CN110817851A - Preparation method of multi-edge graphene and aluminum ion battery prepared by same - Google Patents
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Abstract
The invention discloses a preparation method of polygonal graphene and an aluminum ion battery prepared by the method, wherein the preparation method comprises the following steps: removing the oxide layer on the surface of the nickel particles and connecting the nickel particles with each other; then growing graphene on the surfaces of the flaky nickel particles to form a nickel net structure covering the graphene; covering a layer of PMMA (polymethyl methacrylate) on the surface of the nickel net structure covered with the graphene to obtain a PMMA/graphene/nickel net structure; removing the metal nickel by using acid to obtain a PMMA/graphene structure sample; and finally, removing PMMA to obtain the multi-edge graphene. According to the invention, the nickel particles are used as the template and the catalyst to prepare the independent multi-edge graphene with improved energy density, excellent mechanical strength and excellent conductivity at low temperature through a chemical vapor deposition process, the graphene is an excellent anode material of the rechargeable aluminum ion battery, the method realizes low energy consumption and low cost, large-scale mass production is facilitated, and the aluminum ion battery based on the multi-edge graphene has a wide working temperature range and high coulombic efficiency.
Description
Technical Field
The invention relates to the technical field of graphene electrode materials and aluminum ion batteries, in particular to a preparation method of multi-edge graphene and an aluminum ion battery prepared by the same.
Background
In order to meet the urgent need of the high-efficiency large-scale energy storage industry, the development of advanced energy storage devices has been receiving attention all the time. Among the various emerging batteries, Lithium Ion Batteries (LIBs) have been widely used, although they have high costs, safety problems, and scarce lithium metal resources in the natural world. On the other hand, Aluminum Ion Batteries (AIBs) may be an ideal energy storage device because of their high theoretical capacity, abundant resources, low cost, and safety of aluminum metal cathodes. However, conventional Aluminum Ion Batteries (AIBs) have problems of short cycle life and low discharge voltage. These factors result in Aluminum Ion Batteries (AIBs) still being unable to compete with lithium ion batteries and supercapacitors. To solve these problems, a great deal of research has been focused on developing new cathode materials, including, for example, carbon, transition metal oxide and sulfide-based materials. Through these efforts, the performance of the positive electrode is significantly improved. Nevertheless, these materials still do not meet the needs of practical applications because the complex synthesis process and lower capacity prevent the large-scale manufacture of their commercial batteries. Therefore, the development of advanced Aluminum Ion Batteries (AIBs) and new electrode materials has been considered to be of great importance.
In recent years, graphene has proven promising as an electrode material for aluminum ion batteries because it has not only good mechanical properties but also high electronic conductivity. The good mechanical property can keep the volume change of the electrode in the circulation process to keep the structural integrity, and the high electronic conductivity provides a quick channel for electronic transmission, so that the circulation stability of charge and discharge under high current density is improved. The graphene preparation methods reported at present are all prepared at a high temperature of 1000 ℃, and have the disadvantages of high energy consumption and high production cost. Therefore, it is still a great challenge to prepare high-quality graphene as a rechargeable aluminum ion battery anode by using a low energy consumption method.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of multi-edge graphene, which can realize low energy consumption and low cost production and is beneficial to large-scale mass production, and an aluminum ion battery prepared by the preparation method.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of polygonal border graphene comprises the following steps:
removing the oxide layer on the surface of the nickel particles and connecting the nickel particles with each other;
growing graphene on the surfaces of the flaky nickel particles to form a nickel net structure covering the graphene;
covering a layer of PMMA (polymethyl methacrylate) on the surface of the nickel net structure covered with the graphene to obtain a PMMA/graphene/nickel net structure;
removing the metal nickel by using acid to obtain a PMMA/graphene structure sample;
and removing the PMMA to obtain the multi-edge graphene.
Further, the method for removing the oxide layer on the surface of the nickel particles and interconnecting the nickel particles comprises the steps of using the nickel particles as a three-dimensional template and a catalyst, namely cleaning the nickel particles, putting the nickel particles into a quartz boat and putting the quartz boat into a horizontal tube furnace, heating the quartz boat to the temperature of 400 ℃ and 650 ℃ under vacuum, continuously introducing argon and hydrogen, annealing for 10-20min at constant temperature, removing the oxide layer on the surface of the nickel particles and continuously interconnecting the nickel particles.
Further, the nickel particle size is 200nm to 4000nm, and it is further preferable that the nickel particle size is 1 to 3um in view of production cost and energy consumption.
