CN114873573A - NaTi 2 (PO4) 3 @ C micro-nano composite material and preparation method and application thereof - Google Patents
NaTi 2 (PO4) 3 @ C micro-nano composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a NaTi 2 (PO 4 ) 3 The @ C micro-nano composite material and the preparation method and the application thereof; preparation: s1, adding a sodium source, a titanium source and a phosphorus source into a dispersing agent, stirring and dispersing to form mixed slurry; s2, ball-milling the mixed slurry, heating for reaction, and cooling to obtain NaTi 2 (PO 4 ) 3 A material; s3, mixing a carbon source and NaTi 2 (PO 4 ) 3 The material is added to water andevenly stirred and dried in vacuum to obtain the NaTi 2 (PO 4 ) 3 A base precursor material; s4, under the protective atmosphere, for NaTi 2 (PO 4 ) 3 Heating and calcining the base precursor material, and cooling to obtain NaTi 2 (PO 4 ) 3 @ C micro-nano composite material. The application comprises the following steps: the prepared NaTi 2 (PO 4 ) 3 The @ C micro-nano composite material is used as a negative electrode material of the sodium ion battery. The preparation method is a green and environment-friendly process method, no harmful or corrosive gas is generated in the preparation process, no solid waste is generated, and the preparation method conforms to the concept of atom economy and environmental protection of green chemistry; the method has the advantages of simple process, low cost due to common raw materials, simple requirements on equipment for technical process conditions and simple process route.
Description
Technical Field
The invention relates to the field of micro-nano materials, in particular to NaTi 2 (PO 4 ) 3 A @ C micro-nano composite material and a preparation method and application thereof.
Background
Over the past few decades, lithium ion batteries have been widely used as rechargeable energy storage devices. However, the lack of lithium resources limits the further development of lithium ion batteries. However, sodium ion batteries are recognized as being rechargeable due to their much richer sodium reserves and higher safetyA good candidate for charging energy storage. Recently, NASICON type NaTi 2 (PO 4 ) 3 The material is an attractive sodium-ion battery cathode material due to high sodium-ion conductivity, very flat charge-discharge stationary period, relatively high theoretical capacity of 133mAh/g and excellent thermal stability. Delmas et al first studied sodium ions in NaTi 2 (PO 4 ) 3 The storage mechanism in the (sodium titanium phosphate) electrode structure was found to be that at room temperature, NaTi 2 (PO 4 ) 3 The structure can satisfy the reversible insertion of two sodium ions by chemical or electrochemical means. NaTi 2 (PO 4 ) 3 The output voltage of the electrode material was about 2.1V, which also indicates that the electrode material undergoes a two-phase reaction at this voltage. NaTi 2 (PO 4 ) 3 Has higher charge and discharge platform, and can reduce the possibility of forming SEI interface film and depositing metal sodium on the surface of electrode material. However, NaTi 2 (PO 4 ) 3 The conductivity is low and the charge transfer kinetics are slow during sodium ion insertion/extraction, resulting in poor rate performance and cycling stability. Currently, there are three main effective strategies to improve conductivity and electrochemical performance in response to this problem: (1) adding NaTi 2 (PO 4 ) 3 The particles are designed to be nano-scale, so that the transmission path of ions and electrons can be shortened, and the electrolyte is easy to permeate; (2) in the presence of NaTi 2 (PO 4 ) 3 The outer surface of the conductive coating is coated or loaded by a material with good conductivity so as to improve the conductivity of the conductive coating; (3) the sodium ion diffusion kinetics are enhanced by heterogeneous atomic doping. However, these solutions are complex and require high equipment and are costly.
Disclosure of Invention
Aiming at solving the problem of NaTi 2 (PO 4 ) 3 The invention provides NaTi with simple process 2 (PO 4 ) 3 A preparation method of the @ C micro-nano composite material; the preparation method provided by the invention is a green environment-friendly and low-cost process.
