CN107256808A - A kind of three-dimensional grapheme load C oO quantum dot composite electrode materials and preparation method thereof - Google Patents

A kind of three-dimensional grapheme load C oO quantum dot composite electrode materials and preparation method thereof Download PDF

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CN107256808A
CN107256808A CN201710437377.7A CN201710437377A CN107256808A CN 107256808 A CN107256808 A CN 107256808A CN 201710437377 A CN201710437377 A CN 201710437377A CN 107256808 A CN107256808 A CN 107256808A
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dimensional grapheme
quantum dot
electrode materials
composite electrode
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CN107256808B (en
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曹丽云
康倩
王瑞谊
李嘉胤
黄剑锋
程娅伊
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Shaanxi University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • 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
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of three-dimensional grapheme load C oO quantum dot composite electrode materials and preparation method thereof, it is by volume first (1~5)：60, oleyl amine is added in ethanol solution, A is obtained；By cobalt salt, C18H33NaO2It is added to precipitating reagent in A, is uniformly mixing to obtain B；Add graphene oxide into B, be uniformly mixing to obtain C；Ultrasonically treated, then progress microwave hydrothermal reaction is carried out to C, sediment is generated；Isolate sediment and wash drying, then 1~3h is incubated in 300~500 DEG C of atmosphere furnace, be cooled to room temperature, obtain three-dimensional grapheme load C oO quantum dot composite electrode materials.The CoO quantum dot sizes that the present invention is obtained are small, quickly transmitted beneficial to electronics, accelerate reaction rate in charge and discharge process, increase reactivity site；The network structure of three-dimensional grapheme alleviates the volumetric expansion that the insertion abjection of charge and discharge process ion is brought, and protects CoO particles, stabilizing material structure.

Description

A kind of three-dimensional grapheme load C oO quantum dot composite electrode materials and its preparation Method
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, and in particular to a kind of three-dimensional grapheme load CoO quantum dot composite electrode materials and preparation method thereof.
Background technology
Since the nineties, with developing rapidly for integrated circuit and electronic information technology, various portable electric appts (such as mobile phone, notebook computer) is gradually promoted popularization, and the miniaturization and energetic to electrochmical power source propose higher want Ask.The demand in epoch greatly promotes the hair of safe and environment-friendly, inexpensive, high-energy-density and long circulation life secondary cell technology Exhibition.Lithium ion battery, as a kind of new power storage devices, due to its energy density height, service life cycle length, electrode Material volume is small, environment is not almost polluted and the advantages of higher security performance, is increasingly paid attention to by the mankind, is recognized To be a very promising portable energy store.It is commercially use at present for the negative material of lithium ion battery Graphite type material due to theoretical capacity it is relatively low (372mAh/g), be difficult fast charging and discharging, overcharging resisting overdischarge ability and difficult To meet the requirement of development, it would be highly desirable to develop new negative material.Transition metal oxide (such as Fe2O3、Mn3O4、Co3O4、CoO Deng) because higher theoretical capacity receives much concern in recent years, CoO is a kind of lower valency cobalt/cobalt oxide, and theoretical capacity is 719mAh/ G, raw material sources are extensive, it is easy to prepare, but the Volumetric expansion in its own poor electric conductivity and charge and discharge process hinders Its development in terms of electrode material.The method for generally solving both problems is exactly the nanosizing and and carbon of scantling Class material is combined.Graphene is the carbon material that a kind of two dimension has high conductivity, high-mechanical property and high-specific surface area, is generally used To load the carrier of oxide or hydroxide, and three-dimensional grapheme is a kind of three dimensional matrix with network-like structure, can be with The faster transmission of electronics is realized, while also having higher mechanical strength and bigger specific surface area.Usual oxide and three-dimensional The compound method of graphene is all complex cumbersome.
