CN113964302A - Carbon nanotube/birnessite/graphene composite positive electrode material with hierarchical structure, preparation method and application - Google Patents
Carbon nanotube/birnessite/graphene composite positive electrode material with hierarchical structure, preparation method and application Download PDFInfo
- Publication number
- CN113964302A CN113964302A CN202111109573.4A CN202111109573A CN113964302A CN 113964302 A CN113964302 A CN 113964302A CN 202111109573 A CN202111109573 A CN 202111109573A CN 113964302 A CN113964302 A CN 113964302A
- Authority
- CN
- China
- Prior art keywords
- birnessite
- carbon nanotube
- hierarchical structure
- graphene
- graphene composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a carbon nanotube/birnessite/graphene composite cathode material with a hierarchical structure, a preparation method and application. Uniformly dispersing the carbon nano tube subjected to surface treatment in a potassium permanganate aqueous solution to obtain a dispersion solution, carrying out hydrothermal treatment on the dispersion solution, washing a product, freeze-drying a precipitate, dispersing high-conductivity graphene and the obtained carbon nano tube/birnessite composite fiber in a mixed solution of ethyl cellulose, ethanol and terpineol, removing ethanol in the obtained mixed system, coating the formed ink on a substrate by scraping, carrying out vacuum drying, and finally removing the ethyl cellulose to obtain the carbon nano tube/birnessite/graphene composite anode material with high capacity, high multiplying power and long cycle life.
Description
Technical Field
The invention belongs to the field of anode materials of water-based zinc ion batteries, and particularly relates to a carbon nanotube/birnessite/graphene composite anode material with a hierarchical structure, a preparation method and application.
Background
At present, the urgent need for efficient utilization of renewable energy sources such as wind energy, solar energy and the like worldwide is increased rapidly, and the development of a large-scale energy storage technology matched with the urgent need to realize reasonable consumption of electric energy in a power transmission and distribution network is urgently needed. For large-scale energy storage, the core requirements are low cost, high safety, long life and high energy storage density. Among the existing solutions, the electrochemical energy storage based battery technology has the advantages of high energy storage density, flexible installation, strong expansibility, etc. and is considered as the most competitive choice. However, the application of the lithium ion battery technology in large-scale energy storage is hindered by the disadvantages of the current mainstream lithium ion battery technology in cost and safety. Therefore, the development of new technology for low-cost and high-safety batteries is urgently needed.
Rechargeable aqueous zinc ion batteries are a secondary battery technology that has emerged in recent years. The rechargeable aqueous zinc ion battery has unusual performances in the aspects of safety, cost, energy density and the like, and is considered as one of ideal schemes for large-scale energy storage, due to the advantages of high specific volume capacity, low cost, high safety, environmental friendliness, abundant reserves, high safety of aqueous electrolyte, high ionic conductivity and the like of the zinc metal negative electrode.
The positive electrode material is a key material of the water-based zinc ion battery and directly determines the performance of the battery. Among common cathode materials, manganese dioxide has the advantages of high specific capacity, low cost, low toxicity and high discharge voltage, and is the most valuable cathode material at present. However, the inherent low conductivity and poor structural stability of manganese dioxide make the actual specific capacity, rate capability and cycling stability of manganese dioxide perform poorly, limiting its practical application.
The existing conclusion shows that the ion/electron conductivity and the structural stability of the manganese dioxide can be effectively improved through reasonable material design strategies such as crystal form regulation, cation pre-intercalation, hetero atom doping, micro-nano structure design or conductive material compounding and the like, so that the electrochemical performance of the manganese dioxide is optimized. At present, one or two optimization strategies are adopted, but the performance of the obtained manganese dioxide electrode is still poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the carbon nanotube/birnessite/graphene composite positive electrode material with the hierarchical structure, the preparation method and the application, the preparation process is simple, the cost is low, the large-scale production is easy, and the rechargeable water system zinc ion battery positive electrode material with high capacity, high multiplying power and long cycle life is obtained.
