CN111525122A - NaTi2(PO4)3Negative electrode material of-porous carbon nanofiber sodium ion battery and preparation method thereof - Google Patents
NaTi2(PO4)3Negative electrode material of-porous carbon nanofiber sodium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of negative electrode materials of sodium-ion batteries and discloses a NaTi2(PO4)3The porous carbon nanofiber sodium ion battery negative electrode material comprises the following formula raw materials and components: titanium acetylacetonate, hexadecyl trimethyl ammonium bromide and CH3COONa、NH4H2PO4And the ZIF-8 loads CNTs and polyacrylonitrile. The NaTi2(PO4)3Preparing a porous carbon nanofiber sodium ion battery cathode material and acetylacetone titanium as an organic titanium source to obtain nano-shaped NaTi2(PO4)3Uniformly grown on ZIF-8In the pore and mesoporous structure, nano NaTi is avoided2(PO4)3The agglomeration and accumulation of the NaTi are beneficial to the sodium ion extraction and insertion process, the electrostatic spinning method and the thermal cracking method to form the NaTi2(PO4)3Carbon nanofiber material, which produces a large number of channels and pore structures, is NaTi2(PO4)3The volume expansion provides elastic buffering, the mechanical stress is reduced, the electrochemical stability of the electrode material and the rate capability of the sodium ion battery are improved, and the nitrogen-doped carbon nanofiber has good conductivity.
Description
Technical Field
The invention relates to the technical field of negative electrode materials of sodium ion batteries, in particular to NaTi2(PO4)3-porous carbon nanofiber sodium ion battery negative electrode material and preparation method thereof.
Background
The sodium ion battery is a secondary rechargeable battery, is similar to the working principle of the lithium ion battery, and mainly works by moving sodium ions between a positive electrode and a negative electrode, the sodium ions are inserted and separated back and forth between the two electrodes in the charging and discharging process, the sodium ions are separated from the positive electrode and inserted into the negative electrode through an electrolyte during charging, and the negative electrode is in a sodium-rich state; during discharging, sodium ions are extracted from the negative electrode and are inserted into the positive electrode through the electrolyte, the positive electrode is in a sodium-rich state, compared with a lithium ion battery, the sodium salt raw material in the sodium ion battery is rich in reserve and low in price, the sodium ion battery can use low-concentration electrolyte, so that the cost is reduced, and the sodium ions and aluminum are difficult to form an alloy.
Transition metal phosphates such as NaTi2(PO4)3Has an open three-dimensional network structure, has good ion conductivity, can provide a rapid transmission channel for sodium ions, has low potential, and is a sodium ion battery cathode material with great development potential, but NaTi2(PO4)3The conductivity is poor, the transmission and diffusion of electrons are inhibited, the redox reaction of the electrode is not facilitated, and the radius of the sodium ions is much larger than that of the lithium ions, so that the sodium ions are continuously separated from and embedded in the negative electrode material in the charging and discharging process, the volume expansion of the matrix of the electrode material can be caused, the electrochemical stability of the electrode material is influenced, and the rate capability and the electrochemical cycle stability of the sodium ion battery are reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides NaTi2(PO4)3The negative electrode material of the-porous carbon nanofiber sodium ion battery and the preparation method thereof solve the problem of NaTi2(PO4)3The poor conductivity of the electrode material solves the problem of sodium ion in NaTi2(PO4)3The electrode material is released and embedded, which causes the electrode material to expand in volumeTo a problem of (a).
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: NaTi2(PO4)3The porous carbon nanofiber sodium ion battery cathode material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 22-26 parts of titanium acetylacetonate, 6-11 parts of hexadecyl trimethyl ammonium bromide and 6-9 parts of CH3COONa, 8-13 parts of NH4H2PO44-6 parts of ZIF-8 loaded CNTs and 34-55 parts of polyacrylonitrile.
Preferably, in the ZIF-8 loaded CNTs, ZIF-8 is a zeolite imidazole framework material 2-methylimidazole zinc salt, CNTs are carbon nanotubes, and the preparation method of the ZIF-8 loaded CNTs comprises the following steps:
(1) adding methanol solvent, carbon nanotube and 2-methylimidazole into a reaction flask, placing the reaction flask in an ultrasonic disperser, performing ultrasonic dispersion treatment for 30-60min, and adding Zn (NO) into the reaction flask3)2And placing the mixture in a constant-temperature water bath kettle, heating the mixture to 40-70 ℃, uniformly stirring the mixture for reaction for 2-4 hours, decompressing and concentrating the solution to remove the solvent, and washing the solid product by using distilled water and ethanol.
(2) And (3) placing the solid product in a planetary ball mill, adding an ethanol solvent, wherein the revolution speed is 400-.
Preferably, the carbon nanotube, 2-methylimidazole and Zn (NO)3)2The mass ratio of the components is 1:8-14: 6.5-11.5.