Dhanya Puthusseri, Satishchandra Ogale etc. [Dhanya Puthusseri, Satishchandra Ogale,Srinivasan Madhavi,and Vanchiappan Aravindan.3D Interconnected Porous Graphene Sheets Loaded with Cobalt Oxide Nanoparticles for Lithium-Ion Battery Anodes[J].Energy Techol,2016,4:1-8.] first by by polyphenyl second Alkene benzene sulfonic acid sodium salt calcines 4h in 1000 DEG C of inert atmospheres and obtains three-dimensional grapheme, then by the graphene prepared and a certain amount of Acetylacetone cobalt is added to 90 DEG C of insulation 10h in the mixed solution of isopropanol and acetic acid, then 300 DEG C of heat treatment 3h obtain Co3O4- Three-dimensional porous graphene complex.Capacity may remain in 700mAh/g under 500mA/g current density.This method was made before this It is standby go out three-dimensional grapheme carry out compound, the relatively complicated and prepared Co of cobalt oxide and graphene again3O4- three-dimensional porous stone Co in black alkene compound3O4The larger about 200nm or so of particle size, size is larger, is distributed also more heterogeneity.Hongyu Suna, Yanguo Liu etc. [Hongyu Sun, Yanguo Liu, Yanlong Yu, Mashkoor Ahmad, Ding Nan, Jing Zhu.Mesoporous Co3O4nanosheets-3D graphene networks hybrid materials for high-performance lithium ion batteries[J]Electrochim.Acta,2014,118:1-9] lead to first Cross CVD and be put into foam copper and be connected with Ar and H2In the tube furnace of gaseous mixture, then 1000 DEG C of insulation 10min are passed through C again2H2Most Obtained sample ferric nitrate etching gets rid of foam copper eventually, obtains three-dimensional grapheme.Then by prepared three-dimensional grapheme It is immersed in the solution containing cobalt source and is incubated 8h at 95 DEG C, is dried again after having reacted, then 450 DEG C are heat-treated in atmosphere 2h obtains Co3O4- three-dimensional grapheme compound.Products therefrom is under 178mA/g current density, and capacity is after the circle of circulation 50 630mAh/g.Yongmin He etc. [Yongmin He, Wanjun Chen, Xiaodong Li, Zhenxing Zhang, Jiecai Fu,Changhui Zhao,and Erqing Xie.Freestanding Three-Dimensional Graphene/MnO2Composite Networks As Ultralight and Flexible Supercapacitor Electrodes[J]ACS Nano,2013,7:174-182.] prepare the three-dimensional stones of MnO2- using CVD and electrochemical deposition Black alkene compound, as electrode material for super capacitor, specific capacity can reach 130F/g.Three-dimensional grapheme is prepared with CVD It is relatively conventional method, but this method generally requires, using nickel foam as template, three-dimensional grapheme, Zhi Houzai to be deposited thereon Nickel foam is got rid of by the method for etching, unnecessary impurity may be brought in this process, and process is more multiple It is miscellaneous.
The content of the invention
It is an object of the invention to overcome problems of the prior art, there is provided a kind of three-dimensional grapheme load C oO amounts Son point composite electrode material and preparation method thereof, by three-dimensional grapheme and CoO it is compound reach raising electrode material electric conductivity and Stability.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
Comprise the following steps：
1) it is by volume (1~5)：60, oleyl amine is added in ethanol solution, solution A is obtained；
2) by cobalt salt, C18H33NaO2It is added to precipitating reagent in solution A, is uniformly mixing to obtain solution B；Wherein, cobalt salt, C18H33NaO2With step 1) in ethanol solution ratio be (0.5~3) mmol：(0.5~3) mmol：70mL；
3) add graphene oxide into solution B, be uniformly mixing to obtain suspension C；Wherein, graphene oxide and step 1) ratio of ethanol solution is (0.06~0.12) g in：60mL；
4) ultrasonically treated, then progress microwave hydrothermal reaction is carried out to suspension C, sediment is generated；
5) isolate sediment and wash drying, obtain predecessor；
6) predecessor is incubated 1~3h in 300~500 DEG C of atmosphere furnace, is subsequently cooled to room temperature, obtain three-dimensional graphite Alkene load C oO quantum dot composite electrode materials.
