CN113725444A - Ruthenium/carbon nanotube flexible positive electrode material and preparation method and application thereof - Google Patents
Ruthenium/carbon nanotube flexible positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ruthenium/carbon nanotube flexible positive electrode material and a preparation method and application thereof, belonging to the technical field of energy storage and nano material preparation. The high-performance flexible positive electrode material for the battery is prepared by adopting filter paper as a flexible porous matrix and combining a carbon nanotube adsorption and ruthenium nanoparticle loading process. The ruthenium/carbon nano tube flexible positive electrode material shows higher discharge capacity and excellent cycling stability in organic electrolyte, solves the problems of poor flexibility and unstable cycling of the positive electrode material prepared by the conventional method, and particularly solves the problem of large-scale production of the key electrode material of the high-specific-energy flexible lithium-oxygen battery.
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
At present, the transitional exploitation and utilization of single fossil energy causes 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 clean energy sources (such as wind, solar and geothermal) have seasonal, regional and intermittent distribution characteristics, which limit their reasonable application. In order to more efficiently and rationally apply clean energy, new energy storage and conversion technologies are applied, such as lithium ion batteries, fuel cells, supercapacitors, metal air batteries, and the like, wherein the lithium ion batteries that 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 requirements of people on power batteries which can be used for a longer and longer-term endurance cannot be met. Thus, a search for a battery power system with higher energy density was initiated, wherein the lithium-oxygen battery has the highest theoretical energy density (11700W h kg) among all rechargeable batteries-1) But is of great interest. Despite such high theoretical energy density, the actual energy density and rate capability of lithium-oxygen batteries is far from being expected, which is mainly limited by the cathode material that provides catalytic activity and stores the discharge product. Moreover, at present, the development of wearable electronic equipment is promoted by the demands of people on technologies such as artificial intelligence, human-computer interaction and health monitoring, and the development of the wearable electronic equipment with more convenient application depends on the flexible characteristic of the electrode substrate. Therefore, the development of the high-efficiency and flexible cathode material becomes the key of the practical application of the high-specific-energy wearable lithium-oxygen battery.
The positive electrode material of the lithium-oxygen battery is generally formed by compounding a conductive substrate and an electro-catalytic material, on one hand, most conductive substrates (such as foamed nickel, carbon paper and the like) have high cost and poor flexibility, and are not beneficial to large-scale application and wearable device application of the lithium-oxygen battery; on the other hand, the activity and stability of the currently adopted anode electrocatalytic material are poor, and the improvement of the energy efficiency and the cycle stability of the lithium-oxygen battery is severely restricted. The filter paper is widely applied to electrochemical energy storage devices as a cheap, easily-obtained and porous flexible matrix, 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 nanoparticles 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 nanotube flexible positive electrode material, a preparation method and application thereof, wherein the prepared positive electrode material is applied to the organic electrolyte of a lithium-oxygen battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a ruthenium/carbon nanotube flexible anode material is composed of filter paper and a ruthenium/carbon nanotube nano composite; wherein: the filter paper is used as a flexible substrate of the anode material; the ruthenium/carbon nanotube nano composite is characterized in that ruthenium nanoparticles are deposited on carbon nanotubes and loaded on flexible substrate filter paper.
The filter paper is quantitative filter paper for laboratories, the thickness of the filter paper is 0.2-1mm, and the pore diameter range is 1-120 mu m; the ruthenium/carbon nano tube nano composite is formed by compounding ruthenium nano particles and multi-wall carbon nano tubes, wherein the size of the ruthenium nano particles is 1-20nm, the tube 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 anode material, the weight percentage of the ruthenium nano-particles is 1-5 wt%, and the weight percentage of the carbon nano-tubes is 4-8 wt%. The preparation method of the ruthenium/carbon nanotube flexible anode material comprises the following steps:
(1) preparing a carbon nano tube dispersion liquid: placing 50-100 mg of 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) preparing a carbon nano tube/filter paper flexible matrix: soaking a piece of quantitative filter paper with the diameter of 3-6cm into the carbon nanotube dispersion liquid obtained in the step (1), performing 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 nanotube/filter paper flexible matrix;
(3) preparing a ruthenium/carbon nanotube flexible positive electrode material: and (3) immersing the carbon nanotube/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, washing for 3-6 times by using 100-500 ml of deionized water, and drying for 8-12 hours at room temperature to obtain the ruthenium/carbon nanotube filter paper flexible anode material.
