC)2Putting the porcelain boat of DMF into an atmosphere furnace, and then introducing protective gas nitrogen into the atmosphere furnace until the furnace is O2Completely discharging;
fourthly, O in the furnace to be subjected to atmosphere2After exhausting, the temperature in the atmosphere furnace is raised to 300 ℃ to remove the precursor Ni3(BTC)2DMF is subjected to pre-carbonization for 5h to obtain pre-carbonized Ni3(BTC)2·DMF；
Fifthly, pre-carbonized Ni obtained in the fourth step3(BTC)2Mixing DMF and sulfur powder according to the mass ratio of 10:2, then placing the mixture into a porcelain boat, placing the porcelain boat into an atmosphere furnace, introducing protective gas nitrogen into the atmosphere furnace for 30min in advance, slowly (slowly, 5 ℃/min) raising the temperature in the atmosphere furnace to 650 ℃, and carrying out pre-carbonization on the Ni prepared in the step SO43(BTC)2Carrying out vulcanization treatment on DMF for 5h, and cooling the obtained product to room temperature along with a furnace to obtain Ni3S2-a C composite material;
sixthly, using the Ni obtained in the fifth step3S2the-C composite material is made into an electrode plate and is used for a positive electrode of a secondary nickel-zinc battery.
The operation steps and reaction conditions of the above examples four and five are the best conditions for carrying out the invention.
As shown in fig. 5, the nano Ni prepared in the first to fourth examples3S2the-C composite materials were respectively prepared into electrode sheets to be tested for electrochemical performance, and it can be seen from FIG. 5 that under the same test conditions, the nano Ni prepared in example four3S2The electrochemical performance of the-C composite material is the best, and the larger the capacity is, the nano Ni prepared in the fourth embodiment3S2The more outstanding the electrochemical performance of the-C composite material.
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 (8)
1. Preparation of nano Ni3S2-C composite material, characterized in that it comprises the following steps:
s01: adding a nickel source and trimesic acid into a solvent for dissolving to obtain a clear solution, and thenTransferring the clear solution into a reaction kettle, sealing the reaction kettle, keeping the reaction temperature at 80-250 ℃, keeping the temperature for 1-20 h, cooling to room temperature, separating the product, cleaning and drying to obtain a precursor Ni3(BTC)2·DMF；
S02: subjecting the precursor Ni obtained in the step S01 to a protective gas atmosphere3(BTC)2Pre-carbonizing for 1 to 6 hours with DMF to obtain pre-carbonized precursor Ni3(BTC)2·DMF；
S03: subjecting the pre-carbonized precursor Ni to a protective gas atmosphere3(BTC)2Mixing DMF and sulfur powder, then carrying out high-temperature vulcanization for 1 to 10 hours, and cooling to obtain Ni3S2-a C composite material.
2. Preparation of nano Ni according to claim 13S2-C composite material, characterized in that: the nickel source is one or a mixture of more of nitrate of nickel, acetate of nickel, sulfate of nickel, oxide of nickel, chloride of nickel and fluoride of nickel.
3. Preparation of nano Ni according to claim 13S2-C composite material, characterized in that: the solvent used in the solvent thermal reaction is one or a mixture of water, N-N dimethylformamide, methanol and ethanol.
4. Preparation of nano Ni according to claim 13S2-C composite material, characterized in that: the step S02 is to the precursor Ni3(BTC)2The temperature at which DMF is pre-carbonized is from 250 ℃ to 350 ℃.
5. Preparation of nano Ni according to claim 13S2-C composite material, characterized in that: ni as the pre-carbonized precursor in the step S033(BTC)2The temperature at which DMF is sulfided is at least 50 ℃ higher than the boiling temperature of the sulfur powder。
6. The method for preparing nano Ni according to claim 53S2-C composite material, characterized in that: in the step S03, the pre-carbonized precursor Ni3(BTC)2The mass ratio of DMF to sulfur powder is in the range of 10:1 to 1: 1.
7. Preparation of nano Ni according to claim 13S2-C composite material, characterized in that: the protective gas used in the steps S02 and S03 is a mixture of one or more of nitrogen, argon, hydrogen and carbon monoxide.
8. The method for preparing nano Ni according to any one of claims 1 to 73S2-use of a method for the production of a C composite material, characterized in that: the prepared nano Ni3S2the-C composite material can be used as a positive electrode material of a secondary nickel-zinc battery.
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| CN104201380A (en) * | 2014-08-19 | 2014-12-10 | 北京科技大学 | Preparation method of nano Ni3S2 material with lamellar structure |
| CN106076377A (en) * | 2016-06-06 | 2016-11-09 | 复旦大学 | A kind of cobalt sulfide nickel carbon nanotube carbon nano-fiber composite material of phosphorus doping and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104201380A (en) * | 2014-08-19 | 2014-12-10 | 北京科技大学 | Preparation method of nano Ni3S2 material with lamellar structure |
| CN106076377A (en) * | 2016-06-06 | 2016-11-09 | 复旦大学 | A kind of cobalt sulfide nickel carbon nanotube carbon nano-fiber composite material of phosphorus doping and preparation method thereof |
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