The invention is realized by the following technical scheme:
NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material is characterized by comprising the following steps:
s1, adding a sodium source, a titanium source and a phosphorus source into a dispersing agent, stirring and dispersing to form mixed slurry;
s2, ball-milling the obtained mixed slurry, heating the mixed slurry in a reaction kettle for reaction, and cooling the reaction product to obtain NaTi 2 (PO 4 ) 3 A material;
s3, adding a carbon source and the NaTi 2 (PO 4 ) 3 Adding the materials into water, stirring uniformly, and then drying in vacuum to obtain NaTi 2 (PO 4 ) 3 A base precursor material;
s4, under the protective atmosphere, treating the NaTi 2 (PO 4 ) 3 Heating and calcining the base precursor material, and then cooling to obtain NaTi 2 (PO 4 ) 3 @ C micro-nano composite material.
Further, a NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material comprises the following steps: step S1, selecting the sodium source from one of sodium hydroxide, sodium carbonate, sodium phosphate and sodium tartrate; the titanium source is selected from nano titanium dioxide or titanic acid; the phosphorus source is selected from phosphoric acid or sodium phosphate; the dispersant is pure water.
Further, a NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material comprises the following steps: step S1, the molar ratio of the sodium source to the titanium source to the phosphorus source is 1: (2-3): (3-5).
Further, a NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material comprises the following steps: step S2, placing the mixed slurry into a planetary ball mill for ball milling for 4-8 hours, transferring the mixed slurry into a reaction kettle, heating to 90-180 ℃ at a heating rate of 10-20 ℃/min, keeping the temperature for reaction for 3-8 hours after heating, and cooling to room temperature after reaction to obtain NaTi 2 (PO 4 ) 3 A material.
Further, a NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material comprises the following steps: step S3, mixing the carbon source and the NaTi 2 (PO 4 ) 3 Adding into deionized water, magnetically stirring at 70-100 deg.C for 1-6 hr, and vacuum drying at 70-90 deg.C for 4-10 hr to obtain NaTi 2 (PO 4 ) 3 A base precursor material.
Further, a NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material comprises the following steps: and step S3, the carbon source is selected from one of rice flour, wheat flour, sweet potato flour, corn flour and tapioca flour. Preferably, the carbon source used in the invention is one of rice flour, wheat flour, sweet potato flour, corn flour and tapioca flour, and the raw material source is wide, easy to obtain and low in cost.
Further, a NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material comprises the following steps: step S3, the carbon source, water and NaTi 2 (PO 4 ) 3 The mass ratio of the materials is 1: (4-6): (8-10). Preferably, the carbon source, water and NaTi 2 (PO 4 ) 3 The mass ratio of the materials is 1: 5: 10.
further, a NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material comprises the following steps: step S4, adding the NaTi 2 (PO 4 ) 3 Placing the base precursor material in a tubular furnace or a box-type furnace, introducing protective atmosphere into the furnace, controlling the air flow rate at 200- 2 (PO 4 ) 3 @ C micro-nano composite material; wherein the protective atmosphere is inert atmosphere. The inert gas atmosphere is preferably a nitrogen gas atmosphere or an argon gas atmosphere.
NaTi 2 (PO 4 ) 3 The @ C micro-nano composite material is characterized by being prepared by the preparation method. The invention prepares NaTi 2 (PO 4 ) 3 The @ C micro-nano composite material is simple in process, low in cost and environment-friendly.
NaTi 2 (PO 4 ) 3 Application of @ C micro-nano composite material, and is characterized in that NaTi prepared by the preparation method 2 (PO 4 ) 3 Application of the @ C micro-nano composite material in a sodium ion battery cathode material. The NaTi prepared by the invention 2 (PO 4 ) 3 The @ C micro-nano composite material used as a negative electrode material of a sodium ion battery can show excellent electrochemical performance and cycling stability.
The invention has the beneficial effects that:
(1) the invention provides NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material is a green and environment-friendly process method, no harmful or corrosive gas is generated in the preparation process, no solid waste is generated, and the preparation method accords with the atom economy and environment-friendly concept of green chemistry.
(2) The invention provides NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material has the advantages of simple process, low cost due to the fact that the used raw materials are common raw materials, simple requirements on equipment for technical process conditions and simple process route.
(3) In the invention of NaTi 2 (PO 4 ) 3 The @ C micro-nano composite material preparation process adopts rice flour, wheat flour, sweet potato flour, corn flour or tapioca flour as a carbon source to carry out carbon coating on the sodium titanium phosphate, the raw material sources are extremely wide, the production cost is greatly reduced, and meanwhile, a new application is developed for the raw materials such as the rice flour, the wheat flour, the sweet potato flour, the corn flour or the tapioca flour.
