CN113725444B - Ruthenium/carbon nano tube flexible positive electrode material and preparation method and application thereof - Google Patents
Ruthenium/carbon nano tube flexible positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ruthenium/carbon nano tube flexible positive electrode material, a preparation method and application thereof, and belongs to the technical field of energy storage and nano material preparation. The method specifically adopts filter paper as a flexible porous matrix, and combines the carbon nano tube adsorption and ruthenium nano particle loading process to prepare the high-performance flexible positive electrode material of the battery. The ruthenium/carbon nano tube flexible positive electrode material has higher discharge capacity and excellent cycling stability in organic electrolyte, and solves the problems of poor flexibility and unstable cycling of the positive electrode material prepared by the conventional method, in particular the problem of large-scale production of key electrode materials of high specific energy flexible lithium-oxygen batteries.
Description
Technical Field
The invention belongs to the technical field of energy storage and nano material preparation, and particularly relates to a ruthenium/carbon nano tube flexible anode material, and a preparation method and application thereof.
Background
Currently, the transitional exploitation and utilization of single fossil energy sources raise serious energy and environmental crisis. In order to solve the problems caused by the single energy structure, people gradually pay attention to the development of clean energy, but the clean energy (such as wind energy, solar energy and geothermal energy) has seasonal, regional and intermittent distribution characteristics, and the reasonable application of the clean energy is limited. For more efficient and rational application of clean energy, new energy storage and conversion technologies are being applied, such as lithium ion batteries, fuel cells, supercapacitors, metal air batteries, etc., wherein lithium ion batteries, which have been commercialized, greatly facilitate people's lives and productions. Because the energy density of the lithium ion battery is close to the theoretical value, the requirement of people on the power battery with longer and longer endurance cannot be met. Thus, battery powered systems with higher energy densities have been explored, in which lithium-oxygen cells, due to the highest theoretical energy density among all rechargeable cells (11700W h kg -1 ) And is of great concern. Despite having such high theoretical energyThe practical energy density and rate capability of a lithium-oxygen battery is far from being desirable, which is limited primarily by the positive electrode materials that provide catalytic activity and store discharge products. Moreover, the development of wearable electronic devices is driven by the current demands of people for technologies such as artificial intelligence, man-machine interaction, health monitoring and the like, and the development of the wearable electronic devices with more convenient application depends on the flexible characteristics of electrode matrixes. Therefore, development of efficient and flexible cathode materials becomes a key to the practical application of high specific energy and wearable lithium-oxygen batteries.
The anode material of the lithium-oxygen battery is generally formed by compounding a conductive matrix and an electrocatalytic material, on one hand, most of the conductive matrixes (such as foam nickel, carbon paper and the like) have higher cost and poorer flexibility, and are not beneficial to the large-scale application of the lithium-oxygen battery and the application of wearable devices; on the other hand, the currently adopted anode electrocatalytic material has poor activity and stability, and severely restricts the improvement of the energy efficiency and the cycling stability of the lithium-oxygen battery. The filter paper is used as a cheap, easily-obtained and porous flexible matrix to be widely applied to electrochemical energy storage devices, and the ruthenium-based catalytic material has higher catalytic activity on electrochemical reaction in the lithium-oxygen battery, so that the combination of the filter paper and ruthenium nano particles is expected to promote the development and practical application of the flexible lithium-oxygen battery with low cost and long endurance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a ruthenium/carbon nano tube flexible positive electrode material, a preparation method and application thereof, and the prepared positive electrode material is applied to organic electrolyte of a lithium-oxygen battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a ruthenium/carbon nanotube flexible positive electrode material, the positive electrode material is made up of filter paper and ruthenium/carbon nanotube nano-composite; wherein: the filter paper is used as a flexible matrix of the positive electrode material; the ruthenium/carbon nano tube nano composite is formed by depositing ruthenium nano particles on carbon nano tubes and loading the ruthenium nano particles on flexible matrix filter paper.