Preferably, the planet ball mill includes the ball-milling device, the ball-milling device be provided with the vacuum tank body the outer heat preservation of the outside fixedly connected with of vacuum tank body, vacuum tank body top swing joint have the top cap swing joint has the sliding ball in the top cap, sliding ball and rotary rod fixed connection, the rotary rod fixedly connected with ball-milling tank body, ball-milling tank body below is provided with the recess, top cap and interior heat preservation swing joint.
Preferably, the NaTi2(PO4)3The preparation method of the porous carbon nanofiber sodium ion battery negative electrode material comprises the following steps:
(1) adding ethanol solvent and 22-26 parts of acetylacetone titanium into a reaction bottle, 4-6 parts of ZIF-8 loaded CNTs, 6-11 parts of hexadecyl trimethyl ammonium bromide and 6-9 parts of CH3COONa and 8-13 parts of NH4H2PO4Placing a reaction bottle in a constant-temperature water bath kettle, heating to 40-60 ℃, uniformly stirring for 1-2h, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 140 ℃ for reaction at 120-10 h, cooling the solution to room temperature, distilling under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, placing the solid product in an atmosphere resistance furnace, introducing a mixed gas of argon and hydrogen at a volume ratio of 6-10:1, at a heating rate of 3-8 ℃/min, at a heating rate of 680-740 ℃, carrying out heat preservation treatment for 2-4h, and preparing to obtain the nano-NaTi2(PO4)3Loading carbon nanotubes;
(2) adding N, N-dimethylformamide solvent, 34-55 parts of polyacrylonitrile and nano NaTi into a reaction bottle2(PO4)3Loading carbon nano tubes, placing the solution in a constant-temperature water bath kettle, heating to 40-60 ℃, uniformly stirring for 12-18h to form a spinning solution, pouring the spinning solution into a micro injector, controlling the voltage of an electrostatic spinning machine to be 19-22kV, controlling the flow rate of the electrostatic spinning solution to be 0.5-1mL/h, controlling the receiving distance between a receiver of electrostatic spinning and the needle of the micro injector to be 15-20cm, and carrying out an electrostatic spinning process to prepare a nano spinning fiber precursor;
(3) placing the precursor of the nano spinning fiber in an atmosphere resistance furnace and introducing nitrogen, wherein the heating rate is 2-5 ℃/min, the temperature is raised to 580-620 ℃, the calcination treatment is carried out for 2-3h, and the calcination product is NaTi2(PO4)3-porous carbon nanofiber sodium ion battery negative electrode material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the NaTi2(PO4)3-porous carbon nanofiber sodium ion batteryThe negative electrode material is prepared by taking a carbon nano tube as a carrier, loading a zeolite imidazole framework material ZIF-8 with a porous structure on the surface of the nano tube by a liquid phase deposition method, and preparing nano-shaped NaTi by an in-situ growth method by taking titanium acetylacetonate as an organic titanium source and a hexadecyl trimethyl ammonium bromide sacrificial template2(PO4)3Uniformly grows in the pores and mesoporous structure of the ZIF-8, and effectively avoids the nano NaTi2(PO4)3Thereby generating a large number of electrochemically active sites while uniformly dispersing nano-NaTi2(PO4)3Is more beneficial to the process of sodium ion extraction and insertion, thereby promoting the electrode oxidation reduction reaction, enhancing the energy density of the sodium ion battery, simultaneously, the carbon nano tube has excellent conductivity, and greatly improving the NaTi2(PO4)3The conductive performance of the cathode material promotes the transmission and diffusion of electrons.
The NaTi2(PO4)3A porous carbon nanofiber sodium ion battery cathode material is prepared by carrying out electrostatic spinning on nano NaTi2(PO4)3Compounding the loaded carbon nanotube and polyacrylonitrile to form a nanofiber material, and thermally cracking the nanofiber material to form NaTi2(PO4)3In the high-temperature thermal cracking process of the ZIF-8, zinc atoms with low boiling points are heated and sublimated into zinc vapor to be volatilized, the zinc vapor can be used as a pore-forming agent, so that the carbon nanofibers generate a large number of pore channels and pore structures, the porous structure of the carbon nanofibers can enhance the wettability of the electrode material and electrolyte, simultaneously provide diffusion channels for the transmission of sodium ions and electrons, reduce transmission paths, and the pore channels and the pore structures are NaTi2(PO4)3The volume expansion provides elastic buffer, reduces mechanical stress and protects the NaTi2(PO4)3The function of a matrix improves the electrochemical stability of an electrode material and the rate capability of a sodium-ion battery, a monomer in ZIF-8 is nitrogen-containing 2-methylimidazole, nitrogen atoms enter a carbon layer of carbon nanofibers in an intercalation manner during a thermal cracking process to form nitrogen-doped porous carbon, the electronegativity of nitrogen is greater than that of carbon, and the carbon material shows good performanceGood positive electricity property, thereby enhancing the conductivity of the electrode material.
Drawings
FIG. 1 is a schematic front view of a ball milling tank of a planetary ball mill;
FIG. 2 is a schematic diagram of the thermal insulation layer of the ball of the planetary ball mill.
