阅读说明：本技术 双针头静电纺丝的Li3VO4/C纤维锂离子电池负极材料的制备方法 (Double-needle electrostatic spinning Li3VO4Preparation method of/C fiber lithium ion battery cathode material ) 是由 倪世兵 许真 李道波 于 2021-08-18 设计创作，主要内容包括：本发明提供一种双针头静电纺丝的Li-(3)VO-(4)/C纤维锂离子电池负极材料的制备方法。LiNO-(3)加入到N,N-二甲基甲酰胺中在室温下搅拌至形成无色均质溶液；同时取偏钒酸铵、草酸加入N,N-二甲基甲酰胺搅拌至形成蓝色透明溶液,分别再向溶液加入聚乙烯吡咯烷酮并搅拌,以获得均匀的粘性静电纺丝溶液；将前驱体溶液分别转移至静电纺丝注射器中进行双针头混纺,以得到Li源、V源交织的纺布；干燥后将烘干后的纺布置于N-(2)环境中,在200-300℃下预烧后在500-800℃下煅烧得到Li-(3)VO-(4)/C纤维。本发明首次利用双针头混纺技术制备Li-(3)VO-(4)/C复合纤维作为锂离子电池负极材料,提高了纳米纤维的产量,所得样品具有特殊纤维交织节点,显示了优异的电化学性能。(The invention provides a double-needle electrostatic spinning Li 3 VO 4 fiber/CA preparation method of a lithium ion battery cathode material. LiNO 3 Adding the mixture into N, N-dimethylformamide, and stirring at room temperature to form a colorless homogeneous solution; simultaneously adding ammonium metavanadate and oxalic acid into N, N-dimethylformamide, stirring until a blue transparent solution is formed, respectively adding polyvinylpyrrolidone into the solution, and stirring to obtain a uniform viscous electrostatic spinning solution; respectively transferring the precursor solution to an electrostatic spinning injector for double-needle blending to obtain a Li source and V source interwoven woven fabric; drying, and placing the dried spun fabric in N 2 In the environment, calcining at the temperature of 500-800 ℃ after presintering at the temperature of 200-300 ℃ to obtain Li 3 VO 4 a/C fiber. The invention prepares Li by using a double-needle blending technology for the first time 3 VO 4 the/C composite fiber is used as a lithium ion battery cathode material, the yield of the nanofiber is improved, the obtained sample has special fiber interweaving nodes, and excellent electrochemical performance is shown.)

1. Double-needle electrostatic spinning Li₃VO₄The preparation method of the/C fiber lithium ion battery cathode material is characterized in that the specific preparation process of the material is as follows:

(1) taking a certain amount of LiNO₃Adding the mixture into a proper amount of N, N-dimethylformamide, and stirring at room temperature to form a colorless homogeneous solution which is used as a solution A; simultaneously, adding a proper amount of ammonium metavanadate and oxalic acid into a proper amount of N, N-dimethylformamide, stirring for 30min to form a blue transparent solution serving as a solution B, respectively adding a certain amount of polyvinylpyrrolidone into the solution A, B, and stirring for 12h to obtain a uniform viscous electrostatic spinning solution;

(2) respectively transferring the homogeneous viscous solution A, B obtained in the step (1) to an electrostatic spinning injector for spinning to obtain electrostatic spinning cloth interwoven by a Li source and a V source;

(3) quickly transferring the spun fabric obtained in the step (2) to a forced air drying oven at the temperature of 60-80 ℃ for drying for 10-12h, and placing the dried fabric in N₂In the environment, pre-burning at the temperature of 200-300 ℃ for 2-5h at the temperature rise rate of 3 ℃/min, and then calcining at the temperature of 500-800 ℃ for 5-6h to obtain the lithium ion battery cathode material Li₃VO₄a/C fiber.

2. The double-needle electrospun Li according to claim 1₃VO₄The preparation method of the/C fiber lithium ion battery cathode material is characterized in that LiNO in the step (1)₃The mol ratio of oxalic acid to ammonium metavanadate is 3-4: 5-6: 1.

