CN110739158A - surface-modified oxygen-containing functional group-containing graphene for super capacitor - Google Patents
surface-modified oxygen-containing functional group-containing graphene for super capacitor Download PDFInfo
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- CN110739158A CN110739158A CN201910897247.0A CN201910897247A CN110739158A CN 110739158 A CN110739158 A CN 110739158A CN 201910897247 A CN201910897247 A CN 201910897247A CN 110739158 A CN110739158 A CN 110739158A
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides surface-modified oxygen-containing functional group-containing supercapacitor graphene materials, and preparation and application thereof.A graphene surface-modified oxygen-containing functional group prevents graphitization and agglomeration among graphene sheets, improves the capability of graphene surface for affinity with electrolyte, and provides pseudo-capacitance capacity by highly reversible redox reaction, so that the graphene is supercapacitor electrode materials with good performance4And NaNO3Concentrated sulfuric acid as oxidant through low-temperature and medium-temperature neutralizationThe graphene provided by the invention has very high specific capacity, good rate performance and ultra-long cycle stability when used as a supercapacitor electrode material, and has broad application prospects in the field of energy storage.
Description
Technical Field
The invention relates to the technical field of electrode materials of supercapacitors, in particular to graphene materials for supercapacitors with surface-modified oxygen-containing functional groups, and preparation and application thereof.
Background
The electrochemical capacitor, also called a super capacitor, has the advantages of orders of magnitude higher power density than a battery, ultra-long cycle life, no potential safety hazard and the like, and has wide application prospect in the fields of high-power equipment such as electric vehicles, high-power electronic equipment, uninterruptible power supplies, new energy power generation temporary storage, pulse power supplies and the like.
Among the numerous carbon-based electrode materials, graphene has a thickness of up to 2630m2Theoretical specific surface area of/g and 6X 103The high conductivity of the graphene is considered to be electric double layer electrode materials with application prospects, and is also a hot spot of the research of the super capacitor nowadays.
The patent adopts graphene surface modified oxygen-containing functional groups to reduce self agglomeration and improve the affinity with electrolyte. The oxygen-containing functional groups on the surface of the graphene can prevent graphitization and agglomeration among graphene sheets and improve the capacity of an affinity electrolyte, so that the graphene keeps more surface active sites and realizes higher utilization rate of the surface active sites, thereby realizing higher performance of the double electric layer super capacitor. Meanwhile, highly reversible redox reaction can be carried out on the oxygen-containing functional groups on the surface of the graphene, so that additional pseudo-capacitor charge storage capacity is provided, and the super-capacitor performance of the graphene is improved.
The patent discloses graphene with surface modified oxygen-containing functional groups and preparation and application thereof, the disclosed graphene obviously reduces graphitized agglomeration through mutual repulsion of the surface oxygen-containing functional groups, good hydrophilicity improves affinity with electrolyte, and simultaneously, the graphene realizes higher super capacitance performance because the reversible redox of the functional groups provides additional charge storage capacity.
Disclosure of Invention
The invention aims to provide graphene materials for a super capacitor, which have low agglomeration performance, good electrolyte affinity, pseudo-capacitance performance for providing additional charge storage capacity, low production cost and surface modification of oxygen-containing functional groups, and also provides methods for preparing the surface modification oxygen-containing functional group graphene materials and application of the super capacitor.
The technical scheme adopted by the invention is as follows:
graphene materials for the supercapacitor with the surface-modified oxygen-containing functional groups, wherein the graphene materials have high specific surface area and high conductivity of common graphene, and the graphene materials with the surface-modified oxygen-containing functional groups can prevent graphitization and agglomeration between adjacent sheets, improve the capacity of affinity electrolyte and provide additional charge storage performance by highly reversible redox reaction, and are supercapacitor electrode materials with good performance.
