CN110577208B - Sodium-philic conductive carbon nanotube framework material and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of sodium battery electrode materials, and particularly relates to a sodium-philic conductive carbon nanotube framework material as well as a preparation method and application thereof. The sodic conductive carbon nanotube framework material comprises a network framework, the main body of the network framework is a conductive carbon nanotube three-dimensional network with macroscopic orientation, the network framework is connected with sodic oxygen-containing functional groups, the sodic oxygen-containing functional groups have strong interaction with metal sodium, the deposition behavior of the metal sodium can be changed, the deposition stripping of the metal sodium can be stabilized, and therefore the sodic conductive carbon nanotube framework material can be used for preparing a composite electrode (cathode) of a sodium-air full battery, and the cycle life of the sodium-air full battery with greatly improved cycle life can be obtained. The preparation method is simple in preparation process, can realize the high-capacity long-cycle sodium metal cathode, and has good application prospect in the field of high-energy-density batteries.
Description
Technical Field
The invention belongs to the technical field of sodium battery electrode materials, and particularly relates to a sodium-philic conductive carbon nanotube skeleton material as well as a preparation method and application thereof.
Background
Since its birth, lithium ion batteries have gradually taken a leading position in the energy storage market. However, with the rapid development of portable electronic devices, electric vehicles, power grid storage, and the like, the demand for lithium ion batteries will increase rapidly. The content of lithium element in the earth crust is rare, and the pure dependence on a lithium ion battery system will inevitably cause the exhaustion of lithium resources. Therefore, it is imperative to develop new battery systems other than lithium batteries to replace lithium batteries. The physical and chemical properties of the sodium battery are most similar to those of the lithium battery, and the sodium element is abundant in earth crust and low in cost, so that the sodium battery is likely to become a battery system for replacing the lithium battery. The sodium metal has high theoretical specific capacity of 1166 milliampere-hour/gram, can greatly improve the energy density of the battery, and meets the requirements of the electric automobile and the like on the high-energy-density battery at present. However, sodium metal can cause the growth of sodium dendrite due to uneven nucleation and growth in the charging and discharging processes, and the sodium dendrite pierces a diaphragm to cause short circuit in the battery, thereby causing safety accidents such as combustion and explosion. In addition, the side reaction of the sodium metal and the electrolyte can continuously consume the electrolyte and the battery capacity. Therefore, the practical application and high-capacity and long-life cycle of metallic sodium are not realized at present.
In order to solve the problems of the sodium metal negative electrode, some research reports have been reported. On one hand, the electrolyte of the battery is optimized, such as the components and the concentration of the electrolyte, and the like, so as to obtain a solid electrolyte interface with higher stability. On the other hand, the solid electrolyte with high mechanical strength or the solid electrolyte interface with high strength is modified on the surface of the metal sodium to inhibit the growth and puncture of the sodium dendrite. However, these methods do not address the root cause of sodium dendrite growth, i.e., heterogeneous nucleation and growth. Recently, there are reports in the literature of the effect of different deposition substrates on the deposition behavior of sodium metal. The deposition behavior of metallic sodium is strongly dependent on the initial nucleation of sodium. The metal particles such as gold, silver, tin and the like with sodium affinity have strong interaction with the metal sodium, so that the metal sodium can be uniformly nucleated at the sodium affinity sites preferentially, and further, the concentrated growth of dendritic crystals is avoided. However, the introduction of these metal particles with a relatively large mass into the substrate skeleton inevitably reduces the overall specific capacity of the electrode, which is contrary to the goal of realizing a high specific capacity electrode. According to the calculation result of the first principle, atoms with strong electronegativity, such as nitrogen, oxygen, sulfur and the like, have strong interaction with sodium atoms and can play a good stabilizing role in the deposition of metallic sodium. Therefore, designing a conductive framework with high sodium affinity and light weight may play a good stabilizing role in the growth of metallic sodium, and achieve the goals of high capacity and long cycle life.
Disclosure of Invention
The invention aims to provide a sodium-philic conductive carbon nanotube framework material capable of effectively stabilizing deposition and stripping of metal sodium, and a preparation method and application thereof.