In the step (1), the carbon nanotube is a hydroxylated multi-walled carbon nanotube.
In the step (2), each repeated immersion process is performed in the carbon nanotube dispersion that was used in the previous time.
In the step (3), the ruthenium chloride solution is a ruthenium chloride aqueous solution, and the concentration of the 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 cathode material can be applied to an organic electrolyte lithium-oxygen battery: the organic electrolyte is a tetraglycol dimethyl ether solution of lithium bistrifluoromethanesulfonylimide, the concentration is 0.5-2 mol/L, and the first discharge capacity is 1000-5000mA h g-1And stabilizing for 30-100 circles.
The design idea of the invention is as follows:
the positive electrode material required for the development of a low-cost, high-specific-energy, long-life, flexible lithium-oxygen battery should have the following factors: firstly, the matrix of the anode material is cheap and easy to obtain; secondly, the conductive material has higher conductivity and a hierarchical pore structure; moreover, the catalyst has higher electrocatalytic activity; finally, the matrix of the anode material has good flexibility. In order to realize the characteristics, the invention adopts cheap porous filter paper as a flexible matrix of the anode material, a conductive material (carbon nano tube) is coated on the matrix, and finally an electrocatalytic active phase (ruthenium nano particle) is loaded to reduce the overpotential in the charging and discharging process. Thereby 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 a tetraethylene glycol dimethyl ether solution of lithium bistrifluoromethane sulfimide as an electrolyte and is used for promoting the smooth charging and discharging process of the battery anode. The cost of the lithium-oxygen battery cathode 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 cathode material in wearable electronic equipment. The improvement of the overall performance of the lithium-oxygen battery mainly depends on the porosity, the conductivity and the catalytic activity of the cathode material. The porosity of the electrode material is to realize the smooth proceeding of the mass transfer process of the electrochemical reaction, including the transmission of oxygen and the transmission of electrolyte, and the lithium-oxygen battery can generate insoluble discharge products during discharging, and the excessive accumulation of the discharge products can influence the further mass transfer process, so that the multi-level pore structure of the anode material can also provide enough space for the deposition of the discharge products; the positive electrode 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 not only needs a low-cost and flexible substrate, but also needs to have good porosity, conductivity and catalytic activity. However, the conventional nickel foam substrate has high cost, poor flexibility and high density, which is not beneficial to improving the specific mass capacity of the battery, and in addition, the conventional carbon paper substrate also has high cost and poor flexibility. Generally, the preparation of the catalytic material with porosity, conductivity and high activity is carried out under the conditions of high-temperature calcination or hydrothermal treatment, which relates to a high-energy consumption process and is not beneficial to large-scale application, and the charging and discharging overpotential of the current anode material is still higher and the cycling stability is poorer. According to the invention, cheap porous filter paper is used as a flexible matrix of the anode material, and after the anode material is soaked in a carbon nanotube solution, a carbon nanotube conducting layer is adsorbed, so that the mass transfer is facilitated, and the transfer of electrons and reactants is facilitated; the ruthenium nano-particles with electrocatalytic activity are loaded through the processes of adsorption and chemical reduction at normal temperature, so that the reduction of charging and discharging 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 shows higher discharge capacity and charge-discharge cycle stability in organic electrolyte.
The invention has the following advantages and beneficial effects:
1. the matrix of the cathode material adopts porous flexible filter paper, has the advantages of low price, easy obtaining 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 the advantages and the prospect of being applied to wearable electronic equipment.
2. The carbon nano tube is used as a conductive material in the anode material, so that smooth conduction of electrons can be promoted; the ruthenium nano-particles are used as an active phase, so that the charging and discharging overpotential can be reduced, and the energy efficiency of the battery is improved.
3. The preparation method of the anode material comprises the following steps: soaking porous filter paper in the carbon nanotube dispersion liquid, and adsorbing to form a conductive layer; then ruthenium nano particles are deposited by using adsorption and chemical reduction methods, the preparation 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 shows higher discharge capacity and charge-discharge cycle stability in organic electrolyte.