Further, step 1) per 60mL ethanol solution in the absolute ethyl alcohol containing 35~55mL.
Further, step 1) 5~10min of middle stirring, obtain solution A；Step 2) 10~20min of middle stirring, obtain molten Liquid B.
Further, step 2) in cobalt salt, C18H33NaO2Mol ratio with precipitating reagent is 1：1：10.
Further, step 2) in cobalt salt use Co (CH3COO)2·4H2O, precipitating reagent uses CO (NH2)2。
Further, step 3) in 30~60min of magnetic agitation obtain suspension C.
Further, step 4) in ultrasonically treated 2~10h；Suspension C after ultrasound is poured into polytetrafluoroethyllining lining It is reloaded into reactor outer lining, is placed in after sealing in microwave hydrothermal reactor, 100~160 DEG C is heated to by room temperature, insulation 2~ 6h, then naturally cools to room temperature, generates sediment.
Further, step 5) in, by centrifuging out sediment, and washed with ethanol and vacuum is put into after 3~6 times does The dry dry 10~15h of 70~90 DEG C of case.
Further, step 6) in, predecessor is placed in porcelain boat, the quartz for the atmosphere tube type stove that atmosphere is argon gas is placed in Guan Zhong, heating rate is 3~10 DEG C of min-1, 0.1~0.5sccmmin of argon air-flow velocity-1。
One kind utilizes three-dimensional grapheme load C oO quantum dot composite electrode materials made from preparation method as described above, The size of CoO quantum dots is in 5~10nm in the material, and the material Average specific capacities are 785~808.7mAh/g.
Compared with prior art, the present invention has following beneficial technique effect：
The present invention obtains precursors by microwave solvothermal method, after presoma is washed and dried, with reference to Low Temperature Thermal The structure of three-dimensional grapheme load C oO quantum dots has successfully been prepared in processing, and graphene is crimped in the presence of oleyl amine Three-dimensional structure is obtained, cobalt ions and ureaclastic hydroxyl and carbanion is dispersed in ethanol solution on graphene Nucleating growth, because the speed of the nucleation under the collective effect of oleic acid sodium molecule and oleyl amine molecule and growth can be restricted, with CoO obtained by causing is the CoO quantum dots that size is 5-10nm.This method preparation process is simple, is obtaining three-dimensional grapheme CoO quantum dots have also been obtained simultaneously, the chemical property of CoO negative poles is more efficiently improved.
The present invention by solvent-thermal method structure with reference to as being thermally treated resulting in three-dimensional grapheme load C oO quantum dots, its The size of middle CoO quantum dots is supported on the surface of three-dimensional grapheme about in 5~10nm or so, and less particle size is favourable In the quick transmission of electronics, the reaction rate of redox reaction in charge and discharge process is accelerated.On the other hand small particle chi Very little specific surface area is also than larger, and the avtive spot of reaction can also increase, and be conducive to the efficient progress of electrochemical reaction.Three-dimensional stone The network structure of black alkene can not only alleviate the volumetric expansion that lithium ion or sodium ion insertion abjection are brought in charge and discharge process, Play a part of protecting CoO particles, can be with the structure of stabilizing material.The pore space structure of another aspect three-dimensional structure can be added The contact area of material and electrolyte, more sites are provided for electrochemical reaction.The characteristics of in these structures, is all to material electricity The lifting of chemical property is very helpful, and the compound Average specific capacities are 785~808.7mAh/g, also to lithium/sodium ion The research and development of the negative material of battery has very important significance.
Brief description of the drawings
Fig. 1 is the X-ray diffraction of three-dimensional grapheme load C oO quantum dot compounds prepared by the embodiment of the present invention 1 (XRD) collection of illustrative plates.
Fig. 2 is three-dimensional grapheme load C oO quantum dots compound sweeping under 40K multiplying powers prepared by the embodiment of the present invention 1 Retouch Electronic Speculum (SEM) photo.