(4) The NaTi prepared by the process of the invention 2 (PO 4 ) 3 The @ C micro-nano composite material can show excellent cycle stability after being used as an electrode active material of a sodium ion battery to be assembled into the sodium ion battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows NaTi prepared in examples 1, 2 and 3 of the present invention 2 (PO 4 ) 3 X-ray diffraction patterns (XRD) of @ C micro-nano composite materials;
FIG. 2 shows NaTi prepared in examples 1, 2 and 3 of the present invention 2 (PO 4 ) 3 Scanning Electron Microscope (SEM) of the @ C micro-nano composite material; in FIG. 2, a represents NaTi prepared in example 1 2 (PO 4 ) 3 Scanning electron microscope image of @ C micro-nano composite material, b represents NaTi prepared in example 2 2 (PO 4 ) 3 Scanning electron microscope picture of @ C micro-nano composite material, C represents NaTi prepared in example 3 2 (PO 4 ) 3 Scanning electron microscope images of the @ C micro-nano composite material;
FIG. 3 shows NaTi prepared in example 1 of the present invention 2 (PO 4 ) 3 And (6) testing the cycle performance of the @ C micro-nano composite material assembled sodium ion battery.
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. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material comprises the following specific steps:
s1, mixing the raw materials according to a molar ratio of 1: 2: 3, adding sodium phosphate (a sodium source), nano titanium dioxide (a titanium source) and phosphoric acid (a phosphorus source) into pure water, and uniformly stirring and dispersing to obtain mixed slurry;
s2, placing the obtained mixed slurry in a planetary ball mill for ball milling for 4 hours, then completely transferring the mixed slurry into a reaction kettle, heating to 90 ℃ at the heating rate of 15 ℃/min, keeping the temperature for reaction for 6 hours after heating, and cooling to room temperature after reaction to obtain the NaTi 2 (PO 4 ) 3 A material;
s3, mixing carbon source (rice flour), deionized water and NaTi 2 (PO 4 ) 3 The mass ratio of materials is 1: 5: 10, mixing rice flour and NaTi 2 (PO 4 ) 3 The material was added to deionization and magnetically stirred at 80 ℃ for 3 hours, then placed in a vacuum oven and vacuum dried at 85 ℃ for 6 hours to obtain NaTi 2 (PO 4 ) 3 A base precursor material;
s4, mixing the NaTi 2 (PO 4 ) 3 Placing the base precursor material in a tube furnace, introducing protective atmosphere (inert gas) into the tube furnace, controlling the air flow rate to be 250mL/min, heating to 900 ℃ at the speed of 10 ℃/min, keeping the temperature after heating, calcining for 8 hours, and cooling to room temperature to obtain the NaTi 2 (PO 4 ) 3 @ C micro-nano composite material.
Example 2
NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material comprises the following specific steps:
s1, mixing the raw materials according to a molar ratio of 1: 3: 4, adding sodium hydroxide (a sodium source), nano titanium dioxide (a titanium source) and phosphoric acid (a phosphorus source) into pure water, and uniformly stirring and dispersing to obtain mixed slurry;
s2, placing the obtained mixed slurry in a planetary ball mill for ball milling for 6 hours, then transferring all the mixed slurry to a reaction kettle, heating to 180 ℃ at the heating rate of 20 ℃/min, keeping the temperature for reaction for 4 hours after heating, and cooling to room temperature after reaction to obtain the NaTi 2 (PO 4 ) 3 A material;
s3, mixing carbon source (wheat flour), deionized water and NaTi 2 (PO 4 ) 3 The mass ratio of materials is 1: 4: adding wheat flour and NaTi to 8 2 (PO 4 ) 3 The material was added to deionization and magnetically stirred at 90 ℃ for 5 hours, then placed in a vacuum oven and vacuum dried at 75 ℃ for 7 hours to give NaTi 2 (PO 4 ) 3 A base precursor material;
s4, mixing the NaTi 2 (PO 4 ) 3 Placing the base precursor material in a box-type furnace, introducing protective atmosphere (inert gas) into the furnace, controlling the gas flow rate to be 850mL/min, heating to 800 ℃ at the speed of 8 ℃/min, keeping the temperature after heating, calcining for 9 hours, and cooling to room temperature to obtain the NaTi 2 (PO 4 ) 3 @ C micro-nano composite material.