Furthermore, the flow rate of the argon gas introduced into the tube furnace is 600-800sccm, and the flow rate of the hydrogen gas is 70-100 sccm.
Further, introducing methane gas with a certain flow into the reaction tubular furnace and continuously introducing the gas for 3-10min for growing the graphene on the surfaces of the flaky nickel particles; then the methane gas is closed, and the mixture is rapidly cooled to room temperature under the environment of 600-800sccm argon gas and 70-100sccm hydrogen gas at the rate of 150-250 ℃ min < -1 >.
Further, the flow rate of the methane gas introduced into the tubular furnace for reaction is 20-40 sccm.
Further, the method for covering a layer of PMMA on the surface of the nickel net structure covered with the graphene is to dropwise coat the nickel particles covered with the graphene on the surface with 4.5% polymethyl methacrylate solution (the solvent is acetyl butanone), and then bake the nickel particles covered with the graphene at the temperature of 100-120 ℃ for 20-60min to completely cure the PMMA, so that the PMMA/graphene/nickel net structure is obtained.
Further, the method for removing the metal nickel by using the acid comprises the step of etching the PMMA/graphene/nickel net sample obtained in the step of obtaining a PMMA/graphene structure sample in a hydrochloric acid (HCl) solution of 2-5m at the temperature of 70-90 ℃ for 4-8h to remove nickel.
Further, the method for removing PMMA comprises the steps of treating the PMMA/graphene structure sample obtained in the previous step with acetone vapor at the temperature of 50-60 ℃ for 0.5-2h, finally rinsing with clear water, and freeze-drying to obtain pure polygonal graphene.
The aluminum ion battery prepared from the multi-edge graphene adopts the multi-edge graphene as a positive electrode, an aluminum foil as a negative electrode and glass fiber as a diaphragm, the electrolyte adopts a solvent of 1-ethyl-3-methylimidazole chloride, and the electrolyte adopts aluminum chloride salt ([ EMIm)]Cl/AlCl31.3 mol).
The invention provides a multi-edge graphene which is prepared by a Chemical Vapor Deposition (CVD) process at a low temperature (below 600 ℃) by using commercially available nickel particles as a template and a catalyst, and an obtained multi-edge graphene sample which is independent and good in flexibility is an excellent positive electrode material of a rechargeable aluminum ion battery. This novel multi-limbed graphene has the following significant advantages:
(1) the graphene is synthesized at low temperature, so that low-energy consumption and low-cost production can be realized, and large-scale mass production is facilitated;
(2) compared with a CVD method for preparing graphene by using foamed nickel as a template, the small-sized nickel particles have higher surface area to volume ratio, are beneficial to adsorbing more carbon atoms in the CVD process, and can promote the activity of the surface atoms by high surface energy and effectively increase the deposition amount of graphene.
(3) The multilateral graphene, which facilitates surface compression, exhibits excellent flexibility and bendability with an areal density of about 1.5 to 2.5mg cm-2。
(4) The aluminum ion battery based on the multi-edge graphene has the advantages that the graphene is used as a continuous electron conduction substrate, the multi-edge and interconnected structures effectively increase large current transmission, and active sites for embedding/de-embedding aluminum tetrachloride anions are effectively increased. Therefore the multi-edge graphene positive electrode was at 8000mA g even after long (20000) cycles-1Still obtain high capacity (90mAh g) at high current density-1) And high coulombic efficiency (>99.2％)。
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of the preparation of multi-limbed graphene according to the present invention;
FIG. 2 is a schematic diagram of a process for preparing multi-limbed graphene according to the present invention;
FIG. 3 is an SEM photograph of a polygonal border graphene provided by the present invention;
FIG. 4 is a schematic diagram of the flexibility exhibited by multilateral graphene provided in accordance with the present invention after compression;
FIG. 5 is a diagram of the electrochemical performance of the multi-limbed graphene applied to the anode of an aluminum-ion battery according to the present invention;
FIG. 6 is a temperature performance diagram of the cycling of the multi-limbed graphene applied to the anode of an aluminum-ion battery at different temperatures, according to the present invention;
fig. 7 is a schematic diagram of a mechanism study of the aluminum-ion battery based on the multi-edge graphene provided by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1 and 2, a method for preparing polygonal border graphene comprises the following steps:
