CN113380987A - Carbon nano tube buffer layer/sodium composite cathode and preparation method and application thereof - Google Patents

Carbon nano tube buffer layer/sodium composite cathode and preparation method and application thereof Download PDF

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CN113380987A
CN113380987A CN202110635498.9A CN202110635498A CN113380987A CN 113380987 A CN113380987 A CN 113380987A CN 202110635498 A CN202110635498 A CN 202110635498A CN 113380987 A CN113380987 A CN 113380987A
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sodium
buffer layer
carbon nanotube
carbon
nano tube
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彭慧胜
程翔然
叶蕾
王兵杰
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Fudan University
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of sodium metal battery cathode materials, and particularly relates to a preparation method of a carbon nano tube buffer layer/metal sodium composite cathode material, which comprises the following steps: placing the carbon nano tube buffer layer on the surface of the metal sodium, dropwise adding an electrolyte, and standing; the electrolyte comprises sodium salt and an organic solvent. The preparation method is simple in preparation process and high in efficiency, can realize the high-current and long-cycle sodium metal cathode, and has good application prospect in the field of high-energy-density batteries.

Description

Carbon nano tube buffer layer/sodium composite cathode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium metal battery cathode materials, and particularly relates to a carbon nano tube buffer layer/metal sodium composite cathode material and a preparation method and application thereof.
Background
With the rapid development of battery technology, lithium batteries now dominate the market of portable electronic products and gradually expand to the field of large-scale energy storage. However, the lithium resource stock is low, the cost is high, and the development requirement for establishing a large-scale high-energy-density energy storage system cannot be met. Sodium is abundant in the earth crust, the cost is low, and the sodium battery has electrochemical characteristics similar to those of a lithium battery, so that the sodium battery is expected to replace the lithium battery to become a new generation battery. The theoretical specific capacity of the sodium metal is up to 1166 milliampere-hour/gram, so that the energy density of the battery can be greatly improved, and the requirement of an electric automobile on the battery can be met. However, the metal sodium is very active and can generate side reaction with the electrolyte, so that the electrolyte is continuously consumed, and the battery capacity is reduced. And sodium metal can cause the growth of sodium dendrite due to uneven nucleation and deposition in the charging and discharging process, and can pierce through a diaphragm in serious cases to cause short circuit and even cause safety accidents such as combustion, explosion and the like. Therefore, practical use of sodium metal has not yet been realized.
In order to solve the above problems, some studies have been reported. On the one hand, by modifying the electrolyte system, such as the components and concentration of the electrolyte solution, a stable solid electrolyte interface is formed on the surface of the negative electrode. On the other hand, the growth of the dendritic crystal is inhibited by adopting a solid electrolyte with high mechanical strength or modifying a layer of solid electrolyte interface with high mechanical strength and stable chemical property on the surface of the metal sodium cathode. However, these methods do not fundamentally solve the problem of dendrite growth, i.e., the non-uniform nucleation and growth of sodium on the surface of sodium metal. In recent years, there is a literature on the nucleation deposition of sodium uniformly thereon by designing the structure of the substrate skeleton. The reported methods for preparing the sodium/framework composite negative electrode generally include two types: the first method melts metallic sodium and then adsorbs the molten metallic sodium onto a substrate skeleton; the second method employs electrodeposition, which allows sodium to be embedded within the matrix. The two methods need to be carried out in an anhydrous and oxygen-free environment, and the preparation steps are complicated.
Disclosure of Invention
On the basis of the common general knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily without departing from the concept and the protection scope of the invention.
The invention aims to solve the technical problem of providing a stable carbon nano tube buffer layer/sodium electrode composite material, and a simple, convenient and efficient preparation method and application thereof.
In order to solve the above technical problems, a first aspect of the present invention provides a method for preparing a carbon nanotube buffer layer/sodium composite anode, comprising the steps of: placing the carbon nano tube buffer layer on the surface of the metal sodium, dropwise adding an electrolyte, and standing; the electrolyte comprises sodium salt and an organic solvent.
As a preferable technical scheme, the concentration of the sodium salt of the electrolyte is 0.5-1 mol/L.
As a preferable technical scheme, the dropping amount of the electrolyte in the invention is 1-10 mu l/cm2。
As a preferable technical scheme, the standing time in the invention is 1-30 minutes.
As a preferable technical scheme, the carbon nano tube buffer layer is prepared by a suspension catalytic chemical vapor deposition method.