The filter paper is quantitative filter paper for laboratory, the thickness of the filter paper is 0.2-1mm, and the aperture range is 1-120 mu m; the ruthenium/carbon nano tube nano composite is formed by compositing ruthenium nano particles and multi-wall carbon nano tubes, wherein the size of the ruthenium nano particles is 1-20nm, the diameter of the multi-wall carbon nano tubes is 6-50nm, the wall thickness is 2-10nm, and the length is 0.5-30 mu m.
In the positive electrode material, the weight percentage of ruthenium nano particles is 1-5wt%, and the weight percentage of carbon nano tubes is 4-8wt%. The preparation method of the ruthenium/carbon nano tube flexible positive electrode material comprises the following steps:
(1) Preparation of carbon nanotube dispersion: taking 50-100 mg of carbon nano tube, placing in 100 ml of deionized water, and performing ultrasonic dispersion for 8-12 hours at room temperature to obtain carbon nano tube dispersion liquid;
(2) Preparation of a carbon nanotube/filter paper flexible matrix: immersing a piece of quantitative filter paper with the diameter of 3-6cm into the carbon nano tube dispersion liquid obtained in the step (1), carrying out ultrasonic treatment for 2-4 hours at normal temperature, taking out the filter paper, drying for 8-12 hours at room temperature, and repeating the process for 3-6 times to obtain a carbon nano tube/filter paper flexible matrix;
(3) Preparation of ruthenium/carbon nano tube flexible positive electrode material: immersing the carbon nano tube/filter paper flexible matrix obtained in the step (2) into 20-60 ml of ruthenium chloride solution for 20-60 minutes, taking out, then putting into 30-60 ml of sodium borohydride solution for reaction for 30-60 minutes, taking out, flushing with 100-500 ml of deionized water for 3-6 times, and drying at room temperature for 8-12 hours to obtain the ruthenium/carbon nano tube filter paper flexible anode material.
In the step (1), the carbon nanotubes are hydroxylated multiwall carbon nanotubes.
In the step (2), each repeated immersing process is performed in the carbon nanotube dispersion liquid used in the previous time.
In the step (3), the ruthenium chloride solution is a ruthenium chloride aqueous solution, and the concentration of ruthenium chloride is 6-18 g/L; the sodium borohydride solution is an aqueous solution of sodium borohydride, and the concentration of the sodium borohydride is 20-80 g/L.
The positive electrode material can be applied to an organic electrolyte lithium-oxygen battery: the organic electrolyte is tetraethylene glycol dimethyl ether solution of lithium bis (trifluoromethanesulfonyl) imide, the concentration is 0.5-2 mol/L, and the electrolyte is put for the first timeCapacitance of 1000-5000mA h g -1 The stabilizing cycle is 30-100 circles.
The design idea of the invention is as follows:
the positive electrode materials required for development of low cost, high specific energy, long life, flexible lithium-oxygen batteries should have the following factors: firstly, the matrix of the positive electrode material is cheap and easy to obtain; secondly, the conductive material has higher conductivity and a hierarchical pore structure; furthermore, has higher electrocatalytic activity; finally, the matrix of the positive electrode material has good flexibility. In order to realize the characteristics, the invention adopts the filter paper with low cost and multiple holes as a flexible substrate of the anode material, the substrate is coated with a conductive material (carbon nano tube), and finally the electrocatalytic active phase (ruthenium nano particles) is loaded to reduce the overpotential in the charge and discharge process. Thus obtaining the flexible lithium-oxygen battery anode material with low cost, high performance and long service life.