s01, removing an oxidation layer on the surface of the nickel particles and connecting the nickel particles with each other, using the nickel particles as a three-dimensional template and a catalyst, namely cleaning the commercially available nickel particles, putting the nickel particles into a quartz boat and putting the quartz boat into a horizontal tube furnace, then heating the quartz boat to the temperature of 400 ℃ and 650 ℃ under vacuum, then continuously introducing argon and hydrogen, annealing for 10-20min at constant temperature, removing the oxidation layer on the surface of the nickel particles and continuously connecting the nickel particles with each other, wherein the size of the nickel particles is 200nm-4000nm, the further preferable size of the nickel particles is 1-3um in view of production cost and energy consumption, the flow of argon introduced into the tube furnace is 800sccm and the flow of hydrogen is 70-100 sccm;
s02, growing graphene on the surface of the flaky nickel particles to form a nickel net structure covering the graphene, introducing methane gas with a certain flow into the reaction tube furnace, continuously introducing the methane gas for 3-10min, then closing the methane gas, and performing 150-250 ℃ min in an environment of 600-800sccm argon gas and 70-100sccm hydrogen gas-1Rapidly cooling to room temperature at the speed of (1), wherein the flow rate of the methane gas introduced into the tubular furnace for reaction is 20-40 sccm;
s03, covering a layer of PMMA on the surface of the nickel net structure covered with the graphene, dripping 4.5% of polymethyl methacrylate solution (the solvent is acetyl butanone) on the nickel particles covered with the graphene, and then baking for 20-60min at the temperature of 100-120 ℃ to completely cure the PMMA to obtain a PMMA/graphene/nickel net structure;
s04, removing metallic nickel by using acid, and etching the obtained PMMA/graphene/nickel screen sample in a hydrochloric acid (HCl) solution of 2-5m at the temperature of 70-90 ℃ for 4-8h to remove nickel, so as to obtain a PMMA/graphene structure sample;
and S05, removing PMMA to obtain high-quality multi-edge graphene, treating the PMMA/graphene structure sample obtained by the above step for 0.5-2h by using acetone vapor at the temperature of 50-60 ℃, and finally rinsing by using clear water and freeze-drying to obtain pure multi-edge graphene.
The invention also provides an aluminum ion battery prepared by adopting the multi-edge graphene, wherein the multi-edge graphene is adopted as a positive electrode of the aluminum ion battery, an aluminum foil is adopted as a negative electrode, glass fiber is adopted as a diaphragm, the electrolyte adopts a solvent 1-ethyl-3-methylimidazole chloride, and the electrolyte adopts an aluminum chloride salt ([ EMIm)]Cl/AlCl31.3 mol). The aluminum ion battery adopts nickel foil as the current collectors of the positive electrode and the negative electrode, and the bag-type aluminum ion battery is assembled in a glove box filled with argon.
Example 1
A preparation method of polygonal border graphene comprises the following steps:
s01, removing the surface oxide layer of the nickel particles and connecting the nickel particles with each other: using 2um nickel particles as a three-dimensional template and a catalyst, putting the nickel particles into a quartz boat, putting the quartz boat into a horizontal tube furnace, heating the quartz boat to 600 ℃ under vacuum, continuously introducing 700sccm argon and 80sccm hydrogen, annealing for 15min at a constant temperature, removing an oxide layer on the surfaces of the nickel particles and continuously connecting the nickel particles with one another;
s02, growing graphene on the surfaces of the flaky nickel particles to form a graphene-covered nickel net structure: introducing 30sccm of methane gas into the reaction tubular furnace, and continuously introducing the gas for 5 min; then closing the methane gas, and rapidly cooling to room temperature at the speed of 200 ℃ min < -1 > in the environment of 700sccm argon gas and 80sccm hydrogen gas;
s03, covering a layer of PMMA on the surface of the nickel net structure covered with the graphene: dropwise coating 4.5% polymethyl methacrylate solution (solvent is acetyl butanone) on the nickel particles with the surfaces covered with the graphene, and then baking for 30min at 110 ℃ to completely cure the PMMA to obtain a PMMA/graphene/nickel net structure;
s04, removing metallic nickel by acid: etching the PMMA/graphene/nickel net sample obtained in the above step in a 3m hydrochloric acid (HCl) solution at 80 ℃ for 5 hours to remove nickel, so as to obtain a PMMA/graphene structure sample;
s05, removing PMMA: and (4) treating the sample obtained in the step S04 with acetone vapor at 550 ℃ for 1h, finally rinsing with clear water and freeze-drying to obtain pure polygonal graphene.
