CN111326706B - Carbon-coated niobium pentoxide composite reduced graphene oxide material, preparation and application - Google Patents
Carbon-coated niobium pentoxide composite reduced graphene oxide material, preparation and application Download PDFInfo
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- CN111326706B CN111326706B CN201811533677.6A CN201811533677A CN111326706B CN 111326706 B CN111326706 B CN 111326706B CN 201811533677 A CN201811533677 A CN 201811533677A CN 111326706 B CN111326706 B CN 111326706B
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Abstract
The invention belongs to the field of inorganic chemical nano materials and related electrochemical technologies, and relates to a preparation method of a carbon-coated niobium pentoxide composite reduced graphene oxide material and a general method applied to an aluminum ion battery anode. The method comprises the steps of firstly, taking glucose as a carbon source, taking niobium pentachloride as a niobium source, uniformly mixing and stirring the carbon source and graphene oxide, then obtaining a carbon-coated niobium pentoxide composite redox graphene oxide precursor by using a microwave treatment method, and then carrying out high-temperature heat treatment to obtain the carbon-coated niobium pentoxide composite redox graphene oxide precursor. The discharge specific capacity of the lithium ion battery is still higher under high current density, which shows that the lithium ion battery has very great application prospect as a large-capacity aluminum ion battery anode active material. Meanwhile, the raw materials are glucose, niobium pentachloride, graphene oxide and the like, so that the source is wide, the price is low, and the electrode material is simple, rapid and controllable in preparation process, mild in condition and simple and easy in equipment.
Description
Technical Field
The invention relates to a preparation method of a carbon-coated niobium pentoxide composite reduced graphene oxide material and application of the material as an aluminum ion battery anode, and belongs to the field of inorganic nano materials and electrochemistry.
Background
The aluminum ion battery is a chargeable and dischargeable battery based on transmission of aluminum ions between a positive electrode and a negative electrode, and has the characteristics of high energy density, good safety, no pollution, long cycle life, quick charge and slow discharge and the like. Based on the advantages, the aluminum ion battery can become a main energy device of portable electronic products such as mobile phones, cameras and notebook computers in the future, and is also very likely to be applied to future products such as power cars and portable wearable electronic equipment. Therefore, research on aluminum ion batteries and electrode materials thereof is becoming a focus of social attention.
The currently found anode materials of aluminum ion batteries mainly comprise the following types, one is carbon materials including graphite, graphene and the like, but the discharge capacity of the materials is low (generally less than 100mAh g)-1) (ii) a Another class of transition metal oxides, such as copper oxide, vanadium pentoxide, etc., although they have a high theoretical specific capacity, they have poor conductivity and a low discharge voltage plateau; in addition, some transition metal sulfides, such as molybdenum sulfide, nickel sulfide, tin sulfide, etc., are included, but the sulfides generally have poor conductivity and poor structural stability. Therefore, finding a suitable aluminum ion battery anode material and improving the energy density and the cycle stability of the aluminum ion battery anode material are the key points of the aluminum ion battery anode material research, and the used methods mainly comprise nanocrystallization treatment, a method for compounding a carbon material and a transition metal oxide and the like, so that the purposes of increasing the specific surface area of the composite material, optimizing the pore structure and enhancing the conductivity and the cycle stability are achieved. Among various transition metal oxides, niobium pentoxide has the advantages of simple synthesis process, low price and good structural stability, and is a candidate of an ideal aluminum ion battery cathode material.
At present, the research on the transition metal oxide aluminum ion battery anode material mainly focuses on preparing a material with high specific surface area, a porous structure, reasonable pore size distribution, smaller internal resistance, high conductivity, high cost performance and good cycle stability. The composite material is compounded with a carbon material with good conductivity, so that the problems of poor conductivity and low discharge voltage plateau of the transition metal oxide can be improved in a targeted manner, and the capacity and the cycling stability of the composite material are increased. Therefore, how to optimize various structural parameters of the carbon @ transition metal oxide composite material to obtain excellent electrochemical performance becomes a hotspot of research.
Firstly, mixing a graphene oxide, glucose and niobium pentachloride mixture according to a certain proportion, carrying out microwave treatment to obtain a carbon-coated niobium pentoxide composite reduced graphene oxide precursor, and then carrying out high-temperature heat treatment to promote niobium oxide to crystallize, thus finally obtaining the carbon-coated niobium pentoxide composite reduced graphene oxide composite material. Electrochemical performance tests show that the carbon-coated niobium pentoxide composite reduced graphene oxide composite material obtained by treatment with 700-900W shows excellent electrochemical performance of the positive electrode of the aluminum ion battery.
Disclosure of Invention
The invention aims to avoid the defects of the prior art and provides a carbon-coated niobium pentoxide composite reduced graphene oxide composite aluminum ion battery positive electrode material and a preparation method thereof.