The preparation method of surface-modified oxygen-containing functional group-containing graphene for the supercapacitor comprises the following steps:
a)3g of graphite and 1.5g of NaNO3Adding 70ml of concentrated sulfuric acid under ice bath condition, stirring uniformly, and adding 9g of KMnO4Ice-cooling for 6-48 h; then heating to 35 ℃, and preserving heat for 6-48 h; deionized water was then added and the mixture was stirred for 6 to 48 hours at 98 ℃. After the reaction was completed, 20ml of 30% by mass H was added2O2And then diluting with dilute hydrochloric acid, performing suction filtration to obtain a filter cake, then performing centrifugal cleaning, and performing ultrasonic treatment to obtain the graphene oxide with high oxidation degree. In the step, the oxidation time of the low-temperature stage, the medium-temperature stage and the high-temperature stage is 10 to 200 times that of the traditional preparation method, and the prepared graphene oxide has higher oxidation degree.
b) The method comprises the steps of fully dispersing graphene oxide with high oxidation degree in a solvent, carrying out hydrothermal treatment at the temperature of 120-250 ℃, carrying out suction filtration and cleaning with water, and carrying out freeze drying to obtain graphene with a surface modified with oxygen-containing functional groups, partially reducing the graphene with high oxidation degree under hydrothermal conditions in the step to convert the graphene oxide into the graphene but not to generate agglomeration due to the residual oxygen-containing functional groups on the surface, wherein the solvent is of water, ethanol and ethylene glycol or a mixed solvent of the solvents according to a proportion of , and the agglomeration in the graphene drying process is prevented by using a freeze drying method.
Compared with the prior art, the graphene material for the surface-modified oxygen-containing functional group supercapacitor adopting the technical scheme has the beneficial effects that:
(1) the preparation method can obtain the graphene with the surface modified with the oxygen-containing functional group.
(2) The oxygen-containing functional groups on the surface of the graphene can prevent graphitization and agglomeration among graphene sheets and improve the capability of an affinity electrolyte, so that the graphene keeps more surface active sites, the utilization rate of the surface active sites is high, and the high performance of the double electric layer super capacitor is realized.
(3) The surface oxygen-containing functional group of the graphene can perform highly reversible oxidation-reduction reaction to provide additional charge storage capacity, and the super-capacitance performance of the graphene is improved.
(4) In the step 1, the oxidation time of the method at the low temperature, the medium temperature and the high temperature is 10 to 200 times that of the traditional method, and the prepared graphene oxide has higher oxidation degree.
(5) Compared with graphene oxide prepared by a traditional method, partial reduction is carried out under the same hydrothermal condition, and the graphene obtained by the method can be uniformly dispersed in a solvent and does not agglomerate.
(6) Compared with the traditional graphene, the graphene prepared by the invention has hydrophilic functional groups on the surface and good affinity with water-system electrolyte.
(7) Compared with the traditional graphene, the graphene surface functional group prepared by the method provided by the invention provides additional pseudo-capacitance performance and has higher charge energy storage capacity.
(8) The method for reducing the graphene oxide does not need to add any reducing agent, does not discharge any harmful chemical components, and is simple and easy, and low in preparation cost and preparation energy consumption.
(9) The graphene prepared by the invention is charged and discharged in a potential range of-1-0V (reference to Hg/HgO), the specific current of 1A/g or the specific discharge capacity of 3mV/s at a scanning rate is more than 300F/g, the current density or the scanning rate can be maintained more than 60% after being increased by 50 times, and the specific capacity retention rate of 20,000 cycles is more than 90%.
Drawings
Fig. 1 is a transmission electron microscope image of graphene oxide according to the present invention.
Fig. 2 is a scanning electron microscope image of the surface-modified graphene containing oxygen functional groups according to the present invention.
Fig. 3 is a transmission electron microscope image of the surface-modified graphene containing oxygen functional groups according to the present invention.
Fig. 4 is a graph of specific capacity versus specific current for graphene according to examples 1, 2, 3, and 4.
Fig. 5 is a plot of specific capacity versus scan rate for graphene according to examples 1, 2, 3, and 4.
