CN109830649B - Preparation process of flexible electrode with long cycle life and high specific capacity - Google Patents
Preparation process of flexible electrode with long cycle life and high specific capacity Download PDFInfo
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- CN109830649B CN109830649B CN201910033360.4A CN201910033360A CN109830649B CN 109830649 B CN109830649 B CN 109830649B CN 201910033360 A CN201910033360 A CN 201910033360A CN 109830649 B CN109830649 B CN 109830649B
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Abstract
The invention relates to a preparation process of a flexible electrode with long cycle life and high specific capacity, which comprises the following steps: (1) acid treatment of the multi-wall carbon nano-tube; (2) preparing an electrode: mixing and dispersing a manganese source and the multi-walled carbon nanotubes treated in the step (1) in a solution according to a preset proportion, adsorbing manganese ions in the manganese source to the multi-walled carbon nanotubes through electrostatic interaction at a preset temperature, adding a carbonate solution, reacting for a preset time to generate manganese carbonate anchored on the multi-walled carbon nanotubes, performing vacuum filtration and drying to form a flexible film, and finally continuously reacting for a preset time at a preset temperature in an inert gas atmosphere to decompose the manganese carbonate to form manganese oxide. The preparation method is simple and easy to implement, the used raw materials are low in price, and the prepared product is good in flexibility and high in active substance content and has long cycle life and high specific capacity when being used as the flexible negative electrode of the lithium battery.
Description
Technical Field
The invention belongs to the technical field of electrode material preparation, and particularly relates to a preparation process of a flexible electrode with long cycle life and high specific capacity.
Background
With the progress and development of human society, people have more and more demands on lithium ion batteries, and meanwhile, the demands on the lithium ion batteries are higher and higher. In particular, the development of new energy automobiles requires high energy density and long cycle life of lithium ion batteries, and nowadays smart wearable devices require flexibility of lithium ion batteries, and these requirements are greatly dependent on electrode materials. The lithium ion battery cathode material which is commercially applied at present is mainly graphite, but the graphite material has low theoretical specific capacity and poor flexibility, and cannot meet the application requirement of the flexible lithium ion battery with long cycle life and high energy density. Therefore, the research on the anode and cathode electrode materials with high specific capacity and good flexibility has important purposes and significance. However, in the prior art, the preparation method of the flexible electrode with long cycle life and high energy density is complex and tedious and has high cost; and the prepared electrode has poor flexibility, short cycle life and low energy density.
Therefore, the preparation method is simple and easy to implement, the cost is low, the environment is protected, and the prepared electrode has long cycle life and high specific capacity when being used as the cathode of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a preparation process which is simple and easy in process and low in cost, and when the prepared electrode is used as a lithium ion battery cathode, the prepared electrode has long cycle life and high specific capacity.
The above purpose is realized by the following technical scheme: a preparation process of a flexible electrode with long cycle life and high specific capacity comprises the following steps:
(1) acid treatment of the multi-wall carbon nano-tube;
(2) preparing a flexible electrode with long cycle life and high specific capacity: mixing and dispersing a manganese source and the multi-walled carbon nanotubes treated in the step (1) in a solution according to a preset ratio, adsorbing manganese ions in the manganese source to the multi-walled carbon nanotubes through electrostatic interaction, then adding a carbonate solution, reacting for 2-6 h at 0 ℃ to generate manganese carbonate quantum dots anchored on the multi-walled carbon nanotubes, performing vacuum filtration and drying to form a flexible film, and finally continuously reacting for 2-4 h for a preset time at 550-700 ℃ in an inert gas atmosphere to decompose the manganese carbonate quantum dots to form manganese oxide quantum dots, wherein the mass ratio of the multi-walled carbon nanotubes to the manganese oxide quantum dots is 4: 4-10.