The invention mainly discloses a lithium-oxygen battery anode material, which is applied to a battery anode taking tetraethylene glycol dimethyl ether solution of lithium bistrifluoromethane sulfonyl imide as electrolyte and is used for promoting the smooth proceeding of the charge and discharge process of the battery anode. The cost of the lithium-oxygen battery anode material directly influences the scale process of the whole battery, and the flexibility of the matrix material determines the application prospect of the lithium-oxygen battery anode material in wearable electronic equipment. The improvement of the overall performance of the lithium-oxygen battery mainly depends on the porosity, conductivity and catalytic activity of the positive electrode material. The porous electrode material is used for realizing the smooth progress of the mass transfer process of the electrochemical reaction, comprising the transmission of oxygen and the transmission of electrolyte, and the lithium-oxygen battery can generate insoluble discharge products when discharging, and excessive accumulation of the discharge products can influence the further mass transfer process, so that the multi-stage pore structure of the anode material can provide enough space for the deposition of the discharge products; the anode material needs to have good conductivity so as to be beneficial to the transfer of electrons in the electrochemical reaction process and promote the rapid progress of the electrochemical reaction on the surface of the electrode; the active phase of the positive electrode material is used for reducing the overpotential of the battery in the charge and discharge process, improving the energy efficiency of the battery in the charge and discharge process and prolonging the service life of the battery. The lithium-oxygen battery positive electrode material needs not only a substrate which is low in cost and flexible, but also good in porosity, conductivity and catalytic activity. However, the traditional foam nickel matrix has higher cost, poorer flexibility and higher density, which is unfavorable for improving the mass specific capacity of the battery, and the common carbon paper matrix has higher cost and poorer flexibility. The general preparation of the catalytic material with porosity, conductivity and high activity is carried out under the conditions of high-temperature calcination or hydrothermal, which relates to a high-energy consumption process, is unfavorable for large-scale application, and the charge-discharge overpotential of the current positive electrode material is still higher and the cycle stability is poorer. The invention adopts the cheap porous filter paper as the flexible matrix of the anode material, and adsorbs a carbon nano tube conductive layer after being soaked in the carbon nano tube solution, thereby being beneficial to mass transfer and transfer of electrons and reactants; ruthenium nano particles with electrocatalytic activity are loaded through adsorption and chemical reduction processes at normal temperature, so that the reduction of charge and discharge overpotential is facilitated, and the cycle life of the battery is prolonged. The flexible positive electrode material of the lithium-oxygen battery obtained by the method has higher discharge capacity and charge-discharge cycling stability in the organic electrolyte.
The invention has the advantages and beneficial effects as follows:
1. the matrix of the positive electrode material adopts porous flexible filter paper, has the advantages of low cost, easy obtainment and easy assembly, and can greatly reduce the production cost; the porous matrix can provide a channel for a mass transfer process, and the flexible characteristic of the porous matrix enables the porous matrix to have advantages and prospects in application in wearable electronic equipment.
2. The carbon nano tube is used as a conductive material in the positive electrode material, so that smooth conduction of electrons can be promoted; the ruthenium nano particles are used as an active phase, so that the charge-discharge overpotential can be reduced, and the energy efficiency of the battery can be improved.
3. The preparation method of the positive electrode material comprises the following steps: soaking porous filter paper in the carbon nano tube dispersion liquid, and adsorbing to form a conductive layer; then ruthenium nano particles are deposited by utilizing adsorption and chemical reduction methods, the manufacturing process is simple, the energy consumption is low, the environment is friendly, and the large-scale production is easy.
4. The lithium-oxygen battery anode material provided by the invention has higher discharge capacity and charge-discharge cycling stability in organic electrolyte.
Drawings
FIG. 1 is a practical diagram and a morphological characterization of the ruthenium/carbon nanotube flexible positive electrode material prepared in example 1; wherein: (a) An optical photograph of a ruthenium/carbon nanotube flexible positive electrode material (b) SEM image of the ruthenium/carbon nanotube flexible positive electrode material;
FIG. 2 is a graph showing the experimental results of a lithium oxygen battery in which the ruthenium/carbon nanotube flexible cathode material of example 3 was tested in an organic electrolyte; wherein: (a) a first discharge capacity map; (b) a charge-discharge cycle test chart;
fig. 3 is a graph showing charge-discharge cycle stability performance of the positive electrode material.
