CN112038614B - Negative electrode material for sodium ion battery and preparation method thereof - Google Patents
Negative electrode material for sodium ion battery and preparation method thereof Download PDFInfo
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a negative electrode material for a sodium ion battery and a preparation method thereof2SnO2Growing the carbon nano-spheres in situ to obtain the cathode material. Due to the unique shape and structure of the nano carbon ball, more expansion spaces are provided for the nano tin dioxide in the charging and discharging processes, and the loaded nano tin dioxide increases the specific capacity of the nano carbon ball. The negative electrode material shows good specific capacity, cycle performance and rate capability in a battery negative electrode, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a negative electrode material for a sodium ion battery and a preparation method thereof.
Background
With the gradual depletion of fossil energy, new energy sources, such as wind energy, solar energy, and tidal energy, have attracted extensive attention from various countries all over the world. The new energy sources have the characteristics of low utilization rate, intermittence and difficulty in grid-connected power generation. In order to enable the large-scale use of these clean and renewable new energy sources, the development of energy storage devices is imperative. The lithium ion battery has excellent electrochemical performance, is the most successful battery commercialized at present, and is widely applied to the fields of mobile phones, notebook computers, electric vehicles and the like. However, the storage of lithium resources is limited and unevenly distributed, and the cost of lithium ion batteries as large-scale energy storage devices is too high to satisfy the requirement of large-scale use of new energy. Lithium and sodium are in the same main group and adjacent positions in the periodic table of elements, and have very similar physical and chemical properties; meanwhile, the sodium ion battery has the advantages of abundant sodium resource reserves, low cost, environmental friendliness, uniform distribution in the earth crust and an energy storage mechanism very similar to that of the lithium ion battery. Therefore, sodium ion batteries are considered to be the most likely replacements for lithium ion batteries for large-scale energy storage systems. However, sodium ion batteries also suffer from the inherent disadvantage of low capacity, and due to the large radius of sodium ions, finding a suitable sodium intercalation material is a difficult point. Therefore, the development of a negative electrode material with high specific capacity is imperative.
Tin dioxide (SnO)2) The lithium ion battery cathode material has the advantages of low price, high theoretical specific capacity, high energy density and the like, and is widely researched as a lithium ion battery cathode material. Due to SnO2The method has the advantages of low price, high theoretical specific capacity, high energy density and the like, has large development space in the sodium ion battery, and is expected to greatly improve the capacity of the sodium ion battery. But because of SnO in the process of charging and discharging2Volume expansion may occur and may be detached from the current collector. And therefore to mitigate the adverse effects of swelling.
In order to solve the above problems, for example, the invention patent 20161004965.9 discloses a spherical SnO assembled by nano particles2A preparation method of a sodium ion battery negative electrode material comprises the step of obtaining C/SnO by a hydrothermal method by taking PVP and sodium citrate as carbon sources2A composite material. However, the obtained material is firstly washed by 409 mAh/g under the current density of 100mA/g, and the cycle of 70 times is attenuated to 225mAh/g, so that the material is poor in cycle stability, and the electrochemical performance is not excellent. The invention patent 201610049015.6 discloses a prism-assembled spherical SnO2Preparation method of sodium ion battery negative electrode material, 1) SnCl4·5H2O and C6H12N4Dissolving in deionized water with equal amount to obtain solution A and solution B; 2) slowly adding the solution B into the solution A under the action of continuous magnetic stirring to form a uniform solution C, and dropwise adding a NaOH solution E into the solution C to form a solution D; 3) carrying out homogeneous hydrothermal reaction; 4) after the reaction is finished, taking out the precursor, washing to obtain a white precursor, and freeze-drying to obtain spherical SnO assembled with prisms2The negative electrode material of the sodium-ion battery is obtained, but the obtained material is circularly attenuated to 200 mAh/g from 400 mAh/g after 40 times under the current density of 100mA/g, so that the capacity retention rate is insufficient, and the circulating stability is poor. Although the above materials solve SnO to some extent2The problem of volume expansion, but the cycle stability is poor,the specific capacity is low, and the high requirements of people on various performances of the negative electrode material cannot be met.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a negative electrode material for a sodium ion battery and a preparation method thereof, and solves the problems of the prior art based on SnO2Poor cycling stability and insufficient specific capacity of the cathode material.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a negative electrode material for a sodium-ion battery comprises the following steps:
1) heating to 600-800 ℃ at a heating rate of 5-7 ℃/min in a tubular furnace filled with inert gas, then closing the inert gas, introducing acetylene gas, fully reacting, after the reaction is finished, closing the acetylene gas, introducing the inert gas, and cooling to normal temperature to obtain carbon nanospheres;
2) mixing the nano carbon spheres obtained in the step 1) with SnCl4.5H2Mixing O powder uniformly, then placing the mixture into a high-pressure hydrothermal reaction kettle for full reaction, soaking the mixture in absolute ethyl alcohol and deionized water in sequence after the reaction is finished, and drying the mixture to obtain NCSs/SnO2；
3) NCSs/SnO obtained in the step 2)2And (3) placing the anode material in a tubular furnace, and carrying out heat treatment under the protection of inert gas to obtain the anode material.
