CN103441246A - Preparation method and application of three-dimensional nitrogen-doped graphene base tin dioxide composite material - Google Patents
Preparation method and application of three-dimensional nitrogen-doped graphene base tin dioxide composite material Download PDFInfo
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- CN103441246A CN103441246A CN2013102573588A CN201310257358A CN103441246A CN 103441246 A CN103441246 A CN 103441246A CN 2013102573588 A CN2013102573588 A CN 2013102573588A CN 201310257358 A CN201310257358 A CN 201310257358A CN 103441246 A CN103441246 A CN 103441246A
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Abstract
The present invention discloses a preparation method and an application of a three-dimensional structure nitrogen-doped graphene base tin dioxide composite material. According to the preparation method, two-dimensional graphene with a single layer carbon atom structure is adopted as a carrier, and polyethyleneimine is adopted as a nitrogen source and a cross-linking agent to prepare the three-dimensional nitrogen-containing graphene base metal oxide nanometer composite material, wherein metal oxide nanoparticles obtained through the method are uniformly supported on the nitrogen-containing graphene skeleton. Electrochemistry test results show that the three-dimensional structure nitrogen-doped graphene base metal oxide composite material obtained through the preparation method has excellent cycle stability and rate performance, and discharge capacity of the tin dioxide material can be 1000 mAh.g<-1> under a charge-discharge current of 200 mAg<-1>.
Description
Technical field
The present invention relates to method and the application thereof of the nitrogen-doped graphene Base Metal tin ash 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 has obtained increasing attention.Hybrid vehicle and electric automobile industry development are rapid, and lithium ion battery is widely used as wherein important energy storage device.Lithium ion battery has energy density high, and some good performances such as good cycle, also be considered to one of the most effective energy storage mode at present, and therefore, further improving its energy density and cycle performance is also difficult point and the focus of instantly studying.
The negative pole of lithium ion battery is the important component part of battery, and its structure and performance directly affect capacity and the cycle performance of lithium ion battery.Commercial lithium ion battery negative material be take graphite as main at present, and the graphite cost is low, and wide material sources are suitable for commercialization; But its capacity is lower, theoretical capacity is only 372mAh g
-1, while applying in the field that needs high-energy output, be restricted.
Metal oxide SnO
2deng have very high specific capacity as lithium ion battery negative material, its specific capacity is up to 700-1000mAh g
-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 opening circuit of active material and collector.Therefore, all there is capacity attenuation problem rapidly in the most metals oxide during as lithium ion cell electrode, and this has also limited development and the practical application of metal oxide as lithium ion battery negative material.
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, for example electrode material is carried out to modification, comprise the preparation of doping, compound and nano material, improve the performance of electrode material 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, preparing novel nanostructure aspect has become the focus of current research.
The material with carbon element of Heteroatom doping has more excellent conductivity of pure material with carbon element etc. that its unique premium properties is arranged; Make its carrier that can be used as good metal oxide, by absorbing the change in volume stress of metal oxide in the lithium ion battery charge and discharge process, thereby strengthen the cycle performance of metal oxide.Therefore, the material with carbon element of Heteroatom doping and metal oxide are carried out to the negative material of the composite material of the novel nano structure that combined structure goes out as lithium ion battery, be expected to significantly improve the performance of lithium ion battery, and also there is far reaching significance for its expansion application.
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 application thereof with nitrogen-doped graphene Base Metal oxide composite of three-dimensional structure.Particularly, the Graphene of the two dimension of employing monolayer carbon atomic structure is as carrier, and polymine, as the nitrogenous source presoma, is prepared the graphene-based metal oxide nano composite material of three-dimensional nitrogen 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 of graphene-based metal oxide composite of the nitrogen doping with three-dimensional structure.
Preparation method of the present invention adopts two step synthesis to have the nitrogen-doped graphene Base Metal oxide composite of three-dimensional structure.At first, metal chloride, at the graphene oxide surface hydrolysis, is obtained to graphene-based metal oxide nano-sheet by situ synthesis; Secondly, the crosslinked action that utilizes polymine under the condition of hydro-thermal is that this nanometer sheet is self-assembled into three-dimensional structure, introduces nitrogenous source simultaneously, by the calcining carbonization, obtains three-dimensional nitrogen-doped graphene tin ash composite material.