Detailed Description
In the specific embodiment of the invention, porous filter paper is adopted as a flexible matrix, ruthenium/carbon nano tube flexible anode material (Ru@CNT/FP anode material) obtained by depositing ruthenium nano particles after soaking carbon nano tube dispersion liquid is composed of ruthenium nano particles, carbon nano tubes and porous filter paper, wherein the ruthenium nano particles are active components of the anode material, the carbon nano tubes are conductive layers, and the porous filter paper is a flexible mass transfer matrix. Wherein the mass of the carbon nano tube used for preparing the carbon nano tube dispersion liquid is 50-100 mg (preferably 60-80 mg), and the ultrasonic dispersion time at room temperature is 8-12 hours. In the positive electrode material, the weight percentage of ruthenium nano particles is 1.5-4wt% and the weight percentage of carbon nano tubes is 5-7wt%.
The cathode material can effectively improve the discharge capacity and the charge-discharge cycle stability of a lithium-oxygen battery in an organic electrolyte, oxygen is introduced for 30-60 minutes before the test, the flow is 50-100 ml/min, and the used organic electrolyte is tetraethylene glycol dimethyl ether solution of lithium bis (trifluoromethanesulfonyl) imide, and the concentration is 0.5-2 mol/l.
The preparation process of the Ru@CNT/FP flexible positive electrode material comprises the following steps:
(1) Preparation of carbon nanotube dispersion: taking 60-80 mg of carbon nano tube, placing the carbon nano tube in 100 ml of deionized water, and performing ultrasonic dispersion for 8-12 hours at room temperature to obtain carbon nano tube dispersion liquid;
(2) Preparation of a carbon nanotube/filter paper flexible matrix: immersing a piece of quantitative filter paper with the diameter of 3-6cm (preferably 3.5-5 cm) in the carbon nano tube dispersion liquid obtained in the step (1), carrying out ultrasonic treatment for 2-4 hours at normal temperature, taking out the filter paper, drying for 8-12 hours at room temperature, and repeating the process for 3-6 times to obtain a carbon nano tube/filter paper flexible matrix;
(3) Preparation of ruthenium/carbon nano tube flexible positive electrode material: immersing the carbon nano tube/filter paper flexible matrix obtained in the step (2) into 20-60 milliliters (preferably 30-50 milliliters) of ruthenium chloride solution for 20-60 minutes, taking out, then putting into 30-60 milliliters of sodium borohydride solution for reaction for 30-60 minutes, taking out, flushing with 100-500 milliliters of deionized water for 3-6 times, and drying at room temperature for 8-12 hours to obtain the Ru@CNT/FP flexible anode material.
The specific process of assembling the organic lithium-oxygen battery by utilizing Ru@CNT/FP flexible positive electrode material and testing the performance of the battery is as follows:
(1) Before assembling the button cell, placing the prepared Ru@CNT/FP flexible anode material in a vacuum oven, and drying for 8-12 hours at 100-160 ℃; taking out after drying, and cutting into wafers with the diameter of 0.8-1.6cm by using a slicing machine; putting a round piece of positive electrode material into a glove box for assembly, sequentially assembling the positive electrode, a glass fiber diaphragm and a lithium piece, and respectively dripping 10-50 microliters of tetraethylene glycol dimethyl ether solution of lithium bis (trifluoromethanesulfonyl) imide on the positive electrode piece and the diaphragm, wherein the concentration is 0.5-2 moles/liter; after the assembly by the tablet press, the mixture was activated for 3 to 8 hours in a glove box.