1. A vacuum tank body; 2. an outer insulating layer; 3. a top cover; 4. a sliding ball; 5. rotating the rod; 6. ball milling a tank body; 7. a groove; 8. an inner heat-insulating layer.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: NaTi2(PO4)3The porous carbon nanofiber sodium ion battery cathode material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 22-26 parts of titanium acetylacetonate, 6-11 parts of hexadecyl trimethyl ammonium bromide and 6-9 parts of CH3COONa, 8-13 parts of NH4H2PO44-6 parts of ZIF-8 loaded CNTs and 34-55 parts of polyacrylonitrile.
In the ZIF-8 loaded CNTs, ZIF-8 is a zeolite imidazole framework material 2-methylimidazole zinc salt, CNTs are carbon nano tubes, and the preparation method of the ZIF-8 loaded CNTs comprises the following steps:
(1) adding methanol solvent, carbon nanotube and 2-methylimidazole into a reaction flask, placing the reaction flask in an ultrasonic disperser, performing ultrasonic dispersion treatment for 30-60min, and adding Zn (NO) into the reaction flask3)2The mass ratio of the three components is 1:8-14:6.5-11.5, the three components are placed in a constant temperature water bath kettle, the temperature is heated to 40-70 ℃, the reaction is carried out for 2-4h under uniform stirring, the solution is decompressed and concentrated to remove the solvent, and distilled water and ethanol are used for washing the solid product.
(2) Placing the solid product into a planetary ball mill, wherein the planetary ball mill comprises a ball milling device, the ball milling device is provided with a vacuum tank body, an outer heat-insulating layer is fixedly connected to the outside of the vacuum tank body, a top cover is movably connected to the upper portion of the vacuum tank body, a sliding ball is movably connected to the inside of the top cover, the sliding ball is fixedly connected with a rotating rod, the ball milling tank body is fixedly connected with the rotating rod, a groove is formed in the lower portion of the ball milling tank body, an ethanol solvent is added into the top cover and the inner heat-insulating layer in a movable connection mode, the revolution rotating speed is 400-plus 480rpm, the rotating speed is 200-plus 240rpm, ball milling is carried out until the material passes through a screen.
NaTi2(PO4)3The preparation method of the porous carbon nanofiber sodium ion battery negative electrode material comprises the following steps:
(1) adding ethanol solvent and 22-26 parts of acetylacetone titanium into a reaction bottle, 4-6 parts of ZIF-8 loaded CNTs, 6-11 parts of hexadecyl trimethyl ammonium bromide and 6-9 parts of CH3COONa and 8-13 parts of NH4H2PO4Placing a reaction bottle in a constant-temperature water bath kettle, heating to 40-60 ℃, uniformly stirring for 1-2h, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 140 ℃ for reaction at 120-10 h, cooling the solution to room temperature, distilling under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, placing the solid product in an atmosphere resistance furnace, introducing a mixed gas of argon and hydrogen at a volume ratio of 6-10:1, at a heating rate of 3-8 ℃/min, at a heating rate of 680-740 ℃, carrying out heat preservation treatment for 2-4h, and preparing to obtain the nano-NaTi2(PO4)3And carrying the carbon nano-tube.
(2) Adding N, N-dimethylformamide solvent, 34-55 parts of polyacrylonitrile and nano NaTi into a reaction bottle2(PO4)3Loading carbon nano tubes, placing the solution in a constant-temperature water bath kettle, heating to 40-60 ℃, uniformly stirring for 12-18h to form a spinning solution, pouring the spinning solution into a micro injector, controlling the voltage of an electrostatic spinning machine to be 19-22kV, controlling the flow rate of the electrostatic spinning solution to be 0.5-1mL/h, controlling the receiving distance between a receiver of electrostatic spinning and the needle of the micro injector to be 15-20cm, and carrying out electrostatic spinning process to prepare the precursor of the nano spinning fiber.
(3) Placing the precursor of the nano spinning fiber in an atmosphere resistance furnace and introducing nitrogen, wherein the heating rate is 2-5 ℃/min, the temperature is raised to 580-620 ℃, the calcination treatment is carried out for 2-3h, and the calcination product is NaTi2(PO4)3-porous carbon nanofiber sodium ion battery negative electrode material.
Adding NaTi2(PO4)3And (3) placing the porous carbon nanofiber sodium-ion battery negative electrode material in an N-methyl pyrrolidone solvent, adding acetylene black serving as a conductive agent and polyvinylidene fluoride serving as a binder, uniformly stirring, uniformly coating the solution on a copper foil, and fully drying to prepare the sodium-ion battery negative electrode working electrode.