Drawings
FIG. 1 is a diagram showing the actual diagram and the morphology of the ruthenium/carbon nanotube flexible positive electrode material prepared in example 1; wherein: (a) optical photograph of ruthenium/carbon nanotube flexible positive electrode material (b) SEM picture of ruthenium/carbon nanotube flexible positive electrode material;
FIG. 2 is the experimental results of the lithium-oxygen battery tested by the ruthenium/carbon nanotube flexible positive electrode material in organic electrolyte in example 3; 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 used as a flexible matrix, ruthenium/carbon nanotube flexible positive electrode material (Ru @ CNT/FP positive electrode material) obtained by depositing ruthenium nanoparticles after soaking in carbon nanotube dispersion liquid is composed of ruthenium nanoparticles, carbon nanotubes and porous filter paper, the ruthenium nanoparticles are active ingredients of the positive electrode material, the carbon nanotubes are conductive layers, and the porous filter paper is a flexible mass transfer matrix. Wherein the mass of the carbon nanotubes used in the preparation of the carbon nanotube dispersion is 50 to 100 mg (preferably 60 to 80 mg), and the ultrasonic dispersion time at room temperature is 8 to 12 hours. In the anode material, the weight percentage of the ruthenium nano-particles is 1.5-4 wt%, and the weight percentage of the carbon nano-tubes is 5-7 wt%.
The positive electrode material can effectively improve the discharge capacity and charge-discharge cycle stability of the lithium-oxygen battery in organic electrolyte, oxygen is introduced for 30-60 minutes before testing, the flow rate is 50-100 ml/min, and the used organic electrolyte is a tetraglyme solution of lithium bistrifluoromethanesulfonylimide, and the concentration is 0.5-2 mol/l.
The preparation process of the Ru @ CNT/FP flexible positive electrode material is as follows:
(1) preparing a carbon nano tube dispersion liquid: placing 60-80 mg of 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) preparing a carbon nano tube/filter paper flexible matrix: soaking a piece of quantitative filter paper with the diameter of 3-6cm (preferably 3.5-5cm) in the carbon nanotube dispersion liquid obtained in the step (1), performing ultrasonic treatment at normal temperature for 2-4 hours, taking out the filter paper, drying at room temperature for 8-12 hours, and repeating the process for 3-6 times to obtain the carbon nanotube/filter paper flexible matrix;
(3) preparing a ruthenium/carbon nanotube flexible positive electrode material: and (3) soaking the carbon nanotube/filter paper flexible matrix obtained in the step (2) into 20-60 ml (preferably 30-50 ml) of ruthenium chloride solution for 20-60 minutes, taking out, then placing into 30-60 ml of sodium borohydride solution for reaction for 30-60 minutes, taking out, washing 3-6 times with 100-500 ml of deionized water, and drying at room temperature for 8-12 hours to obtain the Ru @ CNT/FP flexible positive electrode material.
The specific process of assembling the organic lithium-oxygen battery by using the Ru @ CNT/FP flexible positive electrode material and testing the performance of the battery is as follows:
(1) before assembling the button cell, the prepared Ru @ CNT/FP flexible positive electrode material is placed in a vacuum oven and dried for 8-12 hours at the temperature of 100 ℃ and 160 ℃; taking out after drying, and cutting into round pieces with diameter of 0.8-1.6cm by a slicer; putting the disc-shaped positive electrode material into a glove box for assembly, sequentially assembling the positive electrode, a glass fiber diaphragm and a lithium sheet, and respectively dropwise adding 10-50 microliters of lithium bis (trifluoromethane) sulfonimide tetraethylene glycol dimethyl ether solution on the positive electrode sheet and the diaphragm, wherein the concentration is 0.5-2 mol/liter; after the assembly by the tablet press is finished, the mixture is activated for 3 to 8 hours in a glove box.