3. the double-needle electrospun Li according to claim 1₃VO₄The preparation method of the/C fiber lithium ion battery cathode material is characterized in that in the solution A: the mass of the N, N-dimethylformamide accounts for 74-76% of the total mass, and the mass of the polyvinylpyrrolidone accounts for 16-18% of the total mass; in solution B: the mass of the N, N-dimethylformamide accounts for 62-64% of the total mass, and the mass of the polyvinylpyrrolidone accounts for 10-12% of the total mass.

4. The double-needle electrospun Li according to claim 1₃VO₄The preparation method of the/C fiber lithium ion battery cathode material is characterized in that in the step (2), the electrostatic spinning adopts double-needle blending to interweave the fibers, the spinning voltage is 15-20 kV, the spinning time is 2-4h, the ambient temperature is 40-60 ℃ during spinning, and the spinning distance is 23 cm.

5. The double-needle electrospun Li according to claim 1₃VO₄The preparation method of the/C fiber lithium ion battery cathode material is characterized in that in the step (3), the sintering atmosphere of the tube furnace is N₂Presintering temperature is 200 ℃, temperature rising speed is 3 ℃/min, presintering time is 3h,then calcined at 600 ℃ for 5h at the heating rate of 3 ℃/min.

Technical Field

The invention relates to a novel lithium ion battery cathode material, in particular to a method for preparing Li by blending double-needle electrostatic spinning₃VO₄A method for preparing a negative electrode material of a/C fiber lithium ion battery belongs to the field of electrochemical power sources.

Background

Most of the energy consumed globally at present comes from non-renewable primary energy sources, such as crude oil, natural gas, coal and the like, but the energy sources are unevenly distributed on the earth and are non-renewable, so that potential energy safety hazards are brought to many countries. The development of novel clean energy is urgently needed, however, compared with fossil energy, green energy such as hydroenergy, wind energy, solar energy, tidal energy and the like, the capacity is greatly influenced by environmental changes, and stable power output is difficult, which brings great inconvenience to grid connection, storage, transportation and use of power. Therefore, the development of high-performance green energy storage materials is a key ring for the development of clean energy.

Lithium ion batteries have been rapidly developed in recent decades as one of the representatives of green energy storage materials. The lithium ion battery has the advantages of good cycle performance, small self-discharge, high coulombic efficiency and the like, but with the continuous improvement of the demand of people on portable electronic products, higher requirements are also put forward on the energy density of the lithium ion battery. The key for improving the electrochemical performance of the lithium ion battery is to select positive and negative electrode materials with good performance. The current commercial lithium ion battery cathode material is mainly a carbon material, the theoretical specific capacity is relatively low, the rate capability is poor, and the requirements of the next generation of high-performance lithium ion battery are difficult to meet. Therefore, it has become a trend to explore new lithium ion battery negative electrode materials.

Li₃VO₄Is a novel lithium ion battery cathode material, has higher volume capacity than commercial graphite and is higher than Li₄Ti₅O₁₂Has lower voltage platform and higher specific capacity, and is an ideal cathode candidate material of the lithium ion battery. However, Li₃VO₄The electron conductivity and ion conductivity of the negative electrode material are relatively low, which may result in large polarization during charge/discharge, resulting in poor kinetics of the electrochemical reaction. Based on the background, the patent develops a fiber interweaving connection Li₃VO₄The electronic conductivity of the composite material is improved by means of the conductivity of carbon, and the lithium ion diffusion and stability in the material are enhanced by utilizing the nano fiber interweaving structure. Finally, Li is prepared₃VO₄the/C composite material is used as a lithium ion battery cathode material and shows excellent electrochemical performance.