Example 1
(1) Preparing a ZIF-8 loaded CNTs component 1: adding methanol solvent, carbon nanotube and 2-methylimidazole into a reaction flask, placing the reaction flask in an ultrasonic disperser, performing ultrasonic dispersion treatment for 30min, and adding Zn (NO) into the reaction flask3)2The mass ratio of the three components is 1:8:6.5, the three components are placed in a constant-temperature water bath kettle, heated to 40 ℃, stirred at a constant speed for reaction for 2 hours, the solution is decompressed and concentrated to remove the solvent, distilled water and ethanol are used for washing a solid product, the solid product is placed in a planetary ball mill, the planetary ball mill comprises a ball milling device, the ball milling device is provided with a vacuum tank body, the outer part of the vacuum tank body is fixedly connected with an outer heat insulation layer, a top cover is movably connected above the vacuum tank body, and a sliding ball is movably connected in the top cover and fixedly connected with a rotating rod, a ball milling tank body is fixedly connected with the rotating rod, a groove is arranged below the ball milling tank body, the top cover is movably connected with the inner heat-insulating layer and is added with an ethanol solvent, the revolution speed is 400rpm until the revolution speed is 200rpm, ball milling is carried out until the material passes through a 1000-mesh screen, the material is subjected to reduced pressure concentration to remove the solvent, and the material is fully dried to prepare the ZIF-8 loaded CNTs component 1.
(2) Preparation of nano-NaTi2(PO4)3Loading carbon nanotube component 1: adding ethanol solvent and 22 parts of titanium acetylacetonate, 4 parts of ZIF-8 loaded CNTs component 1, 6 parts of hexadecyl trimethyl ammonium bromide and 6 parts of CH into a reaction bottle3COONa and 8 parts NH4H2PO4Placing a reaction bottle in a constant-temperature water bath kettle, heating to 40 ℃, stirring at a constant speed for 1h, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 120 ℃, reacting for 6h, cooling the solution to room temperature, distilling under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, fully drying, placing the solid product in an atmosphere resistance furnace, introducing mixed gas of argon and hydrogen in a volume ratio of6:1, heating up to 680 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation treatment for 2h to prepare the nano NaTi2(PO4)3Carrying the carbon nanotube component 1.
(3) Preparation of NaTi2(PO4)3Porous carbon nanofiber sodium ion battery negative electrode material 1: adding N, N-dimethylformamide solvent, 55 parts of polyacrylonitrile and nano NaTi into a reaction bottle2(PO4)3Loading a carbon nanotube component 1, placing the solution in a constant-temperature water bath kettle, heating to 40 ℃, uniformly stirring for 12 hours to form a spinning solution, pouring the spinning solution into a micro injector, carrying out an electrostatic spinning process to prepare a nano spinning fiber precursor, placing the nano spinning fiber precursor in an atmosphere resistance furnace, introducing nitrogen, heating to 580 ℃ at a heating rate of 2 ℃/min, carrying out calcination treatment for 2 hours, wherein the calcination product is the NaTi2(PO4)3A porous carbon nanofiber sodium ion battery negative electrode material 1.
(4) Adding NaTi2(PO4)3Putting the porous carbon nanofiber sodium-ion battery negative electrode material 1 in an N-methyl pyrrolidone solvent, adding a conductive agent acetylene black and a binder polyvinylidene fluoride, uniformly stirring, uniformly coating the solution on a copper foil, and fully drying to prepare the sodium-ion battery negative electrode working electrode 1.
Example 2
(1) Preparing a ZIF-8 loaded CNTs component 2: adding methanol solvent, carbon nanotube and 2-methylimidazole into a reaction flask, placing the reaction flask in an ultrasonic disperser, performing ultrasonic dispersion treatment for 60min, and adding Zn (NO) into the reaction flask3)2The mass ratio of the three components is 1:8:6.5, the three components are placed in a constant-temperature water bath kettle, the mixture is heated to 70 ℃, the mixture is stirred at a constant speed for reaction for 2 hours, the solution is decompressed and concentrated to remove the solvent, distilled water and ethanol are used for washing a solid product, the solid product is placed in a planetary ball mill, the planetary ball mill comprises a ball milling device, the ball milling device is provided with a vacuum tank body, an external heat-insulating layer is fixedly connected to the outside of the vacuum tank body, and an external heatThe ZIF-8 loaded CNTs component 2 is prepared by connecting a top cover, wherein a sliding ball is movably connected in the top cover, the sliding ball is fixedly connected with a rotating rod, a ball milling tank body is fixedly connected with the rotating rod, a groove is arranged below the ball milling tank body, the top cover is movably connected with an inner heat insulation layer, an ethanol solvent is added, the revolution speed is 400rpm until the revolution speed is 200rpm, ball milling is carried out until materials pass through a 1800-mesh screen, the materials are subjected to reduced pressure concentration to remove the solvent, and the materials are fully dried.
