CN104671232A - Preparation method of graphene and application of prepared graphene - Google Patents
Preparation method of graphene and application of prepared graphene Download PDFInfo
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- CN104671232A CN104671232A CN201310617981.XA CN201310617981A CN104671232A CN 104671232 A CN104671232 A CN 104671232A CN 201310617981 A CN201310617981 A CN 201310617981A CN 104671232 A CN104671232 A CN 104671232A
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- 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 invention discloses a method for preparing graphene. The method is characterized in that the graphene is applied in a lithium battery as an electrode to show excellent electrochemical property; under the 0.2C testing multiplying power, the first-time specific discharge capacity is 922mAhg<-1>, and after circulation for 10 times, the specific discharge capacity is maintained to be 380Ahg<-1> still. The method for preparing the graphene under simple and mild condition has the advantages that the graphite oxide is prepared by two-step mixed reaction, so that the reaction temperature is greatly reduced; furthermore, hydrazine hydrate is utilized as a reduction agent, so that the reduction temperature is reduced; the reaction condition is mild, the operation is simple, the convenient and effective effects are achieved, the cost for industrially producing the graphene is greatly reduced, and the electrochemical property of the graphene prepared by the method is excellent.
Description
Technical field
The invention belongs to battery material field, be specifically related to a kind of Graphene electrodes material obtained by simple reaction and its preparation method and application.
Background technology
The core of lithium ion battery is lithium storage materials.As a kind of novel carbon nanomaterial, the specific surface area that Graphene is larger and good electric property thereof determine its great potential in field of lithium ion battery, and its theoretical capacity is 740 ~ 780 mAh g
-1, be about 2 times of conventional graphite material, have been reported as lithium ion battery negative material using Graphene.But also there is not the pertinent literature report utilizing described the method to prepare Graphene and the application in lithium cell thereof at present.
Summary of the invention
The invention discloses a kind of method preparing Graphene, this Graphene is used in lithium cell as electrode materials, show excellent chemical property.Under the test multiplying power of 0.2 C, its first discharge specific capacity is 922 mA h g
-1, circulate after 10 times, its specific storage still remains on 380 mAh g
-1.Prepare the method for Graphene under the invention provides a kind of simple mild conditions, the method prepares graphite oxide by two step hybrid reactions, significantly reduces temperature of reaction, utilizes hydrazine hydrate as reductive agent simultaneously, and reduction temperature reduces.The method reaction conditions is gentle, effectively simple, convenient, significantly reduces the cost of suitability for industrialized production Graphene, Graphene electrochemical performance prepared by the method.
For achieving the above object, the present invention adopts following technical scheme:
Prepare a method for graphene oxide as above, by 3 g graphite, 3 g NaNO
3, and the vitriol oil of 300 ml 98 % stir in ice-water bath, 18 g KMnO
4slowly be added to mixed solution, react 2 h; Then proceed in the water-bath of 35 DEG C and continue reaction 12 h, then mixed solution is diluted to 900 ml, add the H of 100 ml 30 %
2o
2stir 30 min, solution changes golden yellow into by brown, centrifugation, and product successively uses HCl and the distilled water wash of 5 %, is graphite oxide after product drying.
Prepare a method for Graphene as above, ultrasonic for graphite oxide 1h is dispersed in the uniform dispersion forming 10mg/mL in DMF solution; Dispersion liquid is transferred in hydrothermal reaction kettle, take hydrazine hydrate as reductive agent, reacts 12 h at 160 DEG C of temperature, and the product obtained adopts washing with alcohol, obtains Graphene after drying.
An application for Graphene as above, lithium cell is assembled: Graphene in mass ratio: polyvinylidene difluoride (PVDF): be coated in 0.25 cm equably after acetylene black=80:10:10 mixed grinding
2copper sheet on do positive pole, reference electrode and metallic lithium is to electrode, ionogen is 1M LiClO
4eC+DEC+EMC solution; In described EC+DEC+EMC solution, the volume ratio of EC, DEC, EMC is 1:1:1; All assemblings are all carried out in glove box.