Disclosure of Invention

Based on double-needle electrostatic spinning blending technology, LiNO is used₃Oxalic acid, ammonium metavanadate, polyvinylpyrrolidone and N, N-dimethylformamide as raw materials to obtain Li₃VO₄The preparation method of the/C nanofiber composite material as the lithium ion battery negative electrode material comprises the following steps:

(1) taking a certain amount of LiNO₃Adding the mixture into a proper amount of N, N-dimethylformamide, and stirring at room temperature to form a colorless homogeneous solution which is used as a solution A; simultaneously, adding a proper amount of ammonium metavanadate and oxalic acid into a proper amount of N, N-dimethylformamide, stirring for 30min to form a blue transparent solution serving as a solution B, respectively adding a certain amount of polyvinylpyrrolidone into the solution A, B, and stirring for 12h to obtain a uniform viscous electrostatic spinning solution;

LiNO in step (1)₃The mol ratio of oxalic acid to ammonium metavanadate is 3-4: 5-6: 1.

in solution a: the mass of the N, N-dimethylformamide accounts for 74-76% of the total mass, and the mass of the polyvinylpyrrolidone accounts for 16-18% of the total mass; in solution B: the mass of the N, N-dimethylformamide accounts for 62-64% of the total mass, and the mass of the polyvinylpyrrolidone accounts for 10-12% of the total mass.

(2) Respectively transferring the homogeneous viscous solution A, B obtained in the step (1) into an electrostatic spinning injector, and spinning for 2-4h under the conditions that the voltage is 15-20 kV and the temperature is 40-60 ℃ to obtain Li source and V source interwoven electrostatic spun cloth;

(3) quickly transferring the spun fabric obtained in the step (2) to a forced air drying oven at the temperature of 60-80 ℃ for drying for 10-12h, and placing the dried fabric in N₂In the environment, pre-burning at the temperature of 200-300 ℃ for 2-5h at the temperature rise rate of 3 ℃/min, and then calcining at the temperature of 500-800 ℃ for 5h to obtain the lithium ion battery cathode material Li₃VO₄a/C fiber. The sintering atmosphere of the tube furnace in the step (3) is N₂The presintering temperature is 200 ℃, the temperature rising speed is 3 ℃/min, the presintering time is 3h, and then the calcination is carried out for 5h at 600 ℃ at the temperature rising speed of 3 ℃/min.

The method comprises the steps of carrying out jet spinning on a polymer solution in a strong electric field, utilizing a double-needle blending process in an electrostatic spinning system for the first time, and combining high-temperature solid phase sintering to obtain the Li containing special nodes₃VO₄the/C fiber interweaving structure enhances the lithium ion diffusion in the composite material.

The principle is as follows: 1) through the reaction of oxalic acid and ammonium metavanadate, VO is generated²⁺While C is₂O₄ ^2-Can promote Li⁺、VO²⁺Uniformly compounding with polyvinylpyrrolidone in a microscale; 2) the polyvinylpyrrolidone is used as a linear template, and Li is adsorbed by a high-voltage electric field⁺And VO²⁺The polyvinylpyrrolidone is charged and deformed, and finally the polyvinylpyrrolidone is attenuated into nano-fibers containing Li and V; 3) by the shape of the fiber, the Li and V sources are fixed in a nanometer range, so that the reaction activity of Li and V is enhanced, and the agglomeration of Li and V is inhibited; 4) uses the fiber intersection point containing Li and V source as Li in the high-temperature sintering process⁺、VO²⁺Channels that diffuse efficiently, thereby forming Li with special nodes₃VO₄a/C fiber interweaving structure with a large amount of Li accumulated at nodes₃VO₄Particles, carbon fibers having a large amount of Li formed therein₃VO₄Ultra-small nanoparticles. The nodes are beneficial to enhancing the structural stability of the material, and the activity of the composite material can be remarkably improved by the ultra-small nanoparticles. Prepared Li₃VO₄the/C fiber as the negative electrode of the lithium ion battery shows excellent comprehensive electrochemical performance.

The invention relates toLi prepared by double-needle electrostatic spinning blending₃VO₄The method for preparing the negative electrode material of the/C fiber lithium ion battery has the following remarkable characteristics:

(1) the synthesis process is simple, the cost is low, and the repeatability is strong;

(2) the double needles are used in the electrostatic spinning system, so that the yield of the nano fibers can be improved;

(3) prepared Li₃VO₄the/C fiber has special nodes, and a large amount of Li is gathered at the nodes₃VO₄Particles with Li inside the fiber₃VO₄Ultra-small nanoparticles, with a fiber diameter of about 400-600 nm;

(4) prepared Li₃VO₄the/C fiber is used as a negative electrode material of a lithium ion battery for the first time, and has high capacity and excellent cycle stability.