As a preferred technical solution, the method for preparing the carbon nanotube buffer layer in the present invention at least includes the steps of:
(1) dissolving ferrocene and thiophene as composite catalysts in a carbon source solution by ultrasonic waves;
(2) injecting a carbon source solution into the furnace cavity through a peristaltic pump, wherein the temperature of the cavity is controlled to be 1000-1500 ℃;
(3) meanwhile, introducing reducing gas and carrier gas into the furnace, wherein the flow rate of the reducing gas is 1200-1800 standard condition ml/min, and the flow rate of the carrier gas is 300-450 standard condition ml/min;
(4) cracking a carbon source into carbon atoms, depositing the carbon atoms on the surface of the catalyst, and growing to obtain the carbon nanotube aerogel;
(5) and leading the carbon nanotube aerogel to the bottom of the furnace along with the airflow, leading the carbon nanotube aerogel out of the bottom of the furnace by using a metal wire, obtaining a carbon nanotube film after passing through a water tank, and collecting the carbon nanotube film to obtain the carbon nanotube film.
As a preferred technical scheme, the thickness of the carbon nano tube buffer layer is 10-50 μm; the carbon nano tube buffer layer is composed of carbon nano tube bundles, and the length of the carbon nano tube bundles is 40-70 mu m.
As a preferable technical solution, the sodium salt in the present invention includes at least one of sodium hexafluorophosphate, sodium perchlorate and sodium trifluoromethanesulfonate; the organic solvent comprises at least one of diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate.
The second aspect of the invention provides a carbon nanotube buffer layer/sodium composite cathode, which is obtained by the preparation method of the carbon nanotube buffer layer/sodium composite cathode.
The third aspect of the invention provides an application of the carbon nano tube buffer layer/sodium composite cathode, which is applied to assembled batteries.
Compared with the prior art, the invention has the following remarkable advantages and effects:
the invention provides a stable carbon nano tube buffer layer/sodium electrode composite negative electrode material, the preparation process is simple, the method is efficient, the large-current long-cycle sodium metal negative electrode can be realized, and the stable carbon nano tube buffer layer/sodium electrode composite negative electrode material has a good application prospect in the field of high-energy-density batteries. The carbon nano tube buffer layer in the composite cathode material is prepared by a floating catalytic chemical vapor deposition method, has a structure with high orientation and high crystallinity, shows good mechanical property, and can effectively inhibit the growth of sodium dendrite; and also has high specific surface area, and can uniformly disperse sodium ion flow. The prepared carbon nano tube buffer layer/sodium composite negative electrode can realize the dendrite-free deposition stripping of the metal sodium.
Drawings
FIG. 1 is a schematic diagram of the deposition process of sodium on a carbon nanotube buffer layer/sodium composite electrode and a pure sodium electrode. Wherein, a is the deposition/stripping process of sodium on the carbon nano tube buffer layer/sodium composite electrode; b, deposition/stripping process of sodium on metallic sodium.
FIG. 2 shows a material characterization of a carbon nanotube film. Wherein, a, the electron microscopic image of the prepared carbon nano tube buffer layer shows that the length of the carbon nano tube bundle is as high as 50 microns and the structure of macroscopic orientation arrangement is displayed; b, a Raman spectrum of the prepared carbon nano tube buffer layer shows that the prepared carbon nano tube has high crystallinity; c, a nitrogen adsorption/desorption curve is formed, and the specific surface area of the carbon nano tube buffer layer is as high as 134.2 square meters per gram; d, a tensile stress-strain diagram, wherein the Young modulus of the carbon nano tube film is up to 3.2 GPa.
FIG. 3 shows the cycling performance of the carbon nanotube buffer layer/sodium composite electrode. Wherein, a, under the current density of 1 milliampere/square centimeter, the sodium/carbon nanotube composite electrode can stably circulate for 1000 hours, and the voltage is sharply increased after the pure sodium electrode circulates for 280 hours; b, under the condition of a larger current density of 5 milliampere/square centimeter, the carbon nano tube buffer layer/sodium composite cathode can stably circulate for 600 hours, and the voltage of the pure sodium electrode is sharply increased after 68 hours of circulation.
FIG. 4 shows the rate capability of the carbon nanotube buffer layer/sodium composite electrode. The carbon nano tube buffer layer/sodium composite electrode can still be stably deposited and stripped under the current density of 8 milliampere/square centimeter; while pure sodium electrodes have a sharp voltage increase due to interface instability.
Figure 5 electron microscopy images of carbon nanotube buffer/sodium composite electrode after cycling. Wherein, a, no obvious dendritic crystal grows on the surface of the carbon nano tube buffer layer/sodium composite electrode; and b, the surface of the pure sodium electrode has violent dendritic growth.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to the drawings and the embodiments, but the present invention is not limited to the scope of the embodiments.