The main constituent materials of the flexible electrode prepared by the invention are multi-walled carbon nanotubes and manganese oxide quantum dots. The invention uses multi-wall carbon nano-tube as raw material as flexible self-supporting body and current collector, uses its strong mechanical flexibility and good conductivity, and mixes with manganese source after simple pretreatment, because the multi-wall carbon nano-tube is acid-treated and has hydroxyl group and negative charge, and the manganese ion has positive charge, and after uniformly mixing them by stirring, because one of them has positive charge and one has negative charge, under the electrostatic interaction, the manganese ion is adsorbed on the multi-wall carbon nano-tube, at 0 deg.C, the addition of carbonate solution makes the manganese ion and carbonate react, and under the above-mentioned conditions, the reaction speed is slow, so that the manganese carbonate formed after reaction is small, after vacuum filtration, drying and annealing treatment, the manganese oxide quantum dot formed by decomposition is anchored on the multi-wall carbon nano-tube, and verified that the manganese oxide quantum dot has a large specific surface area because the diameter is between 3-5nm, thereby increasing more active sites, material utilization and buffer space for volume expansion, resulting in long cycle life and high specific capacity.
The method adopts the methods of electrostatic self-assembly, vacuum filtration and annealing treatment to anchor the manganese oxide quantum dots on the multi-walled carbon nano-tube, so as to obtain the flexible electrode with large specific surface area, high material utilization rate and good toughness; the preparation method of the invention is simple and easy, the cost is low, and the prepared flexible electrode with long cycle life and high specific capacity enhances the mechanical flexibility and the conductivity of the composite material due to the introduction of the multi-wall carbon nano tube; meanwhile, the manganese oxide quantum dots are small in size, large in specific surface area and many in active sites, so that the manganese oxide quantum dots have higher utilization rate and more volume expansion buffer spaces, and the performance of the electrode material is improved.
The further technical scheme is that in the step (2), the manganese source is one or more of manganese sulfate hexahydrate, manganese nitrate and manganese chloride. Preferably, the manganese source is manganese sulfate hexahydrate.
The further technical scheme is that in the step (2), the carbonate is ammonium bicarbonate. Tests prove that the finally generated manganese oxide quantum dots under the condition are the manganese oxide quantum dots.
The further technical scheme is that in the step (2), the ratio of the multi-walled carbon nanotubes to the manganese source is controlled so that the mass ratio of the multi-walled carbon nanotubes to the manganese oxide quantum dots in the flexible electrode with long cycle life and high specific capacity is 4: 4-10; preferably, the mass ratio of the multi-walled carbon nanotubes to the manganese oxide quantum dots in the flexible electrode with long cycle life and high specific capacity is 4: 8.2.
The further technical scheme is that the reaction time after the carbonate solution is added in the step (2) is 3 hours, and the flexible film continuously reacts for 3 hours at the temperature of 600 ℃.
The further technical scheme is that the step (1) further comprises the steps of washing and drying the acidified multi-wall carbon nano-tubes.
The further technical scheme is that the acid source for acidifying the carbon nano tube in the step (1) is one or more of concentrated sulfuric acid, concentrated hydrochloric acid and concentrated nitric acid.
The further technical scheme is that the acid source is concentrated nitric acid, and the amount of the concentrated nitric acid in the step (1) is 3-12 ml. Preferably, the amount of acidified concentrated nitric acid is 5 ml.
The further technical proposal is that the inert gas is nitrogen or argon. Argon is preferred.
The further technical scheme is that the diameter of the carbon nano tube is 18-28 nm. Preferably 20 nm.
The further technical scheme is that the drying in the step (2) is one or more of vacuum freeze drying, vacuum high-temperature drying and normal-temperature air drying. Preferably by vacuum freeze drying.