The invention is realized by the following technical scheme:
the carbon nanotube/birnessite/graphene composite cathode material with the hierarchical structure is characterized in that the inner layer of the composite cathode material is a carbon nanotube, the middle layer of the composite cathode material is birnessite layered nanosheets, the nanosheets grow on the surface of the carbon nanotube in an array shape, and the outermost layer of the composite cathode material is high-conductivity graphene.
Preferably, the diameter of the carbon nanotube is 20-50 nm, the thickness of the birnessite layered nanosheet is 3-5 nm, the length of the birnessite layered nanosheet is 20-40 nm, and the thickness of the high-conductivity graphene is less than 3 nm.
A preparation method of a carbon nanotube/birnessite/graphene composite cathode material with a hierarchical structure comprises the following steps:
step 1, uniformly dispersing the carbon nano tube subjected to surface treatment in a potassium permanganate aqueous solution, wherein the mass ratio of the carbon nano tube to the potassium permanganate is (0.5-3) to (2-6), obtaining a dispersion solution, carrying out hydrothermal treatment on the dispersion solution, and then washing a product in a reaction solution to obtain a precipitate;
step 2, freeze-drying the precipitate to obtain carbon nano tube/birnessite composite fibers, and dispersing the high-conductivity graphene and the carbon nano tube/birnessite composite fibers into a mixed solution of ethyl cellulose, ethanol and terpineol according to the mass ratio of 1 (1-9) to obtain a mixed system;
and 3, removing ethanol in the mixed system, coating the obtained ink on a substrate in a scraping manner, drying in vacuum, and removing ethyl cellulose to obtain the carbon nanotube/birnessite/graphene composite anode material with the hierarchical structure.
Preferably, step 1 performs nitric acid acidification or plasma treatment on the carbon nanotubes to obtain surface-treated carbon nanotubes.
Preferably, in the step 1, the dispersion liquid is kept at the temperature of 110-130 ℃ for 5-6 hours and then washed.
Preferably, in the step 2, the precipitate is subjected to freeze drying for 15-36 hours to obtain the carbon nanotube/birnessite composite fiber.
Preferably, in the mixed solution in the step 2, the volume ratio of the ethanol to the terpineol is (5-30): 1.
Preferably, the concentration of the graphene in the mixed system in the step 2 is 0.5-2 mg/mL; the mass ratio of the graphene to the ethyl cellulose is (1-4): 1.
Preferably, the ink is dried on the substrate in vacuum in the step 3, and then is annealed for 1-3 hours at the temperature of 280-320 ℃, so that the carbon nanotube/birnessite/graphene composite cathode material with the hierarchical structure is obtained.
The application of the carbon nanotube/birnessite/graphene composite cathode material with the hierarchical structure in a water-based zinc ion battery.
Compared with the prior art, the invention has the beneficial effects that:
according to the carbon nanotube/birnessite/graphene composite cathode material with the hierarchical structure, the carbon nanotube is used as an inner layer, a layer of birnessite layered nanosheets arranged in an array form uniformly grows on the surface of the carbon nanotube, and the nanosheets are used as an outermost layer to wrap high-conductivity graphene, so that the hierarchical structure of the carbon nanotube/birnessite/graphene is formed. The carbon nano tube is used as a conductive inner channel and a growth substrate of the birnessite, the birnessite is a layered manganese dioxide crystal, and a large amount of water and potassium ions are rich between layers of the birnessite. Interlayer water and potassium ions have larger interlayer spacing, so that zinc ions can be conveniently inserted and removed, the water and the potassium ions can play a role in pillaring to stabilize the crystal structure of the zinc-manganese composite material, the structural collapse and the manganese dissolution are inhibited, and the circulation stability is improved. The birnessite nanosheets vertically grow on the surface of the carbon nanotube in an array shape, the conductivity is improved, meanwhile, the contact between an electrode and electrolyte is facilitated due to the good porous structure of the birnessite nanosheets, and the reaction kinetics performance is improved. The graphene-coated carbon nanotube/birnessite composite fiber is used as an adhesive and a conductive outer channel, and the high-conductivity graphene replaces the traditional insulating adhesive to endow the composite electrode with high conductivity. The composite cathode material benefits from a nano-array structure, a multi-level conductive network design and high-conductivity graphene layer coating, and shows excellent ion/electron conductivity and good structural stability, so that the composite cathode material with high capacity, high multiplying power and long cycle life is obtained, and can be applied to a rechargeable aqueous zinc ion battery as a cathode material.