Thus, the nano-tetragonal SnO grown in situ is increased by means of heat treatment2The degree of crystallization of the nano SnO is increased along with the increase of the heat treatment temperature in the roasting process2Sintering of the particle portion, SnO2The crystallinity is enhanced, and the nano SnO can be increased by improving the crystallinity2While more active sites are added by the heat treatment. In addition, SnO is more inclined than that of rhombic type2The electrical conductivity is not good, and the tetragonal nano SnO obtained by the invention2Has better conductivity and larger irreversible capacity, and the conductivity is improved to reduce the internal resistance of the battery.
Preferably, the feeding rate of the acetylene is 90-110 mL/min.
Preferably, the nano carbon spheres are mixed with SnCl4.5H2The mass ratio of O is 1: 1.
Preferably, the hydrothermal reaction is carried out at a temperature rising speed of 2-4 ℃/min to 160-180 ℃ and is kept for 10-12 h.
Preferably, the drying temperature is 80-100 ℃, and the time is 12-16 h.
Preferably, the heat treatment is carried out for 2 hours under the condition that the temperature is increased to 600-1000 ℃ at the speed of 5-10 ℃/min.
The invention also aims at the negative electrode material prepared by the preparation method.
The invention also aims to provide application of the negative electrode material in the aspect of manufacturing sodium-ion batteries
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts CVD method to prepare nano carbon spheres, and nano SnO is grown in situ2SnO2Growing on the carbon nanospheres in situ. Because of the unique shape and structure of the nano carbon spheres, the nano carbon spheres have uniform particle size, better dispersibility and regular shape, and the spherical particles are favorable for shortening the diffusion path of lithium ions, improving the contact between the material and the electrolyte, further improving the migration rate of the lithium ions, providing more expansion space for nano tin dioxide in the charging and discharging process, so that the nano SnO is enabled2The problem of volume expansion is solved when the alloying reaction takes place. Meanwhile, the loaded nano tin dioxide increases the specific capacity of the nano carbon ball. In the invention, SnO2The composite material obtained by compounding with the nano carbon spheres can greatly improve the capacity and the conductivity of the sodium ion battery while keeping good circulation stability, and solves the problem of nano SnO2Poor conductivity.
2. The cathode material prepared by the invention adopts the CVD method to prepare the nano carbon spheres, has low temperature and low energy consumption, does not need subsequent treatment procedures, and is simple, convenient and economic. The catalyst used in the method is simple, convenient and time-saving. Then SnO is reacted by simple hydrothermal reaction2Loaded on the nano carbon spheres by regulating the temperature and the reaction time of the hydrothermal reactionThe load degree is regulated and controlled, and the load capacity is controlled by regulating and controlling the proportion of the nano carbon spheres and the stannic chloride pentahydrate, so that the electrochemical performance of the sodium ion battery is improved. Finally, the conductivity of the electrode is improved through a heat treatment process, and the internal resistance of the sodium-ion battery is reduced. The cathode material prepared by the invention can be directly used as a sodium ion battery, the structural characterization and the electrochemical characteristics of the sodium ion battery are tested, and the cathode material has good specific capacity, cycle performance and rate capability in the battery cathode and has good application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of the negative electrode material prepared by the invention.
FIG. 2 is a graph of the cycling performance of the negative electrode material prepared in the invention at a current density of 100 mA/g; a is example 1 and B is example 2.
FIG. 3 is a graph of rate capability of the negative electrode material prepared by the invention under different current densities; a is example 1 and B is example 2.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. The experimental procedures are not specifically described in the following examples, and are carried out in a conventional manner using reagents which are generally commercially available.
Preparation method of negative electrode material for sodium ion battery
Example 1
1) Putting the catalyst into a quartz boat, uniformly paving the quartz boat, putting the quartz boat into a heating tube of a device, heating the quartz boat to 600 ℃ at the heating rate of 5 ℃/min in a tube furnace filled with inert gas, closing the inert gas, introducing acetylene gas at the rate of 100 mL/min, reacting for 1 h, closing the acetylene gas, introducing the inert gas, and cooling to the normal temperature to obtain the nano carbon spheres.