The invention provides a preparation method of a carbon nano tube buffer layer/sodium composite negative electrode, which comprises the following steps: placing the carbon nano tube buffer layer on the surface of the metal sodium, dropwise adding an electrolyte, and standing; the electrolyte comprises sodium salt and an organic solvent.
In some embodiments, the composition is prepared byThe preparation method of the carbon nano tube buffer layer/sodium composite cathode comprises the following steps: cutting the carbon nanotube film to 1-1.5cm2The carbon nano tube buffer layer is placed on the surface of the metal sodium with the same size, the electrolyte is dripped, and the mixture is stood; the electrolyte comprises sodium salt and an organic solvent.
In some embodiments, the electrolyte has a sodium salt concentration of 0.5 to 1 mol/L; preferably, the concentration of the sodium salt of the electrolyte is 1 mol/L.
In some embodiments, the electrolyte is added in a drop-wise amount of 1 to 10. mu.l/cm2(ii) a Preferably, the dropping amount of the electrolyte is 3-7 mu l/cm2(ii) a More preferably, the dropping amount of the electrolyte is 5 μ l/cm2。
In some embodiments, the time of standing is 1 to 30 minutes; preferably, the standing time is 5-10 minutes; further preferably, the time for standing is 5 minutes.
In some embodiments, the carbon nanotube buffer layer is made by a suspension catalytic chemical vapor deposition process.
In some embodiments, the method for preparing the carbon nanotube buffer layer at least comprises the following steps:
(1) dissolving ferrocene and thiophene as composite catalysts in a carbon source solution by ultrasonic waves;
(2) injecting a carbon source solution into the furnace cavity through a peristaltic pump, wherein the temperature of the cavity is controlled to be 1000-1500 ℃;
(3) meanwhile, introducing reducing gas and carrier gas into the furnace, wherein the flow rate of the reducing gas is 1200-1800 standard condition ml/min, and the flow rate of the carrier gas is 300-450 standard condition ml/min;
(4) cracking a carbon source into carbon atoms, depositing the carbon atoms on the surface of the catalyst, and growing to obtain the carbon nanotube aerogel;
(5) and leading the carbon nanotube aerogel to the bottom of the furnace along with the airflow, leading the carbon nanotube aerogel out of the bottom of the furnace by using a metal wire, obtaining a carbon nanotube film after passing through a water tank, and collecting the carbon nanotube film to obtain the carbon nanotube film.
In some preferred embodiments, the method for preparing the carbon nanotube buffer layer includes the steps of:
(1) dissolving 1-2g of ferrocene and 1-2g of thiophene as composite catalysts in 94-96g of carbon source solution by ultrasonic waves;
(2) pumping a carbon source solution containing a catalyst into the furnace cavity from the upper top of the vertically placed tubular furnace cavity through a peristaltic pump, wherein the temperature of the cavity is controlled at 1200-1300 ℃;
(3) meanwhile, introducing reducing gas and carrier gas into the furnace, wherein the flow rate of the reducing gas is 1200-1600 standard condition ml/min, and the flow rate of the carrier gas is 300-400 standard condition ml/min;
(4) cracking a carbon source into carbon atoms, depositing the carbon atoms on the surface of the catalyst, and growing to obtain the carbon nanotube aerogel;
(5) and leading the carbon nanotube aerogel to the bottom of the furnace along with the airflow, leading the carbon nanotube aerogel out of the bottom of the furnace by using a metal wire, obtaining a carbon nanotube film after passing through a water tank, and winding and collecting the carbon nanotube film to obtain the carbon nanotube film.
In some embodiments, the carbon source solution comprises at least one of hydrocarbons, alcohols, ketones; preferably, the carbon source solution is selected from alcohols; further preferably, the carbon source solution is selected from ethanol.
The kind of the reducing gas in the present invention is not particularly limited, and is preferably selected from hydrogen; the carrier gas in the present invention is not particularly limited, and is preferably selected from argon gas.
In some embodiments, the carbon nanotube buffer layer has a thickness of 10 to 50 μm; the carbon nano tube buffer layer is composed of carbon nano tube bundles, and the length of the carbon nano tube bundles is 40-70 mu m.
In some preferred embodiments, the carbon nanotube buffer layer has a thickness of 10 to 30 μm; the carbon nano tube buffer layer is composed of carbon nano tube bundles, and the length of each carbon nano tube bundle is 50 micrometers.