In the present invention, preparing the concrete grammar with three-dimensional nitrogen-doped graphene Base Metal tin ash composite material comprises the steps:
At first, the graphene oxide that is 1mg/mL by concentration (GO) dimethyl formamide (DMF) solution, ultrasonic mixing;
Secondly, after adding metal oxide precursor in above-mentioned dispersion liquid, after mixing 60-90 ℃ of insulation 12 hours;
Finally, above-mentioned reacted solution is carried out centrifugal, deionized water washing, the concentrated deionized water dispersion liquid obtained is stand-by;
At first, be placed in the vial of 10mL to the dispersion liquid of above-mentioned graphene-based metal oxide nano-sheet, add the crosslinking agent of a certain amount of concentration known, after mixing, and the water heating kettle Direct Hydrothermal processing that vial is placed in to 80mL;
Secondly, by the block freeze drying calcination processing obtained after above-mentioned reaction, finally obtain the composite material of the nitrogen-doped graphene base tin ash of three-dimensional structure;
Wherein, described metal oxide precursor is stannic chloride pentahydrate (SnCl
45H
2o).Crosslinking agent is polymine (PEI), is again the nitrogenous source presoma simultaneously.
In the specific embodiment of the present invention, before in dispersion liquid, adding metal chloride, first add hydrochloric acid in dispersion liquid, regulator solution pH to 1-3; Then after adding metal chloride under intense agitation, then at 60～90 ℃ of insulation 1-5 hour.
In the specific implementation, the stannic chloride pentahydrate added in step 1 and the mass ratio of graphene oxide are preferably 2.27:1 in the present invention;
In preparation method of the present invention, while in step 2, nanometer sheet being carried out to the three-dimensional assembling, adopt the method for hydro-thermal self assembly.
In a preferred embodiment of the invention, the product that step 2 obtains 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, and this is not particularly limited.
In preparation method of the present invention, metal oxide particle is loaded on to the Graphene surface, suppressed to a certain extent the reunion of its particle, increase specific area, thereby improve the capacity of material.The material of this three-dimensional structure simultaneously, not only can alleviate metal oxide as stannic oxide particle the change in volume in charge and discharge process, suppress the pulverizing of its particle and come off, thereby having improved greatly the cyclical stability of material.The nitrogen doping can effectively improve the ratio of carbon oxygen in material, thereby suppresses the oxidation of organic bath, has improved to a certain extent the cycle performance of material.And, thereby three-dimensional structure be conducive to electrolyte and material fully contact the conductivity that can improve whole electrode material, realize the quick transmission of electronics, thereby make material there is high high rate performance.
On the other hand, the present invention also provides a kind of application with graphene-based metal tin ash composite material of three-dimensional structure.
Of the present invention have the graphene-based metal tin ash composite material advantageous applications of three-dimensional structure in lithium ion battery negative material.The composite material of three-dimensional structure of the present invention during as lithium ion battery negative material, can also strengthen its cycle performance when improving the negative material capacity.
In the specific embodiment of the invention scheme, it is negative material that the button-shaped half-cell of lithium ion be take the graphene-based metal tin ash composite material that has as mentioned above three-dimensional structure, just very lithium metal, the ethyl carbonate that electrolyte is lithium hexafluoro phosphate solution or dimethyl carbonate solution.
The present invention adopts the two-dimentional Graphene of monolayer carbon atomic structure as skeleton, and stannic chloride pentahydrate is as tin source presoma, and polymine, as crosslinking agent, is prepared the graphene-based metal stannic oxide nanometer composite material of three-dimensional structure by simple two-step method.The method has technique simple, mild condition, the advantage such as with low cost.The metal oxide nanoparticles obtained by the inventive method loads on the Graphene skeleton equably, has micron-sized structure simultaneously.Through electro-chemical test, prove, prepared composite material has excellent cyclical stability and high rate performance; Experiment showed, at 0.2Ag
-1charging or discharging current under: the discharge capacity of the tin dioxide material made can reach 1010mAhg
-1.Therefore, the present invention provides good experimental data and theoretical the support for metal oxide in research and the application of electrochemical field.
Technique effect below with reference to accompanying drawing to design of the present invention, concrete structure and generation is described further, to understand fully purpose of the present invention, feature and effect.
The 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, the TEM figure that c is embodiment 1.