Compared with the prior art, the electrode prepared by the process of the invention, which is prepared by the methodThe active material has smaller size reaching 3-5nm, higher specific surface area, more active sites and shorter ion transport distance, thereby having good electrochemical lithium storage performance. The specific surface area can reach 104.2m by test2g-1The electrodes can be bent and remain intact; the experimental result shows that when the electrode prepared by the method is used as the negative electrode of the lithium ion battery, the cycle life is long, and the capacity retention rate is up to 133% after the electrode is cycled for 1000 times under the current density of 1A/g; meanwhile, the material has high specific capacity, and after the material is cycled for 1000 times under the current density of 1A/g, the discharge specific capacity is up to 883.3 mAh/g. The preparation method has low cost and simple and easy process, and the prepared electrode has long cycle life and high specific capacity.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, illustrate embodiments of the invention and together with the description serve to explain the invention and are not to limit the invention.
FIG. 1 is an XRD pattern of a long cycle life, high specific capacity flexible electrode made in accordance with example 1 of the present invention, wherein
FIG. 1 is a graph showing the results of 1000 times of long cycle tests performed at a current density of 1A/g when the electrode is used as a negative electrode of a lithium battery;
FIG. 2 is a bending test chart of a flexible electrode with long cycle life and high specific capacity prepared in example 1 of the present invention;
figure a of figure 3 is an SEM picture of a long cycle life high specific capacity flexible electrode prepared in example 1 of the present invention,
FIG. b is a TEM image of a long-cycle-life, high-specific-capacity flexible electrode prepared in example 1 of the present invention;
FIG. 4 is a BET adsorption curve of a long cycle life, high specific capacity flexible electrode prepared in example 1 of the present invention, wherein the inset in FIG. 3 is a pore size distribution plot of the electrode;
FIG. 5 is a TGA graph of a long cycle life, high specific capacity flexible electrode made according to example 1 of the present invention;
fig. 6 a is a cyclic voltammetry curve of a long-cycle-life, high-specific-capacity flexible electrode prepared in example 1 of the present invention as a negative electrode material of a lithium battery; fig. b and c are a charge-discharge curve and a rate graph of the flexible electrode prepared in example 1 of the present invention at a current density of 0.2A/g as a negative electrode material of a lithium battery, respectively; FIG. d is a graph of the cycling of the flexible electrode prepared in example 1 of the present invention at a current density of 0.2A/g.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way. Furthermore, features from embodiments in this document and from different embodiments may be combined accordingly by a person skilled in the art from the description in this document.
Example 1
Weighing commercial 300mg of multi-wall carbon nano-tubes, putting the multi-wall carbon nano-tubes into a sand core, putting the sand core and 5ml of concentrated nitric acid into a reaction kettle, putting an iron shell into the reaction kettle, transferring the mixture into a hydrothermal furnace, carrying out acidification treatment at 200 ℃ for 2 hours, and cleaning and drying the acidified multi-wall carbon nano-tubes. Weighing 40mg of acid-treated multi-walled carbon nanotube and 1mmol of manganese sulfate hexahydrate, putting the multi-walled carbon nanotube and the manganese sulfate hexahydrate in a beaker, adding 50ml of water, stirring, crushing and ultrasonically treating to fully disperse the multi-walled carbon nanotube and the manganese sulfate hexahydrate uniformly, stirring for 1h, adding 3mmol of ammonium bicarbonate, continuously stirring for 3h at 0 ℃, then carrying out vacuum filtration and vacuum freeze drying treatment, putting the obtained flexible membrane in a tubular furnace, and annealing for 3h in argon at 600 ℃ to form the manganese oxide quantum dot and multi-walled carbon nanotube flexible composite electrode.
Specific properties of the product: the manganese oxide and multi-wall carbon nanotube flexible electrode contains manganese oxide and carbon materials and has long cycle life and high specific capacity through XRD representation and illustration; the prepared electrode is determined to have better flexibility through a bending test; the manganese oxide quantum dots are anchored on the multi-wall carbon nano-tube through SEM and TEM characterization, the diameter of the manganese oxide quantum dots is 3-5nm, and the manganese oxide quantum dots are relatively uniformly distributed and do not have an agglomeration phenomenon; the specific surface area is calculated by a specific surface area test to be 104.2m2g-1(ii) a The manganese oxide content was 67.4% as determined by thermogravimetric analysis.
