CN108133830B - A kind of preparation method of graphene/ultramicro active charcoal Particles dispersed electrode material - Google Patents
A kind of preparation method of graphene/ultramicro active charcoal Particles dispersed electrode material Download PDFInfo
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- CN108133830B CN108133830B CN201711441088.0A CN201711441088A CN108133830B CN 108133830 B CN108133830 B CN 108133830B CN 201711441088 A CN201711441088 A CN 201711441088A CN 108133830 B CN108133830 B CN 108133830B
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- graphene
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- carbosphere
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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
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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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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 discloses a kind of graphite/alkene ultramicro active charcoal Particles dispersed electrode materials and preparation method thereof.The composite material is made of graphene and active carbon particle, passes through one step fabricated in situ of liquid laser irradiation method when the composite material.The specific process steps are as follows: firstly, carbon ball is activated followed by potassium hydroxide by the obtained carbosphere of hydro-thermal method；Then carbosphere is dispersed in different solvents from graphene oxide according to different proportion and is irradiated under the conditions of different pulse lasers using pulse laser, and then graphene/ultramicro active charcoal particulate composite is made.Graphene of the invention/ultramicro active carbon composite shows high specific capacity high rate performance when being used as electrode material for super capacitor.This preparation method has many advantages, such as that novel, easy to operate, preparation cost is low, product purity is high.
Description
Technical field
The present invention relates to a kind of preparation method of combination electrode material more particularly to a kind of graphene/ultramicro active charcoals
The preparation method of grain combination electrode material；Belong to field of energy source materials.
Background technique
In recent years, carbon-based material (carbon nano-particle, carbon nanotube, graphene etc.) is with its unique advantage, in super electricity
Container electrode Material Field causes the extensive concern of researcher, especially absorbent charcoal material.The specific surface of absorbent charcoal material
Product, pore structure, particle size and electric conductivity etc. all have an impact to the performance of supercapacitor, wherein the particle ruler in relation to active carbon
Very little and electric conductivity Effective Regulation is still the difficult point studied at present.
Graphene promotes the electric conductivity of active carbon due to being widely used as conductive substrates with good electric conductivity.Example
Such as, Liu et al. people (J. Power Sources 2014, 258, 290-296) graphene/work is prepared for by hydrothermal carbonization method
Property charcoal combination electrode material, under the sweep speed of 1 mV/s, maximum specific capacitance can reach 210 F/g.Although effectively mentioning
The high electric conductivity of active carbon, but this method preparation process is relatively complicated, and the size of active carbon is also difficult to control.Zhao etc.
People (Electrochim. Acta 2016, 189, 22-31.) use method of electrostatic spinning synthesizing graphite alkene/active carbon composite wood
Material, improves the electric conductivity of absorbent charcoal material, accelerates the transfer of electronics in electrode transmission process, to improve the active carbon
The specific capacity of material.But material preparation process is cumbersome, preparation condition is harsh, and the size of active carbon cannot equally regulate and control,
So that the application of the composite material is restricted.
Based on the above research, although can effectively improve the electric conductivity of active carbon by graphene, however, how to regulate and control to subtract
The size of active carbon, is rarely reported in small graphene/absorbent charcoal composite material.Therefore those skilled in the art are dedicated to exploitation one
Kind graphene/ultramicro active charcoal Particles dispersed electrode material and preparation method thereof, this method will be with important scientific research meanings
Justice and application value.
Summary of the invention
Present invention aims at the deficiency for solving above-mentioned existing technology of preparing, a kind of simple, novel graphene/super is provided
The preparation method of micro- activated carbon composite electrode material.The combination electrode material of this method preparation is used as electrode material for super capacitor
When, the specific capacity of the electrode is greatly improved, solves the problems, such as that conventional method is difficult to realize high-purity preparation and high specific capacitance.
