CN113964302B - Hierarchical carbon nanotube/birnessite/graphene composite positive electrode material, preparation method and application - Google Patents
Hierarchical carbon nanotube/birnessite/graphene composite positive electrode material, preparation method and application Download PDFInfo
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Abstract
The invention relates to a hierarchical carbon nanotube/birnessite/graphene composite positive electrode material, a preparation method and application thereof. The method comprises the steps of uniformly dispersing surface-treated carbon nanotubes in potassium permanganate aqueous solution to obtain dispersion liquid, carrying out hydrothermal treatment on the dispersion liquid, washing a product, freeze-drying a precipitate, dispersing high-conductivity graphene and obtained carbon nanotube/birnessite composite fibers in mixed liquid of ethyl cellulose, ethanol and terpineol, removing ethanol in the obtained mixed system, scraping formed ink on a substrate, carrying out vacuum drying, and finally removing ethyl cellulose to obtain the carbon nanotube/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 water-based zinc ion battery anode materials, and particularly relates to a hierarchical carbon nano tube/birnessite/graphene composite anode material, a preparation method and application.
Background
At present, the urgent demand for the efficient utilization of renewable energy sources such as wind energy, solar energy and the like in the world is increasing, and the development of a large-scale energy storage technology matched with the urgent demand is urgent to realize the reasonable consumption of electric energy in a transmission and distribution network. For large-scale energy storage, the core requirements are low cost, high safety, long service life and high energy storage density. In the prior art, the battery technology based on electrochemical energy storage has the advantages of high energy storage density, flexible installation, strong expansibility and the like, and is considered to be the most competitive choice. However, the disadvantages of the current mainstream lithium ion battery technology in terms of cost and safety prevent the application of the current mainstream lithium ion battery technology in the aspect of large-scale energy storage. Therefore, there is an urgent need to develop new battery technologies with low cost and high safety.
Rechargeable aqueous zinc ion batteries are one of the secondary battery technologies that have been emerging in recent years. The rechargeable aqueous zinc ion battery has the advantages of high specific volume capacity, low cost, high safety, environmental friendliness, abundant reserves, high safety and high ion conductivity of aqueous electrolyte and the like, has insignificant performance in the aspects of safety, cost, energy density and the like, and is considered as one of ideal schemes for large-scale energy storage.
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 positive electrode materials, manganese dioxide has the advantages of high specific capacity, low cost, low toxicity and high discharge voltage, and is the positive electrode material with the highest application value at present. However, the inherent low conductivity and poor structural stability of manganese dioxide make its practical specific capacity, rate capability and cycling stability perform poorly, limiting its practical application.
It has been concluded that the ionic/electronic conductivity and structural stability of manganese dioxide can be effectively improved by reasonable material design such as crystal form regulation, cation pre-embedding, hetero-atom doping, micro-nano structural design or conductive material compounding, and the electrochemical performance can be optimized. One or two of the above optimization strategies are currently 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 nano tube/birnessite/graphene composite positive electrode material with a hierarchical structure, a preparation method and application, and the preparation method is simple in process, low in cost and easy for large-scale production, 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 inner layer of the composite positive electrode material is a carbon nano tube, the middle layer is a birnessite layered nano sheet, the nano sheet grows on the surface of the carbon nano tube in an array shape, and the outermost layer is high-conductivity graphene.
Preferably, the diameter of the carbon nano tube is 20-50 nm, the thickness of the birnessite layered nano sheet is 3-5 nm, the length is 20-40 nm, and the thickness of the high-conductivity graphene is less than 3nm.
A preparation method of a hierarchical carbon nano tube/birnessite/graphene composite positive electrode material comprises the following steps:
step 1, uniformly dispersing surface-treated carbon nanotubes in a potassium permanganate aqueous solution, wherein the mass ratio of the carbon nanotubes to the potassium permanganate is (0.5-3): 2-6 to obtain a dispersion liquid, performing hydrothermal treatment on the dispersion liquid, and then washing a product in the reaction liquid to obtain a precipitate;
step 2, freeze-drying the precipitate to obtain carbon nano tube/birnessite composite fiber, and dispersing the high-conductivity graphene and the carbon nano tube/birnessite composite fiber in a mixed solution of ethyl cellulose, ethanol and terpineol according to the mass ratio of 1 (1-9) to obtain a mixed system;
and step 3, firstly removing ethanol in the mixed system, then scraping and coating the obtained ink on a substrate, and vacuum drying, and finally removing ethyl cellulose to obtain the carbon nano tube/birnessite/graphene composite anode material with a hierarchical structure.
Preferably, step 1 carries out nitric acid or plasma treatment on the carbon nanotubes to obtain the surface-treated carbon nanotubes.
Preferably, the dispersion liquid in the step 1 is kept at 110-130 ℃ for 5-6 hours, and then washed.