Fig. 3 is three-dimensional grapheme load C oO quantum dots compound sweeping under 220K multiplying powers prepared by the embodiment of the present invention 1 Retouch Electronic Speculum (SEM) photo.
Three-dimensional grapheme load C oO quantum dots compound prepared by Fig. 4 embodiment of the present invention 1 is under 200nm enlargement ratios Transmission electron microscope (TEM) photo.
Fig. 5 is the three-dimensional grapheme load C oO quantum dots compound of the preparation of the embodiment of the present invention 1 under 10nm enlargement ratios HRTEM figure.
Fig. 6 is that three-dimensional grapheme load C oO quantum dots compound prepared by the embodiment of the present invention 1 is close in 500mA/g electric currents The cycle performance figure of the lower circle of circulation 50 of degree.
Embodiment
The present invention is described in further details below in conjunction with the accompanying drawings.
The present invention comprises the following steps：
1) 5~25mL deionized waters are added in 55~35mL absolute ethyl alcohols, are configured to 60mL mixed solvents A；
2) 1~5mL oleyl amines are added in mixed solvent A, stirs 5~10min, obtain solution B；
3) 0.5~3mmol Co (CH are taken3COO)2·4H2O, 0.5~3mmolC18H33NaO2, 5~30mmol CO (NH2)2, according to mol ratio 1:1:10 sequentially add in solution B, and 10~20min of stirring obtains solution C；
4) 0.06~0.12g graphene is added in solution C, 30~60min of magnetic agitation obtains suspension D；
5) by the ultrasonically treated 2~10h of suspension D；
6) the suspension D after ultrasound is poured into polytetrafluoroethyllining lining and be reloaded into reactor outer lining, sealed rearmounted In microwave hydrothermal reactor, 100~160 DEG C are heated to by room temperature, 2~6h is incubated, then naturally cools to room temperature, sunk Shallow lake E；
7) precipitation is centrifuged and washed with ethanol 3~6 times, 70~90 DEG C of dryings 10 of vacuum drying chamber are put into after washing ~15h obtains predecessor F；
8) predecessor F is placed on into porcelain boat to be built in the quartz ampoule of atmosphere tube type stove, it is 3~10 DEG C to set heating rate min-1, 0.1~0.5sccmmin of argon air-flow velocity-1, reaction temperature is 300~500 DEG C, and soaking time is 1~3h, treats anti- Room temperature is naturally cooled to after the completion of answering, the compound of three-dimensional grapheme load C oO quantum dots is just can obtain.
The present invention reaches the purpose for improving electrode material electric conductivity and stability by the way that three-dimensional grapheme and CoO are combined, So as to obtain the electrode material of electrochemical performance.
Embodiment 1：
1) 25mL deionized waters are added in 35mL absolute ethyl alcohols, are configured to 60mL mixed solvents A；
2) 1mL oleyl amines are added in mixed solvent A, stirs 5min, obtain solution B；
3) 0.5mmol Co (CH are taken3COO)2·4H2O, 0.5mmolC18H33NaO2, 5mmol CO (NH2)2, according to rubbing You compare 1:1:10 sequentially add in solution B, and stirring 10min obtains solution C；
4) 0.06g graphene is added in solution C, magnetic agitation 30min obtains suspension D；
5) by the ultrasonically treated 2h of suspension D；
6) the suspension D after ultrasound is poured into polytetrafluoroethyllining lining and be reloaded into reactor outer lining, sealed rearmounted In microwave hydrothermal reactor, 100 DEG C are heated to by room temperature, 6h is incubated, then naturally cools to room temperature, obtains precipitating E；
7) precipitation is centrifuged and washed with ethanol 3 times, be put into after washing before the dry 15h of 70 DEG C of vacuum drying chamber obtains Drive thing F；
8) predecessor F is placed on into porcelain boat to be built in the quartz ampoule of atmosphere tube type stove, it is 3 DEG C of min to set heating rate-1, argon air-flow velocity 0.1sccmmin-1, reaction temperature is 300 DEG C, and soaking time is natural cooling after the completion of 3h, question response To room temperature, the compound of three-dimensional grapheme load C oO quantum dots just can obtain.