The preparation method comprises the following specific steps:
preparing graphene oxide;
the synthesis steps of the graphene oxide are as follows: mixing graphite powder and sodium nitrate, filling the mixture into a container, pouring a certain amount of concentrated sulfuric acid, stirring the mixture in an ice-water bath at the temperature of 0-4 ℃, and slowly adding potassium permanganate for more than 2 times in a period of time. Then removing the ice water bath, moving the mixture into an oil bath kettle, and reacting for a period of time at the temperature of between 35 and 37 ℃. Then slowly adding a certain amount of water, raising the temperature to 98 ℃ for reaction for a period of time, then moving out of the oil bath pot, adding a certain amount of water, and adding a certain amount of hydrogen peroxide after naturally cooling to room temperature. And then washing for more than 2 times by using a dilute hydrochloric acid solution with the mass fraction of 5%, then washing for more than 2 times by using deionized water until the pH value of the solution is 6, and carrying out ultrasonic treatment for 3 hours for later use.
The mass ratio of the graphite powder to the sodium nitrate is 2:1, the mass ratio of the graphite powder to the potassium permanganate is 1:3, and the mass ratio of the graphite powder to the concentrated sulfuric acid is 40 mg/mL.
The mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the hydrogen peroxide is 30%.
The reaction time is 2-3 hours at the temperature of 35 ℃; the reaction time is 10-15 minutes at the temperature of 98 ℃.
The amount of water added in the two times is 45-50 mL and 40-50 mL respectively.
The purpose of the acid washing with 5% diluted hydrochloric acid is to remove sulfate, manganese ions and other miscellaneous ions.
Preparing a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
dissolving graphene oxide, niobium pentachloride and glucose in polyethylene glycol-400, and then carrying out ultrasonic treatment for a period of time to promote uniform mixing. Then, after uniformly stirring, transferring the obtained solution into a three-mouth bottle, and treating for 6-10 minutes at the power of 700-900W to obtain a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
the mass ratio of the graphite oxide to the niobium pentachloride is 1:5.4, the mass ratio of the graphite oxide to the glucose is 1:3.6, and the mass concentration of the graphite oxide in the polyethylene glycol-400 is 2.5 mg/mL.
The ultrasonic treatment time is 15-30 minutes.
Step three, high-temperature heat treatment;
washing the precursor with water and anhydrous ethanol for more than 2 times respectively to remove impurities; then freeze-drying for a period of time; and then calcining the dried carbon-coated niobium pentoxide composite reduced graphene oxide sample at a certain temperature for a period of time under an inert atmosphere to promote the sample to be better crystallized.
The freeze drying temperature is about-40 to-50 ℃; the freeze-drying time is about 8-12 hours.
The high-temperature calcination temperature is 600-800 ℃, and the high-temperature calcination time is 1-3 hours.
Step four, preparing the positive electrode of the aluminum ion battery;
weighing the obtained carbon-coated niobium pentoxide composite reduced graphene oxide material, mixing the carbon-coated niobium pentoxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dropwise adding N-methyl-2-pyrrolidone by a dropper, stirring uniformly, coating the uniformly mixed electrode material on tantalum foil, and drying in vacuum for a period of time. Then, a 2032 type button cell was assembled by using an ionic liquid as an electrolyte, which was prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride in a molar ratio of 1.3:1, and a metal aluminum counter electrode, a glass fiber membrane (GF/D) as a separator, in a glove box. And then, carrying out electrochemical performance test on the prepared battery at a voltage range of 0.01-2.0V by using a LAND-CT2001A battery test system.
The vacuum drying temperature is 60-80 ℃, and the drying time is 8-12 hours.
Test results show that the carbon-coated niobium pentoxide composite reduced graphene oxide material obtained by the invention has good circulation stability, and when 50mAg is selected-1The current density is taken as the test current, and after 50 cycles of charge and discharge, the specific capacity of the electrode material still reaches 108.1mAh g-1。
The carbon-coated niobium pentoxide composite reduced graphene oxide material obtained by the invention is characterized in that: the reduced graphene oxide in the composite material has a typical nano-sheet structure, and the granular niobium pentoxide is distributed on the surface of the reduced graphene oxide and has a large specific surface area.
Compared with the prior art, the invention has the beneficial effects that:
(1) the raw materials adopted by the invention are glucose, niobium chloride and graphene oxide, the material source is simple, the green and safe effects are achieved, the price is low, and the large-scale production can be realized.
(2) By adopting a microwave treatment method, graphene in the composite material can be effectively reduced, and niobium pentoxide particles in the composite material are promoted to have smaller particle size, so that the circulation stability of the material is enhanced, and the purpose of improving the electrochemical performance of the material can be achieved.
(3) The electrode material obtained by the method has higher specific capacity and the stability of the electrode material is well maintained.