Fig. 2 is the cycle performance figure of the three-dimensional nitrogen-doped graphene base tin ash composite material of embodiments of the invention 1 as lithium ion battery negative material.
Fig. 3 is the high rate performance figure of the three-dimensional nitrogen-doped graphene base tin ash composite material of embodiments of the invention 1 as lithium ion battery negative material.
Embodiment
Embodiment 1
The first step, prepare graphene-based stannic oxide nanometer sheet:
(1) dimethyl formamide solution of 1mg/mL graphene oxide (50mL) is ultrasonic, form the dispersion liquid mixed;
(2) add concentrated hydrochloric acid in above-mentioned dispersion liquid, regulator solution pH to 2; Add stannic chloride pentahydrate (SnCl under vigorous stirring
45H
2o), add 80 ℃ 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, with deionized water washing, repeated centrifugation, washing operation four times, concentrated obtaining than thick liquid, be graphene-based stannic oxide nanometer sheet.
The graphene-based tin ash composite material of second step, the doping of preparation three-dimensional structure nitrogen:
(1) get the PEI aqueous solution that adds 1mL in the viscous fluid of graphene-based stannic oxide nanometer sheet of above-mentioned preparation of the above-mentioned 5mg/mL concentrated, after mixing, be placed in the hot 12-18h of Water Under of 180 ℃;
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 ℃ of calcining carbonization 2h, finally obtain the nitrogen-doped graphene base tin ash composite material of three-dimensional structure, the SEM of this material and TEM photo are as shown in Fig. 1 a-c.
The gained composite material of take is assembled into the button-shaped half-cell of lithium ion (being lithium metal to electrode) as lithium ion battery negative material, and the button-shaped half-cell of this lithium ion is carried out to electro-chemical test, and its cycle performance figure, high rate performance figure are respectively as shown in Figure 2,3.
As can be seen from Figure 2 the nitrogen doped and compounded material of three-dimensional structure has demonstrated high capacity (1010mAhg
-1), and very superior cycle performance.Material is at 0.2mA g
-1under charging or discharging current, after 100 circle circulations, still keeping 1000mAhg
-1capacity.As shown in Figure 3, material is at large electric current 8Ag
-1large electric current under still maintain 200mAhg
-1capacity, when electric current returns to 0.2mA g
-1the time, capacity can return to 1010mAh g equally
-1, this is very excellent high rate performance concerning tin dioxide material.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area just can design according to the present invention be made many modifications and variations without creative work.Therefore, all technical staff in the art, all should be in the determined protection range by 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 (8)
1. the preparation method of the nitrogen-doped graphene base tin ash composite material of a three-dimensional structure, is characterized in that, comprises the following steps;
Step 1, prepare graphene-based metal oxide nano-sheet:
At first, add a small amount of concentrated hydrochloric acid in the graphene oxide dimethyl formamide solution that is 1mg/mL to concentration, ultrasonic mixing;
Secondly, after adding metal oxide precursor in above-mentioned solution, 60-90 ℃ of insulation 12 hours;
Finally, above-mentioned reacted solution is carried out centrifugal, deionized water washing, the concentrated deionized water dispersion liquid obtained is stand-by;
Step 2, the three-dimensional graphene-based tin ash aeroge of preparation:
At first, be placed in the vial of 20mL to the dispersion liquid of above-mentioned graphene-based metal oxide nano-sheet, add the polymine of a certain amount of concentration known, after mixing, and the water heating kettle Direct Hydrothermal processing that vial is placed in to 150mL;
Secondly, by the block freeze drying calcination processing obtained after above-mentioned reaction, finally obtain the nitrogen-doped graphene base tin ash composite material of three-dimensional structure.
2. the preparation method of the nitrogen-doped graphene base tin ash composite material of a kind of three-dimensional structure as claimed in claim 1, is characterized in that, described metal oxide precursor is stannic chloride pentahydrate.
3. the preparation method of the nitrogen-doped graphene base tin ash composite material of a kind of three-dimensional structure as claimed in claim 1, is characterized in that, polymine is nitrogenous source.
4. the preparation method of the nitrogen-doped graphene base tin ash composite material of a kind of three-dimensional structure as claimed in claim 1, is characterized in that, polymine is crosslinking agent.
5. the preparation method of the nitrogen-doped graphene base tin ash 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 metal oxide precursor is 1:2.27.