Beneficial effect of the present invention: this Graphene is used in lithium cell by the present invention, shows excellent electrochemical performance.Under the test multiplying power of 0.2C, its first discharge specific capacity is 922 mA h g
-1, circulate after 10 times, its specific storage still remains on 380 mAh g
-1.Prepare the method for Graphene under the invention provides a kind of simple mild conditions, the method prepares graphite oxide by two step hybrid reactions, significantly reduces temperature of reaction, utilizes hydrazine hydrate as reductive agent simultaneously, and reduction temperature reduces.The method reaction conditions is gentle, effectively simple, convenient, significantly reduces the cost of suitability for industrialized production Graphene, Graphene electrochemical performance prepared by the method.
Accompanying drawing explanation
Fig. 1 is the electrochemical property test figure of grapheme material of the present invention.
Fig. 1 illustrates and is used in lithium cell by this grapheme material, shows excellent chemical property.Under the test multiplying power of 0.2 C, its first discharge specific capacity is 922 mAh g
-1, circulate after 10 times, its specific storage still remains on 380 mAh g
-1.
Embodiment
embodiment 1
Prepare a method for graphene oxide as above, by 9 g graphite, 9g NaNO
3, and the vitriol oil of 900 ml 98 % stir in ice-water bath, 54 g KMnO
4slowly be added to mixed solution, react 2 h; Then proceed in the water-bath of 35 DEG C and continue reaction 12 h, then mixed solution is diluted to 2700 ml, add the H of 300 ml 30 %
2o
2stir 30 min, solution changes golden yellow into by brown, centrifugation, and product successively uses HCl and the distilled water wash of 5 %, is graphite oxide after product drying.
Prepare a method for Graphene as above, ultrasonic for graphite oxide 1h is dispersed in the uniform dispersion forming 10mg/mL in DMF solution; Dispersion liquid is transferred in hydrothermal reaction kettle, take hydrazine hydrate as reductive agent, at 160 DEG C of temperature, reacts 12 h, and the product obtained adopts washing with alcohol, obtains Graphene after drying.
An application for Graphene as above, lithium cell is assembled: Graphene in mass ratio: polyvinylidene difluoride (PVDF): be coated in 0.25 cm equably after acetylene black=80:10:10 mixed grinding
2copper sheet on do positive pole, reference electrode and metallic lithium is to electrode, ionogen is 1M LiClO
4eC+DEC+EMC solution; In described EC+DEC+EMC solution, the volume ratio of EC, DEC, EMC is 1:1:1; All assemblings are all carried out in glove box.
embodiment 2
Prepare a method for graphene oxide as above, by 3 g graphite, 3g NaNO
3, 300 ml 98 % the vitriol oil stir in ice-water bath, 18 g KMnO
4slowly be added to mixed solution, react 2 h; Then proceed in the water-bath of 35 DEG C and continue reaction 12 h, then mixed solution is diluted to 900 ml, add the H of 100 ml 30 %
2o
2stir 30 min, solution changes golden yellow into by brown, centrifugation, and product successively uses HCl and the distilled water wash of 5 %, is graphite oxide after product drying.
Prepare a method for Graphene as above, ultrasonic for graphite oxide 1h is dispersed in the uniform dispersion forming 10mg/mL in DMF solution; Dispersion liquid is transferred in hydrothermal reaction kettle, take hydrazine hydrate as reductive agent, at 120 DEG C of temperature, reacts 10 h, and the product obtained adopts washing with alcohol, obtains Graphene after drying.
An application for Graphene as above, lithium cell is assembled: Graphene in mass ratio: polyvinylidene difluoride (PVDF): be coated in 0.25 cm equably after acetylene black=80:10:10 mixed grinding
2copper sheet on do positive pole, reference electrode and metallic lithium is to electrode, ionogen is 1M LiClO
4eC+DEC+EMC solution; In described EC+DEC+EMC solution, the volume ratio of EC, DEC, EMC is 1:1:1; All assemblings are all carried out in glove box.
embodiment 3
Prepare a method for graphene oxide as above, by 3 g graphite, 3g NaNO
3, 300 ml 98 % the vitriol oil stir in ice-water bath, 18 g KMnO
4slowly be added to mixed solution, react 2 h; Then proceed in the water-bath of 35 DEG C and continue reaction 12 h, then mixed solution is diluted to 900 ml, add the H of 100 ml 30 %
2o
2stir 30 min, solution changes golden yellow into by brown, centrifugation, and product successively uses HCl and the distilled water wash of 5 %, is graphite oxide after product drying.