Preferably, the sediment is freeze-dried for 15-36 h in the step 2, so as to obtain the carbon nano tube/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 step 2 in the mixed system is 0.5-2 mg/mL; the mass ratio of the graphene to the ethylcellulose is (1-4): 1.
Preferably, the step 3 is to anneal the ink for 1 to 3 hours at the temperature of 280 to 320 ℃ after vacuum drying the ink on a substrate, and then obtain the hierarchical carbon nano tube/birnessite/graphene composite anode material.
Application of hierarchical carbon nanotube/birnessite/graphene composite positive electrode material in water-based zinc ion battery.
Compared with the prior art, the invention has the beneficial effects that:
according to the carbon nano tube/birnessite/graphene composite anode material with the hierarchical structure, the carbon nano tube is used as an inner layer, a layer of birnessite layered nano sheets distributed in an array form uniformly grows on the surface of the carbon nano tube, and the nano sheets are used as an outermost layer to wrap high-conductivity graphene, so that the hierarchical structure of the carbon nano tube/birnessite/graphene is formed. The carbon nano tube serves as a conductive inner channel and a growth substrate of birnessite, and the birnessite is a layered manganese dioxide crystal, and a large amount of water and potassium ions are enriched between layers of the birnessite. The interlayer water and potassium ions have larger interlayer spacing, so that zinc ions can be conveniently inserted and separated, and the water and potassium ions can play a role of pillaring to stabilize the crystal structure, inhibit structural collapse and manganese dissolution, and improve the circulation stability. The birnessite nano-sheets are vertically grown on the surface of the carbon nano-tube in an array shape, so that the conductivity is improved, the contact between the electrode and the electrolyte is facilitated due to the good porous structure, and the reaction dynamics performance is improved. And graphene coats the carbon nano tube/birnessite composite fiber and simultaneously serves as an adhesive and a conductive outer channel of the composite fiber, and the high-conductivity graphene replaces the traditional insulating adhesive to endow the composite electrode with high conductivity. The composite anode material benefits from the nano array structure, the multi-stage conductive network design and the high-conductivity graphene layer coating, and shows excellent ionic/electronic conductivity and good structural stability, so that the composite anode material with high capacity, high multiplying power and long cycle life is obtained, and can be applied to rechargeable water-based zinc ion batteries as an anode material.
The invention relates to a preparation method of a hierarchical carbon nano tube/birnessite/graphene composite positive electrode material, which comprises the steps of carrying out surface treatment on the carbon nano tube, increasing oxygen-containing groups on the surface of the carbon nano tube so as to improve the reactivity and hydrophilicity, 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 forming a core by freeze dryingCarbon Nanotubes (CNT)/birnessite (K) of shell structure x MnO 2· yH 2 O, KMO) composite fiber (CNT/KMO), then compounding the CNT/KMO with graphene (G) through a graphene ink technology, specifically dispersing the CNT/birnessite composite fiber and graphene in a mixed solution of ethyl cellulose, ethanol and terpineol, and finally sequentially removing the ethanol, the terpineol and the ethyl cellulose by means of a substrate scraping method, thereby finally obtaining the CNT/birnessite/graphene (CNT/KMO/G) composite anode material with a hierarchical structure and excellent performance. The invention adopts four optimization strategies simultaneously, including manganese dioxide crystal form regulation and control, cation pre-embedding, nano structure design and multi-stage conductive framework compounding, and benefits from the synergistic effect of the four strategies, namely the layered structure of the birnessite, the columnar support effect of the pre-embedding of water molecules and potassium ions, the vertical orientation array structure of the birnessite nano sheet and the advantages superposition complementation of the double conductive frameworks of the inner layer of the carbon nano tube and the outer layer of the graphene, and the composite anode material simultaneously shows high ionic electronic conductivity, good contact between electrolyte and an electrode and high structural stability, thereby further showing high specific capacity, 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 chart of a carbon nanotube/birnessite composite fiber obtained in example 1 of the present invention;
FIG. 2 is a transmission electron micrograph of a carbon nanotube/birnessite composite fiber obtained in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of a carbon nanotube/birnessite/graphene composite positive electrode material obtained in example 1 of the present invention;
FIG. 4 is a charge-discharge curve at a current density of 0.3A/g for a typical battery formed from the composite positive electrode material obtained in example 1 of the present invention.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
The invention relates to a hierarchical carbon nano tube/birnessite/graphene composite anode material, which has a hierarchical structure: 1) The inner layer is a carbon nano tube with the diameter of 20-50 nanometers and the length of several micrometers and serves as a conductive inner bone and a substrate of the birnessite; 2) The interlayer is a birnessite layered nano-sheet, and is rich in a large amount of water and potassium ions, and has a chemical formula of K x MnO 2· yH 2 O(0<x<0.5,0.1<y<2) The thickness of the nano sheet is 3-5 nanometers, the length is 20-40 nanometers, and the nano sheet grows on the surface of the carbon nano tube in an array shape and serves as an active substance 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 layer 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 pores, thereby showing the characteristics of high specific capacity, high rate capability and long cycle life.