(2) Preparation of nano-NaTi2(PO4)3Loading carbon nanotube component 2: adding ethanol solvent and 23 parts of titanium acetylacetonate, 4.5 parts of ZIF-8 loaded CNTs component 2, 7 parts of hexadecyl trimethyl ammonium bromide and 6.5 parts of CH into a reaction bottle3COONa and 9 parts NH4H2PO4Placing a reaction bottle in a constant-temperature water bath kettle, heating to 60 ℃, uniformly stirring for 1h, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 120 ℃, reacting for 6h, cooling the solution to room temperature, carrying out reduced pressure distillation to remove the solvent, washing the solid product with distilled water and ethanol, fully drying, placing the solid product in an atmosphere resistance furnace, introducing mixed gas of argon and hydrogen at a volume ratio of 6:1, heating at a heating rate of 3 ℃/min, heating to 680 ℃, carrying out heat preservation treatment for 4h, and preparing to obtain the nano-NaTi2(PO4)3Supporting carbon nanotube component 2.
(3) Preparation of NaTi2(PO4)3Porous carbon nanofiber sodium ion battery negative electrode material 2: adding N, N-dimethylformamide solvent, 50 parts of polyacrylonitrile and nano NaTi into a reaction bottle2(PO4)3Loading a carbon nanotube component 2, placing the solution in a constant-temperature water bath kettle, heating to 40 ℃, uniformly stirring for 18h to form a spinning solution, pouring the spinning solution into a micro injector, carrying out an electrostatic spinning process to prepare a nano-spinning fiber precursor, placing the nano-spinning fiber precursor in an atmosphere resistance furnace, introducing nitrogen, heating to 580 ℃ at a heating rate of 5 ℃/min, carrying out calcination treatment for 2h, wherein the calcination product is the NaTi2(PO4)3A porous carbon nanofiber sodium ion battery negative electrode material 2.
(4) Adding NaTi2(PO4)3Placing the porous carbon nanofiber sodium-ion battery negative electrode material 2 in an N-methyl pyrrolidone solvent, adding acetylene black serving as a conductive agent and polyvinylidene fluoride serving as a binder, uniformly stirring, uniformly coating the solution on a copper foil, and fully drying to prepare the sodium-ion battery negative electrode working electrode 2.
Example 3
(1) Preparing a ZIF-8 loaded CNTs component 3: adding methanol solvent, carbon nanotube and 2-methylimidazole into a reaction flask, placing the reaction flask in an ultrasonic disperser, performing ultrasonic dispersion treatment for 45min, and adding Zn (NO) into the reaction flask3)2The mass ratio of the three components is 1:11:9, the three components are placed in a constant-temperature water bath kettle, heated to 55 ℃, stirred at a constant speed for reaction for 3 hours, the solution is decompressed and concentrated to remove the solvent, distilled water and ethanol are used for washing a solid product, the solid product is placed in a planetary ball mill, the planetary ball mill comprises a ball milling device, the ball milling device is provided with a vacuum tank body, an external heat insulation layer is fixedly connected to the outside of the vacuum tank body, a top cover is movably connected above the vacuum tank body, and a sliding ball is movably connected in the top cover and fixedly connected with a rotating rod, a ball milling tank body is fixedly connected with the rotating rod, a groove is arranged below the ball milling tank body, the top cover is movably connected with the inner heat-insulating layer and is added with an ethanol solvent, the revolution speed is 440rpm until the revolution speed is 220rpm, ball milling is carried out until the material passes through a 1500-mesh screen, the material is subjected to reduced pressure concentration to remove the solvent, and the material is fully dried to prepare the ZIF-8 loaded CNTs component 3.
(2) Preparation of nano-NaTi2(PO4)3Loading carbon nanotube component 3: adding ethanol solvent and 24 parts of titanium acetylacetonate into a reaction bottle, 5 parts of ZIF-8 loaded CNTs component 3, 8 parts of hexadecyl trimethyl ammonium bromide and 7.5 parts of CH3COONa and 11.5 parts NH4H2PO4Placing the reaction bottle in a constant temperature water bath kettle, heating to 50 deg.C, stirring at constant speed for 1.5h, pouring the solution into a polytetrafluoroethylene reaction kettle, placing in a reaction kettle heating box, heating to 130 deg.C, reacting for 8h, cooling the solution to room temperature,distilling under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, fully drying, placing the solid product in an atmosphere resistance furnace, introducing mixed gas of argon and hydrogen, heating to 710 ℃ at a volume ratio of 8:1 and a heating rate of 5 ℃/min, preserving heat for 3h, and preparing to obtain the nano-NaTi2(PO4)3Supporting carbon nanotube component 3.
(3) Preparation of NaTi2(PO4)3Porous carbon nanofiber sodium ion battery negative electrode material 3: adding N, N-dimethylformamide solvent, 45 parts of polyacrylonitrile and nano NaTi into a reaction bottle2(PO4)3Loading a carbon nanotube component 3, placing the solution in a constant-temperature water bath kettle, heating to 50 ℃, uniformly stirring for 15 hours to form a spinning solution, pouring the spinning solution into a micro injector, carrying out an electrostatic spinning process to prepare a nano spinning fiber precursor, placing the nano spinning fiber precursor in an atmosphere resistance furnace, introducing nitrogen, heating to 600 ℃ at a heating rate of 3 ℃/min, carrying out calcination treatment for 2.5 hours, wherein the calcination product is the NaTi2(PO4)3A porous carbon nanofiber sodium ion battery negative electrode material 3.
