CN103326007B - The preparation method of three-dimensional graphite thiazolinyl tin dioxide composite material and application thereof - Google Patents
The preparation method of three-dimensional graphite thiazolinyl tin dioxide composite material and application thereof Download PDFInfo
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- CN103326007B CN103326007B CN201310256465.9A CN201310256465A CN103326007B CN 103326007 B CN103326007 B CN 103326007B CN 201310256465 A CN201310256465 A CN 201310256465A CN 103326007 B CN103326007 B CN 103326007B
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method and application thereof of graphene-based tin dioxide composite material of three-dimensional structure.Preparation method of the present invention adopts the Graphene of monolayer carbon atomic structure as carrier, utilizes stannic chloride pentahydrate as tin source presoma, is prepared the graphene-based tin dioxide composite material of three-dimensional structure by the method for hydro-thermal freeze-drying.The tin oxide nano particles obtained by the method equably load, on Graphene skeleton, and is assembled into the aeroge with three-dimensional structure well.Prove through electro-chemical test, the graphene-based tin dioxide composite material of the three-dimensional structure that preparation method of the present invention obtains has excellent cyclical stability and high rate performance, and experiment proves at 100mAg
-1charging or discharging current under, wherein tin dioxide material discharge capacity can reach 800mAhg
-1.
Description
Technical field
The present invention relates to a kind of method and application thereof of graphene-based tin dioxide composite material of three-dimensional structure, belong to material science and technical field of electrochemistry.
Background technology
Along with day by day highlighting of energy and environment problem, New Energy Industry obtains increasing attention.Rapidly, lithium ion battery is widely used as wherein important energy storage device for hybrid vehicle and electric automobile industry development.Lithium ion battery has energy density high, some excellent performances such as good cycle, is also considered to one of the most effective energy storage mode at present, and therefore, its energy density of raising and cycle performance are also the difficult point and focus instantly studied further.
The negative pole of lithium ion battery is the important component part of battery, and its Structure and Properties directly affects capacity and the cycle performance of lithium ion battery.The lithium ion battery negative material of current commercialization is based on graphite, and graphite cost is low, and wide material sources are suitable for commercialization; But its capacity is lower, and theoretical capacity is only 372mAhg
-1, be restricted when applying in the field exported needing high-energy.
Metal oxide is as Fe
3o
4, SnO
2have very high specific capacity Deng as lithium ion battery negative material, its specific capacity is up to 700-1000mAhg
-1; But most of metal oxide, especially SnO
2as electrode material, in charge and discharge process, change in volume is up to 200-300%, and this change in volume can cause the efflorescence of electrode, causes the open circuit of active material and collector.Therefore, most metals oxide, as all there is capacity attenuation problem rapidly during lithium ion cell electrode, which also limits metal oxide as the development of lithium ion battery negative material and practical application.
At present, for expanding the application of metal oxide in lithium ion battery negative material, these problems that researchers exist for metal oxide conduct in-depth research, such as modification is carried out to electrode material, comprise the preparation of coated, doping, compound and nano material, improved the performance of electrode material by these methods, particularly carry out the compound of nanoscale at metal oxide and material with carbon element, prepare the focus that novel nanostructure aspect has become research at present.
Material with carbon element has the premium properties of its uniqueness: stability, good conductivity, light weight; Make it as the carrier of good metal oxide, by absorbing the change in volume stress of metal oxide in lithium ion battery charge and discharge process, thus the cycle performance of metal oxide can be strengthened.Therefore, material with carbon element and metal oxide are carried out the negative material of composite material as lithium ion battery of the novel nano structure that combined structure goes out, be expected to the performance significantly improving lithium ion battery, and also there is far reaching significance for its expansive approach.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention is to provide a kind of composite material that can strengthen the three-dimensional structure of metal oxide cycle performance.
For achieving the above object, the invention provides a kind of preparation method and the application thereof with the carbon coated graphite thiazolinyl metal oxide composite of three-dimensional structure.Particularly, adopt the Graphene of monolayer carbon atomic structure as three-dimensional framework, stannic chloride pentahydrate, as tin source presoma, prepares the graphene-based metal tin dioxide composite material of three-dimensional structure.
The present invention solves above-mentioned technical problem by the following technical programs:
On the one hand, the invention provides a kind of preparation method with the graphene-based metal tin dioxide composite material of three-dimensional structure.
Preparation method of the present invention adopts two step synthesis to have the graphene-based metal tin dioxide composite material of three-dimensional structure.First, adopt metal chloride to be hydrolyzed at graphenic surface, obtain graphene-based metal oxide nano-sheet by situ synthesis; Secondly, by hydro-thermal, this nanometer sheet is assembled into three-dimensional graphene-based metal oxide composite; Finally, by freeze drying, obtain the composite material of three-dimensional structure.