(2) When the positive electrode material is used for testing the first discharge capacity of the lithium-oxygen battery, firstly introducing oxygen with the flow rate of 50-100 ml/min (preferably 60-80 ml/min) for 30-60 min (preferably 40-50 min), then closing the oxygen and starting the battery test; protection voltage condition is set as<(1.8-2.4) V (preferably 1.9-2.2V); the discharge current density was 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 anode material is used for carrying out the lithium-oxygen battery cycle charge-discharge test, firstly introducing oxygen with the flow rate of 50-100 ml/min (preferably 60-80 ml/min) for 30-60 min (preferably 40-50 min), then closing the oxygen, and starting the battery test; the cut-off charge-discharge capacitance is set to be 100-charge 1000mA h g-1(preferably 200-800mA h g)-1) (ii) a The charge-discharge current density is set to 100-1000 mAg--1(preferably 200-800mA g)-1) The cycling stability of the Ru @ CNT/FP flexible positive electrode material obtained at the moment is 30-100 circles.
The present invention is described in further detail below by way of specific examples.
Example 1
Taking 60 mg of hydroxylated multi-wall 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), placing the tube in 100 ml of deionized water, and performing ultrasonic dispersion for 10 hours at room temperature to obtain a carbon nano-tube dispersion liquid; soaking a piece of quantitative filter paper (with the thickness of 0.4mm and the aperture of 40-80 μm) with the diameter of 5cm in the carbon nanotube dispersion liquid, performing ultrasonic treatment at normal temperature for 2 hours, taking out the filter paper, drying at room temperature for 10 hours, 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 the carbon nanotube/filter paper flexible matrix; and (3) immersing the obtained carbon nano tube/filter paper flexible matrix into 40 ml of ruthenium chloride aqueous solution with the concentration of 10 g/L for 40 minutes, taking out, putting into 40 ml of sodium borohydride aqueous solution with the concentration of 60 g/L for reacting for 50 minutes, taking out, washing for 5 times by 300 ml of deionized water, and drying at room temperature for 10 hours to obtain a piece of Ru @ CNT/FP flexible cathode material (the weight percentage content of the carbon nano tube is 5 wt%) with the diameter of 5 cm.
The optical photograph result in fig. 1(a) shows the flexible characteristic of the positive electrode material with filter paper as the matrix, and the SEM result in fig. 1(b) shows the porous structure of the Ru @ CNT/FP flexible positive electrode material and the state that the ruthenium nanoparticles are uniformly dispersed, the size of the ruthenium nanoparticles is 2-10nm, and the weight percentage content is 2 wt%.
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), placing the carbon nano tube in 400 ml of deionized water, and performing ultrasonic dispersion for 10 hours at room temperature to obtain carbon nano tube dispersion liquid; soaking four pieces of quantitative filter paper (with the thickness of 0.4mm and the aperture of 40-60 μm) with the diameter of 5cm in the carbon nanotube dispersion liquid, performing ultrasonic treatment at normal temperature for 2 hours, taking out the filter paper, drying at room temperature for 10 hours, repeating the process for 6 times, wherein the carbon nanotube dispersion liquid used in each repeated process is the dispersion liquid used in the previous time, and obtaining the carbon nanotube/filter paper flexible matrix; the obtained carbon nano tube/filter paper flexible matrix is immersed in 160 ml of ruthenium chloride aqueous solution with the concentration of 10 g/L for 40 minutes, taken out, put into 160 ml of sodium borohydride aqueous solution with the concentration of 60 g/L for reaction for 50 minutes, taken out, washed for 6 times by 500 ml of deionized water, and dried for 10 hours at room temperature, so that four pieces of Ru @ CNT/FP flexible cathode materials with the diameter of 5cm (the weight percentage content of the carbon nano tube is 5.2 wt%, the particle size of the ruthenium nano particles is 2-8nm, and the weight percentage content is 2.5 wt%) are obtained.
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 the temperature of 120 ℃; taking out after drying, and cutting into round pieces with the diameter of 1.2cm by a slicing machine; putting the disc-shaped positive electrode material into a glove box for assembly, sequentially assembling the positive electrode, a glass fiber diaphragm and a lithium sheet, and respectively dropwise adding 20 microliters of lithium bis (trifluoromethane) sulfonimide tetraethylene glycol dimethyl ether solution on the positive electrode sheet and the diaphragm, wherein the concentration of the lithium bis (trifluoromethane) sulfonimide tetraethylene glycol dimethyl ether solution is 1.2 mol/liter; after the assembly by the tablet press, the activation was carried out for 4 hours in a glove box.