(4) Adding NaTi2(PO4)3Placing the porous carbon nanofiber sodium ion battery negative electrode material 3 in an N-methyl pyrrolidone solvent, adding acetylene black serving as a conductive agent and polyvinylidene fluoride serving as a binder, uniformly stirring, uniformly coating the solution on a copper foil, and fully drying to prepare the sodium ion battery negative electrode working electrode 3.
Example 4
(1) Preparation of ZIF-8 loaded CNTs component 4: adding methanol solvent, carbon nanotube and 2-methylimidazole into a reaction flask, placing the reaction flask in an ultrasonic disperser, performing ultrasonic dispersion treatment for 60min, and adding Zn (NO) into the reaction flask3)2The mass ratio of the three components is 1:8:11.5, the three components are placed in a constant-temperature water bath kettle, the temperature is heated to 40 ℃, the reaction is carried out for 4 hours under uniform stirring, the solution is decompressed and concentrated to remove the solvent, distilled water and ethanol are used for washing the solid product, and the mixture is prepared byAnd placing the solid product in a planetary ball mill, wherein the planetary ball mill comprises a ball milling device, the ball milling device is provided with a vacuum tank body, an outer heat-insulating layer is fixedly connected to the outside of the vacuum tank body, a top cover is movably connected to the upper part of the vacuum tank body, a sliding ball is movably connected in the top cover, the sliding ball is fixedly connected with a rotating rod, the ball milling tank body is fixedly connected with the rotating rod, a groove is formed in the lower part of the ball milling tank body, an ethanol solvent is added into the top cover and the inner heat-insulating layer in a movable connection mode, the revolution speed is 480rpm until the revolution speed is 240rpm, ball milling is carried out until the material passes through a 1000-mesh.
(2) Preparation of nano-NaTi2(PO4)3Loading carbon nanotube component 4: adding ethanol solvent and 25 parts of titanium acetylacetonate, 5.5 parts of ZIF-8 loaded CNTs component 4, 10 parts of hexadecyl trimethyl ammonium bromide and 8.5 parts of CH into a reaction bottle3COONa and 12 parts NH4H2PO4Placing a reaction bottle in a constant-temperature water bath kettle, heating to 60 ℃, uniformly stirring for 2 hours, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 120 ℃, reacting for 10 hours, cooling the solution to room temperature, carrying out reduced pressure distillation to remove the solvent, washing the solid product with distilled water and ethanol, fully drying, placing the solid product in an atmosphere resistance furnace, introducing mixed gas of argon and hydrogen at a volume ratio of 6:1, heating at a heating rate of 8 ℃/min, heating to 740 ℃, carrying out heat preservation treatment for 2 hours, and preparing to obtain the nano-NaTi2(PO4)3Supporting the carbon nanotube component 4.
(3) Preparation of NaTi2(PO4)3Porous carbon nanofiber sodium ion battery negative electrode material 4: adding N, N-dimethylformamide solvent, 39 parts of polyacrylonitrile and nano NaTi into a reaction bottle2(PO4)3Loading carbon nanotube component 4, heating the solution in a constant temperature water bath to 40 deg.C, stirring at uniform speed for 12h to form a spinning solution, pouring into a micro injector, electrostatic spinning at 22kV for electrostatic spinning machine, flow rate of the electrostatic spinning solution of 0.5mL/h, and receiving distance between the electrostatic spinning receiver and the micro injector needle of 15cm, and performing electrostatic spinning to obtain the final productPutting the precursor of the nano spinning fiber in an atmosphere resistance furnace, introducing nitrogen, heating to 620 ℃ at the heating rate of 2 ℃/min, calcining for 3h to obtain a calcined product, namely NaTi2(PO4)3A porous carbon nanofiber sodium ion battery negative electrode material 4.
(4) Adding NaTi2(PO4)3Placing the porous carbon nanofiber sodium ion battery negative electrode material 4 in an N-methyl pyrrolidone solvent, adding acetylene black serving as a conductive agent and polyvinylidene fluoride serving as a binder, uniformly stirring, uniformly coating the solution on a copper foil, and fully drying to prepare the sodium ion battery negative electrode working electrode 4.
Example 5
(1) Preparation of ZIF-8 loaded CNTs component 5: adding methanol solvent, carbon nanotube and 2-methylimidazole into a reaction flask, placing the reaction flask in an ultrasonic disperser, performing ultrasonic dispersion treatment for 60min, and adding Zn (NO) into the reaction flask3)2The mass ratio of the three components is 1:14:11.5, the three components are placed in a constant-temperature water bath kettle, the solution is heated to 70 ℃, the mixture is stirred at a constant speed for reaction for 4 hours, the solution is decompressed and concentrated to remove the solvent, the solid product is washed by distilled water and ethanol, the solid product is placed in a planetary ball mill, the planetary ball mill comprises a ball milling device, the ball milling device is provided with a vacuum tank body, the outer part of the vacuum tank body is fixedly connected with an outer heat-insulating layer, a top cover is movably, and a sliding ball is movably connected in the top cover and fixedly connected with a rotating rod, a ball milling tank body is fixedly connected with the rotating rod, a groove is arranged below the ball milling tank body, the top cover is movably connected with the inner heat-insulating layer and is added with an ethanol solvent, the revolution speed is 480rpm until the revolution speed is 240rpm, ball milling is carried out until the material passes through an 1800-mesh screen, the material is subjected to reduced pressure concentration to remove the solvent, and the material is fully dried to prepare the ZIF-8 loaded CNTs component 5.
