CN103326007A - Preparation method and application of three-dimensional graphene-based stannic oxide composite material - Google Patents
Preparation method and application of three-dimensional graphene-based stannic oxide composite material Download PDFInfo
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- CN103326007A CN103326007A CN2013102564659A CN201310256465A CN103326007A CN 103326007 A CN103326007 A CN 103326007A CN 2013102564659 A CN2013102564659 A CN 2013102564659A CN 201310256465 A CN201310256465 A CN 201310256465A CN 103326007 A CN103326007 A CN 103326007A
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Abstract
The invention discloses a preparation method and an application of a graphene-based stannic oxide composite material with a three-dimensional structure. The preparation method disclosed by the invention is characterized in that graphene with a single-layer carbon atomic structure is used as a carrier, stannic chloride pentahydrate is used as a tin source precursor, and the graphene-based stannic oxide composite material with the three-dimensional structure is prepared through a hydrothermal freeze-dried method. The stannic oxide nanometer particles obtained by the method are uniformly loaded on a graphene skeleton to be assembled into aerogel with the three-dimensional structure very well. The electrochemical test proves that the graphene-based stannic oxide composite material with the three-dimensional structure obtained by the preparation method has excellent circulation stability and rate capability. Experiments prove that the discharge capacity of the stannic oxide material can reach 800mAh.g<-1> in 100mAh.g<-1> charge-discharge currents.
Description
Technical field
The present invention relates to a kind of method and application thereof of graphene-based 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 are considered at present one of the most effective energy storage mode, and therefore, further improving its energy density and cycle performance also is 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 is 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, and theoretical capacity only is 372mAhg
-1, be restricted when in the field that needs high-energy output, using.
Metal oxide such 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
-1But most of metal oxide, especially SnO
2Change in volume is up to 200-300% in charge and discharge process as electrode material, and this change in volume can cause the efflorescence of electrode, causes opening circuit of active material and collector.Therefore, all there is rapidly problem of capacity attenuation 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, researchers conduct in-depth research for these problems that metal oxide exists, for example electrode material is carried out modification, comprise coating, doping, compound and preparations of nanomaterials, improve 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 present research.
Material with carbon element has its unique premium properties: stability, good conductivity, light weight; Make its carrier that can be used as good metal oxide, by the change in volume stress of absorption metal oxide in the lithium ion battery charge and discharge process, thus the cycle performance of enhancing metal oxide.Therefore, material with carbon element and metal oxide are carried out the composite material of the novel nano structure that combined structure goes out as the negative material of lithium ion battery, be expected to significantly improve the performance of lithium ion battery, and expand to use for it and also have far reaching significance.
Summary of the invention
Because the defects of prior art, technical problem to be solved by this invention provides 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 application thereof with 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 prepares the graphene-based metal tin ash composite material of three-dimensional structure as tin source presoma.
The present invention solves above-mentioned technical problem by the following technical programs:
On the one hand, the invention provides a kind of graphene-based metal tin ash composite manufacture method with three-dimensional structure.
Preparation method of the present invention adopts two step synthesis to have the graphene-based metal tin ash composite material of three-dimensional structure.At first, adopt metal chloride at the Graphene surface hydrolysis, obtain graphene-based metal oxide nano-sheet by in situ synthesis; Secondly, by hydro-thermal this nanometer sheet is assembled into three-dimensional graphene-based metal oxide composite; At last, by freeze drying, obtain the composite material of three-dimensional structure.
In the present invention, the concrete grammar of graphene-based metal tin ash composite material of preparation with three-dimensional shell structure comprises the steps:
Step 1, prepare graphene-based metal oxide nano-sheet:
At first, be a small amount of concentrated hydrochloric acid of the middle adding of graphene oxide (GO) dimethyl formamide solution (DMF) of 1mg/mL to concentration, ultrasonic mixing;
Secondly, add metal chloride in the above-mentioned dispersion liquid after, 60-90 ℃ of insulation 12 hours;
At last, above-mentioned reacted solution is carried out centrifugal, deionized water washing, the concentrated deionized water dispersion liquid that obtains is stand-by;
Step 2, the three-dimensional graphene-based tin ash aeroge of preparation:
At first, the dispersion liquid to above-mentioned graphene-based metal oxide nano-sheet places the vial of 10mL and places the water heating kettle Direct Hydrothermal of 80mL to process vial;
Secondly, the block freeze drying that obtains after the above-mentioned reaction is processed, finally obtained the composite material of the graphene-based tin ash of three-dimensional structure.
Wherein, described metal chloride is preferably stannic chloride pentahydrate (SnCl
45H
2O).