The invention relates to a preparation method of a carbon nano tube/birnessite/graphene composite cathode material with a hierarchical structure, which comprises the steps of firstly carrying out surface treatment on a carbon nano tube, so that oxygen-containing groups on the surface of the carbon nano tube can be increased to improve the reaction activity and the hydrophilicity, then uniformly dispersing the carbon nano tube in a potassium permanganate aqueous solution, growing birnessite on the surface of the carbon nano tube by a one-step hydrothermal method, and freeze-drying to form the Carbon Nano Tube (CNT)/birnessite (K) with a core-shell structurexMnO2·yH2The preparation method comprises the following steps of O, KMO) composite fiber (CNT/KMO), compounding the CNT/KMO with graphene (G) through a graphene ink technology, specifically dispersing the carbon nanotube/birnessite composite fiber and the graphene in a mixed solution of ethyl cellulose, ethanol and terpineol, and finally removing the ethanol, the terpineol and the ethyl cellulose in sequence by means of blade coating of a substrate to finally obtain the carbon nanotube/birnessite/graphene (CNT/KMO/G) composite anode material with a hierarchical structure with excellent performance. The composite positive electrode material simultaneously adopts four optimization strategies comprising manganese dioxide crystal form regulation and control, cation pre-embedding, nano structure design and multi-level conductive framework compounding, benefits from the synergistic effects of the four strategies, namely the layered structure of the birnessite, the pillaring effect of the pre-embedding of water molecules and potassium ions, the vertical orientation array structure of the birnessite nanosheets and the advantage superposition complementation of the double conductive framework of the inner layer of the carbon nanotube and the outer layer of the graphene, and simultaneously shows high ion and electron conductivity, good contact between electrolyte and an electrode and high structural stability, thereby showing high specific volumeVolume, high rate performance and long cycle life. The process combining the one-step hydrothermal method and the graphene ink method has the advantages of low raw material cost, simple and mild process, large-scale production and the like.
Description of the drawings:
FIG. 1 is an X-ray diffraction spectrum of a carbon nanotube/birnessite composite fiber obtained in example 1 of the present invention;
fig. 2 is a transmission electron microscope photograph of the carbon nanotube/birnessite composite fiber obtained in example 1 of the present invention;
fig. 3 is a scanning electron microscope photograph of the carbon nanotube/birnessite/graphene composite positive electrode material obtained in example 1 of the present invention;
fig. 4 is a charge/discharge curve of a typical battery formed by the composite cathode material obtained in example 1 of the present invention at a current density of 0.3A/g.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to a carbon nanotube/birnessite/graphene composite anode material with a hierarchical structure, which is in a hierarchical structure: 1) the inner layer is a carbon nano tube, the diameter of the carbon nano tube is 20-50 nanometers, the length of the carbon nano tube is several micrometers, and the carbon nano tube serves as a conductive inner bone and a substrate of the birnessite; 2) the middle layer is birnessite layered nanosheet, rich in water and potassium ions, and has a chemical formula of KxMnO2·yH2O(0<x<0.5,0.1<y<2) The nano sheets are 3-5 nanometers thick and 20-40 nanometers long, grow on the surface of the carbon nano tube in an array shape and serve as active substances of the composite electrode; 3) the outermost layer is high-conductivity graphene with the thickness<3nm, about 5 microns in size, surface defect free, acting as an adhesive and outer highly conductive framework. The composite electrode combines the advantages of various optimization strategies, and has the advantages of favorable crystal configuration, high ion/electron conductivity, high structural stability and multiple pore diameters, so that the composite electrode has the characteristics of high specific capacity, high rate capability and long cycle life.