2) Weighing 0.62g of the carbon nanospheres obtained in the step 1) and 0.62g of SnCl4.5H2Placing O powder into sealed pulverizer, pulverizing for 30 s to obtain SnCl4.5H2And fully and uniformly mixing the O and the carbon nanospheres. Then placing the mixture into a high-pressure hydrothermal reaction kettle, heating to 180 ℃ at the speed of 2 ℃/min, preserving heat for 10 hours, cooling and then usingWashing with a large amount of deionized water and absolute ethyl alcohol, and drying at 100 ℃ in vacuum for 12h to obtain NCSs/SnO2。
3) NCSs/SnO obtained in the step 2)2Adding the mixture into a corundum crucible, putting the corundum crucible into a tubular furnace under the protective atmosphere of 200 mL/min of nitrogen, and heating the corundum crucible to 600 ℃ at the speed of 10 ℃/min for heat treatment for 2 hours to obtain the cathode material.
Example 2
1) Putting the catalyst into a quartz boat, uniformly paving the quartz boat, putting the quartz boat into a heating tube of a device, heating the quartz boat to 600 ℃ at the heating rate of 5 ℃/min in a tube furnace filled with inert gas, closing the inert gas, introducing acetylene gas at the rate of 100 mL/min, reacting for 1 h, closing the acetylene gas, introducing the inert gas, and cooling to the normal temperature to obtain the nano carbon spheres.
2) Weighing 0.62g of the carbon nanospheres obtained in the step 1) and 0.62g of SnCl4.5H2Placing O powder into sealed pulverizer, pulverizing for 30 s to obtain SnCl4.5H2And fully and uniformly mixing the O and the carbon nanospheres. Then putting the mixture into a high-pressure hydrothermal reaction kettle, heating to 140 ℃ at the speed of 2 ℃/min, preserving the heat for 10 hours, cooling, washing with a large amount of deionized water and absolute ethyl alcohol, and drying at the vacuum temperature of 100 ℃ for 12 hours to obtain NCSs/SnO2。
3) NCSs/SnO obtained in the step 2)2Adding the mixture into a corundum crucible, putting the corundum crucible into a tubular furnace under the protective atmosphere of 200 mL/min of nitrogen, and heating the corundum crucible to 600 ℃ at the speed of 10 ℃/min for heat treatment for 2 hours to obtain the cathode material.
Example 3
1) Putting the catalyst into a quartz boat, uniformly paving the quartz boat, putting the quartz boat into a heating tube of a device, heating the quartz boat to 800 ℃ at the heating rate of 6 ℃/min in a tube furnace filled with inert gas, closing the inert gas, introducing acetylene gas at the rate of 100 mL/min, reacting for 1 h, closing the acetylene gas, introducing the inert gas, and cooling to the normal temperature to obtain the nano carbon spheres.
2) Weighing 0.62g of the carbon nanospheres obtained in the step 1) and 0.62g of SnCl4.5H2O powder is put in a sealedPulverizing for 30 s in pulverizer to obtain SnCl4.5H2And fully and uniformly mixing the O and the carbon nanospheres. Then putting the mixture into a high-pressure hydrothermal reaction kettle, heating to 180 ℃ at the speed of 5 ℃/min, preserving the heat for 10 hours, cooling, washing with a large amount of deionized water and absolute ethyl alcohol, and drying at the vacuum temperature of 100 ℃ for 12 hours to obtain NCSs/SnO2。
3) NCSs/SnO obtained in the step 2)2Adding the mixture into a corundum crucible, putting the corundum crucible into a tubular furnace under the protective atmosphere of 200 mL/min of nitrogen, and heating the corundum crucible to 800 ℃ at the speed of 10 ℃/min for heat treatment for 3 hours to obtain the cathode material.
Second, performance verification
The negative electrode materials prepared in the embodiments 1-3 are applied to a sodium ion battery, so that the negative electrode materials are fully and uniformly mixed with conductive agents Super P and CMC. Then evenly coating the slurry on a copper foil or an aluminum foil, slicing and weighing, using a metal sodium sheet as a counter electrode, using commercial glass fiber as a diaphragm and using 1 mol/L electrolyte (solute is NaClO) in a glove box4Solvent v (ec): v (emc): v (dmc) volume ratio = 1: 1: 1) the sequence of assembling the battery is as follows: and (3) assembling the battery by using the positive electrode shell → the electrode plate → the electrolyte → the diaphragm → the electrolyte → the lithium plate → the current collecting steel plate → the spring plate → the negative electrode shell, and sealing and pressing the battery by using a sealing machine. Finally, standing at room temperature for 12h was carried out in preparation for testing electrochemical properties.