Example 3
NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material comprises the following specific steps:
s1, mixing the raw materials according to a molar ratio of 1: 2: 4, adding sodium hydroxide (a sodium source), titanic acid (a titanium source) and phosphoric acid (a phosphorus source) into pure water, and uniformly stirring and dispersing to obtain mixed slurry;
s2, placing the obtained mixed slurry into a planetary ball mill for ball milling for 7 hours, then completely transferring the mixed slurry into a reaction kettle, heating to 120 ℃ at the heating rate of 10 ℃/min, keeping the temperature for reaction for 5 hours after heating, and cooling to room temperature after reaction to obtain NaTi 2 (PO 4 ) 3 A material;
s3, mixing carbon source (sweet potato powder), deionized water and NaTi 2 (PO 4 ) 3 The mass ratio of materials is 1: 6: 10, mixing sweet potato powder and NaTi 2 (PO 4 ) 3 The material was added to deionization and magnetically stirred at 70 ℃ for 6 hours, then placed in a vacuum oven and vacuum dried at 90 ℃ for 4 hours to obtain NaTi 2 (PO 4 ) 3 A base precursor material;
s4, mixing the NaTi 2 (PO 4 ) 3 Placing the precursor material in a tube furnace, introducing protective atmosphere (inert gas) into the tube furnace, controlling the gas flow rate at 450mL/min, heating to 850 deg.C at 10 deg.C/min, and calcining for 7 hrThen cooled to room temperature to obtain NaTi 2 (PO 4 ) 3 @ C micro-nano composite material.
NaTi of the above example 3 2 (PO 4 ) 3 The reaction equation of the material preparation process is as follows:
NaOH+2Ti(OH) 4 +3H 3 PO 4 ＝NaTi 2 (PO 4 ) 3 +9H 2 and O, the byproducts of the method have no other harmful waste gases or solids except water, and the method accords with the concept of atom economy and environmental protection of green chemistry.
NaTi prepared in the above-mentioned examples 1, 2 and 3 2 (PO 4 ) 3 The X-ray diffraction characterization of the @ C micro-nano composite material is carried out, as shown in figure 1 (in figure 1, a represents example 1, b represents example 2, and C represents example 3), and it can be seen from figure 1 that the position intensity of the diffraction peak is completely consistent with that of a standard map (PDF #84-2008), which indicates that the products obtained in examples 1, 2 and 3 are NaTi 2 (PO 4 ) 3 In the material, carbon is amorphous carbon, so that the XRD contains no peak of carbon.
NaTi prepared in the above-mentioned examples 1, 2 and 3 2 (PO 4 ) 3 The observation (SEM) of the transmission electron microscope microscopic morphology of the @ C micro-nano composite material is shown in FIGS. 2(a-C), and it can be seen from FIGS. 2(a), 2(b) and 2(C) that the samples obtained in example 1, 2 and 3 are relatively uniform, are nanoparticles, and have a size of 300-600 nm.
The application comprises the following steps:
the NaTi prepared in the above example 1 was added 2 (PO 4 ) 3 The @ C micro-nano composite material is used as a negative electrode material of the sodium ion battery, the sodium ion battery is assembled, and the assembling process is as follows:
the NaTi prepared in example 1 was added 2 (PO 4 ) 3 Mixing the @ C micro-nano composite material serving as an active substance, an acetylene black conductive agent and a polyvinylidene fluoride (PVDF) binder uniformly in a ratio of 7:2:1 in N-methylpyrrolidone (NMP) to prepare electrode slurry, placing the electrode slurry in an agate ball milling tank for ball milling for about 1 hour, and then uniformly coating the slurry on the surface of the electrode slurryOn a copper foil, and placed in a vacuum drying oven, dried at 110 ℃ for 12 hours, and then the copper foil was cut into 12mm electrode wafers in a glove box (H) filled with argon gas 2 O<0.1，O 2 <0.1) cell assembly, using metallic lithium plates as counter and reference electrodes, cell separator Celgard 2400 coated separator, electrolyte 1.0mol/L LiPF 6 (EC: DMC: EMC ═ 1:1:1), assembling a LIR2006 type button cell, after the cell is assembled, performing a constant current discharge/charge test at a voltage of 1.5-3V by using Land-2001A (China, Wuhan), and the test result is shown in FIG. 3, and the prepared NaTi can be seen from FIG. 3 2 (PO 4 ) 3 The specific capacity of the first ring of the/C micro-nano composite material is 132.6mAh g -1 After 1000 cycles, the specific discharge capacity is 123.4mAh g -1 The capacity retention rate is 93.1%, and good long-cycle performance is shown.