The invention relates to a preparation method of a carbon nano tube/birnessite/graphene composite positive electrode material with a hierarchical structure, which comprises the following steps:
1) dispersing a certain mass of carbon nano tubes subjected to surface treatment in a potassium permanganate aqueous solution with the concentration of 2-6 mg/mL, wherein the concentration of the carbon nano tubes is 0.5-3 mg/mL;
the surface treatment method of the carbon nano tube is nitric acid acidification or plasma treatment, and is used for increasing oxygen-containing groups on the surface of the carbon nano tube so as to improve the reaction activity and the hydrophilicity;
2) stirring the mixed dispersion liquid obtained in the step 1) at a temperature of 1 hour, transferring the mixed dispersion liquid into a hydrothermal reaction kettle, preserving the heat at the temperature of 110-130 ℃ for 5-6 hours, and naturally cooling the mixed dispersion liquid to the room temperature;
3) centrifuging and washing the product obtained in the step 2) for more than 5 times by using deionized water until the supernatant is neutral, generally performing 5-8 times, and then performing freeze drying for 15-36 hours to obtain the CNT/KMO composite fiber;
4) dispersing high-conductivity graphene with a certain mass in an ethanol and terpineol mixed solution of Ethyl Cellulose (EC), wherein the volume ratio of ethanol to terpineol is (5-30): 1, then adding CNT/KMO composite fibers to obtain a mixed system, wherein the concentration of the high-conductivity graphene in the mixed system is 0.5-2 mg/mL, the concentration of the ethyl cellulose is 0.5-2 mg/mL, the mass ratio of the high-conductivity graphene to the ethylene cellulose is (1-4): 1, the mass ratio of the high-conductivity graphene to the CNT/KMO composite fibers is 1 (1-9), stirring for 0.5 hour, then placing in an oil bath at 95-105 ℃, stirring and heating to remove ethanol to obtain ink, wherein the ink contains CNT/KMO/G/EC;
5) the CNT/KMO/G/EC ink is spread on a hard substrate such as a stainless steel foil or a titanium foil by scraping, then vacuum drying is carried out for 8-12 hours at 75-85 ℃ to remove terpineol, and then air annealing is carried out for 1-3 hours at 280-320 ℃ to remove ethyl cellulose, so that the CNT/KMO/G composite positive electrode material is obtained.
Example 1:
1) adding 200mg of carbon nano tube into 250mL of 5M nitric acid solution, heating, stirring and refluxing for 24 hours at 80 ℃, washing with deionized water until the mixture is neutral, and drying to obtain the carbon nano tube with the surface treated;
2) dispersing 50mg of the carbon nano tube subjected to surface treatment in 150mL of 3mg/mL potassium permanganate solution, stirring at room temperature for 1 hour, transferring to 3 hydrothermal reaction kettles of 100mL, reacting at 120 ℃ for 5 hours, and naturally cooling to room temperature;
3) centrifuging and washing the product obtained in the step 2) for 7 times by using deionized water, and then carrying out cold drying at-50 ℃ for 24 hours to obtain a CNT/KMO composite fiber, wherein an X-ray diffraction spectrum of the CNT/KMO composite fiber is shown in figure 1, the figure 1 shows that the obtained material is a birnessite type manganese dioxide structure, and a core-shell structure of the CNT @ KMO can be seen from a transmission electron microscope picture 2, wherein the diameter of the CNT in the inner part is about 30nm, a KMO layer on the outer layer grows on the surface of the CNT in an array shape along the out-of-plane orientation, and the birnessite nanosheet has a good porous structure and the thickness of a shell layer is about 30 nm;
4) dispersing 15mg of high-conductivity graphene (the thickness is less than 3nm) in 20mL of 0.67mg/mL mixed solution of Ethyl Cellulose (EC) and terpineol, wherein the volume ratio of the ethanol to the terpineol is 10:1, adding 35mg of CNT/KMO composite fiber, stirring for 0.5 hour, placing in an oil bath at 100 ℃, stirring and heating to remove the ethanol, and obtaining CNT/KMO/G/EC ink;
5) the CNT/KMO/G/EC ink is coated on a stainless steel foil in a scraping mode, then vacuum drying is carried out for 10 hours at the temperature of 80 ℃, then air annealing is carried out for 2 hours at the temperature of 300 ℃, and ethyl cellulose is removed, so that the CNT/KMO/G composite positive electrode material is obtained, the microstructure of the CNT/KMO/G composite positive electrode material is shown in figure 3, wherein CNT/KMO composite fibers are uniformly dispersed and embedded in graphene, and the uniform CNT/KMO/G multi-level composite positive electrode material is formed.