Fig. 6 is a graph of the cycling stability of graphene according to example 1.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
a)3g of graphite and 1.5g of NaNO3Adding 70ml of concentrated sulfuric acid under ice bath condition, stirring uniformly, and adding 9g of KMnO4Carrying out ice bath for 12 h; then heating to 35 ℃, and preserving heat for 24 hours; deionized water was then added and the mixture was stirred for 12h at 98 ℃. After the reaction was completed, 20ml of 30% by mass H was added2O2And then diluting with dilute hydrochloric acid, performing suction filtration to obtain a filter cake, then performing centrifugal cleaning, and performing ultrasonic treatment to obtain the graphene oxide with high oxidation degree.
And fully dispersing the graphene oxide prepared in the step into deionized water, performing hydrothermal treatment at the temperature of 200 ℃, performing suction filtration and cleaning with water, and performing freeze drying to obtain the graphene with the surface modified with the oxygen-containing functional group. The mutual repulsion of oxygen-containing functional groups on the surface of graphene prevents the graphitization and agglomeration among graphene sheets, so that a large number of gaps exist among graphene, as shown in fig. 2 and 3.
The specific capacity of the graphene with the surface modified oxygen-containing functional group under the specific current of 1A/g is 339F/g, and the specific capacity is reserved for 70% after the specific current is increased by 50 times; the specific capacity under the scanning rate of 3mV/s is 335F/g, the scanning rate is increased by 50 times, and the specific capacity is reserved by 74 percent; after 20,000 charge-discharge cycles, 90% of the initial capacity can still be retained by the specific capacity.
Example 2
Fully dispersing the graphene oxide prepared in the step of example 1 in deionized water, performing hydrothermal treatment at 180 ℃, performing suction filtration and cleaning with water, and performing freeze drying to obtain graphene with the surface modified with oxygen-containing functional groups.
The specific capacity of the graphene with the surface modified oxygen-containing functional group under the specific current of 1A/g is 321F/g, and the specific capacity is reserved by 71% after the specific current is increased by 50 times; the specific capacity under the scanning rate of 3mV/s is 320F/g, and the scanning rate is increased by 50 times, and the specific capacity is reserved by 77 percent; 95% of the initial capacity can still be retained by the specific capacity after 10,000 charge-discharge cycles.
Example 3
Fully dispersing the graphene oxide prepared in the step of example 1 in deionized water, performing hydrothermal treatment at 140 ℃, performing suction filtration and cleaning with water, and performing freeze drying to obtain graphene with the surface modified with oxygen-containing functional groups.
The specific capacity of the graphene with the surface modified oxygen-containing functional group under the specific current of 1A/g is 330F/g, and the specific capacity is reserved by 67% after the specific current is increased by 50 times; the specific capacity at a scan rate of 3mV/s was 324F/g, with a 50-fold increase in scan rate with 74% specific capacity retention.
Example 4
Fully dispersing the graphene oxide prepared in the step of example 1 in deionized water, performing hydrothermal treatment at 120 ℃, performing suction filtration and cleaning with water, and performing freeze drying to obtain graphene with the surface modified with oxygen-containing functional groups.
The specific capacity of the graphene with the surface modified oxygen-containing functional group under the specific current of 1A/g is 245F/g, and the specific capacity is reserved for 60% after the specific current is increased by 50 times; the specific capacity at a scan rate of 3mV/s was 250F/g, with a 50-fold increase in scan rate with 65% specific capacity retention.
Example 5
a)3g of graphite and 1.5g of NaNO3Adding 70ml of concentrated sulfuric acid under ice bath condition, stirring uniformly, and adding 9g of KMnO4Carrying out ice bath for 6 h; then heating to 35 ℃, and preserving heat for 12 hours; deionized water was then added and the mixture was stirred for 6h at 98 ℃. After the reaction was completed, 20ml of 30% by mass H was added2O2And then diluting with dilute hydrochloric acid, performing suction filtration to obtain a filter cake, then performing centrifugal cleaning, and performing ultrasonic treatment to obtain the graphene oxide with high oxidation degree.
Fully dispersing the graphene oxide prepared in the step into ethanol, performing hydrothermal treatment at the temperature of 180 ℃, performing suction filtration and cleaning with water, and performing freeze drying to obtain the graphene with the surface modified with oxygen-containing functional groups.