To achieve the above object, the present invention provides a kind of graphene/ultramicro active charcoal combination electrode material liquid phases to swash
Photo-irradiation preparation method.The technical solution of the invention is as follows: the carbon material of different proportion being fully ground with potassium hydroxide mixed
It closes, then calcining, washing, are then mixed gained active carbon with graphene oxide by different proportion, in different pulse lasers
Under the conditions of irradiated, finally be made graphene/ultramicro active charcoal Particles dispersed electrode material.
The present invention is achieved through the following technical solutions
The invention discloses a kind of graphene/ultramicro active charcoal Particles dispersed electrode material preparation method, feature exists
In using following steps:
(1) glucose is dissolved in the water, carbosphere is made by hydro-thermal method；
(2) carbosphere and potassium hydroxide are then calcined by different weight ground and mixed more sufficient than progress；Then
It washed, be centrifuged and dried, obtain absorbent charcoal material；
(3) in a solvent, ultrasound is sufficiently mixed for gained absorbent charcoal material and graphene oxide dissolution after will be dry；Institute
State the weight ratio of absorbent charcoal material and graphene oxide are as follows: 90%~99.9%:0.1%~10%；
(4) it using above-mentioned gained mixed solution as liquid phase target, is irradiated under the conditions of pulse laser, the work of laser irradiation
Make condition are as follows: the wavelength nm of 248 nm~1064,1~30 Hz of frequency, energy density is 0.1~10 J pulse-1cm-2, spoke
It is 10~1000 min according to the time；
(5) by acquired solution washing, centrifugation and dry, acquisition graphene/ultramicro active charcoal Particles dispersed electrode material.
The preparation method, it is preferred that the temperature range of hydro-thermal method is 150~200 DEG C in step (1), the reaction time
For 6~24 h.
The preparation method, it is preferred that the temperature that carbosphere is calcined after mixing with potassium hydroxide in step (2) is 600
~900 DEG C, soaking time is 1~5 h.
The preparation method, it is preferred that the weight ratio of carbosphere and potassium hydroxide is 1:1~6 in step (2).
The preparation method, it is preferred that solvent used in step (3) are as follows: water or ethyl alcohol；Absorbent charcoal material and oxidation
The weight percent concentration of graphene in a solvent is 1~10%.
The preparation method, it is preferred that in step (3), the weight ratio of the absorbent charcoal material and graphene oxide are as follows:
92%~96%:8%~4%.
The preparation method, it is preferred that frequency described in step (4) be 5~10 Hz, energy density be 0.1~
0.8 J pulse-1cm-2, irradiation time are 20~100 min.
The preparation method, it is preferred that the particle size of the absorbent charcoal material is 5~500 nm, graphene oxide
The number of plies be 1-10；The specific surface area of combination electrode material is 1000~3000 m2/g.
Compared with prior art, the invention has the benefit that
(1) preparation process of the invention only needs the liquid solution of laser irradiation graphene oxide and active carbon, does not need
The experimental provision of other redox conditions and reagent and complexity, condition is easily-controllable, simple process and low cost, solves often
Advise the problem of preparation process complexity and uncontrollable composite micro-structure and purity.
(2) in graphene/activated carbon composite electrode material of the method for the present invention preparation, active carbon is tight in conjunction with graphene
It is close, and be dispersed on graphene, while the pattern of active carbon, size are controllable.Furthermore graphene has high ratio
Surface area, thus increase the whole energy storage density of composite material.
(3) graphene/activated carbon composite electrode material prepared by the present invention has good electric conductivity and high vibration density
Degree, can greatly improve volume capacity of the electrode material as electrode of super capacitor when.
Make furtherly below with reference to technical effect of the attached drawing to design of the invention, specific material structure and generation
It is bright, to fully understand the purposes, features and effects of the present invention.