Example 2:
1) spreading a carbon nano tube on a glass substrate, and treating the surface of the carbon nano tube in air for 8 minutes by using oxygen plasma under the conditions of 0.3torr and 50W to obtain a surface-treated carbon nano tube;
2) dispersing 60mg of surface-treated carbon nanotubes in 180mL of 3mg/mL potassium permanganate solution, stirring at room temperature for 1 hour, transferring to 4 hydrothermal reaction kettles of 100mL, reacting at 130 ℃ for 6 hours, and naturally cooling to room temperature;
3) centrifuging and washing the product obtained in the step 2) for 8 times by using deionized water, and then carrying out cold drying at the temperature of 55 ℃ below zero for 20 hours to obtain CNT/KMO composite fiber;
4) dispersing 10mg of high-conductivity graphene (the thickness is less than 3nm) in 30mL of a 0.67mg/mL mixed solution of Ethyl Cellulose (EC) and terpineol, wherein the volume ratio of the ethanol to the terpineol is 20:1, then adding 40mg of CNT/KMO composite fiber, stirring for 0.5 hour, placing in an oil bath at 95 ℃, stirring and heating to remove the ethanol, and obtaining CNT/KMO/G/EC ink;
5) the CNT/KMO/G/EC ink is coated on a titanium foil in a scraping way, then vacuum drying is carried out for 9 hours at 85 ℃, and then air annealing is carried out for 2.5 hours at 290 ℃ to remove ethyl cellulose, thus obtaining the CNT/KMO/G composite cathode material.
The invention discloses an application of a carbon nano tube/birnessite/graphene composite positive electrode material with a hierarchical structure in a rechargeable aqueous zinc ion battery, which comprises the following specific steps:
1) cutting the CNT/KMO/G multi-level composite positive electrode material obtained in the example 1 into a wafer with the diameter of 12mm to obtain a water-based zinc ion battery positive electrode;
it should be noted that the composite positive electrode material requires a substrate that is stable in water, because if the positive electrode is immersed in an aqueous electrolyte, the substrate will corrode or electrochemically react, which will be detrimental to the stability and safety of the battery. Stainless steel foils, titanium foils, and carbonaceous substrates (e.g., carbon paper, carbon cloth, carbon felt, etc.) are all preferred inert substrates.
2) Cutting an aluminum foil with the thickness of 100 mu m and the purity of more than 99.999 percent into a circular sheet with the diameter of 12mm to obtain the cathode of the water-based zinc ion battery;
3) weighing ZnSO with proper mass4And MnSO4Adding proper amount of deionized water to prepare 2M ZnSO4+0.2M MnSO4Obtaining an electrolyte of the water-based zinc ion battery;
4) cutting commercial glass fibers (Whatman GF/D47 mm) into 19mm disks to obtain a septum;
5) assembling and sealing the battery by using a 2032 type button battery case according to the sequence of a positive electrode, electrolyte (40 mu L), a diaphragm, the electrolyte (40 mu L), a negative electrode, a gasket and a spring, standing for 12 hours, and then carrying out an electrochemical test;
6) the charge and discharge curves of a typical battery are shown in fig. 4, the discharge platforms of the battery are respectively around 1.4V and 1.3V, and it can be seen from tables 1 and 2 that the composite cathode material has good rate performance and cycle stability.
TABLE 1 Rate Performance of a typical cell
| Current Density (A/g) | 0.3 | 0.5 | 1 | 2 | 3 | 5 | 10 |
| Specific capacity (mAh/g) | 368 | 344 | 294 | 235 | 206 | 171 | 145 |
TABLE 2 Cyclic Performance of a typical cell at 5A/g Current Density
| Number of |
10 | 100 | 1000 | 5000 | 10000 |
| Capacity retention rate | 100％ | 88.3％ | 81.3％ | 74.3％ | 65.3％ |
Claims (10)
1. The carbon nanotube/birnessite/graphene composite cathode material with the hierarchical structure is characterized in that the inner layer of the composite cathode material is a carbon nanotube, the middle layer is a birnessite layered nanosheet, the nanosheet grows on the surface of the carbon nanotube in an array shape, and the outermost layer is high-conductivity graphene.