In the present invention, prepare the concrete grammar with the graphene-based metal tin dioxide composite material of three-dimensional shell structure to comprise the steps:
Step one, prepare graphene-based metal oxide nano-sheet:
First, be add a small amount of concentrated hydrochloric acid in graphene oxide (GO) dimethyl formamide solution (DMF) of 1mg/mL to concentration, ultrasonicly mix;
Secondly, add metal chloride in above-mentioned dispersion liquid after, 60-90 DEG C of insulation 12 hours;
Finally, undertaken centrifugal by above-mentioned reacted solution, deionized water washs, and the concentrated deionized water dispersion liquid obtained is stand-by;
The graphene-based tin ash aeroge of step 2, preparation three-dimensional:
First, be placed in the vial of 10mL to the dispersion liquid of above-mentioned graphene-based metal oxide nano-sheet and vial be placed in the water heating kettle Direct Hydrothermal process of 80mL;
Secondly, by the block freeze drying process obtained after above-mentioned reaction, the composite material of the graphene-based tin ash of three-dimensional structure is finally obtained.
Wherein, described metal chloride is preferably stannic chloride pentahydrate (SnCl
45H
2o).
In the specific embodiment of the present invention, add metal chloride in the DMF dispersion liquid of GO before, first in dispersion liquid, add hydrochloric acid, regulate pH value of solution to 1-3; After adding metal chloride under intense agitation after ultrasonic, then at 60 ~ 90 DEG C of insulation 1-5 hour.
In concrete preparation method of the present invention
The metal chloride added in step one and the mass ratio of graphene oxide are preferably 1.16:1.
In a preferred embodiment of the invention, the concentration of graphene-based metal oxide nano-sheet dispersion liquid is in deionized water preferably 5mg/mL.
In the preparation process in accordance with the present invention, when three-dimensional assembling being carried out to nanometer sheet in step 2, the method for hydro-thermal self assembly is adopted.
In a preferred embodiment of the invention, the product that obtains of step 2 was by freeze drying 48 hours.
In the present invention, adopt cryodesiccated method, those skilled in the art can take the different time according to actual needs, are not particularly limited this.
In the preparation process in accordance with the present invention, by metal oxide particle load at graphenic surface, inhibit the reunion of its particle to a certain extent, increase specific area, thus improve the capacity of material.The material of this three-dimensional structure, not only can alleviate metal oxide as the change in volume of stannic oxide particle in charge and discharge process, suppress the pulverizing of its particle and come off, thus improve the cyclical stability of material greatly simultaneously.And three-dimensional structure is conducive to fully contacting of electrolyte and material thus can improves the conductivity of whole electrode material, realizes the quick transmission of electronics, thus makes material have high high rate performance.
On the other hand, present invention also offers a kind of application with the graphene-based metal tin dioxide composite material of three-dimensional structure.
The graphene-based metal tin dioxide composite material with three-dimensional structure of the present invention is preferably applied in lithium ion battery negative material.When the composite material of three-dimensional structure of the present invention is as lithium ion battery negative material, can also strengthen its cycle performance while raising negative material capacity.
In specific embodiment of the invention scheme, the button-shaped half-cell of lithium ion is to have the graphene-based metal tin dioxide composite material of three-dimensional structure as mentioned above for negative material, just very lithium metal, electrolyte is ethyl carbonate or the dimethyl carbonate solution of lithium hexafluorophosphate solution.
The present invention adopts the two-dimensional graphene of monolayer carbon atomic structure as skeleton, and stannic chloride pentahydrate, as tin source presoma, prepares the graphene-based metal stannic oxide nanometer composite material of three-dimensional structure by simple two-step method.The metal oxide nanoparticles obtained by the inventive method equably load, on Graphene skeleton, has micron-sized structure simultaneously.Prove through electro-chemical test, obtained composite material has excellent cyclical stability and high rate performance; Experiment proves, at 100mAg
-1charging or discharging current under: the discharge capacity of obtained tin dioxide material can reach 700mAhg
-1.Therefore, the present invention is that metal oxide provides good experimental data and theories integration at the investigation and application of electrochemical field.
Be described further below with reference to the technique effect of accompanying drawing to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.
Accompanying drawing explanation
Fig. 1 is the shape appearance figure of the three-dimensional graphite thiazolinyl tin ash of embodiments of the invention 1; Wherein, the TEM figure of embodiment 1 a), b) is respectively, c), d) for the SEM of embodiment 1 schemes.