Drawings
Fig. 1(a) is a scanning electron microscope of a carbon-coated niobium pentoxide composite reduced graphene oxide material;
FIG. 1(b) is a transmission electron microscope photograph of the carbon-coated niobium pentoxide composite reduced graphene oxide material, which is processed at a constant temperature of 600 ℃ for 2 h.
FIG. 2 is an EDS photograph of a carbon-coated niobium pentoxide composite reduced graphene oxide material, which is subjected to constant temperature of 600 ℃ for 2 hours for post-treatment.
FIG. 3 shows that the carbon-coated niobium pentoxide composite reduced graphene oxide is at 50mA g-1Current density of (a).
FIG. 4 is a circulation curve of carbon-coated niobium pentoxide composite reduced graphene oxide at a current density of 50mA/g under different microwave treatment powers.
FIG. 5 is a discharge curve of the cycle curve of carbon-coated niobium pentoxide composite reduced graphene oxide at a current density of 50mA/g for different microwave treatment times.
Detailed Description
The invention will be described in further detail below with reference to the drawings and examples.
The invention relates to a preparation method of a carbon-coated niobium pentoxide composite reduced graphene oxide composite aluminum ion battery anode material, which comprises the following steps:
preparing graphene oxide;
the synthesis steps of the graphene oxide are as follows: mixing graphite powder and sodium nitrate, filling the mixture into a container, pouring a certain amount of concentrated sulfuric acid, stirring the mixture in an ice-water bath at the temperature of 0-4 ℃, and slowly adding potassium permanganate for more than 2 times in a period of time. Then removing the ice water bath, moving the mixture into an oil bath kettle, and reacting for a period of time at the temperature of between 35 and 37 ℃. Then slowly adding a certain amount of water, raising the temperature to 98 ℃ for reaction for a period of time, then moving out of the oil bath pot, adding a certain amount of water, and adding a certain amount of hydrogen peroxide after naturally cooling to room temperature. And then washing for more than 2 times by using a dilute hydrochloric acid solution with the mass fraction of 5%, then washing for more than 2 times by using deionized water until the pH value of the solution is 6, and carrying out ultrasonic treatment for 3 hours for later use.
The mass ratio of the graphite powder to the sodium nitrate is 2:1, the mass ratio of the graphite powder to the potassium permanganate is 1:3, and the mass ratio of the graphite powder to the concentrated sulfuric acid is 40 mg/mL.
The mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the hydrogen peroxide is 30%.
The reaction time is 2-3 hours at the temperature of 35 ℃; the reaction time is 10-15 minutes at the temperature of 98 ℃.
The amount of water added in the two times is 45-50 mL and 40-50 mL respectively.
The purpose of the acid washing with 5% diluted hydrochloric acid is to remove sulfate, manganese ions and other miscellaneous ions.
Preparing a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
dissolving graphene oxide, niobium pentachloride and glucose in polyethylene glycol-400, and then carrying out ultrasonic treatment for a period of time to promote uniform mixing. Then, after uniformly stirring, transferring the obtained solution into a three-mouth bottle, and treating for 6-10 minutes at the power of 700-900W to obtain a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
the mass ratio of the graphite oxide to the niobium pentachloride is 1:5.4, the mass ratio of the graphite oxide to the glucose is 1:3.6, and the mass concentration of the graphite oxide in the polyethylene glycol-400 is 2.5 mg/mL.
The ultrasonic treatment time is 15-30 minutes.
Step three, high-temperature heat treatment;
washing the precursor with water and anhydrous ethanol for more than 2 times respectively to remove impurities; then freeze-drying for a period of time; and then calcining the dried carbon-coated niobium pentoxide composite reduced graphene oxide sample at a certain temperature for a period of time under an inert atmosphere to promote the sample to be better crystallized.
The freeze drying temperature is about-40 to-50 ℃; the freeze-drying time is about 8-12 hours.
The high-temperature calcination temperature is 600-800 ℃, and the high-temperature calcination time is 1-3 hours.
Step four, preparing the positive electrode of the aluminum ion battery;
weighing the obtained carbon-coated niobium pentoxide composite reduced graphene oxide material, mixing the carbon-coated niobium pentoxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dropwise adding N-methyl-2-pyrrolidone by a dropper, stirring uniformly, coating the uniformly mixed electrode material on tantalum foil, and drying in vacuum for a period of time. Then, a 2032 type button cell was assembled by using an ionic liquid as an electrolyte, which was prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride in a molar ratio of 1.3:1, and a metal aluminum counter electrode, a glass fiber membrane (GF/D) as a separator, in a glove box. And then, carrying out electrochemical performance test on the prepared battery at a voltage range of 0.01-2.0V by using a LAND-CT2001A battery test system.
The vacuum drying temperature is 60-80 ℃, and the drying time is 8-12 hours.