(2) When the cathode material is used for carrying out the first discharge capacity test of the lithium-oxygen battery, firstly, oxygen with the flow rate of 50-100 milliliters/min (preferably 60-80 milliliters/min) is introduced for 30-60 minutes (preferably 40-50 minutes), then, the oxygen is closed, and the battery test is started; the protection voltage condition is set to<(1.8-2.4) V (preferably 1.9-2.2V); the discharge current density is set to 100-1000mA g -1 (preferably 200-800mA g) -1 ) The first discharge capacity of the Ru@CNT/FP flexible positive electrode material obtained at the moment is 1000-5000mA h g -1 。
(3) When the cathode material is used for carrying out the cyclic charge and discharge test of the lithium-oxygen battery, firstly, 30-6 of oxygen with the flow rate of 50-100 ml/min (preferably 60-80 ml/min) is introduced0 minutes (preferably 40-50 minutes) and then, oxygen is turned off and the cell test is started; the cut-off charge-discharge capacitance is set to 100-1000mA h g -1 (preferably 200-800mA h g) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the The charge-discharge current density is set to be 100-1000mAg -1 (preferably 200-800mA g) -1 ) The circulation stability of the Ru@CNT/FP flexible positive electrode material obtained at the moment is 30-100 circles.
The present invention will be described in further detail by way of specific examples.
Example 1
Taking 60 mg of hydroxylated multiwall carbon nanotube (the outer diameter of the tube is 20-40nm, the wall thickness is 3-8nm, and the length is 1-20 mu m), placing the multiwall carbon nanotube into 100 ml of deionized water, and performing ultrasonic dispersion for 10 hours at room temperature to obtain carbon nanotube dispersion liquid; immersing a piece of quantitative filter paper (thickness is 0.4mm, aperture is 40-80 μm) with diameter of 5cm in the carbon nanotube dispersion liquid, carrying out ultrasonic treatment for 2 hours at normal temperature, taking out the filter paper, drying for 10 hours at room temperature, repeating the process for 4 times, wherein the carbon nanotube dispersion liquid used in each repeated process is the dispersion liquid used in the previous time, and obtaining a carbon nanotube/filter paper flexible matrix; the obtained carbon nano tube/filter paper flexible matrix is immersed in 40 ml of ruthenium chloride aqueous solution with the concentration of 10 g/L for 40 minutes, taken out, then put into 40 ml of sodium borohydride aqueous solution with the concentration of 60 g/L for reaction for 50 minutes, taken out, washed with 300 ml of deionized water for 5 times, dried at room temperature for 10 hours, and a sheet of Ru@CNT/FP flexible positive electrode material with the diameter of 5cm is obtained (the weight percentage of the carbon nano tube is 5 wt%).
The optical photograph results in fig. 1 (a) show the flexibility characteristics of the positive electrode material with filter paper as a matrix, and the SEM results in fig. 1 (b) show the porous structure of the ru@cnt/FP flexible positive electrode material and the state that ruthenium nanoparticles are uniformly dispersed, wherein the particle size of the ruthenium nanoparticles is 2-10nm, and the weight percentage content is 2wt%.
Example 2
Taking 240 mg of carbon nano tube (the outer diameter of the tube is 20-40nm, the wall thickness is 3-8nm, and the length is 1-20 mu m), putting the carbon nano tube into 400 ml of deionized water, and performing ultrasonic dispersion for 10 hours at room temperature to obtain a carbon nano tube dispersion liquid; immersing four pieces of quantitative filter paper with the diameter of 5cm (the thickness is 0.4mm, the aperture is 40-60 mu m) in the carbon nano tube dispersion liquid, carrying out ultrasonic treatment for 2 hours at normal temperature, taking out the filter paper, drying for 10 hours at room temperature, repeating the process for 6 times, wherein the carbon nano tube dispersion liquid used in each repeated process is the dispersion liquid used in the previous time, and obtaining a carbon nano tube/filter paper flexible matrix; the obtained flexible substrate of the carbon nano tube/filter paper is immersed in 160 milliliters of ruthenium chloride aqueous solution with the concentration of 10 g/L for 40 minutes, taken out, put into 160 milliliters of sodium borohydride aqueous solution with the concentration of 60 g/L for reaction for 50 minutes, taken out, washed 6 times by 500 milliliters of deionized water, and dried at room temperature for 10 hours to obtain four Ru@CNT/FP flexible positive electrode materials with the diameter of 5cm (the weight percentage of the carbon nano tube is 5.2 weight percent, the particle size of the ruthenium nano particles is 2-8nm, and the weight percentage is 2.5 weight percent).