In the specific embodiment of the present invention, in the DMF of GO dispersion liquid, in dispersion liquid, add hydrochloric acid, regulator solution pH to 1-3 first before the adding metal chloride; After under intense agitation, adding metal chloride after ultrasonic, again 60～90 ℃ of insulations 1-5 hour.
In concrete preparation method of the present invention
The metal chloride that adds in the step 1 and the mass ratio of graphene oxide are preferably 1.16:1.
In preferred implementation of the present invention, the concentration of the dispersion liquid of graphene-based metal oxide nano-sheet in deionized water is preferably 5mg/mL.
In preparation method of the present invention, in the step 2 nanometer sheet is carried out three-dimensional when assembling, adopt the method for hydro-thermal self assembly.
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, and this is not particularly limited.
In preparation method of the present invention, metal oxide particle is loaded on the Graphene surface, suppressed to a certain extent the reunion of its particle, increase specific area, thereby improve the capacity of material.Simultaneously the material of this three-dimensional structure not only can be alleviated metal oxide such as the stannic oxide particle change in volume in charge and discharge process, suppresses the pulverizing of its particle and comes off, thereby improved greatly the cyclical stability of material.And, thereby three-dimensional structure be conducive to electrolyte and material fully contact the conductivity that can improve whole electrode material, the quick transmission of realization electronics, thus so that material has 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 can also strengthen its cycle performance during as lithium ion battery negative material when improving the negative material capacity.
In specific embodiments of the present invention, the button-shaped half-cell of lithium ion is take the graphene-based metal tin ash composite material that has as mentioned above three-dimensional structure as negative material, lithium metal just very, electrolyte is ethyl carbonate or the dimethyl carbonate solution of lithium hexafluoro phosphate solution.
The present invention adopts the two-dimentional Graphene of monolayer carbon atomic structure as skeleton, and stannic chloride pentahydrate is prepared the graphene-based metal stannic oxide nanometer composite material of three-dimensional structure as tin source presoma by simple two-step method.The metal oxide nanoparticles that obtains by the inventive method loads on the Graphene skeleton equably, has simultaneously micron-sized structure.Prove through electro-chemical test, prepared composite material has excellent cyclical stability and high rate performance; Experiment showed, at 100mAg
-1Charging or discharging current under: the discharge capacity of the tin dioxide material that makes can reach 700mAhg
-1Therefore, the present invention provides good experimental data and theoretical the support for metal oxide in research and the 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 fully purpose of the present invention, feature and effect.
Description of drawings
Fig. 1 is the shape appearance figure of the three-dimensional grapheme base tin ash of embodiments of the invention 1; Wherein, a), b) be respectively the TEM figure of embodiment 1, c), d) be that the SEM of embodiment 1 schemes.
Fig. 2 is that the three-dimensional grapheme base tin ash composite material of embodiments of the invention 1 is as the cycle performance figure of lithium ion battery negative material.
Fig. 3 is that the three-dimensional grapheme base tin ash composite material of embodiments of the invention 1 is as the high rate performance figure of lithium ion battery negative material.
Embodiment
Embodiment 1
The first step, the graphene-based stannic oxide nanometer sheet of preparation:
(1) dimethyl formamide solution (50mL) of 1mg/mL graphene oxide is ultrasonic, form the dispersion liquid that mixes;
(2) in above-mentioned dispersion liquid, add concentrated hydrochloric acid, regulator solution pH to 2; Under vigorous stirring, add stannic chloride pentahydrate (SnCl
45H
2O), add in 80 ℃ 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, with deionized water washing, repeated centrifugation, washing operation four times, concentrated obtaining than thick liquid is graphene-based stannic oxide nanometer sheet.
The graphene-based tin ash composite material of second step, preparation three-dimensional structure:
(1) the thickness body fluid of getting the graphene-based stannic oxide nanometer sheet that is condensed into the above-mentioned preparation of 10mL places vial, hydrothermal treatment consists, and kept 18 hours at 180 ℃;
(2) with the above-mentioned reacted block materials that obtains, behind freeze drying 48h, finally obtain the graphene-based tin ash composite material of three-dimensional structure, the SEM of the graphene-based tin ash composite material sheet of this three-dimensional structure, TEM photo as Fig. 1 a)-d) shown in.
Be assembled into the button-shaped half-cell of lithium ion (to electrode as lithium metal) take the gained composite material as lithium ion battery negative material, the button-shaped half-cell of this lithium ion is carried out electro-chemical test, its cycle performance figure, high rate performance figure are respectively shown in Fig. 2,3.