As can be seen from the SEM photograph of the multi-edge graphene of fig. 3, the graphene has rich edges and is connected to each other, and such a structure effectively increases the permeation and ion diffusion rates of the electrolyte, thereby effectively improving the performance thereof in the application of the aluminum ion battery. It can be seen from fig. 4 that the compressed multi-limbed graphene has good flexibility and distortion properties.
Preparing a bag type aluminum ion battery: adopting multi-edge graphene as a positive electrode, aluminum foil as a negative electrode and glass fiber as a diaphragm; the electrolyte is prepared from 1-ethyl-3-methylimidazole chloride serving as a solvent and aluminum chloride salt serving as an electrolyte ([ EMIm)]Cl/AlCl31.3 mol). Nickel foil is used as the current collectors of the positive electrode and the negative electrode, the bag-type aluminum ion battery is assembled in a glove box filled with argon, and the aluminum ion battery is electrifiedAnd (5) characterizing chemical properties.
As can be seen from the electrochemical performance chart of the aluminum ion battery having the positive electrode made of polygonal graphene shown in FIG. 5, a)10mV s-1Cyclic voltammogram of scan rate at
And
the peak at (A) is due to AlCl4 -Is de-intercalated into
And
the peak at (A) is due to AlCl4 -Is embedded. b) Different current densities (200 + 10000 mAg)-1) The results of the charging and discharging curves, the charging and discharging behaviors and the cyclic voltammetry curve are consistent; c) rate capability at different current densities of 2000, 4000, 6000, 8000 and 10000mAg-1The lower have 128, 106, 94, 88 and 84mAh g, respectively-1After multiple cycles, when the current density is restored to 2000, the multi-edge graphene anode can still restore the original capacity, and the coulombic efficiency is higher than 92%, so that excellent rate performance and high coulombic efficiency are shown, which should be due to the unique rich graphene edge and interconnected structure of the multi-edge graphene. d) At 8000mAg-1The cycling stability curve chart of the multi-edge graphene anode under high current density shows that the stable specific discharge capacity reaches 90 +/-3 mAh g after a plurality of activation periods-1. Even after 20000 cycles, the positive electrode capacity retention rate is 100%, the coulombic efficiency is still higher than 99.5%, and excellent cycle stability performance is shown. e) Evaluation results of the fast charging and slow discharging performances of the multi-edge graphene anode: it can be in 10000mAg-1Rapidly charged at 200mAg-1Slowly discharged (charging 100s, discharge time over 4830 s).
It is well known that excellent flexibilitySex is very important for wearable energy storage devices. Fig. 6a) shows two flexible aluminum ion batteries in series powering the LED screen. Low temperature and high temperature stable batteries have fundamental significance in practical applications, from portable electronic products to electric vehicles. We therefore investigated the temperature behavior of aluminum ion batteries again, FIGS. 6b) and c) at a current density of 4000mAg-1Next, charge-discharge and cycle curves of the graphene-rich positive electrode at different temperatures were compared. Due to the thermal stability of the ionic liquid electrolyte, we provided aluminum ion cells with high coulombic efficiencies at low (0 ℃) and high temperatures (60 and 80 ℃ (both above 93%). fig. 6d) because of the ideal positive electrode design, the multi-edge positive electrode was 1000mA g at-25 ℃ for aluminum ion cells-1The specific capacity is higher than 66mAhg-1And there was no decay after 600 cycles.
To further study the insertion/detachment mechanism of tetrachloroaluminate ion, as shown in FIG. 7a), for 10000mAg-1Polygonal keratecan after 2000 cycles at current density were analyzed by SEM and TEM. As shown in fig. 7b) the multi-edged graphene structure remained intact, indicating good stability. Furthermore, fig. 7c) shows TEM elemental mapping of fully charged multi-limbed graphene clearly showing that the Cl and Al elements are uniformly distributed throughout the multi-limbed graphene, again confirming the insertion of the tetra-chloroaluminate ions. Fig. 7d) shows that elemental analysis results show low Cl ion and Al element content in the multi-limbed graphene when fully discharged. These results reveal the mechanism of the insertion/extraction of tetrachloroaluminate ions in our rechargeable aluminum ion cells.
In summary, the present invention produces free standing multi-edge graphene with improved energy density, excellent mechanical strength and excellent electrical conductivity by a low temperature CVD process. The method realizes low energy consumption and low cost, and is favorable for large-scale mass production. Aluminum ion batteries based on multi-edge graphene exhibit high capacity (at 8000 mAg)-1The average value is 90 +/-3 mAh g-1) Excellent cycling stability (capacity retention close to 100% even after 20000 cycles) and excellent rate performance (at 2000 and 10000 mAg)-1128 and 84mAh g are respectively obtained under the current density-1Capacity of (d). In addition, multi-edge graphene-based aluminum-ion batteries have a wide operating temperature range (-25 to 80 ℃) and high coulombic efficiency (over 90%).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for preparing multi-limbed graphene, comprising: the preparation method comprises the following steps:
removing the oxide layer on the surface of the nickel particles and connecting the nickel particles with each other;
growing graphene on the surfaces of the flaky nickel particles to form a nickel net structure covering the graphene;
covering a layer of PMMA (polymethyl methacrylate) on the surface of the nickel net structure covered with the graphene to obtain a PMMA/graphene/nickel net structure;
removing the metal nickel by using acid to obtain a PMMA/graphene structure sample;
and removing the PMMA to obtain the multi-edge graphene.
2. The method of claim 1, wherein the step of preparing the multilateral graphene comprises: the method for removing the oxide layer on the surface of the nickel particles and connecting the nickel particles with each other is to use the nickel particles as a three-dimensional template and a catalyst, namely, the nickel particles are cleaned, put into a quartz boat and put into a horizontal tube furnace, then heated to 400-650 ℃ in vacuum, then continuously introduced with argon and hydrogen, annealed for 10-20min at constant temperature, and the oxide layer on the surface of the nickel particles is removed and the nickel particles are continuously connected with each other.
3. The method of claim 2, wherein: the nickel particle size is 200nm-4000 nm.
4. The method of claim 1, wherein the step of preparing the multilateral graphene comprises: the flow rate of the argon gas introduced into the tube furnace is 600-800sccm, and the flow rate of the hydrogen gas is 70-100 sccm.
5. The method of claim 1, wherein the step of preparing the multilateral graphene comprises: the graphene is grown on the surface of the flaky nickel particles by introducing methane gas with a certain flow into a reaction tube furnace, continuously introducing the gas for 3-10min, then closing the methane gas, and performing 150-250 ℃ min under the environment of 600-800sccm argon gas and 70-100sccm hydrogen gas-1Rapidly cooled to room temperature.
6. The method of claim 5, wherein: the flow rate of the methane gas introduced into the tubular furnace for reaction is 20-40 sccm.
7. The method of claim 1, wherein the step of preparing the multilateral graphene comprises: the method for covering a layer of PMMA on the surface of the nickel net structure covered with the graphene comprises the steps of dropwise coating 4.5% polymethyl methacrylate solution (the solvent is acetyl butanone) on the nickel particles covered with the graphene on the surface, and then baking for 20-60min at the temperature of 100-.
8. The method of claim 1, wherein the step of preparing the multilateral graphene comprises: the method for removing the metal nickel by using the acid comprises the step of etching the PMMA/graphene/nickel screen sample obtained in the step of obtaining a PMMA/graphene structure sample in a hydrochloric acid (HCl) solution of 2-5m at the temperature of 70-90 ℃ for 4-8h to remove nickel.
9. The method of claim 1, wherein the step of preparing the multilateral graphene comprises: the PMMA removing method comprises the steps of treating the PMMA/graphene structure sample obtained in the previous step for 0.5-2h by using acetone vapor at the temperature of 50-60 ℃, finally rinsing by using clear water, and freeze-drying to obtain pure polygonal graphene.
10. The utility model provides an adopt aluminium ion battery of above-mentioned many edge graphene preparation which characterized in that: the aluminum ion battery adopts multi-edge graphene as a positive electrode, aluminum foil as a negative electrode, glass fiber as a diaphragm, the electrolyte adopts 1-ethyl-3-methylimidazole chloride as a solvent, and the electrolyte is prepared from aluminum chloride salt.
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| QINGFENG ZHANG ET AL.: "Low-temperature synthesis of edge-rich graphene paper for high-performance aluminum batteries", 《ENERGY STORAGE MATERIALS》 * |
| 艾书伦等: "石墨烯制备方法的研究进展", 《粘结·工程科技Ⅰ》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111564322A (en) * | 2020-06-10 | 2020-08-21 | 青岛粲耀新材料科技有限责任公司 | Graphene super capacitor for battery |
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