Example 3
Before assembling the button cell, the Ru@CNT/FP flexible positive electrode material prepared in the example 1 is placed in a vacuum oven and dried for 10 hours at 120 ℃; taking out after drying, and cutting into wafers with the diameter of 1.2cm by a slicing machine; putting a round piece of positive electrode material into a glove box for assembly, sequentially assembling the positive electrode, a glass fiber diaphragm and a lithium piece, and respectively dripping 20 microliters of tetraethylene glycol dimethyl ether solution of lithium bistrifluoromethane sulfonyl imide on the positive electrode piece and the diaphragm, wherein the concentration is 1.2 mol/liter; after assembly by tablet press, the mixture was activated in a glove box for 4 hours.
When the first discharge capacity test of the lithium-oxygen battery is carried out, firstly, oxygen with the flow rate of 80 milliliters/min is introduced for 40 minutes, then, the oxygen is closed, and the battery test is started; the protection voltage condition is set to<2.0V; the discharge current density was set to 200mA g -1 The first discharge capacity of the Ru@CNT/FP flexible positive electrode material obtained at the moment is 2500mA h g -1 。
When the lithium-oxygen battery cycle charge-discharge test is carried out, firstly, oxygen with the flow rate of 80 milliliters/minute is introduced for 40 minutes, then, the oxygen is closed, and the battery test is started; the cut-off charge-discharge capacitance is set to 500mA h g -1 The method comprises the steps of carrying out a first treatment on the surface of the The charge-discharge current density was set to 500mA g -1 The cycle stability of the Ru@CNT/FP flexible positive electrode material obtained at this time is 52 circles.
The results in fig. 2 (a) show the first discharge capacity value of the positive electrode material, and the results in fig. 2 (b) show the charge-discharge cycle stability performance of the positive electrode material.
Example 4
Before assembling the button cell, the Ru@CNT/FP flexible positive electrode material prepared in example 2 is placed in a vacuum oven and dried for 10 hours at 120 ℃; taking out after drying, and cutting into wafers with the diameter of 1.2cm by a slicing machine; putting a round piece of positive electrode material into a glove box for assembly, sequentially assembling the positive electrode, a glass fiber diaphragm and a lithium piece, and respectively dripping 40 microliters of tetraethylene glycol dimethyl ether solution of lithium bistrifluoromethane sulfonyl imide on the positive electrode piece and the diaphragm, wherein the concentration is 1.2 mol/liter; after assembling the button cell via a tablet press, activation was performed in a glove box for 4 hours.
When the lithium-oxygen battery cycle charge-discharge test is carried out, firstly, oxygen with the flow rate of 80 milliliters/minute is introduced for 60 minutes, then, the oxygen is closed, and the battery test is started; the cut-off charge-discharge capacitance is set to 500mA h g -1 The method comprises the steps of carrying out a first treatment on the surface of the The charge-discharge current density was set to 500mA g -1 The cycle stability of the Ru@CNT/FP flexible positive electrode material obtained at this time is 53 circles.
The results in fig. 3 show the charge-discharge cycle stability performance of the positive electrode material.