Example 1
Preparing graphene oxide;
the graphene oxide synthesis steps are as follows: firstly, 1g of graphite powder (the particle size is not less than 325 meshes) and 0.5g of sodium nitrate are mixed and loaded into a 250mL beaker, then 25mL of concentrated sulfuric acid (the mass fraction is 98%) is poured into the beaker, then the beaker is stirred in an ice-water bath at 0-4 ℃, and 3g of potassium permanganate is slowly added into the beaker in 5 times in the following 1 h. Then the ice water bath was removed, and the beaker with the mixed solution was transferred to an oil bath and reacted at 35 ℃ for 2 hours. Then 47mL of deionized water is slowly added, the temperature is increased to 98 ℃ for reaction for 15Min, then the oil bath pot is removed, 40mL of deionized water with the temperature of about 60 ℃ is added, and 8mL (30 mass percent) is added after the mixed solution is cooled to room temperature. After stirring for 2 hours, washing for 3 times by using a 5% dilute hydrochloric acid solution, then washing for 6 times by using deionized water until the pH value of the solution is 6, and carrying out ultrasonic treatment for 3 hours for later use.
Preparing a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
0.1g of graphene oxide, 0.54g of niobium pentachloride and 0.18g of glucose were dissolved in 40mL of polyethylene glycol-400, and then sonicated for 10 minutes to facilitate their uniform mixing. Then stirring for 10 minutes, transferring the obtained solution into a 250mL three-necked bottle, and treating for 10 minutes at the power of 800W to obtain a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
step three, high-temperature heat treatment;
washing the precursor with deionized water and absolute ethyl alcohol for 3 times respectively to remove impurities; then freeze-drying for 12 hours at the temperature of minus 45 ℃; and then calcining the dried carbon-coated niobium pentoxide composite reduced graphene oxide sample at 600 ℃ for 2 hours under inert atmosphere to promote the sample to be better crystallized.
Step four, preparing the positive electrode of the aluminum ion battery;
weighing 80mg of the obtained carbon-coated niobium pentoxide composite reduced graphene oxide material, mixing the carbon-coated niobium pentoxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dropwise adding 3 drops of N-methyl-2-pyrrolidone by using a dropper, stirring for 2 hours, coating the uniformly mixed electrode material on tantalum foil, and drying for 12 hours at 60 ℃ under a vacuum condition. Then, a 2032 type button cell was assembled by using an ionic liquid as an electrolyte, which was prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride in a molar ratio of 1.3:1, and a metal aluminum counter electrode, a glass fiber membrane (GF/D) as a separator, in a glove box. And then, carrying out electrochemical performance test on the prepared battery at a voltage range of 0.01-2.0V by using a LAND-CT2001A battery test system.
FIG. 1 shows such Nb2O5Environmental scanning and transmission electron microscope photographs of/C/RGO materials. It can be seen that this composite material has a typical nano-platelet structure and uniform grain size of Nb2O5Uniformly distributed on the surface of the reduced graphene oxide, and Nb can be seen from the transmission electron microscope picture2O5The nano-particles have a particle size of about 10 to 12 nm and the carbon layer has a thickness of about 0.5 to 1 nm.
Fig. 2 is an EDS picture of the carbon-coated niobium pentoxide composite reduced graphene oxide material. From the figure, it can be seen that the carbon-coated niobium pentoxide composite reduced graphene oxide material is composed of three elements of carbon, oxygen and niobium, the content of oxygen and niobium respectively accounts for 14.17% and 28.72% of the total mass of the composite material, the mass ratio of the substances is about 2.87:1 and is close to 2.5:1, and the niobium in the carbon-coated niobium pentoxide composite reduced graphene oxide material can be determined to exist in the form of niobium pentoxide (the oxygen-containing functional group in the reduced graphene oxide contains a certain amount of oxygen).
FIG. 3 shows the voltage at 50mA g-1Discharge curves of the prepared material and the comparative material at the current density of (a). As is apparent from the figureThe prepared carbon-coated niobium pentoxide composite reduced graphene oxide composite material has good cycle stability, and the specific discharge capacity of the composite material can still be kept at 108.1mAh g after 50 times of charge-discharge cycles-1。
Example 2
Preparing graphene oxide;
the graphene oxide used in the synthesis of the carbon-coated niobium pentoxide composite reduced graphene oxide composite material comprises the following specific synthesis steps: first, 1.2g of graphite powder (particle size ≧ 325 mesh) and 0.6g of sodium nitrate were mixed and charged into a 250mL beaker, followed by pouring 30mL of concentrated sulfuric acid (mass fraction 98%), stirring in an ice-water bath at 0-4 ℃, and then 3.6g of potassium permanganate was slowly added in 1 hour at 6. Then the ice water bath was removed, and the beaker with the mixed solution was transferred to an oil bath and reacted at 35 ℃ for 2 hours. Then 57mL of deionized water is slowly added, the temperature is increased to 98 ℃ for reaction for 15Min, then the oil bath pot is removed, 40mL of deionized water with the temperature of about 60 ℃ is added, and 10mL (30 mass percent) of the mixed solution is added after the mixed solution is cooled to room temperature. After stirring for 2 hours, washing for 3 times by using a 5% dilute hydrochloric acid solution, then washing for 6 times by using deionized water until the pH value of the solution is 6, and carrying out ultrasonic treatment for 3 hours for later use.