Detailed description of the invention
Fig. 1 is graphene/ultramicro active charcoal Particles dispersed electrode material SEM figure prepared by the embodiment of the present invention 1；
Fig. 2 is that graphene/ultramicro active charcoal Particles dispersed electrode material prepared by the embodiment of the present invention 1 is close in different electric currents
Constant current charge-discharge curve under degree；In figure, abscissa is the time, and ordinate is voltage.
Fig. 3 is graphene/ultramicro active charcoal Particles dispersed electrode material high rate performance prepared by the embodiment of the present invention 1
Figure；In figure, abscissa is current density, and ordinate is specific capacity.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out real under premised on the technology of the present invention
It applies, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to the spy being exemplified below
Determine embodiment.
Embodiment 1
6 g glucose sugar are dissolved in 40 ml water, carbosphere is made by hydro-thermal method.The temperature of hydro-thermal method is 180 DEG C,
Reaction time is 12 h.
It weighs 100 mg carbospheres respectively and 400 mg KOH is fully ground high-temperature calcination after mixing in mortar (temperature is
800 DEG C, the time h), is then washed, is centrifuged and is dried for 2, obtains absorbent charcoal material.
Obtained absorbent charcoal material is added in 20 mL ultrapure waters after weighing 5 mg graphene oxides and 95 mg drying respectively,
Ultrasound is fully dispersed by its.
It is 248 nm, energy in wavelength under the lasting stirring of magnetic stirring apparatus using above-mentioned mixed solution as liquid phase target
Density is 500 mJ pulse-1cm-1, frequency be 10 Hz laser under irradiate 60 min；Centrifuge washing, dry after the reaction was completed
It is dry, obtain graphene/ultramicro active charcoal Particles dispersed electrode material.
Obtained graphene/ultramicro active charcoal Particles dispersed electrode material SEM figure is as shown in Figure 1, it can be seen that 50 nm
The active carbon particle of left and right is dispersed in the surface of graphene.The composite material is prepared into working electrode, in three electrode bodies
Under system (platinized platinum is used as to electrode, and Ag/AgCl electrode is as reference electrode, and the aqueous sodium persulfate solution of 1 M is as electrolyte), carry out
Electrochemical property test.For the combination electrode when current density is 0.5 Ag, specific capacitance is 342 F/g；When current density increases
When to 10 A/g, capability value is 246 F/g, and specific capacity conservation rate reaches 71.9%, shows superior high rate performance (such as Fig. 2
With shown in Fig. 3).Meanwhile specific capacity is still able to maintain 91.5% after 5000 charge and discharge, has good cycle life.
Embodiment 2
4 g glucose sugar are dissolved in 40 ml water, carbosphere is made by hydro-thermal method.The temperature of hydro-thermal method is 150 DEG C,
Reaction time is 6 h.
It weighs 100 mg active carbons respectively and 100 mg KOH is sufficiently mixed high-temperature calcination after grinding in mortar (temperature is
600 DEG C, the time h), is then washed, is centrifuged and is dried for 5, obtains absorbent charcoal material.
20 mL of obtained absorbent charcoal material addition are ultrapure after weighing 0.1 mg graphene oxide and 99.9 mg drying respectively
In water, ultrasound is fully dispersed by its.
It is 1064 nm, energy in wavelength under the lasting stirring of magnetic stirring apparatus using above-mentioned mixed solution as liquid phase target
Metric density is 100 mJ pulse-1cm-1, frequency be 30 Hz laser under irradiate 100 min；After the reaction was completed centrifuge washing,
It is dry, obtain graphene/ultramicro active charcoal Particles dispersed electrode material.
In obtained graphene/ultramicro active charcoal Particles dispersed electrode material, active carbon particle is having a size of 5 nm or so
, and it is dispersed in the surface of graphene.The composite material is prepared into working electrode, (platinized platinum is made under three-electrode system
For to electrode, Ag/AgCl electrode is as reference electrode, and the aqueous sodium persulfate solution of 1 M is as electrolyte), carry out chemical property
Test.For the combination electrode when current density is 0.5 Ag, specific capacitance is 381 F/g；When current density increases to 10 A/g,
Its capability value is 355 F/g, and specific capacity conservation rate reaches 93.1%, shows superior high rate performance.Meanwhile 5000 charge and discharges
Specific capacity is still able to maintain 99.2% after electricity, has good cycle life.