Comparative example 1
Taking 30 mg of hydroxylated multiwall carbon nanotube (the outer diameter of the tube is 20-40nm, the wall thickness is 3-8nm, and the length is 1-20 mu m), placing the multiwall carbon nanotube into 100 ml of deionized water, and performing ultrasonic dispersion for 10 hours at room temperature to obtain carbon nanotube dispersion liquid; immersing a piece of quantitative filter paper (thickness is 0.4mm, aperture is 40-80 μm) with diameter of 5cm in the carbon nanotube dispersion liquid, carrying out ultrasonic treatment for 2 hours at normal temperature, taking out the filter paper, drying for 10 hours at room temperature, repeating the process for 4 times, wherein the carbon nanotube dispersion liquid used in each repeated process is the dispersion liquid used in the previous time, and obtaining a carbon nanotube/filter paper flexible matrix; the obtained flexible substrate of the carbon nano tube/filter paper is immersed in 40 ml of ruthenium chloride aqueous solution with the concentration of 10 g/L for 40 min, taken out, put into 40 ml of sodium borohydride aqueous solution with the concentration of 60 g/L for reaction for 50 min, taken out, washed with 300 ml of deionized water for 5 times, and dried at room temperature for 10 h to obtain a sheet of Ru@CNT/FP flexible positive electrode material with the diameter of 5cm (the weight percentage of the carbon nano tube is 3.1wt%, the particle size of the ruthenium nano particles is 2-8nm, and the weight percentage is 2.3 wt%).
When a battery is assembled according to example 4 and a lithium-oxygen battery cycle charge-discharge test is performed, firstly, oxygen with the flow rate of 80 ml/min is introduced for 60 minutes, then, the oxygen is closed, and the battery test is started; the cut-off charge-discharge capacitance is set to 500mA h g -1 The method comprises the steps of carrying out a first treatment on the surface of the The charge-discharge current density was set to 500mA g -1 The cycle stability of the Ru@CNT/FP flexible positive electrode material obtained at this time is 6 circles.
Comparative example 2
120 mg of hydroxylated multiwall carbon nanotube (with the outer diameter of the tube being 20-40nm, the wall thickness being 3-8nm and the length being 1-20 mu m) is taken and placed in 100 ml of deionized water, and the mixture is subjected to ultrasonic dispersion for 10 hours at room temperature to obtain carbon nanotube dispersion liquid; immersing a piece of quantitative filter paper (thickness is 0.4mm, aperture is 40-80 μm) with diameter of 5cm in the carbon nanotube dispersion liquid, carrying out ultrasonic treatment for 2 hours at normal temperature, taking out the filter paper, drying for 10 hours at room temperature, repeating the process for 4 times, wherein the carbon nanotube dispersion liquid used in each repeated process is the dispersion liquid used in the previous time, and obtaining a carbon nanotube/filter paper flexible matrix; the obtained flexible substrate of the carbon nano tube/filter paper is immersed in 40 ml of ruthenium chloride aqueous solution with the concentration of 10 g/L for 40 min, taken out, put into 40 ml of sodium borohydride aqueous solution with the concentration of 60 g/L for reaction for 50 min, taken out, washed with 300 ml of deionized water for 5 times, and dried at room temperature for 10 h to obtain a sheet of Ru@CNT/FP flexible positive electrode material with the diameter of 5cm (the weight percentage of the carbon nano tube is 9.6wt%, the particle size of the ruthenium nano particles is 2-10nm, and the weight percentage is 3.0 wt%).
When a battery is assembled according to example 4 and a lithium-oxygen battery cycle charge-discharge test is performed, firstly, oxygen with the flow rate of 80 ml/min is introduced for 60 minutes, then, the oxygen is closed, and the battery test is started; the cut-off charge-discharge capacitance is set to 500mA h g -1 The method comprises the steps of carrying out a first treatment on the surface of the The charge-discharge current density was set to 500mA g -1 The cycle stability of the Ru@CNT/FP flexible positive electrode material obtained at this time is 27 circles.