The invention provides a sodium-philic conductive carbon nanotube framework material, which comprises a network framework, wherein the main body of the network framework is a conductive carbon nanotube three-dimensional network with macroscopic orientation, and oxygen-containing functional groups (such as Carboxyl (COOH), hydroxyl (OH), ether bonds (C-O-C), ketones (C = O) and the like) with the atomic percentage of 0-25% (preferably 1-25%) are connected on the network framework; the conductive carbon nanotube network skeleton has sodium affinity, namely has strong interaction with metal sodium, can change the deposition behavior of the metal sodium and stabilize the deposition stripping of the metal sodium.
The invention provides a preparation method of a sodium-philic conductive carbon nanotube framework, which comprises the following specific steps:
(1) And (3) preparing a conductive carbon nanotube network framework. And preparing the macroscopically-oriented carbon nanotube three-dimensional network by using a suspension chemical vapor deposition method. Specifically, ferrocene and thiophene are used as mixed catalysts, ethanol and acetone are used as carbon sources, hydrogen and argon are used as carrier gases, the gas flow rate is 1000-1500 ml/min, and an oriented carbon nanotube three-dimensional network is continuously prepared at the temperature of 1000-1300 ℃; the thickness range of the three-dimensional network of the carbon nano tube is 10-200 microns; in the mixed catalyst, the mass fraction of ferrocene is 94-98%, and the mass fraction of thiophene is 6-2%; in the carbon source, the mass fraction of ethanol is 75-90%, and the mass fraction of acetone is 25-10%; in the carrier gas, the volume fraction of the hydrogen is 80-90%, and the volume fraction of the argon is 20-10%;
(2) Preparing a network framework of the sodium-philic conductive carbon nanotube: placing the conductive carbon nanotube network skeleton prepared in the step (1) in an oxygen plasma treatment instrument, wherein the control parameters are as follows: the processing power is 50-100W, the oxygen flow is 50-200 ml/min, the working pressure is less than 100 Pa, and the processing time is 1-20 min, thus obtaining the target product, namely the sodic conductive carbon nanotube network framework material.
The sodic conductive carbon nanotube network framework material can be used as an electrode material of a sodium-air full cell, and particularly can be used for preparing a composite electrode of the sodium-air full cell.
The preparation steps of the composite electrode are as follows: cutting the sodic conductive carbon nanotube network framework into electrode plates with the size of 1-2 square centimeters, taking the electrode plates as a battery anode and a metal sodium plate as a battery cathode, and assembling the CR2032 button battery. The electrolyte is formed by using sodium trifluoromethanesulfonate (NaTF) as electrolyte salt and diethylene glycol dimethyl ether (DEGDME) as a solvent. The battery separator was Celgard2400. Wherein, the concentration of NaTF is 0.5-1.5 mol/L. Firstly, circulating the button cell for 2-4 circles within the current range of 0.1-0.5 milliampere/square centimeter and the voltage range of 0-0.5 volt, removing pollutants on the surface of an electrode and forming a stable solid electrolyte membrane; then, the metallic sodium is electrodeposited on the network framework by adopting a constant current with the current magnitude of 0.5-2 milliamperes/square centimeter. And after the deposition is finished, disassembling the CR2032 battery to obtain the sodium-sodium affinity oxygen functionalized oriented carbon nanotube framework composite electrode.
The composite electrode is used as a negative electrode of a sodium-air battery, the oriented carbon nanotube film is used as a positive electrode, sodium trifluoromethanesulfonate (NaTF) is used as electrolyte salt, diethylene glycol dimethyl ether (DEGDME) is used as a solvent in an electrolyte, and Woltmann glass fiber filter paper is used as a diaphragm to assemble a Woltmann (Swagelok) sodium-air battery. Wherein, the concentration of NaTF is 0.5-1.5 mol/L. The assembled cells were tested by placing them directly in air. Electrochemical test parameters were 1000 milliamps/gram current density, 500 milliamp-hours/gram specific capacity. Because of the stabilizing effect of the sodium-philic conductive carbon nano tube network skeleton on the deposition stripping process of the metal sodium, the growth of sodium dendrite is inhibited, and the cycle life of the sodium-air battery is greatly prolonged.
