CN105895384B - A kind of graphene/ultra micro cobaltosic oxide Particles dispersed electrode material preparation method - Google Patents
A kind of graphene/ultra micro cobaltosic oxide Particles dispersed electrode material preparation method Download PDFInfo
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- CN105895384B CN105895384B CN201610302686.9A CN201610302686A CN105895384B CN 105895384 B CN105895384 B CN 105895384B CN 201610302686 A CN201610302686 A CN 201610302686A CN 105895384 B CN105895384 B CN 105895384B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of graphene/ultra micro Co3O4Liquid laser irradiation/ablation preparation method of Particles dispersed electrode material.Specific process step is as follows：By the graphene oxide and Co of different proportion3O4Presoma be sufficiently mixed in different solvents, then under the conditions of different pulse lasers, be made graphene/ultra micro Co3O4Particulate composite.Graphene of the invention/ultra micro Co3O4When particulate composite is used as electrode material for super capacitor, excellent volume and capacity ratio is shown.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/ultra micro Co3O4Particle
Combination electrode material preparation method；Belong to field of nanometer material technology.
Background technique
Cobaltosic oxide（Co3O4）As a kind of typical battery-type electrode chose material, there is high theoretical capacity（3560
Fg-1）, excellent redox active, good environment compatibility and the features such as raw material sources abundant, while compared to
The cell types metal oxide such as Fe, Ni base, Co3O4With better stability, therefore, it is considered to be very promising super
One of capacitor electrode material.But, intrinsic Co3O4Conductivity is lower（10-4~10-2 Scm-1）, and volume in charge and discharge process
It is changed significantly, seriously hinders its application in high-performance super capacitor.
In order to improve Co3O4Electric conductivity and stability, by itself and with superior electrical conductivity can and mechanical performance graphene
Carry out the compound favor for obtaining scientific research personnel.Currently, domestic and international researcher passes through various preparation methods（Such as hydro-thermal method/solvent
Thermal method, sol-gel method, simple liquid phase reactor, chemical vapor deposition（CVD）Deng）Obtain graphene/Co3O4Composite material,
But there are still graphene/Co for wherein most preparation method3O4Nano material micro-structure is not easy to control and preparation condition harshness etc. is asked
Topic.Ujjain et al.（Electrochim.Acta, 2015,169：276-282）Using hydro-thermal method synthesized graphene nanobelt/
Co3O4Nano particle composite material, Co3O4Nano particle（~60 nm）It is dispersed on graphene nano band；In 5 mVs-1
Sweep speed under, the specific capacity of the composite material is 525 Fg-1.Although graphene nanobelt/Co3O4Nano-particles reinforcement material
Material is than synthesized simple Co3O4Specific capacity have a biggish promotion, but the diffusion length due to electrolyte in electrode material
It is shorter（20 nm）, so biggish Co3O4Nano particle can not be by fully effective utilization in electrochemical reaction process.Liao
Et al.（ACS Nano, 2015,9：5310-5317）Pass through microwave plasma enhanced chemical vapor deposition（MPECVD）With it is subsequent
Hydro-thermal method has synthesized vertically oriented graphene/Co on carbon cloth3O4The composite material of nano particle；In 1 mVs-1Scanning
Under rate, volume and capacity ratio is up to 950 Fcm-3.Vertical-growth results in the combination electrode in the graphene on carbon cloth
There are biggish gaps for material internal.Therefore, contained active electrode material is restricted in electrode material unit volume, is formed
So-called " dead volume ".
Liquid laser irradiation/ablation has relevant report in terms of preparing highly conductive graphene and ultramicro powder.Such as
Huang et al.（Carbon, 2011,49 (7): 2431-2436）By pulse laser irradiation graphene oxide water solution, by oxygen
Graphite alkene in-situ reducing and obtain high conductivity.James et al.（ACS Catal., 2013,3：2497-2500）Utilize liquid
Phase laser ablation method obtains the small size being evenly distributed（2.5 nm）Co3O4Nano particle.However, in supercapacitor graphite
Alkenyl combination electrode material preparation aspect, liquid laser irradiation/ablation preparation yet there are no relevant report.Therefore those skilled in the art
Member is dedicated to developing a kind of graphene/ultra micro Co3O4Liquid laser irradiation/ablation preparation method of Particles dispersed electrode material, should
Method will be with important scientific research meaning and application value.
Summary of the invention
Present invention aims to overcome that the deficiency of above-mentioned existing technology of preparing, a kind of simple, novel graphene/super is provided
Micro- Co3O4The preparation method of Particles dispersed electrode material.The combination electrode material of this method preparation is used as electrode of super capacitor material
When material, the volume capacity of the electrode is greatly improved, conventional method is solved and is difficult to realize high volume capacity and high-purity preparation
Problem.
To achieve the above object, the present invention provides a kind of graphene/ultra micro Co3O4The liquid phase of Particles dispersed electrode material
Laser irradiation/ablation preparation method.The technical solution of the invention is as follows：By the graphene oxide and Co of different proportion3O4Before
Body mixing is driven, graphene/ultra micro Co is made under the conditions of different pulse lasers3O4Particulate composite.
Above-mentioned graphene/ultra micro Co3O4The preparation method of Particles dispersed electrode material, specific step is as follows：
（1）By Co3O4Nano particle presoma and graphene oxide press different proportion ultrasonic disperse into different solvents,
Co3O4Nano particle and graphene oxide ratio are：0.1%~10%：90%~99.9%.
（2）Pass through pulse laser spoke under the lasting stirring of magnetic stirring apparatus using above-mentioned mixed solution as liquid phase target
According to/ablation liquid phase target, the operating condition of laser is：The laser of wavelength 248 nm~1064 nm, 1~30 Hz of frequency, energy
Density is 0.1~10 J pulse-1cm-2, irradiation time is 10~1000 min, and centrifuge washing can be obtained after the reaction was completed
Graphene/Co3O4Particles dispersed electrode material.