As shown in figure 1, being the characteristic diffraction peak and CoO standard cards (JCPDS in the XRD spectrum of products therefrom, figure No.:48-1719) it coincide, and the steamed bun peak occurred in 20-30 degree is the characteristic peak of graphene, and it is CoO/ to illustrate products therefrom The compound of graphene.Fig. 2 and Fig. 3 schemes for the SEM of the product under 40K and 220K multiplying powers, as can be seen from the figure three-dimensional network CoO particles are loaded above the graphene-structured of shape.Fig. 4 schemes for the TEM of product, as can be seen from the figure the three-dimensional knot of graphene Structure and the CoO particles grown thereon.Fig. 5 is the HRTEM of product, and CoO lattice fringe can obtain interplanar from figure Away from being matched with XRD.
Comparative example 1：
By the volume ratio of oleyl amine and ethanol solution by original (1~5)：60 change into 6:60, the then electrification of products therefrom Learning performance can decay, as shown in fig. 6, Average specific capacities are reduced to 466.7mAh/g, stable circulation by original 808.7mAh/g Property is also poor.
Embodiment 2：
1) 20mL deionized waters are added in 40mL absolute ethyl alcohols, are configured to 60mL mixed solvents A；
2) 2mL oleyl amines are added in mixed solvent A, stirs 5min, obtain solution B；
3) 1mmol Co (CH are taken3COO)2·4H2O, 1mmolC18H33NaO2, 10mmol CO (NH2)2, according to mol ratio 1:1:10 sequentially add in solution B, and 10~20min of stirring obtains solution C；
4) 0.08g graphene is added in solution C, magnetic agitation 30min obtains suspension D；
5) by the ultrasonically treated 4h of suspension D；
6) the suspension D after ultrasound is poured into polytetrafluoroethyllining lining and be reloaded into reactor outer lining, sealed rearmounted In microwave hydrothermal reactor, 120 DEG C are heated to by room temperature, 4h is incubated, then naturally cools to room temperature, obtains precipitating E；
7) precipitation is centrifuged and washed with ethanol 4 times, be put into after washing before the dry 12h of 80 DEG C of vacuum drying chamber obtains Drive thing F；
8) predecessor F is placed on into porcelain boat to be built in the quartz ampoule of atmosphere tube type stove, it is 5 DEG C of min to set heating rate-1, argon air-flow velocity 0.2sccmmin-1, reaction temperature is 400 DEG C, and soaking time is naturally cold after the completion of 1.5h, question response But to room temperature, the compound of three-dimensional grapheme load C oO quantum dots is just can obtain, the compound Average specific capacities are 802mAh/ g。
Embodiment 3：
1) 15mL deionized waters are added in 45mL absolute ethyl alcohols, are configured to 60mL mixed solvents A；
2) 3mL oleyl amines are added in mixed solvent A, stirs 8min, obtain solution B；
3) 1.5mmol Co (CH are taken3COO)2·4H2O, 1.5mmolC18H33NaO2, 15mmol CO (NH2)2, according to rubbing You compare 1:1:10 sequentially add in solution B, and stirring 15min obtains solution C；
4) 0.1g graphene is added in solution C, magnetic agitation 50min obtains suspension D；
5) by the ultrasonically treated 6h of suspension D；
6) the suspension D after ultrasound is poured into polytetrafluoroethyllining lining and be reloaded into reactor outer lining, sealed rearmounted In microwave hydrothermal reactor, 140 DEG C are heated to by room temperature, 6h is incubated, then naturally cools to room temperature, obtains precipitating E；
7) precipitation is centrifuged and washed with ethanol 5 times, be put into after washing before the dry 10h of 90 DEG C of vacuum drying chamber obtains Drive thing F；
8) predecessor F is placed on into porcelain boat to be built in the quartz ampoule of atmosphere tube type stove, it is 10 DEG C to set heating rate min-1, argon air-flow velocity 0.5sccmmin-1, reaction temperature is 500 DEG C, and soaking time is naturally cold after the completion of 1h, question response But to room temperature, the compound of three-dimensional grapheme load C oO quantum dots is just can obtain, the compound Average specific capacities are 799mAh/ g。