Example 6
a)3g of graphite and 1.5g of NaNO3Adding 70ml of concentrated sulfuric acid under ice bath condition, stirring uniformly, and adding 9g of KMnO4Carrying out ice bath for 24 h; then heating to 35 ℃, and preserving heat for 48 hours; deionized water was then added and the mixture was stirred for 24h at 98 ℃. After the reaction was completed, 20ml of 30% by mass H was added2O2And then diluting with dilute hydrochloric acid, performing suction filtration to obtain a filter cake, then performing centrifugal cleaning, and performing ultrasonic treatment to obtain the graphene oxide with high oxidation degree.
And (3) fully dispersing the graphene oxide prepared in the step into ethylene glycol, performing hydrothermal treatment at the temperature of 220 ℃, performing suction filtration and cleaning with water, and performing freeze drying to obtain the graphene with the surface modified with oxygen-containing functional groups.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1, graphene materials for the super capacitor with surface modified oxygen-containing functional groups, which are characterized in that the graphene materials are prepared by partially reducing graphene oxide with high oxidation degree by a high-temperature hydrothermal treatment method, and the graphene surface isSurface modification of oxygen-containing functional groups; graphene oxide with high oxidation degree is dissolved with KMnO4And NaNO3The oxygen-containing functional group can prevent graphitization and agglomeration among graphene sheet layers, improve the affinity for electrolyte on the surface of graphene, and generate highly reversible redox reaction to improve charge storage capacity, so that the graphene is super capacitor electrode active material with good performance.
2. The method for preparing graphene for the supercapacitor with the surface-modified oxygen-containing functional group according to claim 1, comprising the steps of:
a) mixing KMnO4And NaNO3Dissolving in concentrated sulfuric acid under ice bath condition, and then respectively oxidizing graphite for 6-48 h at low temperature, medium temperature and high temperature; and performing suction filtration, centrifugal cleaning and ultrasonic treatment on the product to obtain the graphene oxide with high oxidation degree.
b) And dispersing the graphene oxide in a solvent, performing high-temperature hydrothermal treatment, performing suction filtration and cleaning with water, and performing vacuum freeze drying to obtain the graphene with the surface modified with the oxygen-containing functional group.
3. The process according to claim 2, wherein the oxidation time in the low, medium and high temperature stages is 6 to 48 hours, which is 10 to 200 times that of the conventional process.
4. The method according to claim 2, wherein the solvent is kinds selected from water, ethanol, ethylene glycol, or a mixture thereof at a ratio of .
5. The method according to claim 2, wherein the temperature of the high-temperature hydrothermal treatment is 120 ℃ to 250 ℃.
6. The graphene according to claim 1, wherein the surface of the graphene is modified with oxygen-containing functional groups, so that the graphene can be prevented from agglomerating, the affinity with an electrolyte is promoted, pseudo-capacitance is generated, and the charge storage performance is improved.
7. The graphene according to claim 1, wherein the graphene is prepared by partially reducing graphene oxide with high oxidation degree by a high-temperature hydrothermal treatment method.
8. The graphene oxide with high degree of oxidation according to claim 1, characterized by being prepared by dissolving KMnO4And NaNO3The concentrated sulfuric acid is prepared by oxidizing graphite for a long time in three stages of low temperature, medium temperature and high temperature.
9. The application of the graphene with the surface modified by the oxygen-containing functional group according to claim 1, wherein the graphene with the surface modified by the oxygen-containing functional group has low aggregation and good electrolyte affinity, so that the graphene keeps more surface active sites, higher utilization rate of the surface active sites is realized, and higher electric double layer super-capacitor performance is realized; and the oxygen-containing functional group can introduce pseudo capacitance to provide additional charge storage capacity, so that the material has higher super capacitance performance.
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| CN103130216A (en) * | 2013-03-25 | 2013-06-05 | 四川大学 | Method for large-scale preparation of oxidized graphene and selective adsorption of thorium in water |
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