(2) Preparation of nano-NaTi2(PO4)3 Component 5 of the supported carbon nanotube: adding ethanol solvent, 26 parts of titanium acetylacetonate, 6 parts of ZIF-8 loaded CNTs component 5, 11 parts of hexadecyl trimethyl ammonium bromide and 9 parts of CH into a reaction bottle3COONa and 13 parts NH4H2PO4Placing the reaction flask inHeating the solution to 60 ℃ in a constant-temperature water bath kettle, stirring the solution at a constant speed for 2 hours, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the solution into a reaction kettle heating box, heating the solution to 140 ℃, reacting the solution for 10 hours, cooling the solution to room temperature, distilling the solution under reduced pressure to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying the solid product, placing the solid product into an atmosphere resistance furnace, introducing mixed gas of argon and hydrogen into the atmosphere resistance furnace, heating the mixed gas at a volume ratio of 10:1 and a heating rate of 8 ℃/min to 740 ℃, preserving the temperature for 4 hours, and preparing the nano-NaTi2(PO4)3Supporting the carbon nanotube component 5.
(3) Preparation of NaTi2(PO4)3Porous carbon nanofiber sodium ion battery negative electrode material 5: adding N, N-dimethylformamide solvent, 34 parts of polyacrylonitrile and nano NaTi into a reaction bottle2(PO4)3Loading a carbon nanotube component 5, placing the solution in a constant-temperature water bath kettle, heating to 60 ℃, uniformly stirring for 18h to form a spinning solution, pouring the spinning solution into a micro injector, carrying out an electrostatic spinning process to prepare a nano spinning fiber precursor, placing the nano spinning fiber precursor in an atmosphere resistance furnace, introducing nitrogen, heating to 620 ℃ at a heating rate of 5 ℃/min, calcining for 3h, wherein the calcining product is NaTi2(PO4)3A porous carbon nanofiber sodium ion battery negative electrode material 5.
(4) Adding NaTi2(PO4)3Placing the porous carbon nanofiber sodium ion battery negative electrode material 5 in an N-methyl pyrrolidone solvent, adding acetylene black serving as a conductive agent and polyvinylidene fluoride serving as a binder, uniformly stirring, uniformly coating the solution on a copper foil, and fully drying to prepare the sodium ion battery negative electrode working electrode 5.
Sodium sheet as anode, glass fiber film as separator, 1mol/L NaClO4+ dimethyl carbonate solution as electrolyte, assembled into a CR-2032 type button half cell in an argon glove box, and the negative working electrode of the sodium ion battery of examples 1-5 was tested for electricity in the CHI660E electrochemical workstationThe chemical performance is tested according to the standard GB/T26800-2011.
In summary, the NaTi2(PO4)3A porous carbon nanofiber sodium ion battery negative electrode material, which is prepared by taking a carbon nanotube as a carrier, loading a zeolite imidazole framework material ZIF-8 with a porous structure on the surface of the nanotube by a liquid phase deposition method, and then preparing nano-morphology NaTi by an in-situ growth method by taking titanium acetylacetonate as an organic titanium source and a hexadecyl trimethyl ammonium bromide sacrificial template2(PO4)3Uniformly grows in the pores and mesoporous structure of the ZIF-8, and effectively avoids the nano NaTi2(PO4)3Thereby generating a large number of electrochemically active sites while uniformly dispersing nano-NaTi2(PO4)3Is more beneficial to the process of sodium ion extraction and insertion, thereby promoting the electrode oxidation reduction reaction, enhancing the energy density of the sodium ion battery, simultaneously, the carbon nano tube has excellent conductivity, and greatly improving the NaTi2(PO4)3The conductive performance of the cathode material promotes the transmission and diffusion of electrons.