Drawings
Fig. 1 is a schematic diagram of the deposition process of sodium metal on different substrates. Wherein, a is the deposition process of metal sodium on a traditional substrate such as copper foil and the like; and b, depositing the metal sodium on the framework of the sodium-philic oxygen functionalized oriented carbon nanotube.
FIG. 2 is a material characterization of a sodilic oxygen-functionalized oriented carbon nanotube scaffold. Wherein, a is a scanning electron microscope picture of the oxygen functionalized oriented carbon nanotube skeleton; b, is a transmission electron microscope picture of the oxygen functionalized aligned carbon nanotube; c, is a cross-sectional scanning electron microscope image of the oxygen-functionalized oriented carbon nanotube backbone; d, is the distribution diagram of carbon and oxygen elements on the cross section of the framework of the oxygen functionalized oriented carbon nanotube.
Fig. 3 shows the shape evolution of the deposition of metallic sodium on the framework of the sodium-philic conductive carbon nanotube network.
Fig. 4 shows the electrochemical performance of the sodium-philic oxygen functionalized oriented carbon nanotube backbone composite electrode. Wherein, a is a deposition stripping curve of the metal sodium; and b, the change rule of the coulomb efficiency along with the number of the circulating turns.
Fig. 5 shows the electrochemical performance of the sodium-sodophilic oxygen functionalized oriented carbon nanotube framework composite electrode for a sodium-air full cell. Wherein, a is a charge-discharge curve of the air battery; and b, the change rule of the air battery discharge platform and the discharge specific capacity along with the cycle number.
Detailed Description
Example 1
(1) Preparing a conductive carbon nanotube network framework: continuously preparing an oriented carbon nanotube three-dimensional network at 1000 ℃ by using ferrocene and thiophene as mixed catalysts, ethanol and acetone as carbon sources, hydrogen and argon as carrier gases and gas flow rate of 1200 ml/min; the thickness of the three-dimensional network of carbon nanotubes is 10 microns; in the mixed catalyst, the mass fraction of ferrocene is 95 percent, and the mass fraction of thiophene is 5 percent; in the carbon source, the mass fraction of ethanol is 80%, and the mass fraction of acetone is 20%; in the carrier gas, the volume fraction of hydrogen was 90%, and the volume fraction of argon was 10%.
(2) Preparing a network framework of the sodium-philic conductive carbon nanotube: placing the conductive carbon nanotube network skeleton prepared in the step (1) into an oxygen plasma processor, and setting parameters: the treatment power is 100 watts, the treatment time is 15 minutes, the oxygen flow is 100 milliliters per minute, and the working air pressure is 70 Pa. After the treatment is finished, the content of oxygen element on the surface of the conductive carbon nanotube network framework is 24.4%.
(3) Preparing a sodium-philic oxygen functionalized oriented carbon nanotube skeleton composite electrode: cutting the sodic conductive carbon nanotube network framework into electrode plates with the size of 1-2 square centimeters, taking the electrode plates as a battery anode and a metal sodium plate as a battery cathode, and assembling the CR2032 button battery. The electrolyte takes sodium trifluoromethanesulfonate (NaTF) as electrolyte salt and diethylene glycol dimethyl ether (DEGDME) as a solvent. The battery separator was Celgard2400. Wherein, the concentration of NaTF is 1 mol/L. Firstly, circulating the button cell for 4 circles in a current range of 0.1 milliampere/square centimeter and a voltage range of 0-0.5 volt, removing pollutants on the surface of an electrode and forming a stable solid electrolyte membrane; metallic sodium was then electrodeposited onto the network framework using a constant current of 0.5 milliamps per square centimeter. The deposition time is 2 hours, and the sodium-sodium affinity oxygen functionalized oriented carbon nanotube framework composite electrode with the surface capacity of 1 mAmp hour/square centimeter is obtained. The composite electrode can realize stable deposition and stripping for 3000 circles, namely 6000 hours under the conditions of constant current of 1 milliampere/square centimeter and surface capacity of 1 milliampere-hour/square centimeter, and coulombic efficiency is kept to be more than 99 percent, as shown in figure 4. The stabilizing effect of the sodium-philic conductive carbon nanotube network skeleton on the metallic sodium is fully demonstrated.