Preparing a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
0.2g of graphene oxide, 1.08g of niobium pentachloride and 0.36g of glucose were dissolved in 60mL of polyethylene glycol-400, and then sonicated for 10 minutes to facilitate their uniform mixing. Then stirring for 10 minutes, transferring the obtained solution into a 250mL three-necked bottle, and treating for 10 minutes at the power of 700W to obtain a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
step three, high-temperature heat treatment;
the precursor was washed 3 times with deionized water and absolute ethanol, respectively, to remove impurities. Then freeze-dried at-45 ℃ for 12 hours. And then calcining the dried carbon-coated niobium pentoxide composite reduced graphene oxide sample at 600 ℃ for 2 hours under inert atmosphere to promote the sample to be better crystallized.
Step four, preparing the positive electrode of the aluminum ion battery;
weighing 100mg of the obtained carbon-coated niobium pentoxide composite reduced graphene oxide material, mixing the carbon-coated niobium pentoxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dripping 5 drops of N-methyl-2-pyrrolidone by using a dropper, stirring for 2 hours, coating the uniformly mixed electrode material on tantalum foil, and drying for 12 hours at 60 ℃ under a vacuum condition. Then, a 2032 type button cell was assembled by using an ionic liquid as an electrolyte, which was prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride in a molar ratio of 1.3:1, and a metal aluminum counter electrode, a glass fiber membrane (GF/D) as a separator, in a glove box. And then, carrying out electrochemical performance test on the prepared battery at a voltage range of 0.01-2.0V by using a LAND-CT2001A battery test system.
The method of the present invention is substantially the same as that employed in example 1, except that the microwave treatment power employed in the preparation of the carbon-coated niobium pentoxide composite reduced graphene oxide precursor was 700W. The electrode material was mixed with the material prepared in example 1 at 50mA g-1The discharge curve at the current density of (a) is shown in fig. 4, from which it can be seen that the specific discharge capacity of the material prepared by the method used in this example is lower than that of example 1 at the same current density. This is because the power of the microwave treatment affects the degree of reduction of graphene oxide in the composite material and the size of the particle size of niobium pentoxide, which in turn affects the conductivity and the cycle stability of the material. By contrast, 800W is found to be a better microwave processing power.
Example 3
Preparing graphene oxide;
the graphene oxide used in the synthesis of the carbon-coated niobium pentoxide composite reduced graphene oxide composite material comprises the following specific synthesis steps: firstly, 1g of graphite powder (particle size ≧ 325 mesh) and 0.5g of sodium nitrate are mixed and loaded into a 250mL beaker, then 25mL of concentrated sulfuric acid (mass fraction 98%) is poured, and the mixture is stirred in an ice-water bath at 0-4 ℃, and then 3g of potassium permanganate is slowly added in 5 times within 1 h. Then the ice water bath was removed, and the beaker with the mixed solution was transferred to an oil bath and reacted at 35 ℃ for 2 hours. Then 47mL of deionized water was slowly added, the temperature was raised to 98 ℃ for 10Min reaction, then the oil bath pan was removed, 40mL of deionized water at about 60 ℃ was added, and 8mL of hydrogen peroxide (30% by mass) was added after the mixed solution was cooled to room temperature. After stirring for 2 hours, washing for 3 times by using a 5% dilute hydrochloric acid solution, then washing for 6 times by using deionized water until the pH value of the solution is 6, and carrying out ultrasonic treatment for 3 hours for later use.
Preparing a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
0.15g of graphene oxide, 0.81g of niobium pentachloride and 0.27g of glucose were dissolved in 50mL of polyethylene glycol-400 at room temperature under normal pressure, and then sonicated for 10 minutes to facilitate uniform mixing thereof. Then stirring for 10 minutes, transferring the obtained solution into a 250m three-necked bottle, and treating for 6 minutes at the power of 800W to obtain a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
step three, high-temperature heat treatment;
the precursor was washed 3 times with deionized water and absolute ethanol, respectively, to remove impurities. Then freeze-dried at-45 ℃ for 12 hours. And then calcining the dried carbon-coated niobium pentoxide composite reduced graphene oxide sample at 600 ℃ for 2 hours under inert atmosphere to promote the sample to be better crystallized.
Step four, preparing the positive electrode of the aluminum ion battery;
weighing 100mg of the obtained carbon-coated niobium pentoxide composite reduced graphene oxide material, mixing the carbon-coated niobium pentoxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dripping 5 drops of N-methyl-2-pyrrolidone by using a dropper, stirring for 2 hours, coating the uniformly mixed electrode material on tantalum foil, and drying for 12 hours at 60 ℃ under a vacuum condition. Then, a 2032 type button cell was assembled by using an ionic liquid as an electrolyte, which was prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride in a molar ratio of 1.3:1, and a metal aluminum counter electrode, a glass fiber membrane (GF/D) as a separator, in a glove box. And then, carrying out electrochemical performance test on the prepared battery at a voltage range of 0.01-2.0V by using a LAND-CT2001A battery test system.