Prepare a method for Graphene as above, ultrasonic for graphite oxide 1h is dispersed in the uniform dispersion forming 10mg/mL in DMF solution; Dispersion liquid is transferred in hydrothermal reaction kettle, take hydrazine hydrate as reductive agent, reacts 24 h at 120 DEG C of temperature, and the product obtained adopts washing with alcohol, obtains Graphene after drying.
An application for Graphene as above, lithium cell is assembled: Graphene in mass ratio: polyvinylidene difluoride (PVDF): be coated in 0.25 cm equably after acetylene black=80:10:10 mixed grinding
2copper sheet on do positive pole, reference electrode and metallic lithium is to electrode, ionogen is 1M LiClO
4eC+DEC+EMC solution; In described EC+DEC+EMC solution, the volume ratio of EC, DEC, EMC is 1:1:1; All assemblings are all carried out in glove box.
embodiment 4
Prepare a method for graphene oxide as above, by 3 g graphite, 3g NaNO
3, 300 ml 98 % the vitriol oil stir in ice-water bath, 18 g KMnO
4slowly be added to mixed solution, react 2 h; Then proceed in the water-bath of 35 DEG C and continue reaction 12 h, then mixed solution is diluted to 900 ml, add the H of 100 ml 30 %
2o
2stir 30 min, solution changes golden yellow into by brown, centrifugation, and product successively uses HCl and the distilled water wash of 5 %, is graphite oxide after product drying.
Prepare a method for Graphene as above, ultrasonic for graphite oxide 1h is dispersed in the uniform dispersion forming 10mg/mL in DMF solution; Dispersion liquid is transferred in hydrothermal reaction kettle, take hydrazine hydrate as reductive agent, reacts 10 h at 220 DEG C of temperature, and the product obtained adopts washing with alcohol, obtains Graphene after drying.
An application for Graphene as above, lithium cell is assembled: Graphene in mass ratio: polyvinylidene difluoride (PVDF): be coated in 0.25 cm equably after acetylene black=80:10:10 mixed grinding
2copper sheet on do positive pole, reference electrode and metallic lithium is to electrode, ionogen is 1M LiClO
4eC+DEC+EMC solution; In described EC+DEC+EMC solution, the volume ratio of EC, DEC, EMC is 1:1:1; All assemblings are all carried out in glove box.
embodiment 5
Prepare a method for graphene oxide as above, by 3 g graphite, 3g NaNO
3, 300 ml 98 % the vitriol oil stir in ice-water bath, 18 g KMnO
4slowly be added to mixed solution, react 2 h; Then proceed in the water-bath of 35 DEG C and continue reaction 12 h, then mixed solution is diluted to 900 ml, add the H of 100 ml 30 %
2o
2stir 30 min, solution changes golden yellow into by brown, centrifugation, and product successively uses HCl and the distilled water wash of 5 %, is graphite oxide after product drying.
Prepare a method for Graphene as above, ultrasonic for graphite oxide 1h is dispersed in the uniform dispersion forming 10mg/mL in DMF solution; Dispersion liquid is transferred in hydrothermal reaction kettle, take hydrazine hydrate as reductive agent, reacts 24 h at 220 DEG C of temperature, and the product obtained adopts washing with alcohol, obtains Graphene after drying.
An application for Graphene as above, lithium cell is assembled: Graphene in mass ratio: polyvinylidene difluoride (PVDF): be coated in 0.25 cm equably after acetylene black=80:10:10 mixed grinding
2copper sheet on do positive pole, reference electrode and metallic lithium is to electrode, ionogen is 1M LiClO
4eC+DEC+EMC solution; In described EC+DEC+EMC solution, the volume ratio of EC, DEC, EMC is 1:1:1; All assemblings are all carried out in glove box.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (4)
1. a preparation method for Graphene, concrete steps are as follows:
(1) by graphite, the vitriol oil, SODIUMNITRATE, potassium permanganate hybrid reaction 2 h in ice bath, then proceed in the water-bath of 35 DEG C and continue reaction 12 h, then mixed solution deionized water dilutes 3 times, adds 30% H of certain volume
2o
2solution stirring 30 min, then use hydrochloric acid soln and the distilled water wash of 5 %, lyophilize obtains graphite oxide;
(2) the ultrasonic 1h of graphite oxide of step (1) is dispersed in N, the dispersion liquid of even 10mg/mL is formed in dinethylformamide solution, and utilize hydrazine hydrate for reductive agent redox graphene at a certain temperature, obtain Graphene through washing drying.