Electrochemical performance tests prove that the prepared manganese oxide quantum dot and multi-walled carbon nanotube flexible electrode are the best when used as a negative electrode of a lithium ion battery.
As can be seen from FIG. 1, the manganese oxide quantum dots and the peaks of the multi-walled carbon nanotube flexible electrode material can be in one-to-one correspondence with the manganese oxide standard card, thereby illustrating that the prepared material contains manganese oxide, and is 25.7. The peaks correspond to those of multi-walled carbon nanotubes. As can be seen from the inset in fig. 1, when the electrode is used as a negative electrode of a lithium battery, the electrode is firstly cycled for 4 times at a current density of 0.1A/g for better activating a material, the specific discharge capacity after the 5 th cycle is 647.2mAh/g, then the electrode is cycled for 1000 times at a current density of 1A/g, the previous 200 cycles can observe that the specific discharge capacity is firstly stable, then gradually rises and then tends to be stable, which is mainly caused by further activation of the material and oxidation of divalent manganese to high-valence manganese to cause more electron transfer, after the electrode is cycled for 1000 times, the specific discharge capacity is 883.3mAh/g, the specific capacity retention rate is as high as 136%, and the electrode has a long cycle life and a high specific capacity.
As can be seen from FIG. 2, the manganese oxide quantum dot and multi-walled carbon nanotube flexible electrode is still intact after bending test, which shows that the electrode has better flexibility.
From the graph a in fig. 3, it can be seen that the manganese oxide and the multi-walled carbon nanotubes are dispersed particularly uniformly without any agglomeration; in the graph b, the manganese oxide quantum dots are anchored on the carbon nanotubes, the diameter is 3-5nm, and no agglomeration phenomenon exists.
From FIG. 4, it can be concluded that the manganese oxide and multi-walled carbon nanotube flexible electrode has a high specific surface area of 104.2m2g-1And the figure inserted in fig. 4 shows that the aperture of the flexible electrode is mainly distributed in the micropores.
From fig. 5, it can be seen that the content of manganese oxide in the material is as high as 67.4%.
From the graph a of fig. 6, it can be seen that there is a pair of redox peaks, and the area enclosed by the third time is larger than that of the second time, indicating that the electrode material is gradually activated; the graphs b and d are respectively a charge-discharge curve and a cycle of the manganese oxide quantum dot and the multi-walled carbon nanotube flexible electrode under 0.1A/g when the manganese oxide quantum dot and the multi-walled carbon nanotube flexible electrode are used as negative electrode materials of a lithium battery, and the manganese oxide quantum dot and the carbon nanotube flexible electrode can be judged to have good cycle stability and high specific capacity through the charge-discharge curve and the cycle graph; as can be seen from the graph d, the electrode still has a very high specific capacity at a large current density of 3.2A/g, thereby illustrating that the manganese oxide quantum dot and the multi-walled carbon nanotube flexible electrode have excellent rate capability.
Example 2
Weighing commercial 300mg of multi-wall carbon nano-tubes, putting the multi-wall carbon nano-tubes into a sand core, putting the sand core and 5ml of concentrated nitric acid into a reaction kettle, putting an iron shell into the reaction kettle, transferring the mixture into a hydrothermal furnace, carrying out acidification treatment at 200 ℃ for 2 hours, and cleaning and drying the acidified multi-wall carbon nano-tubes. Weighing 40mg of acid-treated multi-walled carbon nano-tube and 1mmol of manganese sulfate hexahydrate, putting the multi-walled carbon nano-tube and the manganese sulfate hexahydrate in a beaker, adding 50ml of water, stirring, crushing and ultrasonically dispersing the mixture fully and uniformly, stirring for 1h, adding 3mmol of ammonium bicarbonate, continuously stirring for 3h at 0 ℃, then carrying out vacuum filtration and vacuum freeze drying treatment, putting the obtained flexible membrane in a tubular furnace, and annealing for 4h in argon at 700 ℃ to form the manganese oxide quantum dot and multi-walled carbon nano-tube flexible composite electrode.
