CN103441246B - The preparation method of the graphene-based tin dioxide composite material of three-dimensional N doping and application thereof - Google Patents
The preparation method of the graphene-based tin dioxide composite material of three-dimensional N doping and application thereof Download PDFInfo
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- CN103441246B CN103441246B CN201310257358.8A CN201310257358A CN103441246B CN 103441246 B CN103441246 B CN 103441246B CN 201310257358 A CN201310257358 A CN 201310257358A CN 103441246 B CN103441246 B CN 103441246B
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Abstract
The invention discloses a kind of preparation method and application thereof of nitrogen-doped graphene base tin dioxide composite material of three-dimensional structure.Preparation method of the present invention adopts the two-dimensional graphene of monolayer carbon atomic structure as carrier, using polymine as nitrogenous source and crosslinking agent, prepares three-dimensional nitrogenous graphene-based metal oxide nano composite material.The metal oxide nanoparticles obtained by the method equably load on nitrogenous Graphene skeleton.Prove through electro-chemical test, the nitrogen-doped graphene metal oxides 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 200mAg
-1charging or discharging current under: wherein tin dioxide material discharge capacity can reach 1000mAhg
-1.
Description
Technical field
The present invention relates to method and the application thereof of the nitrogen-doped graphene Base Metal 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 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 doping, compound and nano material, the performance of electrode material is improved by these methods, particularly at metal oxide and material with carbon element, especially the material with carbon element of the Heteroatom doping such as boron nitrogen carries out the compound of nanoscale, prepares the focus that novel nanostructure aspect has become research at present.
The material with carbon element of Heteroatom doping has the more excellent conductivity etc. of pure material with carbon element to have the premium properties of its uniqueness; 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, the material with carbon element of Heteroatom doping 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 of metal oxide cycle performance.
For achieving the above object, the invention provides a kind of preparation method and the application thereof with the nitrogen-doped graphene metal oxides composite material of three-dimensional structure.Particularly, adopt the Graphene of the two dimension of monolayer carbon atomic structure as carrier, polymine, as nitrogenous source presoma, prepares the graphene-based metal oxide nano composite material of three-dimensional N doping.
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 oxide composite of the N doping of three-dimensional structure.
Preparation method of the present invention adopts two step synthesis to have the nitrogen-doped graphene metal oxides composite material of three-dimensional structure.First, metal chloride is hydrolyzed in surface of graphene oxide, obtains graphene-based metal oxide nano-sheet by situ synthesis; Secondly, under the condition of hydro-thermal, utilize the crosslinked action of polymine to be that this nanometer sheet is self-assembled into three-dimensional structure, introduce nitrogenous source simultaneously, by calcining carbonization, obtain three-dimensional nitrogen-doped graphene tin dioxide composite material.
In the present invention, prepare the concrete grammar with three-dimensional nitrogen-doped graphene Base Metal tin dioxide composite material to comprise the steps:
First, be graphene oxide (GO) dimethyl formamide (DMF) solution of 1mg/mL by concentration, ultrasonicly mix;
Secondly, add metal oxide precursor in above-mentioned dispersion liquid after, 60-90 DEG C of insulation 12 hours after mixing;
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, the dispersion liquid to above-mentioned graphene-based metal oxide nano-sheet is placed in the vial of 10mL, adds the crosslinking agent of a certain amount of concentration known, after mixing, and vial is placed in the water heating kettle Direct Hydrothermal process of 80mL;
Secondly, by the block freeze drying calcination processing obtained after above-mentioned reaction, the composite material of the nitrogen-doped graphene base tin ash of three-dimensional structure is finally obtained;
Wherein, described metal oxide precursor is stannic chloride pentahydrate (SnCl
45H
2o).Crosslinking agent is polymine (PEI), is again nitrogenous source presoma simultaneously.
In the specific embodiment of the present invention, before add metal chloride in dispersion liquid, first in dispersion liquid, add hydrochloric acid, regulate pH value of solution to 1-3; Then after adding metal chloride under intense agitation, then at 60 ~ 90 DEG C of insulation 1-5 hour.
In the specific implementation, the stannic chloride pentahydrate added in step one and the mass ratio of graphene oxide are preferably 2.27:1 in the present invention;
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.N doping effectively can improve the ratio of carbon oxygen in material, thus suppresses the oxidation of organic bath, improves the cycle performance of material to a certain extent.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 is as tin source presoma, and polymine, as crosslinking agent, prepares the graphene-based metal stannic oxide nanometer composite material of three-dimensional structure by simple two-step method.The advantages such as the method has technique simple, mild condition, with low cost.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 0.2Ag
-1charging or discharging current under: the discharge capacity of obtained tin dioxide material can reach 1010mAhg
-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 nitrogen-doped graphene base tin ash of embodiments of the invention 1-3; Wherein, a, b are respectively the SEM figure of embodiment 1, and c is the TEM figure of embodiment 1.
Fig. 2 is the cycle performance figure of three-dimensional nitrogen-doped graphene base 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 nitrogen-doped graphene base 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 2.27:1.