2. The carbon nanotube/birnessite/graphene composite positive electrode material of the hierarchical structure according to claim 1, wherein the carbon nanotube has a diameter of 20 to 50nm, a birnessite layered nanosheet has a thickness of 3to 5nm, a length of 20 to 40nm, and a highly conductive graphene has a thickness of <3 nm.
3. A preparation method of a carbon nanotube/birnessite/graphene composite positive electrode material with a hierarchical structure is characterized by comprising the following steps:
step 1, uniformly dispersing the carbon nano tube subjected to surface treatment in a potassium permanganate aqueous solution, wherein the mass ratio of the carbon nano tube to the potassium permanganate is (0.5-3) to (2-6), obtaining a dispersion solution, carrying out hydrothermal treatment on the dispersion solution, and then washing a product in a reaction solution to obtain a precipitate;
step 2, freeze-drying the precipitate to obtain carbon nano tube/birnessite composite fibers, and dispersing the high-conductivity graphene and the carbon nano tube/birnessite composite fibers into a mixed solution of ethyl cellulose, ethanol and terpineol according to the mass ratio of 1 (1-9) to obtain a mixed system;
and 3, removing ethanol in the mixed system, coating the obtained ink on a substrate in a scraping manner, drying in vacuum, and removing ethyl cellulose to obtain the carbon nanotube/birnessite/graphene composite anode material with the hierarchical structure.
4. The method for preparing the carbon nanotube/birnessite/graphene composite cathode material with the hierarchical structure according to claim 3, wherein the carbon nanotube is subjected to nitric acid acidification or plasma treatment in the step 1 to obtain the surface-treated carbon nanotube.
5. The preparation method of the carbon nanotube/birnessite/graphene composite positive electrode material with the hierarchical structure according to claim 3, wherein the dispersion liquid is subjected to heat preservation at 110-130 ℃ for 5-6 hours and then washed in the step 1.
6. The preparation method of the carbon nanotube/birnessite/graphene composite positive electrode material with the hierarchical structure according to claim 3, wherein the precipitate is freeze-dried for 15-36 hours in the step 2 to obtain the carbon nanotube/birnessite composite fiber.
7. The method for preparing the carbon nanotube/birnessite/graphene composite cathode material with the hierarchical structure according to claim 3, wherein the volume ratio of ethanol to terpineol in the mixed solution in the step 2 is (5-30): 1.
8. The preparation method of the carbon nanotube/birnessite/graphene composite cathode material with the hierarchical structure according to claim 3, wherein the concentration of the graphene in the mixed system in the step 2 is 0.5-2 mg/mL; the mass ratio of the graphene to the ethyl cellulose is (1-4): 1.
9. The preparation method of the carbon nanotube/birnessite/graphene composite positive electrode material with the hierarchical structure according to claim 3, wherein the ink is dried on the substrate in vacuum in the step 3, and then is annealed at 280-320 ℃ for 1-3 hours to obtain the carbon nanotube/birnessite/graphene composite positive electrode material with the hierarchical structure.