The invention discloses a preparation method of a hierarchical carbon nano tube/birnessite/graphene composite positive electrode material, which comprises the following steps:
1) Dispersing a certain mass of carbon nano tube 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 tube is 0.5-3 mg/mL;
the surface treatment method of the carbon nano tube is nitric acid or plasma treatment, which is used for increasing oxygen-containing groups on the surface of the carbon nano tube so as to improve the reactivity and the hydrophilicity;
2) Stirring the mixed dispersion liquid obtained in the step 1) for 1 hour at room temperature, transferring the mixed dispersion liquid into a hydrothermal reaction kettle, preserving heat for 5-6 hours at 110-130 ℃, and naturally cooling to room temperature;
3) Centrifuging and washing the product obtained in the step 2) by using deionized water for more than 5 times, wherein the supernatant is neutral, generally for 5-8 times, and then freeze-drying for 15-36 hours to obtain the CNT/KMO composite fiber;
4) Dispersing high-conductivity graphene with a certain mass into an ethanol and terpineol mixed solution of Ethyl Cellulose (EC), wherein the volume ratio of the ethanol to the terpineol is (5-30): 1, then adding a CNT/KMO composite fiber 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 fiber is 1 (1-9), stirring for 0.5 hour, and then placing the mixed system in an oil bath at 95-105 ℃ for stirring and heating to remove the ethanol to obtain ink, wherein the ink contains CNT/KMO/G/EC;
5) The CNT/KMO/G/EC ink is coated on a hard substrate such as stainless steel foil or titanium foil in a scraping way, 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, thus obtaining the CNT/KMO/G composite anode material.
Example 1:
1) 200mg of carbon nano tube is added into 250mL of 5M nitric acid solution, heated, stirred and refluxed for 24 hours at 80 ℃, washed to be neutral by deionized water, and dried to obtain the carbon nano tube with surface treatment;
2) Dispersing 50mg of the surface-treated carbon nano tube in 150mL of 3mg/mL potassium permanganate solution, stirring for 1 hour at room temperature, transferring to 3 100mL hydrothermal reaction kettles, reacting for 5 hours at 120 ℃, and naturally cooling to room temperature;
3) Centrifuging and washing the product obtained in the step 2) with deionized water for 7 times, and then cooling and drying at 50 ℃ below zero for 24 hours to obtain a CNT/KMO composite fiber, wherein an X-ray diffraction spectrum is shown as a graph in figure 1, the graph in figure 1 shows that the obtained material is of a birnessite type manganese dioxide structure, meanwhile, a transmission electron microscope photo of the obtained material is shown as a core-shell structure of CNT@KMO in figure 2, wherein the diameter of the inner CNT is about 30nm, an outer KMO layer grows on the surface of the CNT along an out-of-plane orientation in an array manner, the birnessite nano-sheet has a good porous structure, and the thickness of the shell layer is about 30nm;
4) Dispersing 15mg of high-conductivity graphene (with the thickness of <3 nm) in 20mL of 0.67mg/mL Ethyl Cellulose (EC) ethanol and terpineol mixed solution, 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, and then placing in an oil bath at the temperature of 100 ℃ for stirring and heating to remove the ethanol to obtain CNT/KMO/G/EC ink;
5) The CNT/KMO/G/EC ink is coated on a stainless steel foil in a blade mode, then vacuum drying is carried out for 10 hours at 80 ℃, and ethyl cellulose is removed after air annealing is carried out for 2 hours at 300 ℃, so that the CNT/KMO/G composite anode material can be obtained, the microstructure of the CNT/KMO composite anode material is shown as figure 3, wherein the CNT/KMO composite fiber is uniformly dispersed and embedded in graphene, and the uniform CNT/KMO/G multi-stage composite anode material is formed.