The preferred embodiments of the present invention are described above for illustrative purposes only and are not intended to limit the present invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (10)
1. NaTi 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material is characterized by comprising the following steps:
s1, adding a sodium source, a titanium source and a phosphorus source into a dispersing agent, stirring and dispersing to form mixed slurry;
s2, ball-milling the obtained mixed slurry, heating the mixed slurry in a reaction kettle for reaction, and cooling the reaction product to obtain NaTi 2 (PO 4 ) 3 A material;
s3, adding a carbon source and the NaTi 2 (PO 4 ) 3 Adding the materials into water, stirring uniformly, and then drying in vacuum to obtain NaTi 2 (PO 4 ) 3 A base precursor material;
s4, under the protective atmosphere, treating the NaTi 2 (PO 4 ) 3 Heating and calcining the base precursor material, and then cooling to obtain NaTi 2 (PO 4 ) 3 @ C micro-nano composite material.
2. NaTi according to claim 1 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material is characterized in that in the step S1, the sodium source is selected from one of sodium hydroxide, sodium carbonate, sodium phosphate and sodium tartrate; the titanium source is selected from nano titanium dioxide or titanic acid; the phosphorus source is selected from phosphoric acid or sodium phosphate; the dispersant is pure water.
3. A NaTi according to claim 1 or 2 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material is characterized in that in the step S1, the molar ratio of the sodium source to the titanium source to the phosphorus source is 1: (2-3): (3-5).
4. NaTi according to claim 1 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material is characterized by comprising the steps of S2, placing the mixed slurry in a planetary ball mill for ball milling for 4-8 hours, transferring the mixed slurry into a reaction kettle, heating to 90-180 ℃ at a heating rate of 10-20 ℃/min, carrying out heat preservation reaction for 3-8 hours after heating, and cooling to room temperature after reaction to obtain the NaTi 2 (PO 4 ) 3 A material.
5. NaTi according to claim 1 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material is characterized by comprising the step S3 of mixing the carbon source and the NaTi 2 (PO 4 ) 3 Adding into deionized water, magnetically stirring at 70-100 deg.C for 1-6 hr, and vacuum drying at 70-90 deg.C for 4-10 hr to obtain NaTi 2 (PO 4 ) 3 A base precursor material.
6. A NaTi according to claim 1 or 5 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material is characterized in that the carbon source in the step S3 is selected from rice flour,One of wheat flour, sweet potato powder, corn flour and tapioca flour.
7. A NaTi according to claim 1 or 5 or 6 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material is characterized in that the carbon source, the water and the NaTi are obtained in the step S3 2 (PO 4 ) 3 The mass ratio of the materials is 1: (4-6): (8-10).
8. NaTi according to claim 1 2 (PO 4 ) 3 The preparation method of the @ C micro-nano composite material is characterized by comprising the step S4 of mixing the NaTi 2 (PO 4 ) 3 Placing the base precursor material in a tubular furnace or a box-type furnace, introducing protective atmosphere into the furnace, controlling the air flow rate at 200- 2 (PO 4 ) 3 @ C micro-nano composite material; wherein the protective atmosphere is inert atmosphere.
9. NaTi 2 (PO 4 ) 3 The @ C micro-nano composite material is characterized by being prepared by the preparation method of any one of claims 1-8.
10. NaTi 2 (PO 4 ) 3 Application of @ C micro-nano composite material, characterized in that NaTi prepared by the preparation method of any one of claims 1-8 2 (PO 4 ) 3 Application of the @ C micro-nano composite material in a sodium ion battery cathode material.
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| CN202210412194.0A CN114873573B (en) | 2022-04-19 | 2022-04-19 | NaTi (sodium silicate) 2 (PO 4 ) 3 @C micro-nano composite material and preparation method and application thereof |
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