10. The use of the carbon nanotube/birnessite/graphene composite positive electrode material of hierarchical structure according to claim 1 or 2 in an aqueous zinc-ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111109573.4A CN113964302B (en) | 2021-09-22 | 2021-09-22 | Hierarchical carbon nanotube/birnessite/graphene composite positive electrode material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111109573.4A CN113964302B (en) | 2021-09-22 | 2021-09-22 | Hierarchical carbon nanotube/birnessite/graphene composite positive electrode material, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113964302A true CN113964302A (en) | 2022-01-21 |
| CN113964302B CN113964302B (en) | 2023-06-27 |
Family
ID=79462184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111109573.4A Active CN113964302B (en) | 2021-09-22 | 2021-09-22 | Hierarchical carbon nanotube/birnessite/graphene composite positive electrode material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113964302B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090185327A1 (en) * | 2008-01-17 | 2009-07-23 | Fraser Wade Seymour | Composite electrode comprising a carbon structure coated with a thin film of mixed metal oxides for electrochemical energy storage |
| CN103839698A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene composite electrode material and preparation method and application thereof |
| CN104817075A (en) * | 2015-04-17 | 2015-08-05 | 重庆大学 | Preparation method of highly-dispersed graphene oxide nanobelt liquid |
| CN105047427A (en) * | 2015-08-06 | 2015-11-11 | 清华大学 | Composite electrode material for supercapacitor, preparation method of composite electrode material and supercapacitor |
| CN105513829A (en) * | 2016-02-26 | 2016-04-20 | 济南大学 | Carbon nanotube/carbon fiber composite material and carbon-base/manganese oxide composite electrode material |
| CN106548876A (en) * | 2015-09-22 | 2017-03-29 | 南京绿索电子科技有限公司 | The carbon nano pipe array of superficial oxidation/graphene/manganese dioxide composite material electrode and its preparation method and application |
| CN108417793A (en) * | 2018-02-01 | 2018-08-17 | 复旦大学 | The laminated film and its preparation method and application of carbon-based frame load manganese dioxide nano-plates |
| CN109037608A (en) * | 2018-06-28 | 2018-12-18 | 中南大学 | Manganous oxide/carbon nano tube/graphene anode material and preparation method thereof |
| CN109309217A (en) * | 2018-08-20 | 2019-02-05 | 中国航发北京航空材料研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN109309216A (en) * | 2018-08-20 | 2019-02-05 | 中国航发北京航空材料研究院 | A kind of preparation method of lithium sulfur battery anode material |
| KR20190120911A (en) * | 2018-04-17 | 2019-10-25 | 한국과학기술연구원 | Anode formed solid electrolyte interphase protective layer comprising graphene nanoparticle and lithium metal battery comprising the same |
| CN110729518A (en) * | 2019-09-08 | 2020-01-24 | 复旦大学 | Manganese dioxide/graphene-based water-based zinc ion battery and preparation method thereof |
| CN110993908A (en) * | 2019-11-27 | 2020-04-10 | 浙江大学 | Vertical graphene/manganese dioxide composite material and preparation method and application thereof |
-
2021
- 2021-09-22 CN CN202111109573.4A patent/CN113964302B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090185327A1 (en) * | 2008-01-17 | 2009-07-23 | Fraser Wade Seymour | Composite electrode comprising a carbon structure coated with a thin film of mixed metal oxides for electrochemical energy storage |
| CN103839698A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene composite electrode material and preparation method and application thereof |
| CN104817075A (en) * | 2015-04-17 | 2015-08-05 | 重庆大学 | Preparation method of highly-dispersed graphene oxide nanobelt liquid |
| CN105047427A (en) * | 2015-08-06 | 2015-11-11 | 清华大学 | Composite electrode material for supercapacitor, preparation method of composite electrode material and supercapacitor |
| CN106548876A (en) * | 2015-09-22 | 2017-03-29 | 南京绿索电子科技有限公司 | The carbon nano pipe array of superficial oxidation/graphene/manganese dioxide composite material electrode and its preparation method and application |
| CN105513829A (en) * | 2016-02-26 | 2016-04-20 | 济南大学 | Carbon nanotube/carbon fiber composite material and carbon-base/manganese oxide composite electrode material |
| CN108417793A (en) * | 2018-02-01 | 2018-08-17 | 复旦大学 | The laminated film and its preparation method and application of carbon-based frame load manganese dioxide nano-plates |