The results of the examples and the comparative examples show that the flexible characteristic of the positive electrode material can be realized and the mass transfer process in the electrochemical reaction can be promoted by adopting the cheap porous filter paper as the matrix of the positive electrode material; after the filter paper matrix is soaked in the carbon nanotube solution, a carbon nanotube conducting layer is adsorbed, so that electron transmission in electrochemical reaction is facilitated; ruthenium nano particles with electrocatalytic activity are loaded, which is beneficial to reducing charge and discharge overpotential and prolonging the cycle life of the battery. The obtained flexible positive electrode material of the lithium-oxygen battery has higher discharge capacity and charge-discharge cycling stability in the organic electrolyte.
Claims (6)
1. The application of the ruthenium/carbon nano tube flexible anode material is characterized in that: the positive electrode material consists of filter paper, ruthenium and carbon nano tubes; wherein: the filter paper is used as a flexible matrix of the positive electrode material; firstly, loading carbon nano tubes on flexible matrix filter paper, and then redepositing ruthenium nano particles on the filter paper loaded with the carbon nano tubes;
in the positive electrode material, the weight percentage of ruthenium nano particles is 1-5wt%, the weight percentage of carbon nano tubes is 4-8wt%,
the flexible positive electrode material is applied to an organic electrolyte lithium-oxygen battery;
the method is characterized in that: the filter paper is quantitative filter paper for laboratory, the thickness of the filter paper is 0.2-1mm, and the pore diameter range is 1-120 mu m;
the ruthenium nano-particle size is 1-20nm, the outer diameter of the multi-wall carbon nano-tube is 6-50nm, the wall thickness is 2-10nm, and the length is 0.5-30 μm.
2. The use according to claim 1, characterized in that: in the positive electrode material, the weight percentage of ruthenium nano particles is 1.5-4wt% and the weight percentage of carbon nano tubes is 5-7wt%;
the thickness of the filter paper is 0.3-0.6-mm, and the pore diameter range is 20-100 mu m;
the ruthenium nanoparticle size was 2-10 a nm a.
3. Use according to claim 1 or 2, characterized in that:
the preparation method of the ruthenium/carbon nano tube flexible positive electrode material comprises the following steps:
(1) Preparation of carbon nanotube dispersion: taking 50-100 mg of carbon nano tube, placing in 100 ml of deionized water, and performing ultrasonic dispersion for 8-12 hours at room temperature to obtain carbon nano tube dispersion liquid;
(2) Preparation of a carbon nanotube/filter paper flexible matrix: immersing a piece of quantitative filter paper with the diameter of 3-6cm into the carbon nano tube dispersion liquid obtained in the step (1), carrying out ultrasonic treatment for 2-4 hours at normal temperature, taking out the filter paper, drying for 8-12 hours at room temperature, and repeating the process for 3-6 times to obtain a carbon nano tube/filter paper flexible matrix;
(3) Preparation of ruthenium/carbon nano tube flexible positive electrode material: immersing the carbon nano tube/filter paper flexible matrix obtained in the step (2) into 20-60 ml of ruthenium chloride solution for 20-60 minutes, taking out, then putting into 30-60 ml of sodium borohydride solution for reaction for 30-60 minutes, taking out, flushing with 100-500 ml of deionized water for 3-6 times, and drying at room temperature for 8-12 hours to obtain the ruthenium/carbon nano tube filter paper flexible anode material.
4. A use according to claim 3, characterized in that: in step (2), each repeated immersion process is performed in the carbon nanotube dispersion liquid used in the previous time.
5. A use according to claim 3, characterized in that: in the step (3), the ruthenium chloride solution is ruthenium chloride aqueous solution, and the concentration of ruthenium chloride is 6-18 g/L; the sodium borohydride solution is an aqueous solution of sodium borohydride, and the concentration of the sodium borohydride is 20-80 g/L.
6. The use according to claim 1, characterized in that: the organic electrolyte of the organic electrolyte lithium-oxygen battery is tetraethylene glycol dimethyl ether solution of lithium bistrifluoromethane sulfonyl imide, and the concentration is 0.5-2 mol/L.
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