Specific properties of the product: the manganese oxide and multi-wall carbon nanotube flexible electrode contains manganese oxide and carbon materials and has long cycle life and high specific capacity through XRD representation and illustration; the flexibility is general through a bending test; the manganese oxide quantum dots are anchored on the multi-wall carbon nano-tube through SEM and TEM characterization, the diameter of the manganese oxide quantum dots is 4-8nm, and the manganese oxide quantum dots are relatively uniformly distributed and do not have an agglomeration phenomenon; the specific surface area is 94.2m calculated by the specific surface area test2g-1(ii) a The manganese oxide content was 65.4% as determined by thermogravimetric analysis.
Example 3
Weighing commercial 300mg of multi-wall carbon nano-tubes, putting the multi-wall carbon nano-tubes into a sand core, putting the sand core and 5ml of concentrated nitric acid into a reaction kettle, putting an iron shell into the reaction kettle, transferring the mixture into a hydrothermal furnace, carrying out acidification treatment at 200 ℃ for 2 hours, and cleaning and drying the acidified multi-wall carbon nano-tubes. Weighing 40mg of acid-treated multi-walled carbon nano-tube and 1mmol of manganese sulfate hexahydrate, putting the multi-walled carbon nano-tube and the manganese sulfate hexahydrate in a beaker, adding 50ml of water, stirring, crushing and ultrasonically dispersing the mixture fully and uniformly, stirring for 1h, adding 3mmol of ammonium bicarbonate, continuously stirring for 4h at 0 ℃, then carrying out vacuum filtration and vacuum freeze drying treatment, putting the obtained flexible membrane in a tubular furnace, and annealing for 3h in argon at 600 ℃ to form the manganese oxide quantum dot and multi-walled carbon nano-tube flexible composite electrode.
Specific properties of the product: the manganese oxide and multi-wall carbon nanotube flexible electrode contains manganese oxide and carbon materials and has long cycle life and high specific capacity through XRD representation and illustration; the prepared electrode is determined to have better flexibility through a bending test; the manganese oxide quantum dots are anchored on the multi-wall carbon nano-tube through SEM and TEM characterization, the diameter of the manganese oxide quantum dots is 4-7nm, and the manganese oxide quantum dots are relatively uniformly distributed and do not have an agglomeration phenomenon; the specific surface area is calculated to be 101.2m by a specific surface area test2g-1(ii) a The manganese oxide content was 68.8% as determined by thermogravimetric analysis.
Example 4
Weighing commercial 300mg of multi-wall carbon nano-tubes, putting the multi-wall carbon nano-tubes into a sand core, putting the sand core and 4ml of concentrated nitric acid into a reaction kettle, putting an iron shell into the reaction kettle, transferring the mixture into a hydrothermal furnace, carrying out acidification treatment at 200 ℃ for 2 hours, and cleaning and drying the acidified multi-wall carbon nano-tubes. Weighing 40mg of acid-treated multi-walled carbon nanotube and 1mmol of manganese sulfate hexahydrate, putting the multi-walled carbon nanotube and the manganese sulfate hexahydrate in a beaker, adding 50ml of water, stirring, crushing and ultrasonically dispersing the mixture fully and uniformly, stirring for 1h, adding 3mmol of ammonium bicarbonate, continuously stirring for 2h at 0 ℃, then carrying out vacuum filtration and vacuum freeze drying, putting the obtained flexible membrane in a tubular furnace, and annealing for 4h in argon at 550 ℃ to form the manganese oxide quantum dot and multi-walled carbon nanotube flexible composite electrode.