In some more preferred embodiments, the carbon nanotube buffer layer has a thickness of 30 μm.
In some embodiments, the sodium salt comprises at least one of sodium hexafluorophosphate, sodium perchlorate, sodium triflate; the organic solvent comprises at least one of diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; preferably, the sodium salt is sodium trifluoromethanesulfonate, and the organic solvent is diethylene glycol dimethyl ether.
The second aspect of the invention provides a carbon nanotube buffer layer/sodium composite cathode, which is obtained by the preparation method of the carbon nanotube buffer layer/sodium composite cathode.
The third aspect of the invention provides an application of the carbon nano tube buffer layer/sodium composite cathode, which is applied to assembled batteries.
In some embodiments, the method of assembling a symmetric battery comprises at least the steps of: the symmetric battery is assembled by taking polypropylene as a diaphragm, taking a diethylene glycol dimethyl ether solution of sodium trifluoromethanesulfonate as an electrolyte and taking a carbon nano tube buffer layer/sodium composite electrode as an electrode.
The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions. The reagents and starting materials used in the present invention are commercially available.
Example 1
The preparation method of the carbon nano tube buffer layer comprises the following specific steps:
2g of ferrocene and 2g of thiophene as composite catalysts are ultrasonically dissolved in 96g of ethanol carbon source solution. And pumping the reaction liquid into a vertically arranged cavity of the tubular furnace by a peristaltic pump, wherein the temperature of the cavity is controlled at 1250 ℃. At the same time, hydrogen and argon are introduced into the furnace as reducing gas and carrier gas, respectively. The flow rate of hydrogen was 1200 standard ml/min and the flow rate of argon was 300 standard ml/min. The carbon source is cracked into carbon atoms under the reduction of hydrogen, and the carbon atoms are deposited on the surface of the catalyst to grow the carbon nanotube. The carbon nanotube aerogel reaches the bottom of the furnace along with the air flow, the carbon nanotube aerogel is continuously led out by using a thin iron wire, a carbon nanotube film is obtained after the carbon nanotube aerogel is shrunk by a water tank, and the carbon nanotube film is collected by a scroll through a guide wheel to obtain a carbon nanotube buffer layer with the thickness of 20 microns.
A preparation method of a carbon nano tube buffer layer/sodium composite cathode comprises the following specific steps:
cutting the prepared carbon nanotube film into a size of 1 square centimeter, placing the carbon nanotube film on a metal sodium sheet with the same size, dripping 5 microliters of electrolyte on the surface of the composite electrode, and standing for 5 minutes to obtain the carbon nanotube buffer layer/sodium composite electrode. The electrolyte is diethylene glycol dimethyl ether solution with the concentration of 1mol/L sodium trifluoromethyl sulfonate.
Example 2
The preparation method of the carbon nano tube buffer layer comprises the following specific steps:
1 g of ferrocene and 1 g of thiophene as composite catalysts are ultrasonically dissolved in 94 g of ethanol carbon source solution. And pumping the reaction liquid into a vertically arranged cavity of the tubular furnace by a peristaltic pump, wherein the temperature of the cavity is controlled at 1200 ℃. At the same time, hydrogen and argon are introduced into the furnace as reducing gas and carrier gas, respectively. The flow rate of hydrogen was 1600 standard ml/min and the flow rate of argon was 400 standard ml/min. The carbon source is cracked into carbon atoms under the reduction of hydrogen, and the carbon atoms are deposited on the surface of the catalyst to grow the carbon nanotube. The carbon nanotube aerogel reaches the bottom of the furnace along with the air flow, the carbon nanotube aerogel is continuously led out by using a long iron wire, a carbon nanotube film with the thickness of 30 microns is obtained after the carbon nanotube aerogel is shrunk by a water tank, and the carbon nanotube film is collected by a scroll through a guide wheel.
A preparation method of a carbon nano tube buffer layer/sodium composite cathode comprises the following specific steps:
cutting the prepared carbon nanotube film into a size of 1.5 square centimeters, placing the carbon nanotube film on a metal sodium sheet with the same size, dripping 10 microliters of electrolyte on the surface of the composite electrode, and standing for 10 minutes to obtain the carbon nanotube buffer layer/sodium composite electrode. The electrolyte is diethylene glycol dimethyl ether solution with the concentration of 1mol/L sodium trifluoromethyl sulfonate.