Example 2
(1) Preparing a conductive carbon nanotube network framework: continuously preparing an oriented carbon nanotube three-dimensional network at 1200 ℃ by using ferrocene and thiophene as mixed catalysts, ethanol and acetone as carbon sources, hydrogen and argon as carrier gases and gas flow rate of 1000 ml/min; the thickness of the three-dimensional network of carbon nanotubes is 10 microns; in the mixed catalyst, the mass fraction of ferrocene is 90%, and the mass fraction of thiophene is 10%; in the carbon source, the mass fraction of ethanol is 90%, and the mass fraction of acetone is 10%; in the carrier gas, the volume fraction of hydrogen was 90%, and the volume fraction of argon was 10%.
(2) Preparing a network framework of the sodium-philic conductive carbon nanotube: placing the conductive carbon nanotube network skeleton prepared in the step (1) into an oxygen plasma processor, and setting parameters: the treatment power is 100 watts, the treatment time is 15 minutes, the oxygen flow is 100 milliliters per minute, and the working air pressure is 70 Pa. After the treatment, the content of oxygen element on the surface of the conductive carbon nanotube network skeleton is 24.4%.
(3) Preparing a sodium-sodium affinity oxygen functionalized oriented carbon nanotube skeleton composite electrode: cutting the sodic conductive carbon nanotube network framework into electrode plates with the size of 1-2 square centimeters, taking the electrode plates as a battery anode and a metal sodium plate as a battery cathode, and assembling the CR2032 button battery. The electrolyte takes sodium trifluoromethanesulfonate (NaTF) as electrolyte salt and diethylene glycol dimethyl ether (DEGDME) as a solvent. The battery separator was Celgard2400. Wherein, the concentration of NaTF is 1 mol/L. Firstly, circulating the button cell for 4 circles in a current range of 0.1 milliampere/square centimeter and a voltage range of 0-0.5 volt, removing pollutants on the surface of an electrode and forming a stable solid electrolyte membrane; then, the metal sodium is electrodeposited on the network framework by adopting a constant current with the current magnitude of 0.5 milliampere/square centimeter. The deposition time is 20 hours, and the sodium-sodium affinity oxygen functionalized oriented carbon nanotube framework composite electrode with the surface capacity of 10 mAmp hours/square centimeter is obtained.
(4) The sodium-air battery based on the sodium-sodium affinity oxygen functionalized oriented carbon nanotube skeleton composite electrode is assembled and tested for performance, namely the sodium-sodium affinity oxygen functionalized oriented carbon nanotube skeleton composite electrode obtained in the step (A) is taken out of a CR2032 battery, washed by diethylene glycol dimethyl ether (DEGDME) and dried in the air. The composite electrode is used as a negative electrode of a sodium-air battery, and the oriented carbon nanotube film is used as an air positive electrode, so that the Shivialok (Swagelok) sodium-air battery is assembled. The electrolyte takes sodium trifluoromethanesulfonate (NaTF) as electrolyte salt and diethylene glycol dimethyl ether (DEGDME) as a solvent, wherein the concentration of NaTF is 1 mol/L. The diaphragm adopts Whatman glass fiber filter paper. The assembled cells were tested in air. The sodium-air battery can stably circulate for 100 circles under the current density of 1000 milliampere/gram and the circulation capacity of 500 milliampere-hour/gram, the discharge platform of the sodium-air battery is kept stable within 100 circles without obvious reduction, and the polarization of the battery in the repeated charge and discharge process is reduced, as shown in figure 5. The sodium-air battery with high specific capacity and long cycle life can be realized under the stabilizing action of the network framework of the sodium-philic conductive carbon nano tube. The sodium-philic conductive carbon nanotube network framework has good application prospect in the field of high-energy-density batteries.