Embodiment 4：
1) 10mL deionized waters are added in 50mL absolute ethyl alcohols, are configured to 60mL mixed solvents A；
2) 4mL oleyl amines are added in mixed solvent A, stirs 10min, obtain solution B；
3) 2mmol Co (CH are taken3COO)2·4H2O, 2mmolC18H33NaO2, 20mmol CO (NH2)2, according to mol ratio 1:1:10 sequentially add in solution B, and stirring 20min obtains solution C；
4) 0.12g graphene is added in solution C, magnetic agitation 60min obtains suspension D；
5) by the ultrasonically treated 10h of suspension D；
6) the suspension D after ultrasound is poured into polytetrafluoroethyllining lining and be reloaded into reactor outer lining, sealed rearmounted In microwave hydrothermal reactor, 160 DEG C are heated to by room temperature, 2h is incubated, then naturally cools to room temperature, obtains precipitating E；
7) precipitation is centrifuged and washed with ethanol 6 times, be put into after washing before the dry 12h of 70 DEG C of vacuum drying chamber obtains Drive thing F；
8) predecessor F is placed on into porcelain boat to be built in the quartz ampoule of atmosphere tube type stove, it is 3 DEG C of min to set heating rate-1, argon air-flow velocity 0.1sccmmin-1, reaction temperature is 300 DEG C, and soaking time is natural cooling after the completion of 2h, question response To room temperature, the compound of three-dimensional grapheme load C oO quantum dots is just can obtain, the compound Average specific capacities are 785mAh/g.
Embodiment 5：
1) 5mL deionized waters are added in 55mL absolute ethyl alcohols, are configured to 60mL mixed solvents A；
2) 5mL oleyl amines are added in mixed solvent A, stirs 10min, obtain solution B；
3) 3mmol Co (CH are taken3COO)2·4H2O, 3mmolC18H33NaO2, 30mmol CO (NH2)2, according to mol ratio 1:1:10 sequentially add in solution B, and stirring 20min obtains solution C；
4) 0.12g graphene is added in solution C, magnetic agitation 60min obtains suspension D；
5) by the ultrasonically treated 10h of suspension D；
6) the suspension D after ultrasound is poured into polytetrafluoroethyllining lining and be reloaded into reactor outer lining, sealed rearmounted In microwave hydrothermal reactor, 100 DEG C are heated to by room temperature, 6h is incubated, then naturally cools to room temperature, obtains precipitating E；
7) precipitation is centrifuged and washed with ethanol 6 times, be put into after washing before the dry 10h of 90 DEG C of vacuum drying chamber obtains Drive thing F；
8) predecessor F is placed on into porcelain boat to be built in the quartz ampoule of atmosphere tube type stove, it is 10 DEG C to set heating rate min-1, argon air-flow velocity 0.5sccmmin-1, reaction temperature is 500 DEG C, and soaking time is naturally cold after the completion of 3h, question response But to room temperature, the compound of three-dimensional grapheme load C oO quantum dots is just can obtain, the compound Average specific capacities are 790mAh/ g。
The present invention obtains precursors using microwave solvothermal method, after presoma is washed and dried, then is being connected with argon Low-temperature treatment just can obtain the compound of three-dimensional grapheme load C oO quantum dots in the atmosphere tube type stove of gas.CoO quantum dots Size not only increases the contact area with electrolyte in 5~10nm, small size, also shorten electronics and ion transmission away from From accelerating the electrochemical reaction speed in charge and discharge process.Three-dimensional graphene framework not only stable for structure and also function to Alleviate the effect of volumetric expansion, the transmission of the network of three-dimensional UNICOM to electronics is very helpful, and these characteristics are all effectively Improve the chemical property of CoO electrodes.Preparation method of the present invention is simple, and yield is high, and reaction time is short, is suitable for extensive life Production.