Performance testing
1. And (3) testing charge and discharge cycles: the sodium trifluoromethanesulfonate is dissolved in diethylene glycol dimethyl ether to serve as electrolyte, polypropylene serves as a diaphragm, and the sodium/carbon nanotube composite electrode is assembled into the symmetrical battery. Wherein the concentration of the sodium trifluoromethyl sulfonate is 0.5-1 mol/L. After the symmetrical battery is kept still for 6-12 hours, a charge-discharge cycle test is carried out by adopting a constant current density of 1-5 milliampere/square centimeter and a capacity of 1 milliampere-hour/square centimeter, and the results are as follows:
a, under the current density of 1 milliampere/square centimeter, the sodium/carbon nanotube composite electrode can stably circulate for 1000 hours, and the voltage is sharply increased after the pure sodium electrode circulates for 280 hours; b, under a larger current density of 5 milliampere/square centimeter, the carbon nanotube buffer layer/sodium composite negative electrode can stably circulate for 600 hours, and the voltage of the pure sodium electrode increases sharply after 68 hours of circulation, as shown in fig. 3.
2. And (3) rate performance test: different current densities (1, 2, 4, 8 milliamps/cm), 1 milliamp hour/cm capacity were tested with the following results: the carbon nano tube buffer layer/sodium composite electrode can still be stably deposited and stripped under the current density of 8 milliampere/square centimeter; whereas the voltage increases sharply for pure sodium electrodes due to interface instability, as shown in fig. 4.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a carbon nano tube buffer layer/sodium composite cathode is characterized by comprising the following steps: placing the carbon nano tube buffer layer on the surface of the metal sodium, dropwise adding an electrolyte, and standing; the electrolyte comprises sodium salt and an organic solvent.
2. The method of claim 1, wherein the electrolyte has a sodium salt concentration of 0.5 to 1 mol/L.
3. The method of claim 1, wherein the electrolyte is added dropwise in an amount of 1-10 μ l/cm2。
4. The method of claim 1, wherein the standing time is 1-30 minutes.
5. The method of claim 1, wherein the carbon nanotube buffer layer is formed by suspension catalytic chemical vapor deposition.
6. The method of claim 1, wherein the step of preparing the carbon nanotube buffer layer at least comprises:
(1) dissolving ferrocene and thiophene as composite catalysts in a carbon source solution by ultrasonic waves;
(2) injecting a carbon source solution into the furnace cavity through a peristaltic pump, wherein the temperature of the cavity is controlled to be 1000-1500 ℃;
(3) meanwhile, introducing reducing gas and carrier gas into the furnace, wherein the flow rate of the reducing gas is 1200-1800 standard condition ml/min, and the flow rate of the carrier gas is 300-450 standard condition ml/min;
(4) cracking a carbon source into carbon atoms, depositing the carbon atoms on the surface of the catalyst, and growing to obtain the carbon nanotube aerogel;
(5) and leading the carbon nanotube aerogel to the bottom of the furnace along with the airflow, leading the carbon nanotube aerogel out of the bottom of the furnace by using a metal wire, obtaining a carbon nanotube film after passing through a water tank, and collecting the carbon nanotube film to obtain the carbon nanotube film.
7. The method of claim 6, wherein the carbon nanotube buffer layer has a thickness of 10-50 μm; the carbon nano tube buffer layer is composed of carbon nano tube bundles, and the length of the carbon nano tube bundles is 40-70 mu m.
8. The method of any one of claims 1-7, wherein the sodium salt comprises at least one of sodium hexafluorophosphate, sodium perchlorate, sodium triflate; the organic solvent comprises at least one of diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate.
9. A carbon nanotube buffer layer/sodium composite negative electrode, characterized by being obtained by the method for preparing the carbon nanotube buffer layer/sodium composite negative electrode of any one of claims 1 to 8.
10. The application of the carbon nano tube buffer layer/sodium composite cathode is characterized by being applied to assembled batteries.
CN202110635498.9A 2021-06-08 2021-06-08 Carbon nano tube buffer layer/sodium composite cathode and preparation method and application thereof Pending CN113380987A (en)

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CN108807916A (en) * 2018-06-14 2018-11-13 北京航空航天大学 Application, Symmetrical cells, half-cell and preparation method of the carbon nano-tube film in negative electrode of lithium ion battery
CN110577208A (en) * 2019-08-18 2019-12-17 复旦大学 Sodium-philic conductive carbon nanotube framework material and preparation method and application thereof
CN111900333A (en) * 2020-08-15 2020-11-06 江西理工大学 Lithium-free dendritic crystal anode with carbon nanotube film directly compounded with molten lithium metal and preparation method thereof

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Application publication date: 20210910