6. the preparation method of the nitrogen-doped graphene base tin ash 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.
7. the nitrogen-doped graphene base tin ash composite material of the three-dimensional structure that the preparation method of the nitrogen-doped graphene base tin ash composite material of a kind of three-dimensional structure as claimed in claim 1 obtains.
8. the application of nitrogen-doped graphene base tin ash composite material in lithium ion battery of three-dimensional structure as claimed in claim 1.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104143631A (en) * | 2014-05-12 | 2014-11-12 | 上海大学 | Method for preparing graphene aerogel loaded tin dioxide composite material |
| CN105118966A (en) * | 2015-09-19 | 2015-12-02 | 中国石油大学(华东) | Sn-C composite material with high N content of lithium battery cathode and preparation method of Sn-C composite material |
| CN106941176A (en) * | 2017-05-18 | 2017-07-11 | 广东工业大学 | A kind of SnO as lithium ion battery negative2/ C nano medicine ball and preparation method thereof |
| CN107482152A (en) * | 2017-07-31 | 2017-12-15 | 北京理工大学 | A kind of lithium-sulfur cell strengthens graphene intercalation material with organic polymer |
| CN107651668A (en) * | 2017-09-07 | 2018-02-02 | 山东大学 | A kind of expansible preparation method of the grapheme material of high density N doping |
| CN108987719A (en) * | 2018-07-27 | 2018-12-11 | 盐城市新能源化学储能与动力电源研究中心 | A kind of three-dimensional sulfur doping porous carbon/stannic oxide combination electrode material and preparation method thereof |
| CN110474031A (en) * | 2019-08-20 | 2019-11-19 | 齐鲁工业大学 | A method of Copper-cladding Aluminum Bar mangano-manganic oxide composite material is prepared using polymeric complexing agent |
| CN110473712A (en) * | 2019-08-27 | 2019-11-19 | 华东师范大学 | A kind of derivative nanometer sheet intercalation material of MOF and preparation method and its application |
| 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 |
| CN113782734A (en) * | 2021-08-24 | 2021-12-10 | 南昌大学 | Preparation method of silicon monoxide negative pole piece |
| CN114068895A (en) * | 2021-10-28 | 2022-02-18 | 华南理工大学 | Lignin-based graphene porous carbon nanosheet tin dioxide composite material and preparation and application thereof |
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Cited By (17)
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| CN104143631A (en) * | 2014-05-12 | 2014-11-12 | 上海大学 | Method for preparing graphene aerogel loaded tin dioxide composite material |
| CN105118966A (en) * | 2015-09-19 | 2015-12-02 | 中国石油大学(华东) | Sn-C composite material with high N content of lithium battery cathode and preparation method of Sn-C composite material |
| CN106941176A (en) * | 2017-05-18 | 2017-07-11 | 广东工业大学 | A kind of SnO as lithium ion battery negative2/ C nano medicine ball and preparation method thereof |
| 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 |
| CN107482152A (en) * | 2017-07-31 | 2017-12-15 | 北京理工大学 | A kind of lithium-sulfur cell strengthens graphene intercalation material with organic polymer |
| 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 |
| CN107651668A (en) * | 2017-09-07 | 2018-02-02 | 山东大学 | A kind of expansible preparation method of the grapheme material of high density N doping |
| CN108987719A (en) * | 2018-07-27 | 2018-12-11 | 盐城市新能源化学储能与动力电源研究中心 | A kind of three-dimensional sulfur doping porous carbon/stannic oxide combination electrode material and preparation method thereof |
| 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 |
| CN110474031A (en) * | 2019-08-20 | 2019-11-19 | 齐鲁工业大学 | A method of Copper-cladding Aluminum Bar mangano-manganic oxide composite material is prepared using polymeric complexing agent |
| CN110473712A (en) * | 2019-08-27 | 2019-11-19 | 华东师范大学 | A kind of derivative nanometer sheet intercalation material of MOF and preparation method and its application |
| 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 |
| CN113782734A (en) * | 2021-08-24 | 2021-12-10 | 南昌大学 | Preparation method of silicon monoxide negative pole piece |
| CN114068895A (en) * | 2021-10-28 | 2022-02-18 | 华南理工大学 | Lignin-based graphene porous carbon nanosheet tin dioxide composite material and preparation and application thereof |
| 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 |
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