| KR20190120911A (en) * | 2018-04-17 | 2019-10-25 | 한국과학기술연구원 | Anode formed solid electrolyte interphase protective layer comprising graphene nanoparticle and lithium metal battery comprising the same |
| CN109037608A (en) * | 2018-06-28 | 2018-12-18 | 中南大学 | Manganous oxide/carbon nano tube/graphene anode material and preparation method thereof |
| CN109309217A (en) * | 2018-08-20 | 2019-02-05 | 中国航发北京航空材料研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN109309216A (en) * | 2018-08-20 | 2019-02-05 | 中国航发北京航空材料研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN110729518A (en) * | 2019-09-08 | 2020-01-24 | 复旦大学 | Manganese dioxide/graphene-based water-based zinc ion battery and preparation method thereof |
| CN110993908A (en) * | 2019-11-27 | 2020-04-10 | 浙江大学 | Vertical graphene/manganese dioxide composite material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| JINHUA ZHOU等: ""Flexible all-solid-state micro-supercapacitor based on Ni fiber electrode coated with MnO2 and reduced graphene oxide via electrochemical deposition"", vol. 61 * |
| 赵杰;许慧忠;刘法谦;李伟华;: "磺化石墨烯/多壁碳纳米管/二氧化锰复合材料的制备及其在超级电容器中的应用", no. 03 * |
| 郑加飞;郑明波;李念武;吕洪岭;邱兰;曹洁明;姬广斌;: "石墨烯包覆碳纳米管-硫(CNT-S)复合材料及锂硫电池性能", no. 07, pages 1356 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113964302B (en) | 2023-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107615526B (en) | Sulfur-carbon composite material comprising microporous carbon nanoplatelets for lithium-sulfur batteries and method for preparing same | |
| CN109326768B (en) | Sodium ion battery cathode, preparation method thereof and sodium ion battery | |
| CN111564611A (en) | Silicon-oxygen-carbon composite material, preparation method and lithium battery material | |
| CN111653783B (en) | Porous boron nitride fiber/multiwalled carbon nanotube/sulfur composite lithium-sulfur battery positive electrode material | |
| CN111293301A (en) | Soft and hard carbon composite porous negative electrode material for sodium ion battery and preparation method thereof | |
| CN108963235A (en) | Graphene enhances carbon coating titanium phosphate manganese sodium micron ball electrode material and its preparation method and application | |
| CN109659521A (en) | A kind of preparation method of high-performance sodium-ion battery vanadic anhydride/grapheme composite positive electrode material | |
| CN110817871A (en) | Preparation method and application of nitrogen-doped graphene-based carbon aerogel microspheres | |
| CN110880596B (en) | Positive electrode active material of potassium ion battery and preparation method and application thereof | |
| CN112299388A (en) | Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor | |
| CN107993855A (en) | A kind of preparation method of high voltage sodium ion ultracapacitor | |
| CN111933908A (en) | Gamma irradiation regulated and controlled popcorn hard carbon/SnP3Method for preparing sodium ion battery cathode by composite material | |
| CN113964302B (en) | Hierarchical carbon nanotube/birnessite/graphene composite positive electrode material, preparation method and application | |
| CN108987732B (en) | SiO composite cathode material of lithium ion battery and preparation method thereof | |
| WO2017123532A1 (en) | Nanoparticle/porous graphene composite, synthesizing methods and applications of same | |
| CN113072061B (en) | Preparation method of conductive additive carbon nanotube array of lithium ion battery anode | |
| CN115872387A (en) | Method for preparing nitrogen-sulfur co-doped carbon material from template and lithium/sodium storage application of nitrogen-sulfur co-doped carbon material | |
| CN108878887A (en) | A kind of lithium iron phosphate positive material conductive agent and preparation method thereof | |
| CN113659127A (en) | Carbon nanofiber/lithium titanate composite electrode material and preparation method and application thereof | |
| Yuan et al. | Optimizing oxygen substituents of a carbon cathode for improved capacitive behavior in ethanol-based zinc-ion capacitors | |
| KR102315265B1 (en) | Manufacturing method for mesoporous electrode, mesoporous electrode thereby and super capacitor comprising the mesoporous electrode | |
| CN116014063B (en) | Electrode of water-based zinc ion battery, preparation method and application thereof | |
| CN111313020B (en) | Preparation method of sulfur-doped nitrogen-rich carbon material, electrode and application of sulfur-doped nitrogen-rich carbon material in sodium/potassium ion battery | |
| CN114620713B (en) | Preparation method of Na ion and nonmetal co-doped carbon nanotube and lithium ion battery | |
| JP2016149401A (en) | Hybrid capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |