CN111383847A - Preparation method of graphene-loaded metal oxide electrode material - Google Patents
Preparation method of graphene-loaded metal oxide electrode material Download PDFInfo
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- CN111383847A CN111383847A CN202010217646.0A CN202010217646A CN111383847A CN 111383847 A CN111383847 A CN 111383847A CN 202010217646 A CN202010217646 A CN 202010217646A CN 111383847 A CN111383847 A CN 111383847A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
Abstract
The invention discloses a preparation method of a graphene loaded metal oxide electrode material, which comprises the following steps: dissolving metal salt in a mixed solution of ethanol and ethylene glycol, adding a graphene oxide aqueous solution into the mixed solution, and performing ultrasonic treatment to obtain a uniform GO/metal salt suspension; and (3) taking cleaned foamed nickel, foamed copper and the like, aluminum foil or copper foil as a substrate and a current collector, and coating the suspension on the surface of the metal by an ultrasonic spraying method to obtain the graphene loaded metal oxide electrode material. The metal oxide formed in situ is uniformly distributed on the surface of the graphene, and the electrode material shows good pseudo-capacitance performance. The invention avoids using a binder and does not need annealing treatment, and the electrode preparation process is simple and convenient and is easy to realize batch preparation.
Description
Technical Field
The invention relates to a method for preparing a graphene loaded metal oxide electrode material, and belongs to the technical field of preparation of graphene composite materials.
Background
With the development of modern science and technology, energy and environmental problems gradually become important problems for sustainable development of human society. The traditional fossil fuel has limited reserves, and the waste gas generated by combustion can seriously pollute the environment and cause greenhouse effect, so the clean and renewable new energy technology becomes the focus of attention of people. A super capacitor, also called an electrochemical capacitor, is a novel energy storage device between a conventional capacitor and a secondary battery, and has the advantages of fast charging and discharging speed, long cycle life, wide temperature range, high safety, environmental friendliness and the like, and thus has attracted much attention.
Graphene is a single-layer two-dimensional atomic crystal, and has the advantages of high specific surface area, good conductivity, good chemical and thermal stability and the like, so that the graphene is considered to be an ideal electrode material of a super capacitor. However, a pure graphene electrode only stores energy through an electric double layer mechanism, and the specific capacitance and energy density of the device can not meet the actual requirements. In addition, due to pi-pi interaction existing between graphene sheets, the graphene sheets are easy to re-stack and agglomerate in the actual use process. Transition metal oxides, as a typical pseudocapacitance material, have the advantages of high specific capacitance, low cost, and the like, and thus have been widely studied in recent years. However, the rate performance and the cycling stability of the electrode are not good due to the excessively low conductivity of the metal oxide, so that the practical application of the electrode in a super capacitor is restricted. Therefore, the development of the graphene/metal oxide composite electrode material with high performance and low cost has important significance.
Luo Yazi et al published "ports NiCo" at Electrochemical Acta 2014, Vol 132, 332-2O4-reduced graphene oxide(rGO)composite with superior capacitance retention for super capacitors, spraying a mixed solution of nickel salt, cobalt salt and GO onto a heated nickel foam surface by electrospray and preparing porous rGO/NiCo by post annealing2O4A nanocomposite electrode. However, the electrospray method not only has a very low spray rate, but also requires a long time of annealing to obtain the final electrode material, so that the production efficiency is too low to be suitable for large-scale application.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene-loaded metal oxide electrode material, which is used for preparing a composite electrode with graphene uniformly loaded with metal oxide on a foam metal current collector by a simple and efficient process and avoids the use of a binder.
In order to achieve the above object, the present invention provides a method for preparing a graphene-supported metal oxide electrode material, which is characterized by comprising the following steps:
A) preparing GO by adopting a conventional Hummer's method, uniformly dispersing the GO in deionized water, and preparing GO aqueous solution with the concentration of 0.1-0.7 mg/mL;
B) dissolving metal salt in ethanol and glycol solution, mixing with the GO aqueous solution, and performing ultrasonic treatment to obtain a uniform precursor mixed solution; wherein the mass ratio of GO to the metal salt is 1 (1-20);
C) heating the metal current collector to a preset temperature of 300-; wherein the liquid supply rate is 0.1-0.5mL/min, the ultrasonic power is 0.6-1.5W, and the gas pressure is 0.1-0.2 Mpa.
Preferably, the metal salt in step B) is a water-soluble metal salt of a transition metal element.
More preferably, the metal salt is one or more of a nitrate, a sulfate or a chloride.
Preferably, the metal current collector in step C) includes foamed metal such as nickel foam, copper foam, etc., and also includes commercial aluminum foil and copper foil.
Preferably, the loading amount of the reduced graphene oxide (rGO) and the metal oxide on the surface of the current collector in the step C) is 0.2-10mg/cm2。
According to the invention, GO and a metal salt precursor solution are uniformly coated on the surface of a metal current collector by ultrasonic spraying, and a reduced graphene oxide (rGO) electrode uniformly loaded with metal oxides is obtained in one step by rapid volatilization of an organic solvent and thermal reduction of GO at a higher temperature.
The invention has the beneficial effects that:
(1) the electrode preparation process is simple and convenient, can effectively avoid the agglomeration of graphene, avoids using a binder, does not need annealing treatment, can directly prepare the graphene-based composite electrode material by a simple one-step spraying process, and can obtain good electrochemical performance when being used for a super capacitor.
(2) According to the preparation method of the composite electrode, the metal oxide formed in situ is uniformly distributed on the surface of the graphene, the electrode material shows good pseudo-capacitance performance, the process is simple and convenient, the loading capacity of active substances is high, and the large-scale preparation is facilitated.
Drawings
FIG. 1 is the rGO/NiCo example 12O4An X-ray diffraction pattern of the composite electrode;
FIG. 2 is the rGO/NiCo example 12O4Scanning electron microscope photographs of the composite electrode;
FIG. 3 is the rGO/NiCo example 12O4EDS elemental profile of the composite electrode;
FIG. 4a is rGO/NiCo example 12O4CV curve of the composite electrode;
FIG. 4b is the rGO/NiCo example 12O4GCD curve of the composite electrode;
FIG. 5 is the rGO/NiCo example 12O4The cycle stability curve of the composite electrode at a current density of 10A/g.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
[ example 1 ] rGO/NiCo2O4Composite electrode
Preparing 200mL of 0.7mg/mL GO aqueous solution by using 1 wt% GO raw material slurry;
step 2. preparation of precursor solution
Taking the mass ratio of GO to metal salt as 1: 5 example, 0.23g of Ni (NO) was weighed3)2·6H2O and 0.46g Co (NO)3)2·6H2Dissolving O in 16mL of ethanol and 64mL of ethylene glycol, and adding 200mL of the prepared GO aqueous solution; mixing for 2h under the assistance of ultrasound to obtain a uniform precursor mixed solution;
Firstly, fixing foamed nickel on the surface of a heating table, and heating to 400 ℃; then, the prepared precursor mixed solution is loaded into a needle cylinder, the liquid inlet speed is set to be 0.5mL/min, the carrier gas pressure is set to be 0.2MPa, and the power of an ultrasonic atomization nozzle is adjusted between 0.6W and 1.5W until uniform spraying is obtained; when ultrasonic spraying is started, the spray head moves at the speed of 2mm/s to spray the surface of the sample, the distance between spraying strokes is 2mm, and the rGO/NiCo is obtained2O4A composite electrode material;
step 4, sample characterization and electrochemical performance test
After the spraying is finished, the prepared rGO/NiCo is subjected to2O4And carrying out structure, appearance characterization and electrochemical performance test on the composite electrode.
First, the crystal structure of the prepared sample was analyzed by an X-ray diffraction method. FIG. 1 is the rGO/NiCo example 12O4X-ray diffraction patterns of the composite electrode. Except for three diffractions from Ni substrateThe peaks, the remaining diffraction peaks correspond to the spinel-structured NiCo2O4And (4) phase(s).
FIG. 2 is the rGO/NiCo example 12O4Scanning electron microscope photographs of the composite electrode. It can be clearly seen that the surface of the composite electrode is rough and exhibits a typical wrinkled morphology.
FIG. 3 is the rGO/NiCo example 12O4EDS elemental profile of the composite electrode. It can be seen that the elements Co, Ni, C and O are uniformly distributed throughout the sample.
Pt, Hg/HgO and the prepared sample are respectively used as a counter electrode, a reference electrode and a working electrode to form a three-electrode system, and electrochemical test is carried out in 2mol/L KOH solution. FIG. 4 is the rGO/NiCo example 12O4CV curve and GCD curve of the composite electrode. (a) The figure is a CV curve of the composite electrode under different scanning rates, and an obvious oxidation reduction peak can be observed, which indicates that the pseudocapacitance metal oxide in the electrode material participates in the charge-discharge process. Calculation of rGO/NiCo from the GCD curve of graph (b)2O4The mass specific capacitance of the composite electrode can reach 1086F/g at most.
FIG. 5 is the rGO/NiCo example 12O4Cycling stability curve of the composite electrode at a current density of 10A/g. The electrode has a capacity retention rate of about 97.4% after 3000 times of charge and discharge at a current density of 10A/g, and shows excellent cycle stability.
[ example 2 ] rGO/NiFe2O4Composite electrode
Preparing 200mL of 0.1mg/mL GO aqueous solution by using 1 wt% GO raw material slurry;
step 2. preparation of precursor solution
Taking GO and metal salt with a mass ratio of 1:10 as an example, 0.47g of Ni (NO) is weighed3)2·6H2O and 0.94g Fe (NO)3)2·9H2Dissolving O in 16mL of ethanol and 64mL of ethylene glycol, adding 200mL of the prepared GO aqueous solution, and mixing for 2h under the assistance of ultrasound to obtain a uniform precursor mixed solution;
Firstly, fixing the foam copper on the surface of a heating table, and heating to 350 ℃; then, the prepared precursor mixed solution is loaded into a needle cylinder, the liquid inlet speed is set to be 0.3mL/min, the carrier gas pressure is set to be 0.15MPa, and the power of an ultrasonic atomization nozzle is adjusted between 0.6W and 1.5W until uniform spraying is obtained; when ultrasonic spraying is started, the spray head moves at the speed of 2mm/s to spray the surface of a sample, the distance between spraying strokes is 2mm, and rGO/NiFe is obtained2O4A composite electrode material.
rGO/NiFe obtained according to the preparation method implemented in the example2O4The electrode has a specific capacitance of up to 320F/g in 2M KOH solution.
[ example 3 ] rGO/CoO composite electrode
Preparing 200mL of 0.35mg/mL GO aqueous solution by using 1 wt% GO raw material slurry;
step 2. preparation of precursor solution
Taking GO and metal salt with the mass ratio of 1:15 as an example, 2.1g of Co (NO) is weighed3)2·6H2Dissolving O in 80mL of ethanol, adding 200mL of the prepared GO aqueous solution, and mixing for 2h under the assistance of ultrasound to obtain a uniform precursor mixed solution;
Firstly, fixing a cleaned copper foil on the surface of a heating table, and heating to 500 ℃; and then, filling the prepared precursor mixed solution into a needle cylinder, setting the liquid inlet speed to be 0.1mL/min, setting the carrier gas pressure to be 0.1MPa, and adjusting the power of an ultrasonic atomizing nozzle between 0.6 and 1.5W until uniform spraying is obtained. When ultrasonic spraying is started, the spray head moves at the speed of 2mm/s to spray the surface of a sample, and the distance between spraying strokes is 2mm, so that the rGO/CoO composite electrode material is obtained;
the rGO/CoO composite electrode obtained by the preparation method implemented in the embodiment has the mass specific capacitance of 170F/g at most in a 2M KOH solution.
Claims (5)
1. A preparation method of a graphene-loaded metal oxide electrode material is characterized by comprising the following steps:
A) preparing GO by adopting a conventional Hummer's method, uniformly dispersing the GO in deionized water, and preparing GO aqueous solution with the concentration of 0.1-0.7 mg/mL;
B) dissolving metal salt in ethanol and glycol solution, mixing with the GO aqueous solution, and performing ultrasonic treatment to obtain a uniform precursor mixed solution; wherein the mass ratio of GO to the metal salt is 1 (1-20);
C) heating the metal current collector to a preset temperature of 300-; wherein the liquid supply rate is 0.1-0.5mL/min, the ultrasonic power is 0.6-1.5W, and the gas pressure is 0.1-0.2 Mpa.
2. The method for preparing the graphene-supported metal oxide electrode material according to claim 1, wherein the metal salt in the step B) is a water-soluble metal salt of a transition metal element.
3. The method for preparing the graphene-supported metal oxide electrode material according to claim 2, wherein the metal salt is one or more of nitrate, sulfate or chloride.
4. The method for preparing the graphene-supported metal oxide electrode material according to claim 1, wherein the metal current collector in the step C) comprises one of nickel foam, copper foam, commercial aluminum foil, or commercial copper foil.
5. The method for preparing the graphene-supported metal oxide electrode material according to claim 1, wherein the loading amount of the reduced graphene oxide and the metal oxide on the surface of the current collector in the step C) is 0.2-10mg/cm2。
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Citations (4)
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CN103094540A (en) * | 2013-01-06 | 2013-05-08 | 中物院成都科学技术发展中心 | Method for compounding graphene and metallic oxide/metallic compound and composite material thereof |
CN105492126A (en) * | 2013-03-14 | 2016-04-13 | 纳米技术仪器公司 | Ultrasonic spray coating of conducting and transparent films from combined graphene and conductive nano filaments |
CN109734056A (en) * | 2019-03-08 | 2019-05-10 | 上海理工大学 | Metal oxide/preparation method of fold rGO composite nano materials and the preparation method of fold nano-metal-oxide |
US20190355985A1 (en) * | 2017-02-09 | 2019-11-21 | Korea Institute Of Geoscience And Mineral Resources | Method for preparing silicon-carbon-graphene composite, composite prepared according thereto, and secondary battery to which same is applied |
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Patent Citations (4)
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CN103094540A (en) * | 2013-01-06 | 2013-05-08 | 中物院成都科学技术发展中心 | Method for compounding graphene and metallic oxide/metallic compound and composite material thereof |
CN105492126A (en) * | 2013-03-14 | 2016-04-13 | 纳米技术仪器公司 | Ultrasonic spray coating of conducting and transparent films from combined graphene and conductive nano filaments |
US20190355985A1 (en) * | 2017-02-09 | 2019-11-21 | Korea Institute Of Geoscience And Mineral Resources | Method for preparing silicon-carbon-graphene composite, composite prepared according thereto, and secondary battery to which same is applied |
CN109734056A (en) * | 2019-03-08 | 2019-05-10 | 上海理工大学 | Metal oxide/preparation method of fold rGO composite nano materials and the preparation method of fold nano-metal-oxide |
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