Disperse graphene oxide and Co in specific implementation of the invention3O4Presoma used in liquid solvent be water, second
Alcohol.
In a preferred embodiment of the invention for laser, the frequency is preferably 1~10 Hz, and energy density is
0.1~0.8 J pulse-1cm-2, irradiation time is 20~100 min.
Compared with prior art, beneficial effects of the present invention are：
（1）Preparation process of the invention only needs laser irradiation/ablation graphene oxide and Co3O4Precursor liquid phase
Solution does not need the experimental provision of other redox conditions and reagent and complexity, and condition is easily-controllable, simple process, cost
It is low, solve the problems, such as conventional manufacturing process complexity and uncontrollable composite micro-structure and purity.
（2）Graphene/Co of the method for the present invention preparation3O4In Particles dispersed electrode material, Co3O4It is tight in conjunction with graphene
It is close, and be dispersed on graphene, while Co3O4Pattern, size is controllable.
（3）Graphene/Co prepared by the present invention3O4Particles dispersed electrode material has good electric conductivity and high jolt ramming
Density 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/ultra micro Co prepared by the embodiment of the present invention 13O4The XRD spectrum of particulate composite；
Fig. 2 is graphene/ultra micro Co prepared by the embodiment of the present invention 13O4The transmission electron microscope picture of particulate composite；
Fig. 3 is graphene/ultra micro Co prepared by the embodiment of the present invention 13O4The high-resolution-ration transmission electric-lens of particulate composite
Figure；
Fig. 4 is graphene/ultra micro Co prepared by the embodiment of the present invention 13O4Particulate composite is under different current densities
Constant current charge-discharge curve.
Claims (2)
1. a kind of graphene/ultra micro Co3O4 Particles dispersed electrode material liquid laser irradiation/ablation preparation method, feature
It is, specific step is as follows：
（1）Co3O4 nano particle presoma and graphene oxide are sufficiently mixed in predetermined solvent by predetermined ratio；
（2）It using above-mentioned gained mixed solution as liquid phase target, carries out irradiating/ablation under the conditions of scheduled pulse laser, be made
Graphene/ultra micro Co3O4 particulate composite；
Step（1）Used in Co3O4 nano particle presoma be commercialized Co3O4 particle or laboratory synthesis Co3O4
Grain；
Step（1）Used in solvent be：Water or ethyl alcohol；
Step（1）Middle Co3O4 nano particle and graphene oxide ratio are：0.1%~10%：90%~99.9%；
Step（2）The operating condition of middle laser is：The wavelength nm of 248 nm~1064,1~30 Hz of frequency, energy density 0.1
~10 J pulse-1cm-2, irradiation time are 10~1000 min.
2. preparation method according to claim 1, which is characterized in that step（2）In for laser, the frequency is preferred
For 1~10 Hz, energy density is 0.1~0.8 J pulse-1cm-2, and irradiation time is 20~100 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106398802A (en) * | 2016-09-07 | 2017-02-15 | 济南大学 | Rapid laser preparing method for composite with graphene loaded with spherical inorganic fullerene molybdenum disulfide |
| CN106784596A (en) * | 2016-11-18 | 2017-05-31 | 杭州电子科技大学 | One kind prepares binder free Graphene/SnO using laser irradiation original position2The method of combination electrode |
| CN106784828A (en) * | 2016-12-30 | 2017-05-31 | 尹宗杰 | A kind of layer type casting moulding Graphene metallic composite and preparation method |
| CN106800292A (en) * | 2017-01-16 | 2017-06-06 | 王奉瑾 | The preparation method of graphene oxide and Graphene |
| CN107731544B (en) * | 2017-09-06 | 2019-06-25 | 济南大学 | A kind of graphene zinc ferrite combination electrode material and preparation method thereof |
| CN109179398B (en) * | 2018-10-24 | 2021-01-15 | 国家纳米科学中心 | Noble metal oxide nano composite material, preparation method and application thereof |
| CN109326789B (en) * | 2018-12-11 | 2021-11-30 | 济南大学 | Graphene-coated zinc cobaltate composite electrode material and preparation method thereof |
| CN109590008B (en) * | 2018-12-25 | 2021-06-25 | 天津大学 | Preparation method of laser-synthesized oxygen vacancy adjustable cobaltosic oxide nitrogen-doped graphene |
| CN113634255A (en) * | 2021-08-24 | 2021-11-12 | 武汉理工大学 | Loaded Co3O4Preparation method of granular nano carbon composite catalytic material |
| CN114093682B (en) * | 2021-11-12 | 2022-10-25 | 西安交通大学 | Laser preparation method and application of graphene/Co-CoO composite electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103972496A (en) * | 2014-04-10 | 2014-08-06 | 山东润昇电源科技有限公司 | Co3O4/graphene electrode material preparation method through hydro-thermal coupling spray pyrolysis |
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| CN103972496A (en) * | 2014-04-10 | 2014-08-06 | 山东润昇电源科技有限公司 | Co3O4/graphene electrode material preparation method through hydro-thermal coupling spray pyrolysis |
Non-Patent Citations (2)
| Title |
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| Co3O4 Nanoparticle Water-Oxidation Catalysts Made by Pulsed-Laser Ablation in Liquids;James D. Blakemore等;《ACS Catal.》;20131003;第3卷;第2497-2500页 * |
| Pulsed laser assisted reduction of graphene oxide;Lei Huang等;《Carbon》;20110219;第49卷;第2431-2436页 * |
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