Drawings

Figure 1 XRD pattern of the sample prepared in example 1.

FIG. 2 SEM image of sample prepared in example 1.

FIG. 3 TEM image of the sample prepared in example 1.

FIG. 4 TEM image of the sample prepared in example 1.

FIG. 5 is a graph of (a) first charge and discharge curves and (b) cycle performance of samples prepared according to example 1.

FIG. 6 is a graph of (a) first charge and discharge curves and (b) cycle performance for samples prepared according to example 2.

FIG. 7 SEM image of sample prepared in example 3.

FIG. 8 SEM image of sample prepared in example 4.

Detailed Description

Example 1

Weighing 15 mmol LiNO₃Adding the mixture into 10mL of N, N-dimethylformamide, adding 2.0g of polyvinylpyrrolidone into the mixture, and stirring the mixture at room temperature for 12 hours to form a colorless homogeneous solution serving as a solution A; simultaneously adding 5 mmol ammonium metavanadate and 25 mmol oxalic acid into 10ml N, N-dimethylformamide, adding 1.7g polyvinylpyrrolidone, stirring to form blue transparent solution as solution B, and adding waterRespectively transferring the homogeneous viscous solution A, B to a 5mL electrostatic spinning injector, and spinning for 3h at the temperature of 40 ℃ and the voltage of 20 kV to obtain a Li source and V source interwoven spun fabric; after spinning, the obtained spun fabric is quickly transferred to a blowing drying oven with the temperature of 80 ℃ for drying for 12 hours, and the dried spun fabric is placed in N₂In the environment, pre-burning at 200 ℃ for 3h at the heating rate of 3 ℃/min, and then calcining at 600 ℃ for 5h at the heating rate of 3 ℃/min to obtain Li₃VO₄a/C fiber. The prepared sample is analyzed by XRD (X-ray diffraction) pattern, as shown in figure 1, the obtained diffraction peak and Li₃VO₄(PDF # 38-1247) the SEM of the prepared sample is shown in FIG. 2, and it can be seen that Li₃VO₄the/C fiber is in an interlaced shape and has special nodes. TEM of the sample is shown in FIGS. 3 and 4, and Li is shown₃VO₄/C fiber node accumulating large amount of Li₃VO₄Particles of carbon fiber in which Li is formed₃VO₄Ultra-small nanoparticles.

The material was made into a battery as follows: mixing the prepared sample with acetylene black and polyvinylidene fluoride according to the weight ratio of 8:1:1, preparing slurry by using N-methyl pyrrolidone as a solvent, coating the slurry on a copper foil with the thickness of 10 mu m, drying the copper foil at 60 ℃ for 10 hours, cutting the copper foil into a wafer with the diameter of 14 mm, and drying the wafer at 120 ℃ in vacuum for 12 hours. Using a metal lithium sheet as a counter electrode and a Celgard membrane as a diaphragm, and dissolving LiPF₆And (1 mmol/L) EC + DMC + DEC (volume ratio of 1: 1: 1) solution is used as electrolyte, and the electrolyte is assembled into a CR2025 type battery in an argon protective glove box. Standing for 8 hours after the battery is assembled, and then performing constant-current charge and discharge test by using a CT2001 battery test system, wherein the test voltage is 3-0.01V, and the current density is 200 mA g^-1. FIG. 5 shows Li being produced₃VO₄The first charge and discharge curve and the cycle performance chart of the negative electrode of the/C lithium ion battery. As shown in FIG. 5, the specific capacities of the first charge and discharge were 591.7 mAh g and 848.7 mAh g, respectively^-1The charge and discharge capacities after 50 times of circulation are 625.4 mAh g and 627 mAh g respectively^-1And the electrochemical performance is excellent.