Embodiment 3
8 g glucose sugar are dissolved in 40 ml water, carbosphere is made by hydro-thermal method.The temperature of hydro-thermal method is 200 DEG C,
Reaction time is 24 h.
It weighs 100 mg active carbons respectively and 600 mg KOH is sufficiently mixed high-temperature calcination after grinding in mortar (temperature is
900 DEG C, the time h), is then washed, is centrifuged and is dried for 1, obtains absorbent charcoal material.
20 mL ultrapure waters are added in obtained absorbent charcoal material after weighing 10 mg graphene oxides and 90 mg drying respectively
In, ultrasound is fully dispersed by its.
It is 532 nm, energy in wavelength under the lasting stirring of magnetic stirring apparatus using above-mentioned mixed solution as liquid phase target
Density is 500 mJ pulse-1cm-1, frequency be 1 Hz laser under irradiate 10 min；Centrifuge washing, dry after the reaction was completed
It is dry, obtain graphene ultramicro active charcoal particulate composite.
In obtained graphene/ultramicro active charcoal Particles dispersed electrode material, active carbon particle is having a size of the left side 500 nm
The right side, and it is dispersed in the surface of graphene.The composite material is prepared into working electrode, (platinized platinum is made under three-electrode system
For to electrode, Ag/AgCl electrode is as reference electrode, and the aqueous sodium persulfate solution of 1 M is as electrolyte), carry out chemical property
Test.For the combination electrode when current density is 0.5 Ag, specific capacitance is 326 F/g；When current density increases to 10 A/g,
Its capability value is 233 F/g, and specific capacity conservation rate reaches 71.4%, shows superior high rate performance.Meanwhile 5000 charge and discharges
Specific capacity is still able to maintain 90.3% after electricity, has good cycle life.
Embodiment 4
6 g glucose sugar are dissolved in 40 ml water, carbosphere is made by hydro-thermal method.The temperature of hydro-thermal method is 180 DEG C,
Reaction time is 12 h.
It weighs 100 mg active carbons respectively and 200 mg KOH is sufficiently mixed high-temperature calcination after grinding in mortar (temperature is
700 DEG C, the time h), is then washed, is centrifuged and is dried for 3, obtains absorbent charcoal material.
Obtained absorbent charcoal material is added in 20 mL ethyl alcohol after weighing 1 mg graphene oxide and 99 mg drying respectively, surpasses
Sound is fully dispersed by its.
It is 532 nm, energy in wavelength under the lasting stirring of magnetic stirring apparatus using above-mentioned mixed solution as liquid phase target
Density is 300 mJ pulse-1cm-1, frequency be 10 Hz laser under irradiate 30 min；Centrifuge washing, dry after the reaction was completed
It is dry, obtain graphene ultramicro active charcoal particulate composite.
In obtained graphene/ultramicro active charcoal Particles dispersed electrode material, active carbon particle is having a size of the left side 200 nm
The right side, and it is dispersed in the surface of graphene.The composite material is prepared into working electrode, (platinized platinum is made under three-electrode system
For to electrode, Ag/AgCl electrode is as reference electrode, and the aqueous sodium persulfate solution of 1 M is as electrolyte), carry out chemical property
Test.For the combination electrode when current density is 0.5 Ag, specific capacitance is 338 F/g；When current density increases to 10 A/g,
Its capability value is 235 F/g, and specific capacity conservation rate reaches 69.5%, shows superior high rate performance.Meanwhile 5000 charge and discharges
Specific capacity is still able to maintain 90.6% after electricity, has good cycle life.