When the first discharge capacity of the lithium-oxygen battery is tested, firstly introducing oxygen with the flow rate of 80 ml/min for 40 minutes, then closing the oxygen, and starting the battery test; protection voltage condition is set as<2.0V; the discharge current density was set at 200mA g-1The 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 is subjected to the cycle charge and discharge test, firstly introducing oxygen with the flow rate of 80 ml/min for 40 minutes, then closing the oxygen, and starting the battery test; the cut-off charge-discharge capacitance is set to be 500mA h g-1(ii) a The charge-discharge current density was set to 500mA g-1The cycling stability of the Ru @ CNT/FP flexible positive electrode material obtained at this time was 52 cycles.
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 the example 2 is placed in a vacuum oven and dried for 10 hours at the temperature of 120 ℃; taking out after drying, and cutting into round pieces with the diameter of 1.2cm by a slicing machine; putting the disc-shaped positive electrode material into a glove box for assembly, sequentially assembling the positive electrode, a glass fiber diaphragm and a lithium sheet, and respectively dropwise adding 40 microliters of lithium bis (trifluoromethane) sulfonimide tetraethylene glycol dimethyl ether solution on the positive electrode sheet and the diaphragm, wherein the concentration of the lithium bis (trifluoromethane) sulfonimide tetraethylene glycol dimethyl ether solution is 1.2 mol/liter; after assembling the button cell by a tablet press, it was activated for 4 hours in a glove box.
When the lithium-oxygen battery is subjected to the cycle charge and discharge test, firstly introducing oxygen with the flow rate of 80 ml/min for 60 minutes, then closing the oxygen, and starting the battery test; the cut-off charge-discharge capacitance is set to be 500mA h g-1(ii) a The charge-discharge current density was set to 500mA g-1The cycling stability of the Ru @ CNT/FP flexible positive electrode material obtained at this time was 53 cycles.
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 multi-wall 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), placing the tube in 100 ml of deionized water, and performing ultrasonic dispersion for 10 hours at room temperature to obtain a carbon nano-tube dispersion liquid; soaking a piece of quantitative filter paper (with the thickness of 0.4mm and the aperture of 40-80 μm) with the diameter of 5cm in the carbon nanotube dispersion liquid, performing ultrasonic treatment at normal temperature for 2 hours, taking out the filter paper, drying at room temperature for 10 hours, 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 the 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, put into 40 ml of sodium borohydride aqueous solution with the concentration of 60 g/L for reaction for 50 minutes, taken out, washed for 5 times by 300 ml of deionized water, and dried for 10 hours at room temperature, so that a piece of Ru @ CNT/FP flexible positive electrode material with the diameter of 5cm is obtained (the weight percentage content of the carbon nano tube is 3.1 wt%, the particle size of the ruthenium nano particles is 2-8nm, and the weight percentage content is 2.3 wt%).
Assembling the battery according to the embodiment 4, and when carrying out the cycle charge and discharge test of the lithium-oxygen battery, firstly introducing oxygen with the flow rate of 80 ml/min for 60 minutes, then closing the oxygen, and starting the battery test; the cut-off charge-discharge capacitance is set to be 500mA h g-1(ii) a The charge-discharge current density was set to 500mA g-1The cycling stability of the Ru @ CNT/FP flexible positive electrode material obtained at this time is 6 cycles.
Comparative example 2
Taking 120 mg of hydroxylated multi-wall 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), placing in 100 ml of deionized water, and performing ultrasonic dispersion for 10 hours at room temperature to obtain a carbon nano-tube dispersion liquid; soaking a piece of quantitative filter paper (with the thickness of 0.4mm and the aperture of 40-80 μm) with the diameter of 5cm in the carbon nanotube dispersion liquid, performing ultrasonic treatment at normal temperature for 2 hours, taking out the filter paper, drying at room temperature for 10 hours, 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 the 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, put into 40 ml of sodium borohydride aqueous solution with the concentration of 60 g/L for reaction for 50 minutes, taken out, washed for 5 times by 300 ml of deionized water, and dried for 10 hours at room temperature, so that a piece of Ru @ CNT/FP flexible positive electrode material with the diameter of 5cm is obtained (the weight percentage content of the carbon nano tube is 9.6 wt%, the particle size of the ruthenium nano particles is 2-10nm, and the weight percentage content is 3.0 wt%).