(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 N doping:
(1) get the PEI aqueous solution adding 1mL in the viscous fluid of the graphene-based stannic oxide nanometer sheet of the above-mentioned preparation of the above-mentioned 5mg/mL concentrated, after mixing, be placed in the hot 12-18h of Water Under of 180 DEG C;
Wherein, the consumption mass ratio of graphene oxide and PVA is 1:0.044;
(2) by the above-mentioned reacted block obtained, after freeze drying 48h, through N
2protect lower 300 DEG C of calcining carbonization 2h, finally obtain the nitrogen-doped graphene base tin dioxide composite material of three-dimensional structure, SEM and the TEM photo of this material as illustrated in figures la-c.
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.
As can be seen from Figure 2 the N doping composite material of three-dimensional structure shows high capacity (1010mAhg
-1), and very superior cycle performance.Material is at 0.2mAg
-1under charging or discharging current, after 100 circle circulations, still remain 1000mAhg
-1capacity.As shown in Figure 3, material is at big current 8Ag
-1big current under still maintain 200mAhg
-1capacity, when electric current returns to 0.2mAg
-1time, capacity can return to 1010mAhg equally
-1, 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 (5)
1. a preparation method for the nitrogen-doped graphene base 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 to 1-3 to concentration, ultrasonicly mix;
Secondly, add stannic chloride pentahydrate in above-mentioned solution after, 60-90 DEG C of insulation 12 hours;
Finally, undertaken centrifugal by above-mentioned reacted solution, deionized water washs, and concentrates and obtains comparatively thick liquid, be described graphene-based stannic oxide nanometer sheet;
The graphene-based tin ash aeroge of step 2, preparation three-dimensional:
First, the dispersion liquid of above-mentioned graphene-based stannic oxide nanometer sheet is placed in the vial of 20mL, add the polymine of a certain amount of concentration known as nitrogenous source and crosslinking agent, after mixing, vial is placed in the water heating kettle Direct Hydrothermal process of 150mL;
Secondly, the block obtained after above-mentioned reaction is carried out successively freeze drying, calcining two step process, finally obtain the nitrogen-doped graphene base tin dioxide composite material of three-dimensional structure.
2. the preparation method of the nitrogen-doped graphene base tin dioxide composite material of a kind of three-dimensional structure as claimed in claim 1, is characterized in that, the mass ratio of graphene oxide and stannic chloride pentahydrate is 1:2.27.
3. the preparation method of the nitrogen-doped graphene base tin dioxide composite material of a kind of three-dimensional structure as claimed in claim 1, is characterized in that, the mass ratio of graphene oxide and polymine is 1:0.044.
4. the nitrogen-doped graphene base tin dioxide composite material of three-dimensional structure that obtains of the preparation method of the nitrogen-doped graphene base tin dioxide composite material of a kind of three-dimensional structure as claimed in claim 1.
5. the application of nitrogen-doped graphene base tin dioxide composite material in lithium ion battery of three-dimensional structure as claimed in claim 4.
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|---|---|---|---|---|
| CN104143631B (en) * | 2014-05-12 | 2016-12-07 | 上海大学 | A kind of preparation method of graphene aerogel load tin dioxide composite material |
| CN105118966B (en) * | 2015-09-19 | 2016-08-24 | 中国石油大学(华东) | A kind of high nitrogen-containing tin carbon composite for cathode of lithium battery and preparation method |
| CN106941176B (en) * | 2017-05-18 | 2019-09-27 | 广东工业大学 | A kind of SnO as negative electrode of lithium ion battery2/ C nano medicine ball and preparation method thereof |
| CN107482152B (en) * | 2017-07-31 | 2019-08-06 | 北京理工大学 | A kind of lithium-sulfur cell organic polymer enhancing graphene intercalation material |
| CN107651668B (en) * | 2017-09-07 | 2020-04-07 | 山东大学 | Extensible preparation method of high-density N-doped graphene material |
| CN108987719B (en) * | 2018-07-27 | 2020-11-03 | 盐城市新能源化学储能与动力电源研究中心 | Three-dimensional sulfur-doped porous carbon/tin dioxide composite electrode material and preparation method thereof |
| CN110474031B (en) * | 2019-08-20 | 2022-10-18 | 齐鲁工业大学 | Method for preparing copper-doped manganous-manganic oxide composite material by using polymeric complexing agent |
| CN110473712B (en) * | 2019-08-27 | 2021-02-26 | 华东师范大学 | MOF derived nanosheet intercalation material, and preparation method and application thereof |
| CN112164777A (en) * | 2020-09-23 | 2021-01-01 | 上海应用技术大学 | Three-dimensional layered tin oxide quantum dot/graphene framework composite material and preparation |
| CN113782734B (en) * | 2021-08-24 | 2023-04-07 | 南昌大学 | Preparation method of silicon monoxide negative pole piece |
| CN114068895B (en) * | 2021-10-28 | 2023-01-06 | 华南理工大学 | Lignin-based graphene porous carbon nanosheet tin dioxide composite material and preparation and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324522A (en) * | 2011-10-28 | 2012-01-18 | 中国科学院上海硅酸盐研究所 | Nitrogen-doped graphene/tin oxide nano composite material and preparation method thereof |
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| CN102324522A (en) * | 2011-10-28 | 2012-01-18 | 中国科学院上海硅酸盐研究所 | Nitrogen-doped graphene/tin oxide nano composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Self-Assembled Fe2O3/Graphene Aerogel with High Lithium Storage Performance;Li Xiao et al;《ACS Appl.Mater.& Interfaces》;20130403;第5卷;3764-3769页 * |
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