Wherein, SnO
2/ GFs charge/discharge is respectively the graphene-based tin ash of three-dimensional structure as charge and discharge figure, the SnO of lithium ion battery negative material
2/ GSs charge/discharge is respectively two-dimentional graphene-based tin ash composite material under the equal rate of charge as the charge and discharge figure of lithium ion battery negative material.As can be seen from Figure 2 the composite material of three-dimensional structure has demonstrated higher capacity (850mAhg
-1), and very superior cycle performance.It is still keeping 800mAhg after 70 circle circulations
-1Capacity, the material capacity of two dimension is the in the past 800mAhg of ten circles then
-1Dropped to only 400mAhg
-1As shown in Figure 3, the material of three-dimensional structure is at 500mAg
-1Large electric 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.The ordinary skill that should be appreciated that this area need not creative work and just can design according to the present invention make many modifications and variations.Therefore, all in the art technical staff 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 (7)
1. the graphene-based tin ash composite manufacture method of a three-dimensional structure is characterized in that, may further comprise the steps:
Step 1, the graphene-based stannic oxide nanometer sheet of preparation;
Step 2, the three-dimensional graphene-based tin ash aeroge of preparation.
2. the graphene-based tin ash composite manufacture method of a kind of three-dimensional structure as claimed in claim 1 is characterized in that, prepares graphene-based stannic oxide nanometer sheet and comprises following steps:
At first, be to add a small amount of concentrated hydrochloric acid, ultrasonic mixing in the graphene oxide dimethyl formamide solution of 1mg/mL to concentration;
Secondly, add metal chloride in the mentioned solution after, 60-90 ℃ of insulation 12 hours;
At last, above-mentioned reacted solution is carried out centrifugal, deionized water washing, the concentrated deionized water dispersion liquid that obtains.
3. the graphene-based tin ash composite manufacture method of a kind of three-dimensional structure as claimed in claim 2 is characterized in that, described metal chloride is stannic chloride pentahydrate.
4. the graphene-based tin ash composite manufacture method of a kind of three-dimensional structure as claimed in claim 1 is characterized in that, the three-dimensional graphene-based tin ash aeroge of preparation comprises following steps:
At first, the dispersion liquid to above-mentioned graphene-based metal oxide nano-sheet places the vial of 10mL and places the water heating kettle Direct Hydrothermal of 80mL to process vial;
Secondly, the block freeze drying that obtains after the above-mentioned reaction is processed, finally obtained the composite material of the graphene-based tin ash of three-dimensional structure.
5. a kind of graphene-based tin ash composite manufacture method of three-dimensional structure as claimed in claim 1 is characterized in that, the mass ratio of graphene oxide and described stannic chloride pentahydrate is 1:1.16.
6. the graphene-based tin ash composite material of the three-dimensional structure for preparing of preparation method as claimed in claim 1.
7. the application of graphene-based tin ash composite material in lithium ion battery of three-dimensional structure as claimed in claim 1.
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Cited By (14)
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| CN103606662A (en) * | 2013-11-12 | 2014-02-26 | 上海交通大学 | Preparation method and application of three-dimensional graphene-based tin dioxide composite material |
| CN104143631A (en) * | 2014-05-12 | 2014-11-12 | 上海大学 | Method for preparing graphene aerogel loaded tin dioxide composite material |
| CN104852022A (en) * | 2015-03-27 | 2015-08-19 | 上海大学 | Cathode material for lithium ion battery and preparation method thereof |
| CN105514447A (en) * | 2016-01-13 | 2016-04-20 | 南京理工大学 | Method for preparing antimony-doped tin dioxide aerogel three-dimensional electrode through normal pressure drying |
| CN105826541A (en) * | 2016-06-14 | 2016-08-03 | 中科探能（北京）科技有限公司 | Graphene-doped stannic-oxide-based lithium nano battery cathode material and preparation method |
| CN106219537A (en) * | 2016-08-30 | 2016-12-14 | 安徽师范大学 | The preparation method of a kind of tin ash/graphene composite material, resistor-type gas sensor |
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| CN109167047A (en) * | 2018-09-19 | 2019-01-08 | 哈尔滨工业大学 | Self-supporting three-dimensional grapheme/tin composite lithium ion battery cathode material preparation method |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101478043A (en) * | 2009-01-08 | 2009-07-08 | 上海交通大学 | Negative pole material for lithium ionic cell and preparation process thereof |
| CN102142549A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Graphene nano sheet and SnS2 composite nano material and synthesis method thereof |