The inventionThe method was substantially the same as that employed in example 1, except that the microwave treatment time employed in the preparation of the carbon-coated niobium pentoxide composite reduced graphene oxide precursor was 6 minutes. The electrode material was mixed with the material prepared in example 1 at 50mA g-1The discharge curve at the current density of (a) is shown in fig. 5, from which it can be seen that the specific discharge capacity of the material prepared by the method used in this example is lower than that of example 1 at the same current density. This is because the duration of the microwave treatment affects the degree of reduction of graphene oxide in the composite material and the size of the particle size of niobium pentoxide, which in turn affects the conductivity and the cycling stability of the material. By comparison, 10 minutes was found to be a better microwave treatment time.
Comparative example 1
Preparing graphene oxide;
the graphene oxide synthesis steps are as follows: firstly, 1g of graphite powder (the particle size is not less than 325 meshes) and 0.5g of sodium nitrate are mixed and loaded into a 250mL beaker, then 25mL of concentrated sulfuric acid (the mass fraction is 98%) is poured into the beaker, then the beaker is stirred in an ice-water bath at 0-4 ℃, and 3g of potassium permanganate is slowly added into the beaker in 5 times in the following 1 h. Then the ice water bath was removed, and the beaker with the mixed solution was transferred to an oil bath and reacted at 35 ℃ for 2 hours. Then 47mL of deionized water is slowly added, the temperature is increased to 98 ℃ for reaction for 15Min, then the oil bath pot is removed, 40mL of deionized water with the temperature of about 60 ℃ is added, and 8mL (30 mass percent) is added after the mixed solution is cooled to room temperature. After stirring for 2 hours, washing for 3 times by using a 5% dilute hydrochloric acid solution, then washing for 6 times by using deionized water until the pH value of the solution is 6, and carrying out ultrasonic treatment for 3 hours for later use.
Preparing a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
0.1g of graphene oxide, 0.54g of niobium pentachloride and 0.18g of glucose were dissolved in 40mL of glycerol, and then sonicated for 10 minutes to facilitate uniform mixing thereof. Then stirring for 10 minutes, transferring the obtained solution into a 250mL three-necked bottle, and treating for 10 minutes at the power of 800W to obtain a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
step three, high-temperature heat treatment;
washing the precursor with deionized water and absolute ethyl alcohol for 3 times respectively to remove impurities; then freeze-drying for 12 hours at the temperature of minus 45 ℃; and then calcining the dried carbon-coated niobium pentoxide composite reduced graphene oxide sample at 600 ℃ for 2 hours under inert atmosphere to promote the sample to be better crystallized.
Step four, preparing the positive electrode of the aluminum ion battery;
weighing 80mg of the obtained carbon-coated niobium pentoxide composite reduced graphene oxide material, mixing the carbon-coated niobium pentoxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dropwise adding 3 drops of N-methyl-2-pyrrolidone by using a dropper, stirring for 2 hours, coating the uniformly mixed electrode material on tantalum foil, and drying for 12 hours at 60 ℃ under a vacuum condition. Then, a 2032 type button cell was assembled by using an ionic liquid as an electrolyte, which was prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride in a molar ratio of 1.3:1, and a metal aluminum counter electrode, a glass fiber membrane (GF/D) as a separator, in a glove box. And then, carrying out electrochemical performance test on the prepared battery at a voltage range of 0.01-2.0V by using a LAND-CT2001A battery test system.
The method of the present invention is substantially the same as that employed in example 1, except that the solvent employed in the preparation process of the carbon-coated niobium pentoxide composite reduced graphene oxide precursor is changed to glycerol. The specific discharge capacity of the material prepared by the method adopted in the example is lower than that of the material prepared in the example 1. This is because the polyethylene glycol-400 has the function of a surfactant, and has an influence on the size of the niobium pentoxide particle diameter, which in turn affects the conductivity and the cycle stability of the material. By comparison, PEG-400 was found to be a better solvent.
Comparative example 2
Preparing graphene oxide;
the graphene oxide synthesis steps are as follows: firstly, 1g of graphite powder (the particle size is not less than 325 meshes) and 0.5g of sodium nitrate are mixed and loaded into a 250mL beaker, then 25mL of concentrated sulfuric acid (the mass fraction is 98%) is poured into the beaker, then the beaker is stirred in an ice-water bath at 0-4 ℃, and 3g of potassium permanganate is slowly added into the beaker in 5 times in the following 1 h. Then the ice water bath was removed, and the beaker with the mixed solution was transferred to an oil bath and reacted at 35 ℃ for 2 hours. Then 47mL of deionized water is slowly added, the temperature is increased to 98 ℃ for reaction for 15Min, then the oil bath pot is removed, 40mL of deionized water with the temperature of about 60 ℃ is added, and 8mL (30 mass percent) is added after the mixed solution is cooled to room temperature. After stirring for 2 hours, washing for 3 times by using a 5% dilute hydrochloric acid solution, then washing for 6 times by using deionized water until the pH value of the solution is 6, and carrying out ultrasonic treatment for 3 hours for later use.