1. The negative electrode material prepared by the invention is observed under a scanning electron microscope, and the result is shown in figure 1. It can be seen from the figure that the nano carbon spheres have uniform particle size, better dispersibility and regular shape, and the nano SnO is successfully grown on the surfaces of the nano carbon spheres2. Because the unique morphology of the nano carbon ball and the particles with the spherical structure are beneficial to shortening the diffusion path of lithium ions, the contact between the material and the electrolyte is improved, the migration rate of the lithium ions is further improved, more expansion spaces are provided for the nano tin dioxide in the charging and discharging processes, and meanwhile, the specific capacity of the nano carbon ball is increased by the loaded nano tin dioxide. Compared with the traditional high-molecular hard carbon, the negative electrode material of the sodium-ion battery has more excellent cycling stability and higher specific capacity.
2. The primary charge and discharge performance tests were performed on the batteries assembled from the negative electrode materials obtained in examples 1 to 3 at a current density of 100mA/g, and the results are shown in fig. 2.
As can be seen from the figure, the carbon nanospheres as the substrate material have good cycle performance and can relieve the nano SnO2Volume expansion brought by charging and discharging processes, nano SnO grown by high-pressure hydrothermal reaction at 180 DEG C2Has higher specific capacity. At the current density of 100mA/g, the capacity of 100 cycles is kept at 225mAh/g, and good cycle performance is shown.
3. Batteries assembled by the negative electrode materials prepared in the examples 1 to 3 were cycled 10 times at current densities of 50mA/g, 100mA/g, 200 mA/g, 500 mA/g, 1000 mA/g and 2000 mA/g, respectively, and the results of comparing the rate performance are shown in FIG. 3.
As can be seen from the graph, after sixty times of charge and discharge, the capacity is still maintained at 250 mAh/g after returning to the current density of 50mA/g, and even under the large current density of 2000 mA/g, the capacity is maintained at 100 mAh/g, and good rate performance is shown.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (6)
1. A preparation method of a negative electrode material for a sodium-ion battery is characterized by comprising the following steps:
1) heating to 600-700 ℃ at a heating rate of 5-7 ℃/min in a tubular furnace filled with inert gas, then closing the inert gas, introducing acetylene gas, fully reacting, after the reaction is finished, closing the acetylene gas, introducing the inert gas, and cooling to normal temperature to obtain carbon nanospheres;
2) mixing the nano carbon spheres obtained in the step 1) with the powder uniformly, and then mixingPlacing the mixture in a high-pressure hydrothermal reaction kettle for full reaction, soaking the mixture in absolute ethyl alcohol and deionized water in sequence after the reaction is finished, and drying the mixture to obtain NCSs/SnO2；
3) NCSs/SnO obtained in the step 2)2Placing the anode material in a tubular furnace, and carrying out heat treatment under the protection of inert gas to obtain the anode material;
the introduction rate of the acetylene is 90-110 mL/min;
the nano carbon spheres and SnCl4.5H2The mass ratio of O is 1: 1.
2. The preparation method of the negative electrode material for the sodium-ion battery as claimed in claim 1, wherein the hydrothermal reaction is carried out at a temperature rising rate of 2-4 ℃/min to 160-180 ℃ for 10-12 h.
3. The preparation method of the negative electrode material for the sodium-ion battery as claimed in claim 1, wherein the drying temperature is 80-100 ℃ and the drying time is 12-16 h.
4. The method for preparing the negative electrode material for the sodium-ion battery according to claim 1, wherein the heat treatment is performed for 2 hours under the condition that the temperature is raised to 600-1000 ℃ at a speed of 5-10 ℃/min.
5. A negative electrode material prepared by the preparation method of any one of claims 1 to 4.
6. The use of the negative electrode material of claim 5 in the manufacture of a sodium ion battery.
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| CN114735672B (en) * | 2022-04-24 | 2023-08-25 | 深圳市科信通信技术股份有限公司 | Boron-nitrogen co-doped hard carbon material and preparation method thereof |
| CN114975964A (en) * | 2022-06-28 | 2022-08-30 | 四川轻化工大学 | Polypyrrole-coated tin dioxide/nano carbon sphere negative electrode material, preparation method thereof and sodium ion battery |
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| CN101723315B (en) * | 2009-11-26 | 2012-07-04 | 上海大学 | Preparation method of Sn/C nano composite material with nucleocapsid structure |
| CN101823760B (en) * | 2010-05-13 | 2012-09-05 | 西安交通大学 | Method for preparing nanometer foam stannic oxide of lithium ion battery cathode material |
| CN104183823B (en) * | 2014-08-29 | 2017-02-08 | 华中师范大学 | SnO2, MnO or Mn3O4-based composite material based on three-dimensional carbon sphere framework structure and preparation method of material |
| CN105609722B (en) * | 2015-12-28 | 2017-11-21 | 黑龙江科技大学 | A kind of SnO of dual modification2The preparation method of@C/ graphene nanometer composite negative materials |
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