Assembling the battery according to the embodiment 4, and when carrying out the cycle charge and discharge test of the lithium-oxygen battery, firstly introducing oxygen with the flow rate of 80 ml/min for 60 minutes, then closing the oxygen, and starting the battery test; the cut-off charge-discharge capacitance is set to be 500mA h g-1(ii) a The charge-discharge current density was set to 500mA g-1The cycling stability of the Ru @ CNT/FP flexible positive electrode material obtained at this time was 27 cycles.
The results of the examples and comparative examples show that the flexible characteristics of the cathode material can be realized and the mass transfer process in the electrochemical reaction can be promoted by using the cheap porous filter paper as the matrix of the cathode material; after the filter paper substrate is soaked in the carbon nanotube solution, a carbon nanotube conducting layer is adsorbed, which is beneficial to electron transmission in electrochemical reaction; the loaded ruthenium nano-particles with electrocatalytic activity are beneficial to reducing the over-potential of charge and discharge and prolonging the cycle life of the battery. The obtained flexible positive electrode material of the lithium-oxygen battery shows higher discharge capacity and charge-discharge cycle stability in organic electrolyte.
Claims (9)
1. A ruthenium/carbon nanotube flexible anode material is characterized in that: the anode material consists of filter paper, ruthenium and carbon nano tubes; wherein: the filter paper is used as a flexible substrate of the anode material; firstly, carbon nano-tubes are loaded on flexible substrate filter paper, and then ruthenium nano-particles are deposited on the filter paper loaded with the carbon nano-tubes.
2. The ruthenium/carbon nanotube flexible positive electrode material according to claim 1, wherein: the filter paper is quantitative filter paper for laboratories, the thickness of the filter paper is 0.2-1mm (preferably 0.3-0.6mm), and the pore diameter range is 1-120 μm (preferably 20-100 μm);
the ruthenium nano-particle is 1-20nm (preferably 2-10nm), 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 mu m.
3. The ruthenium/carbon nanotube flexible positive electrode material according to claim 1 or 2, characterized in that: in the cathode material, the weight percentage of the ruthenium nano-particles is 1-5 wt% (preferably 1.5-4 wt%), and the weight percentage of the carbon nano-tubes is 4-8 wt% (preferably 5-7 wt%).
4. The ruthenium/carbon nanotube flexible positive electrode material according to claim 1 or 2, characterized in that: in the step (1), the carbon nanotube is a hydroxylated multi-wall carbon nanotube.
5. A method for preparing the ruthenium/carbon nanotube flexible positive electrode material according to any one of claims 1 to 4, wherein the method comprises the following steps: the method comprises the following steps:
(1) preparing a carbon nano tube dispersion liquid: placing 50-100 mg of 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) preparing a carbon nano tube/filter paper flexible matrix: soaking a piece of quantitative filter paper with the diameter of 3-6cm into the carbon nanotube dispersion liquid obtained in the step (1), performing 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 nanotube/filter paper flexible matrix;
(3) preparing a ruthenium/carbon nanotube flexible positive electrode material: and (3) immersing the carbon nanotube/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, washing for 3-6 times by using 100-500 ml of deionized water, and drying for 8-12 hours at room temperature to obtain the ruthenium/carbon nanotube filter paper flexible anode material.
6. The method for preparing the ruthenium/carbon nanotube flexible positive electrode material according to claim 5, wherein the method comprises the following steps: in the step (2), each repeated immersion process is performed in the carbon nanotube dispersion liquid used in the previous time.
7. The method for preparing the ruthenium/carbon nanotube flexible positive electrode material according to claim 5, wherein the method comprises the following steps: in the step (3), the ruthenium chloride solution is a ruthenium chloride aqueous solution, and the concentration of the 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.
8. Use of the ruthenium/carbon nanotube flexible positive electrode material according to any one of claims 1 to 4, wherein: the flexible positive electrode material is applied to an organic electrolyte lithium-oxygen battery.
9. The use of the ruthenium/carbon nanotube flexible positive electrode material according to claim 8, wherein: the organic electrolyte of the organic electrolyte lithium-oxygen battery is a tetraglyme solution of bis (trifluoromethane) sulfimide lithium, and the concentration is 0.5-2 mol/L.
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