Specific properties of the product: the manganese oxide and multi-wall carbon nanotube flexible electrode contains manganese oxide and carbon materials and has long cycle life and high specific capacity through XRD representation and illustration; the prepared electrode is determined to have better flexibility through a bending test; the manganese oxide quantum dots are anchored on the multi-wall carbon nano-tube through SEM and TEM characterization, the diameter of the manganese oxide quantum dots is 4-8nm, and the manganese oxide quantum dots are relatively uniformly distributed and do not have an agglomeration phenomenon; the specific surface area is calculated to be 98.2m by the specific surface area test2g-1(ii) a Tong (Chinese character of 'tong')The content of manganese oxide was 65.4% by the superheated gravimetric analysis test.
Example 5
Weighing commercial 300mg of multi-wall carbon nano-tubes, putting the multi-wall carbon nano-tubes into a sand core, putting the sand core and 5ml of concentrated nitric acid into a reaction kettle, putting an iron shell into the reaction kettle, transferring the mixture into a hydrothermal furnace, carrying out acidification treatment at 200 ℃ for 2 hours, and cleaning and drying the acidified multi-wall carbon nano-tubes. Weighing 60mg of acid-treated multi-walled carbon nano-tube and 1mmol of manganese sulfate hexahydrate, putting the multi-walled carbon nano-tube and the manganese sulfate hexahydrate in a beaker, adding 50ml of water, stirring, crushing and ultrasonically dispersing the mixture fully and uniformly, stirring for 1h, adding 3mmol of ammonium bicarbonate, continuously stirring for 6h at 0 ℃, then carrying out vacuum filtration and vacuum freeze drying treatment, putting the obtained flexible membrane in a tubular furnace, and annealing for 2h in argon at 600 ℃ to form the manganese oxide quantum dot and multi-walled carbon nano-tube flexible composite electrode.
Specific properties of the product: the manganese oxide and multi-wall carbon nanotube flexible electrode contains manganese oxide and carbon materials and has long cycle life and high specific capacity through XRD representation and illustration; the prepared electrode is determined to have good flexibility through a bending test; the manganese oxide quantum dots are anchored on the multi-wall carbon nano-tube through SEM and TEM characterization, the diameter of the manganese oxide quantum dots is 5-9nm, and the manganese oxide quantum dots are relatively uniformly distributed and do not have an agglomeration phenomenon; the specific surface area is 88.2m calculated by a specific surface area test2g-1(ii) a The manganese oxide content was 55.4% by thermogravimetric analysis.
Example 6
Weighing commercial 300mg of multi-wall carbon nano-tubes, putting the multi-wall carbon nano-tubes into a sand core, putting the sand core and 5ml of concentrated nitric acid into a reaction kettle, putting an iron shell into the reaction kettle, transferring the mixture into a hydrothermal furnace, carrying out acidification treatment at 200 ℃ for 2 hours, and cleaning and drying the acidified multi-wall carbon nano-tubes. Weighing 80mg of acid-treated multi-walled carbon nano-tube and 1mmol of manganese sulfate hexahydrate, putting the multi-walled carbon nano-tube and the manganese sulfate hexahydrate in a beaker, adding 50ml of water, stirring, crushing and ultrasonically dispersing the mixture fully and uniformly, stirring for 1h, adding 2mmol of ammonium bicarbonate, continuously stirring for 3h at 0 ℃, then carrying out vacuum filtration and vacuum freeze drying treatment, putting the obtained flexible membrane in a tubular furnace, and annealing for 3h in argon at 600 ℃ to form the manganese oxide quantum dot and multi-walled carbon nano-tube flexible composite electrode.
Specific properties of the product: the manganese oxide and multi-wall carbon nanotube flexible electrode contains manganese oxide and carbon materials and has long cycle life and high specific capacity through XRD representation and illustration; the prepared electrode has excellent flexibility as determined by a bending test; the manganese oxide quantum dots are anchored on the multi-wall carbon nano-tube through SEM and TEM characterization, the diameter of the manganese oxide quantum dots is 4-6nm, and the manganese oxide quantum dots are relatively uniformly distributed and do not have an agglomeration phenomenon; the specific surface area is calculated to be 70.5m by the specific surface area test2g-1(ii) a The manganese oxide content was 46.4% by thermogravimetric analysis.