Claims (10)

1. a kind of preparation method of three-dimensional grapheme load C oO quantum dot composite electrode materials, it is characterised in that：Including following Step：
1) it is by volume (1~5)：60, oleyl amine is added in ethanol solution, solution A is obtained；
2) by cobalt salt, C18H33NaO2It is added to precipitating reagent in solution A, is uniformly mixing to obtain solution B；Wherein, cobalt salt, C18H33NaO2With step 1) in ethanol solution ratio be (0.5~3) mmol：(0.5~3) mmol：70mL；
3) add graphene oxide into solution B, be uniformly mixing to obtain suspension C；Wherein, graphene oxide and step 1) in The ratio of ethanol solution is (0.06~0.12) g：60mL；
4) ultrasonically treated, then progress microwave hydrothermal reaction is carried out to suspension C, sediment is generated；
5) isolate sediment and wash drying, obtain predecessor；
6) predecessor is incubated 1~3h in 300~500 DEG C of atmosphere furnace, is subsequently cooled to room temperature, obtained three-dimensional grapheme and bear Carry CoO quantum dot composite electrode materials.
2. a kind of preparation method of three-dimensional grapheme load C oO quantum dot composite electrode materials according to claim 1, It is characterized in that：Step 1) per 60mL ethanol solution in the absolute ethyl alcohol containing 35~55mL.
3. a kind of preparation method of three-dimensional grapheme load C oO quantum dot composite electrode materials according to claim 1, It is characterized in that：Step 1) 5~10min of middle stirring, obtain solution A；Step 2) 10~20min of middle stirring, obtain solution B.
4. a kind of preparation method of three-dimensional grapheme load C oO quantum dot composite electrode materials according to claim 1, It is characterized in that：Step 2) in cobalt salt, C18H33NaO2Mol ratio with precipitating reagent is 1：1：10.
5. a kind of preparation method of three-dimensional grapheme load C oO quantum dot composite electrode materials according to claim 1, It is characterized in that：Step 2) in cobalt salt use Co (CH3COO)2·4H2O, precipitating reagent uses CO (NH2)2。
6. a kind of preparation method of three-dimensional grapheme load C oO quantum dot composite electrode materials according to claim 1, It is characterized in that：Step 3) in 30~60min of magnetic agitation obtain suspension C.
7. a kind of preparation method of three-dimensional grapheme load C oO quantum dot composite electrode materials according to claim 1, It is characterized in that：Step 4) in ultrasonically treated 2~10h；Suspension C after ultrasound, which is poured into polytetrafluoroethyllining lining, to be reloaded into It is placed in reactor outer lining, after sealing in microwave hydrothermal reactor, 100~160 DEG C is heated to by room temperature, is incubated 2~6h, then Room temperature is naturally cooled to, sediment is generated.
8. a kind of preparation method of three-dimensional grapheme load C oO quantum dot composite electrode materials according to claim 1, It is characterized in that：Step 5) in, vacuum drying chamber 70 is put into after 3~6 times by centrifuging out sediment, and being washed with ethanol ~90 DEG C of dry 10~15h.
9. a kind of preparation method of three-dimensional grapheme load C oO quantum dot composite electrode materials according to claim 1, It is characterized in that：Step 6) in, predecessor is placed in porcelain boat, in the quartz ampoule for being placed in the atmosphere tube type stove that atmosphere is argon gas, Heating rate is 3~10 DEG C of min-1, 0.1~0.5sccmmin of argon air-flow velocity-1。
10. one kind utilizes three-dimensional grapheme load C oO quantum dot composite electrode materials made from preparation method described in claim 1 Material, it is characterised in that：The size of CoO quantum dots is in 5~10nm in the material, and the material Average specific capacities are 785~ 808.7mAh/g。
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CN114113238A (en) * 2021-11-17 2022-03-01 中国兵器工业集团第二一四研究所苏州研发中心 Gas sensor based on three-dimensional porous graphene @ quantum dot composite material and preparation method thereof

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