Claims (1)
1. a kind of graphene/ultramicro active charcoal Particles dispersed electrode material preparation method, it is characterised in that use following steps:
(1) glucose is dissolved in the water, carbosphere is made by hydro-thermal method；The temperature range of hydro-thermal method is 150~200 DEG C,
Reaction time is 6~24 h；
(2) carbosphere and potassium hydroxide are then calcined by different weight ground and mixed more sufficient than progress；Then it carries out
Washing, centrifugation and drying, obtain absorbent charcoal material；The temperature that carbosphere is calcined after mixing with potassium hydroxide is 600~900 DEG C, is protected
The warm time is 1~5 h；The weight ratio of carbosphere and potassium hydroxide is 1:1~6；
(3) in a solvent, ultrasound is sufficiently mixed for gained absorbent charcoal material and graphene oxide dissolution after will be dry；The work
The weight ratio of property Carbon Materials and graphene oxide are as follows: 92%~96%:8%~4%；Solvent used is water；Absorbent charcoal material and oxygen
The weight percent concentration of graphite alkene in a solvent is 1~10%；
(4) it using above-mentioned gained mixed solution as liquid phase target, is irradiated under the conditions of pulse laser, the work item of laser irradiation
Part are as follows: the wavelength nm of 248 nm~1064, frequency are 5~10 Hz, and energy density is 0.1~0.8 J pulse-1cm-2, irradiation
Time is 20~100 min；
(5) by acquired solution washing, centrifugation and dry, acquisition graphene/ultramicro active charcoal Particles dispersed electrode material；The work
Property Carbon Materials particle size be 5~500 nm, the number of plies of graphene oxide is 1-10；The specific surface area of combination electrode material is
1000~3000 m2/g.
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| CN112133571B (en) * | 2020-09-03 | 2022-05-06 | 方大炭素新材料科技股份有限公司 | Graphene cross-linked activated carbon composite membrane, preparation method and supercapacitor electrode |
| CN112694080B (en) * | 2020-12-28 | 2022-08-19 | 北京化工大学 | Carbon microsphere with embedded conductive network structure, preparation method and energy storage application thereof |
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| CN101844761A (en) * | 2010-05-28 | 2010-09-29 | 上海师范大学 | Method of adopting laser radiation for preparing reduction-oxidation graphene |
| CN103601185A (en) * | 2013-12-05 | 2014-02-26 | 天津工业大学 | Preparation method of spherical porous carbon for super capacitors |
| CN105118678A (en) * | 2015-08-11 | 2015-12-02 | 陕西科技大学 | Preparation method with polysaccharide modified activated carbon as supercapacitor electrode material |
| CN105448540A (en) * | 2015-11-18 | 2016-03-30 | 福建翔丰华新能源材料有限公司 | Super-capacitor high-conductive active carbon electrode manufacturing method |
| CN106044755A (en) * | 2016-05-31 | 2016-10-26 | 中国人民解放军装甲兵工程学院 | Method for preparing graphene by scanning graphite suspension mixed liquor through pulse lasers |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844761A (en) * | 2010-05-28 | 2010-09-29 | 上海师范大学 | Method of adopting laser radiation for preparing reduction-oxidation graphene |
| CN103601185A (en) * | 2013-12-05 | 2014-02-26 | 天津工业大学 | Preparation method of spherical porous carbon for super capacitors |
| CN105118678A (en) * | 2015-08-11 | 2015-12-02 | 陕西科技大学 | Preparation method with polysaccharide modified activated carbon as supercapacitor electrode material |
| CN105448540A (en) * | 2015-11-18 | 2016-03-30 | 福建翔丰华新能源材料有限公司 | Super-capacitor high-conductive active carbon electrode manufacturing method |
| CN106044755A (en) * | 2016-05-31 | 2016-10-26 | 中国人民解放军装甲兵工程学院 | Method for preparing graphene by scanning graphite suspension mixed liquor through pulse lasers |
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