Preparing a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
0.1g of graphene oxide, 0.54g of niobium pentachloride and 0.18g of glucose were dissolved in 40mL of glycerol, and then sonicated for 10 minutes to facilitate uniform mixing thereof. Stirring for 10 minutes, transferring the obtained solution into a reaction kettle with polytetrafluoroethylene as a lining, and carrying out heat preservation reaction at 180 ℃ for 24 hours to obtain a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
step three, high-temperature heat treatment;
washing the precursor with deionized water and absolute ethyl alcohol for 3 times respectively to remove impurities; then freeze-drying for 12 hours at the temperature of minus 45 ℃; and then calcining the dried carbon-coated niobium pentoxide composite reduced graphene oxide sample at 600 ℃ for 2 hours under inert atmosphere to promote the sample to be better crystallized.
Step four, preparing the positive electrode of the aluminum ion battery;
weighing 80mg of the obtained carbon-coated niobium pentoxide composite reduced graphene oxide material, mixing the carbon-coated niobium pentoxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dropwise adding 3 drops of N-methyl-2-pyrrolidone by using a dropper, stirring for 2 hours, coating the uniformly mixed electrode material on tantalum foil, and drying for 12 hours at 60 ℃ under a vacuum condition. Then, a 2032 type button cell was assembled by using an ionic liquid as an electrolyte, which was prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride in a molar ratio of 1.3:1, and a metal aluminum counter electrode, a glass fiber membrane (GF/D) as a separator, in a glove box. And then, carrying out electrochemical performance test on the prepared battery at a voltage range of 0.01-2.0V by using a LAND-CT2001A battery test system.
The method of the present invention is substantially the same as that used in example 1, except that the solvothermal synthesis method is adopted in the preparation process of the carbon-coated niobium pentoxide composite reduced graphene oxide precursor. The specific discharge capacity of the material prepared by the method adopted in the example is lower than that of the material prepared in the example 1. This is because the microwave method can promote the reduction of graphene oxide better, and has an influence on the size and crystallinity of the niobium pentoxide particle size, which in turn affects the conductivity and cycling stability of the material. By comparison, it can be seen that the microwave-assisted synthesis is a better synthesis.
Claims (6)
1. A carbon-coated niobium pentoxide composite reduced graphene oxide material is characterized in that: carbon-coated niobium pentoxide particles are loaded on the surface of the reduced graphene oxide; the niobium pentoxide particles have the particle size of 10-12 nanometers, the mass content of the niobium pentoxide particles in the material is 40-50%, and the thickness of the carbon coating layer is 0.5-1 nanometer;
the preparation method of the carbon-coated niobium pentoxide composite reduced graphene oxide material comprises the following specific steps,
1) preparing graphene oxide;
the method comprises the following steps: firstly, mixing graphite powder and sodium nitrate, putting the mixture into a container, then pouring concentrated sulfuric acid into an ice water bath at 0-4 ℃, stirring, and then respectively adding potassium permanganate into the mixture for more than 2 times; placing the reaction system at 35-37 ℃ for reaction for a period of time; then adding water, and adjusting the temperature of the system to 98 ℃ for reaction for a period of time; then adding water, naturally cooling to room temperature, adding hydrogen peroxide, stirring for a period of time, and washing for more than 2 times by using a dilute hydrochloric acid solution with the mass fraction of 5% to remove sulfate radicals and manganese ion impurities;
then washing for more than 2 times by using deionized water until the pH value of the solution is 6, and carrying out ultrasonic treatment for 3 hours for later use;
the mass ratio of the graphite powder to the sodium nitrate is 2:1, the mass ratio of the graphite powder to the potassium permanganate is 1:3, and the concentration of the graphite powder in concentrated sulfuric acid is 40 mg/mL;
the particle size of the graphite powder is not less than 325 meshes;
the mass concentration of the concentrated sulfuric acid is 98%, and the mass fraction of the used hydrogen peroxide is 30%;
the amount of water added in the two times is 45-50 mL and 40-50 mL respectively;
the reaction time is 2-3 hours at the temperature of 35-37 ℃; keeping the temperature at 98 ℃ for 10-15 minutes;
2) preparing a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
dissolving graphene oxide, niobium pentachloride and glucose in polyethylene glycol-400, and then ultrasonically treating for a period of time to promote the uniform mixing of the graphene oxide, the niobium pentachloride and the glucose; then, after uniformly stirring, transferring the obtained solution into a container, treating for 6-10 minutes by using microwaves with the power of 700-900W, naturally cooling to room temperature, and collecting precipitates to obtain a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
the mass ratio of the graphene oxide to the niobium pentachloride is 1:5.4, the mass ratio of the graphene oxide to the glucose is 1:3.6, and the mass concentration of the graphene oxide in the polyethylene glycol-400 is 2.5 mg/mL;
the ultrasonic treatment time is 15-30 minutes;
3) high-temperature heat treatment;
washing the precursor with water and anhydrous ethanol for more than 2 times respectively to remove impurities; then freeze-drying for a period of time until the sample is dry; then calcining the dried carbon-coated niobium pentoxide composite reduced graphene oxide sample at a certain temperature for a period of time under an inert atmosphere to promote the sample to be better crystallized;
the freeze drying temperature is-40 to-50 ℃; the freeze drying time is 8-12 hours;
the high-temperature calcination temperature is 600-800 ℃, and the high-temperature calcination time is 1-3 hours.