Through electrostatic spinning process, nanometer NaTi is first prepared2(PO4)3Compounding the loaded carbon nanotube and polyacrylonitrile to form a nanofiber material, and thermally cracking the nanofiber material to form NaTi2(PO4)3In the high-temperature thermal cracking process of the ZIF-8, zinc atoms with low boiling points are heated and sublimated into zinc vapor to be volatilized, the zinc vapor can be used as a pore-forming agent, so that the carbon nanofibers generate a large number of pore channels and pore structures, the porous structure of the carbon nanofibers can enhance the wettability of the electrode material and electrolyte, simultaneously provide diffusion channels for the transmission of sodium ions and electrons, reduce transmission paths, and the pore channels and the pore structures are NaTi2(PO4)3The volume expansion provides elastic buffer, reduces mechanical stress and protects the NaTi2(PO4)3The function of the matrix is improvedThe electrochemical stability of the material and the rate capability of the sodium-ion battery are realized, the monomer in the ZIF-8 is nitrogen-containing 2-methylimidazole, nitrogen atoms enter a carbon layer of carbon nanofibers through intercalation in the thermal cracking process to form nitrogen-doped porous carbon, and the electronegativity of nitrogen is greater than that of carbon, so that the carbon material shows good electropositivity, and the conductivity of the electrode material is enhanced.
Claims (5)
1. NaTi2(PO4)3The porous carbon nanofiber sodium ion battery cathode material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 22-26 parts of titanium acetylacetonate, 6-11 parts of hexadecyl trimethyl ammonium bromide and 6-9 parts of CH3COONa, 8-13 parts of NH4H2PO44-6 parts of ZIF-8 loaded CNTs and 34-55 parts of polyacrylonitrile.
2. NaTi according to claim 12(PO4)3-a porous carbon nanofiber sodium ion battery negative electrode material characterized in that: in the ZIF-8 loaded CNTs, ZIF-8 is a zeolite imidazole framework material 2-methylimidazole zinc salt, CNTs are carbon nanotubes, and the preparation method of the ZIF-8 loaded CNTs comprises the following steps:
(1) adding carbon nanotube and 2-methylimidazole into methanol solvent, performing ultrasonic dispersion treatment for 30-60min, and adding Zn (NO)3)2Heating to 40-70 deg.C, reacting for 2-4h, removing solvent from the solution, washing solid product,
(2) and (3) placing the solid product in a planetary ball mill, adding an ethanol solvent, wherein the revolution speed is 480rpm and 200rpm, ball milling is carried out until the material passes through a 1800-mesh screen, removing the solvent from the material, and drying to obtain the ZIF-8 loaded CNTs.
3. NaTi according to claim 22(PO4)3-a porous carbon nanofiber sodium ion battery negative electrode material characterized in that: the carbon nanotube, 2-methylimidazole and Zn (NO)3)2The mass ratio of the components is 1:8-14: 6.5-11.5.
4. NaTi according to claim 22(PO4)3-a porous carbon nanofiber sodium ion battery negative electrode material characterized in that: the planet ball mill includes the ball-milling device, the ball-milling device be provided with the vacuum tank body the outer heat preservation of the outside fixedly connected with of vacuum tank body, vacuum tank body top swing joint have the top cap swing joint have the sliding ball in the top cap, sliding ball and rotary rod fixed connection, the rotary rod fixedly connected with ball-milling tank body, ball-milling tank body below is provided with the recess, top cap and interior heat preservation swing joint.
5. NaTi according to claim 12(PO4)3-a porous carbon nanofiber sodium ion battery negative electrode material characterized in that: the NaTi2(PO4)3The preparation method of the porous carbon nanofiber sodium ion battery negative electrode material comprises the following steps:
(1) adding 22-26 parts of acetylacetone titanium, 4-6 parts of ZIF-8 loaded CNTs, 6-11 parts of hexadecyl trimethyl ammonium bromide and 6-9 parts of CH into an ethanol solvent3COONa and 8-13 parts of NH4H2PO4Heating the solution to 40-60 ℃, uniformly stirring for 1-2h, pouring the solution into a reaction kettle, heating to 120-140 ℃, reacting for 6-10h, removing the solvent from the solution, washing and drying the solid product, placing the solid product into an atmosphere resistance furnace, introducing mixed gas of argon and hydrogen into the atmosphere resistance furnace at the volume ratio of 6-10:1 and the heating rate of 3-8 ℃/min, heating to 680-740 ℃, and carrying out heat preservation treatment for 2-4h to prepare the nano-NaTi2(PO4)3Loading carbon nanotubes;
(2) adding 34-55 parts of polyacrylonitrile and nano NaTi into N, N-dimethylformamide solvent2(PO4)3Loading carbon nano tube, heating the solution to 40-60 ℃, uniformly stirring for 12-18h to form spinning solution, pouring the spinning solution into a micro injector, controlling the voltage of an electrostatic spinning machine to be 19-22kV, controlling the flow rate of the electrostatic spinning solution to be 0.5-1mL/h, and controlling the receiving distance between a receiver of electrostatic spinning and the needle of the micro injectorCarrying out electrostatic spinning process when the distance is 15-20cm to prepare a precursor of the nano spinning fiber;
(3) placing the precursor of the nano spinning fiber in an atmosphere resistance furnace and introducing nitrogen, wherein the heating rate is 2-5 ℃/min, the temperature is raised to 580-620 ℃, the calcination treatment is carried out for 2-3h, and the calcination product is NaTi2(PO4)3-porous carbon nanofiber sodium ion battery negative electrode material.
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