Claims (4)
1. A sodic conductive carbon nanotube framework material is characterized by comprising a network framework, wherein the main body of the network framework is a conductive carbon nanotube three-dimensional network with macroscopic orientation, and oxygen-containing functional groups with the atomic percentage of 1-25% are connected on the network framework; the conductive carbon nanotube network skeleton has sodium affinity, namely has strong interaction with metallic sodium, can change the deposition behavior of the metallic sodium and stabilize the deposition stripping of the metallic sodium; moreover, the sodic conductive carbon nanotube framework material is prepared by the following steps:
(1) Preparation of conductive carbon nanotube network framework
Preparing a macroscopically-oriented carbon nanotube three-dimensional network by a suspension chemical vapor deposition method: continuously preparing an oriented carbon nanotube three-dimensional network at the temperature of 1000-1300 ℃ by using ferrocene and thiophene as mixed catalysts, ethanol and acetone as carbon sources, hydrogen and argon as carrier gases and controlling the gas flow rate to be 1000-1500 ml/min; the thickness range of the three-dimensional network of the carbon nano tube is 10-200 microns; in the mixed catalyst, the mass fraction of ferrocene is 94-98%, and the mass fraction of thiophene is 6-2%; in the carbon source, the mass fraction of ethanol is 75-90%, and the mass fraction of acetone is 25-10%; in the carrier gas, the volume fraction of hydrogen is 80-90%, and the volume fraction of argon is 20-10%;
(2) Preparing a sodium-philic conductive carbon nanotube network framework: placing the conductive carbon nanotube network skeleton prepared in the step (1) in an oxygen plasma treatment instrument, wherein the control parameters are as follows: the processing power is 50-100W, the oxygen flow is 50-200 ml/min, the working pressure is less than 100 Pa, and the processing time is 1-20 min, thus obtaining the target product, namely the sodic conductive carbon nanotube network framework material.
2. The sodic conductive carbon nanotube backbone material of claim 1, wherein the oxygen containing functional group is a carboxyl, hydroxyl, ether linkage or ketone.
3. The application of the sodic conductive carbon nanotube framework material of claim 1 or 2 in the preparation of the composite electrode of the sodium-air full cell comprises the following specific steps:
cutting a sodic conductive carbon nanotube network framework into electrode slices with the size of 1-2 square centimeters, taking the electrode slices as a battery anode, taking a metal sodium slice as a battery cathode, taking sodium trifluoromethanesulfonate as electrolyte salt and diethylene glycol dimethyl ether as an electrolyte solvent to form electrolyte, and taking Celgard2400 as a diaphragm to assemble a CR2032 button battery; wherein, the concentration of NaTF is 0.5-1.5 mol/L; firstly, circulating the button cell for 2-4 circles within the current range of 0.1-0.5 milliampere/square centimeter and the voltage range of 0-0.5 volt, removing pollutants on the surface of an electrode and forming a stable solid electrolyte membrane; then, electrodepositing the metal sodium on the network framework by adopting a constant current with the current magnitude of 0.5-2 milliampere/square centimeter; and after the deposition is finished, disassembling the CR2032 battery to obtain the sodium-sodium affinity oxygen functionalized oriented carbon nanotube framework composite electrode.
4. The sodium-air all-cell is characterized in that the sodium-air all-cell is assembled by using the sodium-philic oxygen functionalized oriented carbon nanotube framework composite electrode obtained by the application of claim 3 as a negative electrode, an oriented carbon nanotube film as a positive electrode, sodium trifluoromethanesulfonate as electrolyte salt and diethylene glycol dimethyl ether as electrolyte solvent to form electrolyte, and a separator which adopts Woltmann glass fiber filter paper.
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| CN113644267B (en) * | 2021-08-03 | 2023-09-29 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN113937293A (en) * | 2021-09-17 | 2022-01-14 | 江苏中科兆能新能源科技有限公司 | Battery cathode material and sodium-halide battery comprising same |
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