Fig. 2 is the cycle performance figure of three-dimensional graphite thiazolinyl tin dioxide composite material as lithium ion battery negative material of embodiments of the invention 1.
Fig. 3 is the high rate performance figure of three-dimensional graphite thiazolinyl tin dioxide composite material as lithium ion battery negative material of embodiments of the invention 1.
Embodiment
Embodiment 1
The first step, prepare graphene-based stannic oxide nanometer sheet:
(1) by ultrasonic for the dimethyl formamide solution (50mL) of 1mg/mL graphene oxide, the dispersion liquid mixed is formed;
(2) in above-mentioned dispersion liquid, add concentrated hydrochloric acid, regulate pH value of solution to 2; Add stannic chloride pentahydrate (SnCl with vigorous stirring
45H
2o), add 80 DEG C of insulations 12 hours, cooling;
Wherein, the SnCl of interpolation
42H
2the quality amount ratio of O and graphene oxide is 1.16:1.
(3) above-mentioned reacted solution is carried out centrifugal, spend deionized water, repeated centrifugation, washing operation four times, concentrate and obtain comparatively thick liquid, be graphene-based stannic oxide nanometer sheet.
The graphene-based tin dioxide composite material of second step, preparation three-dimensional structure:
(1) the thickness body fluid getting the graphene-based stannic oxide nanometer sheet being condensed into the above-mentioned preparation of 10mL is placed in vial, hydrothermal treatment consists, and keeps 18 hours at 180 DEG C;
(2) by the above-mentioned reacted block materials obtained, after freeze drying 48h, finally obtain the graphene-based tin dioxide composite material of three-dimensional structure, SEM, TEM photo of the graphene-based tin dioxide composite material sheet of this three-dimensional structure is as a)-d of Fig. 1) shown in.
Be assembled into the button-shaped half-cell of lithium ion (be lithium metal to electrode) using gained composite material as lithium ion battery negative material, carry out electro-chemical test to the button-shaped half-cell of this lithium ion, its cycle performance figure, high rate performance figure are respectively as shown in Figure 2,3.
Wherein, SnO
2/ GFscharge/discharge is respectively graphene-based tin ash charge and discharge figure, SnO as lithium ion battery negative material of three-dimensional structure
2/ GSscharge/discharge is respectively the charge and discharge figure of the two-dimensional graphene base tin dioxide composite material under equal rate of charge as lithium ion battery negative material.As can be seen from Figure 2 the composite material of three-dimensional structure shows higher capacity (850mAhg
-1), and very superior cycle performance.It still remains 800mAhg after 70 circle circulations
-1capacity, the 800mAhg of the material capacity of two dimension then ten circles in the past
-1drop to only 400mAhg
-1.As shown in Figure 3, the material of three-dimensional structure is at 500mAg
-1big current under still maintain 630mAhg
-1capacity, this is very excellent high rate performance concerning tin dioxide material.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technical staff in the art, all should by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (4)
1. a preparation method for the graphene-based tin dioxide composite material of three-dimensional structure, is characterized in that, comprise the following steps:
Step one, prepare graphene-based stannic oxide nanometer sheet;
First, be add a small amount of concentrated hydrochloric acid in the graphene oxide dimethyl formamide solution of 1mg/mL to regulate pH value of solution to 2 to concentration, ultrasonicly mix;
Secondly, add stannic chloride pentahydrate in above-mentioned solution after, 80 DEG C of insulations, react 12 hours;
Finally, undertaken centrifugal by above-mentioned reacted solution, deionized water washs, and obtains the thick liquid of graphene-based stannic oxide nanometer sheet;
The graphene-based tin dioxide composite material of step 2, preparation three-dimensional;
First, the thick liquid of above-mentioned graphene-based stannic oxide nanometer sheet be placed in the vial of 10mL and vial be placed in the water heating kettle Direct Hydrothermal process of 80mL;
Secondly, by the block freeze drying process obtained after above-mentioned hydrothermal treatment consists, the graphene-based tin dioxide composite material of three-dimensional structure is finally obtained.
2. the preparation method of a kind of graphene-based tin dioxide composite material of three-dimensional structure as claimed in claim 1, it is characterized in that, the mass ratio of graphene oxide and described stannic chloride pentahydrate is 1:1.16.
3. the graphene-based tin dioxide composite material of three-dimensional structure for preparing of preparation method as claimed in claim 1.
4. the application of graphene-based tin dioxide composite material in lithium ion battery of three-dimensional structure that prepare of preparation method as claimed in claim 1.
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Cited By (1)
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