Example 2:
1) Spreading the carbon nano tube on a glass substrate, and treating the surface of the carbon nano tube in air for 8 minutes under the conditions of 0.3torr and 50W by using oxygen plasma to obtain a surface treated carbon nano tube;
2) Dispersing 60mg of the surface-treated carbon nano tube in 180mL of 3mg/mL potassium permanganate solution, stirring for 1 hour at room temperature, transferring to 4 100mL hydrothermal reaction kettles, reacting for 6 hours at 130 ℃, and naturally cooling to room temperature;
3) Centrifuging and washing the product obtained in the step 2) by using deionized water for 8 times, and then cooling and drying at 55 ℃ below zero for 20 hours to obtain the CNT/KMO composite fiber;
4) Dispersing 10mg of high-conductivity graphene (with the thickness of <3 nm) in 30mL of 0.67mg/mL Ethyl Cellulose (EC) ethanol and terpineol mixed solution, wherein the volume ratio of the ethanol to the terpineol is 20:1, adding 40mg of CNT/KMO composite fiber, stirring for 0.5 hour, and then placing in an oil bath at the temperature of 95 ℃ for stirring and heating to remove the ethanol to obtain CNT/KMO/G/EC ink;
5) And (3) scraping the CNT/KMO/G/EC ink on a titanium foil, then drying the titanium foil in vacuum at 85 ℃ for 9 hours, and then annealing the titanium foil at 290 ℃ for 2.5 hours in air to remove ethyl cellulose, thus obtaining the CNT/KMO/G composite anode material.
The invention relates to an application of a hierarchical carbon nano tube/birnessite/graphene composite positive electrode material in a chargeable water system zinc ion battery, which comprises the following specific steps:
1) Cutting the CNT/KMO/G multistage composite positive electrode material obtained in the embodiment 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 the positive electrode is immersed in an aqueous electrolyte, and if the substrate is corroded or electrochemically reacted, the stability and safety of the battery are adversely affected. Stainless steel foil, titanium foil, and carbonaceous substrates (e.g., carbon paper, carbon cloth, carbon felt, etc.) are all desirably 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 wafer with the diameter of 12mm to obtain a water-based zinc ion battery cathode;
3) Weighing ZnSO with proper mass 4 And MnSO 4 Adding proper deionized water to prepare 2M ZnSO 4 +0.2M MnSO 4 Obtaining an electrolyte of the water-based zinc ion battery;
4) Commercial glass fibers (Whatman GF/D47 mm) were cut into 19mm discs to give separators;
5) Using 2032 button battery case, assembling the battery according to the sequence of positive electrode, electrolyte (40 μl), diaphragm, electrolyte (40 μl), negative electrode, gasket and spring, sealing, standing for 12 hr, and performing electrochemical test;
6) The charge and discharge curves of a typical battery are shown in fig. 4, the discharge plateau is around 1.4V and 1.3V, respectively, and it can be seen from tables 1 and 2 that the composite cathode material has good rate performance and cycle stability, respectively.
Table 1 rate performance of typical battery
| 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 cycle performance of typical cells 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 (3)
1. Preparation method of hierarchical carbon nanotube/birnessite/graphene composite positive electrode material, wherein birnessite is K x MnO 2 •yH 2 O, characterized by comprising the steps of:
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) (2-6), obtaining a dispersion liquid, stirring the dispersion liquid for 1 hour at room temperature, transferring the dispersion liquid into a hydrothermal reaction kettle, preserving heat for 5-6 hours at 110-130 ℃, naturally cooling to room temperature, and washing a product in the reaction liquid to obtain a precipitate;
step 2, freeze-drying the precipitate to obtain the carbon nano tube/K x MnO 2 •yH 2 O composite fiber, according to the mass ratio of 1 (1-9), graphene and carbon nano tube/K x MnO 2 •yH 2 The O composite fiber is dispersed in a mixed solution of ethyl cellulose, ethanol and terpineol, wherein the volume ratio of the ethanol to the terpineol is (5-30): 1, the mass ratio of graphene to the ethyl cellulose is (1-4): 1, a mixed system is obtained, the concentration of graphene in the mixed system is 0.5-2 mg/mL, and the concentration of the ethyl cellulose in the mixed system is 0.5-2 mg/mL;
and 3, stirring the mixed system for 0.5 hour, then placing the mixed system in an oil bath with the temperature of 95-105 ℃ for stirring and heating to remove ethanol to obtain ink, then scraping the ink on a stainless steel foil or a titanium foil, drying the ink in vacuum at the temperature of 75-85 ℃ for 8-12 hours, and then annealing the ink for 1-3 hours at the temperature of 280-320 ℃ to obtain the carbon nano tube/birnessite/graphene composite positive electrode material with a hierarchical structure, wherein the inner layer of the composite positive electrode material is a carbon nano tube, the middle layer is a birnessite layered nano sheet, the nano sheet grows on the surface of the carbon nano tube in an array shape, and the outermost layer is graphene.
2. The method for preparing the hierarchical carbon nanotube/birnessite/graphene composite positive electrode material according to claim 1, wherein the step 1 is to subject the carbon nanotube to nitric acid or plasma treatment to obtain the surface-treated carbon nanotube.
3. The method for preparing the hierarchical carbon nanotube/birnessite/graphene composite positive electrode material according to claim 1, wherein the step 2 is characterized in that the precipitate is freeze-dried for 15-36 hours to obtain the carbon nanotube/birnessite composite fiber.
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