Example 2

This example is exactly the same as example 1, and only the burn-in time is extended to 5 hoursThen calcining at 600 ℃ for 5h at the heating rate of 3 ℃/min to obtain the material. The material obtained in example 2 was used to prepare a battery in accordance with example 1. As shown in FIG. 6, the first charge and discharge specific capacities are 607.2 and 838.8 mAh g respectively^-1The charging and discharging capacities after 50 times of circulation are 574.5 mAh g and 576.7 mAh g respectively^-1And the electrochemical performance is better.

Example 3

In this example, the material was obtained by calcining at 600 ℃ for 5 hours at a temperature-raising rate of 3 ℃/min without calcining in exactly the same manner as in example 1. The SEM of the prepared sample is shown in fig. 7, and it can be seen that no fiber morphology can be obtained. The material obtained in example 3 was used to prepare a battery in accordance with example 1. The specific capacities of the first charge and discharge are 445.6 and 528.7 mAh g respectively^-1And the charge and discharge capacities after 50 times of circulation are respectively 397.6 and 446.7 mAh g^-1And the electrochemical performance is better.

Example 4

Weighing 7.5 mmol LiNO₃2.5 mmol of ammonium metavanadate and 12.5 mmol of H₂C₂O₄ ^.2H₂Adding O into a beaker, adding a proper amount of N, N-dimethylformamide, adding 1.8g of polyvinylpyrrolidone into the beaker, stirring for 12h to form a blue transparent solution, transferring the blue transparent solution into a 10mL electrostatic spinning injector, spinning for 3h at 40 ℃ and 20 kV voltage, immediately transferring the obtained spun fabric into an 80 ℃ oven to dry for 12h after spinning is finished, drying, and placing the spun fabric in an N-Dimethylformamide (DMF)₂In the environment, pre-burning at 200 ℃ for 3h at the heating rate of 3 ℃/min, and then calcining at 600 ℃ for 5h at the heating rate of 3 ℃/min to obtain Li₃VO₄a/C fiber. SEM of the sample prepared is shown in FIG. 8, and it can be seen that Li₃VO₄the/C fiber has no special node. The material obtained in example 4 was used to prepare a battery in accordance with example 1. The first charge and discharge specific capacities are 466.2 mAh g and 538.7 mAh g respectively^-1The charging and discharging capacities after 50 times of circulation are 376.5 mAh g and 452.5 mAh g respectively^-1And the electrochemical performance is better.

Example 5

In this example, the mass of polyvinylpyrrolidone in solution A, B was simultaneously increasedFractional, weighing 15 mmol LiNO₃Adding the mixture into 10mL of N, N-dimethylformamide, adding 2.4g of polyvinylpyrrolidone into the mixture, and stirring the mixture at room temperature for 12 hours to form a colorless homogeneous solution serving as a solution A; meanwhile, 5 mmol of ammonium metavanadate and 25 mmol of oxalic acid are added into 10mL of N, N-dimethylformamide, 2.0g of polyvinylpyrrolidone is added into the N, N-dimethylformamide and stirred until a blue transparent solution is formed to be used as a solution B, then the viscous solutions A, B are respectively transferred into 5mL of electrostatic spinning syringes, and the solution blocks a needle head and cannot be subjected to electrostatic spinning. If electrostatic spinning is not performed, it is inferred that the material is likely to agglomerate and the electrochemical performance is poor.

Example 6

In this example, the mass fraction of polyvinylpyrrolidone in solution A, B was reduced at the same time, and 15 mmol of LiNO was weighed₃Adding the mixture into 10mL of N, N-dimethylformamide, adding 1.6g of polyvinylpyrrolidone into the mixture, and stirring the mixture at room temperature for 12 hours to form a colorless homogeneous solution serving as a solution A; meanwhile, 5 mmol of ammonium metavanadate and 25 mmol of oxalic acid are added into 10mL of N, N-dimethylformamide, 1.4g of polyvinylpyrrolidone is added into the N, N-dimethylformamide and stirred until a blue transparent solution serving as a solution B is formed, then the viscous solutions A, B are respectively transferred into 5mL of electrostatic spinning injectors, the solution viscosity is insufficient, the solutions drop in the spinning process, and electrostatic spinning cannot be carried out. If electrostatic spinning is not performed, it is inferred that the material is likely to agglomerate and the electrochemical performance is poor.