Example 7
Weighing commercial 300mg of multi-wall carbon nano-tubes, putting the multi-wall carbon nano-tubes into a sand core, putting the sand core and 5ml of concentrated nitric acid into a reaction kettle, putting an iron shell into the reaction kettle, transferring the mixture into a hydrothermal furnace, carrying out acidification treatment at 200 ℃ for 2 hours, and cleaning and drying the acidified multi-wall carbon nano-tubes. Weighing 40mg of acid-treated multi-walled carbon nanotube and 1.5mmol of manganese sulfate hexahydrate, putting the multi-walled carbon nanotube and the manganese sulfate hexahydrate in a beaker, adding 50ml of water, stirring, crushing and ultrasonically dispersing the mixture fully and uniformly, stirring for 1h, adding 5mmol of sodium carbonate, continuing stirring for 3h at 0 ℃, then carrying out vacuum filtration and vacuum freeze drying treatment, putting the obtained flexible membrane in a tubular furnace, and annealing for 3h in argon at 600 ℃ to form the manganese oxide quantum dot and multi-walled carbon nanotube flexible composite electrode.
Specific properties of the product: manganese oxide and a multi-wall carbon nanotube flexible electrode containing manganese oxide and a carbon material are determined through XRD characterization; the prepared electrode is determined to have poor flexibility through a bending test; the manganese oxide anchored on the multi-wall carbon nanotube is determined through SEM and TEM characterization, the diameter of the manganese oxide is 10-25nm, and meanwhile, the manganese oxide is not uniformly distributed and has serious agglomeration phenomenon and is not a manganese oxide quantum dot. The specific surface area is 40.5m calculated by a specific surface area test2g-1(ii) a The manganese oxide content was 75.4% by thermogravimetric analysis.
Example 8
Weighing commercial 300mg of multi-wall carbon nano-tubes, putting the multi-wall carbon nano-tubes into a sand core, putting the sand core and 5ml of concentrated nitric acid into a reaction kettle, putting an iron shell into the reaction kettle, transferring the mixture into a hydrothermal furnace, carrying out acidification treatment at 200 ℃ for 2 hours, and cleaning and drying the acidified multi-wall carbon nano-tubes. Weighing 40mg of acid-treated multi-walled carbon nanotube and 0.6mmol of manganese sulfate hexahydrate, putting the multi-walled carbon nanotube and the manganese sulfate hexahydrate into a beaker, adding 50ml of water, stirring, crushing and ultrasonically dispersing the mixture fully and uniformly, stirring for 1h, adding 2mmol of sodium carbonate, continuing stirring for 3h at 0 ℃, then carrying out vacuum filtration and vacuum freeze drying treatment, putting the obtained flexible membrane into a tubular furnace, and annealing for 3h at 600 ℃ in argon to form the manganese oxide quantum dot and multi-walled carbon nanotube flexible composite electrode.
Specific properties of the product: manganese oxide and a multi-wall carbon nanotube flexible electrode containing manganese oxide and a carbon material are determined through XRD characterization; the prepared electrode is determined to have good flexibility through a bending test; the manganese oxide anchored on the multi-walled carbon nanotubes was determined by SEM and TEM characterization, while the manganese oxide was more uniformly distributed, but not the manganese oxide quantum dots. The specific surface area is calculated by a specific surface area test to be 100.5m2g-1(ii) a The manganese oxide content was 51.4% by thermogravimetric analysis.
Other carbonates except ammonium bicarbonate, such as ammonium carbonate and sodium bicarbonate, are selected, and experiments show that the manganese oxide of the product is not the manganese oxide quantum dot. The diameter of the multi-wall carbon nano tube is 18-28 nm, and preferably 20 nm.