2. The carbon-coated niobium pentoxide composite reduced graphene oxide material according to claim 1, wherein:
the reduced graphene oxide is of a nano-flake structure, the thickness of the nano-flake structure is 3-5 nanometers, and the carbon-coated niobium pentoxide is distributed on the surface of the reduced graphene oxide.
3. A method for preparing the carbon-coated niobium pentoxide composite reduced graphene oxide material as claimed in claim 1 or 2, which is characterized in that: the specific steps are as follows,
1) preparing graphene oxide;
the method comprises the following steps: firstly, mixing graphite powder and sodium nitrate, putting the mixture into a container, then pouring concentrated sulfuric acid into an ice water bath at 0-4 ℃, stirring, and then respectively adding potassium permanganate into the mixture for more than 2 times; placing the reaction system at 35-37 ℃ for reaction for a period of time; then adding water, and adjusting the temperature of the system to 98 ℃ for reaction for a period of time; then adding water, naturally cooling to room temperature, adding hydrogen peroxide, stirring for a period of time, and washing for more than 2 times by using a dilute hydrochloric acid solution with the mass fraction of 5% to remove sulfate radicals and manganese ion impurities;
then washing for more than 2 times by using deionized water until the pH value of the solution is 6, and carrying out ultrasonic treatment for 3 hours for later use;
the mass ratio of the graphite powder to the sodium nitrate is 2:1, the mass ratio of the graphite powder to the potassium permanganate is 1:3, and the concentration of the graphite powder in concentrated sulfuric acid is 40 mg/mL;
the particle size of the graphite powder is not less than 325 meshes;
the mass concentration of the concentrated sulfuric acid is 98%, and the mass fraction of the used hydrogen peroxide is 30%;
the amount of water added in the two times is 45-50 mL and 40-50 mL respectively;
the reaction time is 2-3 hours at the temperature of 35-37 ℃; keeping the temperature at 98 ℃ for 10-15 minutes;
2) preparing a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
dissolving graphene oxide, niobium pentachloride and glucose in polyethylene glycol-400, and then ultrasonically treating for a period of time to promote the uniform mixing of the graphene oxide, the niobium pentachloride and the glucose; then, after uniformly stirring, transferring the obtained solution into a container, treating for 6-10 minutes by using microwaves with the power of 700-900W, naturally cooling to room temperature, and collecting precipitates to obtain a carbon-coated niobium pentoxide composite reduced graphene oxide precursor;
the mass ratio of the graphene oxide to the niobium pentachloride is 1:5.4, the mass ratio of the graphene oxide to the glucose is 1:3.6, and the mass concentration of the graphene oxide in the polyethylene glycol-400 is 2.5 mg/mL;
the ultrasonic treatment time is 15-30 minutes;
3) high-temperature heat treatment;
washing the precursor with water and anhydrous ethanol for more than 2 times respectively to remove impurities; then freeze-drying for a period of time until the sample is dry; then calcining the dried carbon-coated niobium pentoxide composite reduced graphene oxide sample at a certain temperature for a period of time under an inert atmosphere to promote the sample to be better crystallized;
the freeze drying temperature is-40 to-50 ℃; the freeze drying time is 8-12 hours;
the high-temperature calcination temperature is 600-800 ℃, and the high-temperature calcination time is 1-3 hours.
4. The method of claim 3, wherein: the inert atmosphere is nitrogen and/or argon.
5. The use of the carbon-coated niobium pentoxide composite reduced graphene oxide material according to claim 1 or 2 as a positive electrode active material in an aluminum ion battery positive electrode.
6. Use according to claim 5, characterized in that:
the positive electrode material of the aluminum ion battery comprises the following components in a mass ratio of 8:1:1, carbon-coated niobium pentoxide composite reduced graphene oxide material, conductive carbon black and adhesive polyvinylidene fluoride.
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