| CN102198966A (en) * | 2011-04-03 | 2011-09-28 | 长安大学 | Electrolysis electrode loaded with graphene modified tin dioxide and preparation method thereof |
| CN102244250A (en) * | 2011-06-14 | 2011-11-16 | 清华大学深圳研究生院 | Graphene macroscopic body/tin oxide composite lithium ion battery anode material and process thereof |
| CN102255072A (en) * | 2010-05-17 | 2011-11-23 | 国家纳米科学中心 | Preparation method of stannic oxide or metallic tin and grapheme lamella composite material |
| CN102324502A (en) * | 2011-09-14 | 2012-01-18 | 重庆大学 | Preparation method of flower-like tin dioxide and graphene composite material |
| CN102437320A (en) * | 2011-11-21 | 2012-05-02 | 北京师范大学 | Graphene-coated mesoporous metallic oxide, and preparation method and use thereof |
| CN102496721A (en) * | 2011-12-21 | 2012-06-13 | 浙江大学 | Graphene-based composite lithium ion battery film cathode material and preparation method thereof |
| CN102569750A (en) * | 2012-03-21 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Cathode composite material of lithium ion battery and preparation method thereof |
| CN102891319A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Preparation method of graphite composite material of lithium ion battery |
| CN103035916A (en) * | 2012-11-28 | 2013-04-10 | 华中科技大学 | Preparation method of nano tin dioxide-graphene composite material and product thereof |
-
2013
- 2013-06-25 CN CN201310256465.9A patent/CN103326007B/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101478043A (en) * | 2009-01-08 | 2009-07-08 | 上海交通大学 | Negative pole material for lithium ionic cell and preparation process thereof |
| CN102255072A (en) * | 2010-05-17 | 2011-11-23 | 国家纳米科学中心 | Preparation method of stannic oxide or metallic tin and grapheme lamella composite material |
| CN102142549A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Graphene nano sheet and SnS2 composite nano material and synthesis method thereof |
| CN102198966A (en) * | 2011-04-03 | 2011-09-28 | 长安大学 | Electrolysis electrode loaded with graphene modified tin dioxide and preparation method thereof |
| CN102244250A (en) * | 2011-06-14 | 2011-11-16 | 清华大学深圳研究生院 | Graphene macroscopic body/tin oxide composite lithium ion battery anode material and process thereof |
| CN102324502A (en) * | 2011-09-14 | 2012-01-18 | 重庆大学 | Preparation method of flower-like tin dioxide and graphene composite material |
| CN102437320A (en) * | 2011-11-21 | 2012-05-02 | 北京师范大学 | Graphene-coated mesoporous metallic oxide, and preparation method and use thereof |
| CN102496721A (en) * | 2011-12-21 | 2012-06-13 | 浙江大学 | Graphene-based composite lithium ion battery film cathode material and preparation method thereof |
| CN102569750A (en) * | 2012-03-21 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Cathode composite material of lithium ion battery and preparation method thereof |
| CN102891319A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Preparation method of graphite composite material of lithium ion battery |
| CN103035916A (en) * | 2012-11-28 | 2013-04-10 | 华中科技大学 | Preparation method of nano tin dioxide-graphene composite material and product thereof |
Non-Patent Citations (1)
| Title |
|---|
| LI XIAO ET AL: "Self-Assembled Fe2O3/Graphene Aerogel with High Lithium Storage Performance", 《ACS APPL. MATER. INTERFACES》 * |
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| CN103606662A (en) * | 2013-11-12 | 2014-02-26 | 上海交通大学 | Preparation method and application of three-dimensional graphene-based tin dioxide composite material |
| CN104143631A (en) * | 2014-05-12 | 2014-11-12 | 上海大学 | Method for preparing graphene aerogel loaded tin dioxide composite material |
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| CN107032340A (en) * | 2017-05-22 | 2017-08-11 | 河北工程大学 | A kind of simple method for preparing of lanthanide oxide/stannic oxide/graphene nano composite |
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| CN109167047A (en) * | 2018-09-19 | 2019-01-08 | 哈尔滨工业大学 | Self-supporting three-dimensional grapheme/tin composite lithium ion battery cathode material preparation method |
| CN109626361A (en) * | 2018-11-09 | 2019-04-16 | 清华大学深圳研究生院 | Stablize its sodium-ion battery of high-specific surface area carbon negative pole material and preparation method and application of component modification |
| CN112234196A (en) * | 2020-09-04 | 2021-01-15 | 陕西科技大学 | Sn nano half-moon tooth particle-2 DLMG composite material synthesized by organic molecule constrained reaction and method |
| CN112234196B (en) * | 2020-09-04 | 2022-11-08 | 陕西科技大学 | Sn nano half-moon tooth particle-2 DLMG composite material synthesized by organic molecule constrained reaction and method |
| 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 |
| CN114426301A (en) * | 2020-10-29 | 2022-05-03 | 北京小米移动软件有限公司 | Tin oxide/sulfur-doped graphene composite material, preparation method thereof and battery |
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