Manganese oxide quantum dot and carbon nanotube flexible electrode characterization
The structure and morphology of the manganese oxide quantum dot and carbon nanotube flexible electrode are characterized by a Ragaku D (manufactured by Japan science) X-ray Diffractometer (XRD), a Transmission Electron Microscope (TEM) with a model JEOLJEM-2100 (Japan Electron Co., Ltd.) and a Scanning Electron Microscope (SEM) with a model S4800. N is a radical of2Adsorption (Micromeritics TriStar II 3020) test; the specific surface area is calculated according to Brunauer-Emmett-Teller (BET) theory, and the Pore Size Distribution (PSD) is calculated by a Barrett-Joyner-Halenda (BJH) model; the manganese oxide content was analyzed by a model NETZSCH TG 209F1Libra thermogravimetric analyzer.
Manganese oxide quantum dot and multi-walled carbon nanotube flexible electrode battery assembly and electrochemical performance test
Cutting manganese oxide quantum dots and a multi-walled carbon nanotube flexible electrode into a round sheet with the mass of 0.8-1.5mg to be directly used as a working electrode, taking a metal lithium sheet as a counter electrode, and taking 1mol/L LiPF6EC/DMC/EMC (1: 1) is used as electrolyte, polypropylene celgard 2325 is used as a diaphragm, and the electrolyte is assembled into a 2025 type button half cell in a glove box with argon atmosphere and water content less than 1 muL/L. The constant current charge and discharge test (GCD) is carried out on a Xinwei battery test system, and the test voltage range is 0.01-3.00V. The Cyclic Voltammetry (CV) test and the alternating current impedance (EIS) test were performed on an electrochemical workstation of type chenhua CHI 660.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation process of a flexible electrode with long cycle life and high specific capacity is characterized by comprising the following steps:
(1) acid treatment of the multi-wall carbon nano tube, wherein an acid source in the acid treatment is concentrated nitric acid;
(2) preparing a flexible electrode with long cycle life and high specific capacity: mixing and dispersing a manganese source and the multi-walled carbon nanotubes treated in the step (1) in water according to a preset ratio, adsorbing manganese ions in the manganese source to the multi-walled carbon nanotubes through electrostatic interaction, then adding a carbonate solution, reacting for 2-6 h at 0 ℃ to generate manganese carbonate quantum dots anchored on the multi-walled carbon nanotubes, performing vacuum filtration and drying to form a flexible film, and finally continuously reacting for 2-4 h at 550-700 ℃ in an inert gas atmosphere to decompose the manganese carbonate quantum dots to form manganese oxide quantum dots, wherein the mass ratio of the multi-walled carbon nanotubes to the manganese oxide quantum dots is 4: 4-10, and the carbonate adopted in the step (2) is ammonium bicarbonate.
2. The process for preparing a long-cycle-life, high-specific-capacity flexible electrode according to claim 1, wherein the manganese source used in the step (2) is one or more of manganese sulfate hexahydrate, manganese nitrate and manganese chloride.
3. The process for preparing a flexible electrode with long cycle life and high specific capacity according to claim 2, wherein the step (1) further comprises cleaning and drying the multi-walled carbon nanotubes after acid treatment.
4. The process for preparing a flexible electrode with long cycle life and high specific capacity according to claim 1, wherein the amount of concentrated nitric acid in the step (1) is 3-12 ml.
5. The process of claim 4, wherein the inert gas is normal nitrogen or normal argon.
6. The process for preparing a long-cycle-life, high-specific-capacity flexible electrode according to claim 4, wherein the diameter of the multi-walled carbon nanotube is 18-28 nm.
7. The process for preparing a flexible electrode with long cycle life and high specific capacity according to claim 1, wherein the drying in the step (2) is one or more of vacuum freeze drying, vacuum high-temperature drying and drying in air at normal temperature.
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| CN103762366A (en) * | 2013-11-25 | 2014-04-30 | 国家电网公司 | Preparation method of carbon nanotube composite electrode |
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| CN108172409B (en) * | 2018-01-10 | 2020-05-12 | 西北师范大学 | Preparation method of graphene quantum dot/manganese hydroxide composite material with three-dimensional flower-like structure |
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