2. a graphene preparation method as claimed in claim 1, is characterized in that in step (1), graphite: nitrate: the mass ratio of potassium permanganate is 1:1:6, and added vitriol oil volumetric quantities is 100 times of graphite quality numerical value.
3. a graphene preparation method as claimed in claim 1, it is characterized in that the reduction temperature of hydrazine hydrate in step (2) is 120 ~ 220 DEG C, the recovery time is 1 ~ 24 h.
4. an application for Graphene as claimed in claim 1, is characterized in that: lithium cell is assembled: Graphene in mass ratio: polyvinylidene difluoride (PVDF): be coated in 0.25 cm equably after acetylene black=80:10:10 mixed grinding
2copper sheet on do positive pole, reference electrode and metallic lithium is to electrode, ionogen is 1M LiClO
4eC+DEC+EMC solution; In described EC+DEC+EMC solution, the volume ratio of EC, DEC, EMC is 1:1:1; All assemblings are all carried out in glove box.
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280273A (en) * | 2016-11-10 | 2017-01-04 | 过冬 | A kind of Graphene/epoxy resin composite material and preparation method thereof |
| CN106784835A (en) * | 2017-02-23 | 2017-05-31 | 南阳师范学院 | A kind of preparation method of carbon negative electrode material of lithium ion cell |
| CN106853965A (en) * | 2016-12-30 | 2017-06-16 | 绍兴文理学院 | A kind of preparation method of negative material Graphene and electrochemical property test method |
| CN108281655A (en) * | 2018-01-30 | 2018-07-13 | 南京红太阳新能源有限公司 | The preparation method of silicon/carbon/graphite in lithium ion batteries alkene negative material |
| CN109179403A (en) * | 2018-11-20 | 2019-01-11 | 运城学院 | A kind of preparation method of graphite oxide |
| CN109244368A (en) * | 2018-11-19 | 2019-01-18 | 北京师范大学 | A kind of application of nitrogen-doped graphene in negative electrode of lithium ion battery preparation |
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|---|---|---|---|---|
| CN102275908A (en) * | 2011-07-07 | 2011-12-14 | 中南大学 | Preparation method of graphene material |
| CN102306757A (en) * | 2011-08-26 | 2012-01-04 | 上海交通大学 | Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material |
| 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 |
| CN103145122A (en) * | 2013-03-25 | 2013-06-12 | 西北工业大学 | Preparation method of nitrogen-doped graphene |
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2013
- 2013-11-29 CN CN201310617981.XA patent/CN104671232A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275908A (en) * | 2011-07-07 | 2011-12-14 | 中南大学 | Preparation method of graphene material |
| CN102306757A (en) * | 2011-08-26 | 2012-01-04 | 上海交通大学 | Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material |
| 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 |
| CN103145122A (en) * | 2013-03-25 | 2013-06-12 | 西北工业大学 | Preparation method of nitrogen-doped graphene |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280273A (en) * | 2016-11-10 | 2017-01-04 | 过冬 | A kind of Graphene/epoxy resin composite material and preparation method thereof |
| CN106853965A (en) * | 2016-12-30 | 2017-06-16 | 绍兴文理学院 | A kind of preparation method of negative material Graphene and electrochemical property test method |
| CN106784835A (en) * | 2017-02-23 | 2017-05-31 | 南阳师范学院 | A kind of preparation method of carbon negative electrode material of lithium ion cell |
| CN108281655A (en) * | 2018-01-30 | 2018-07-13 | 南京红太阳新能源有限公司 | The preparation method of silicon/carbon/graphite in lithium ion batteries alkene negative material |
| CN109244368A (en) * | 2018-11-19 | 2019-01-18 | 北京师范大学 | A kind of application of nitrogen-doped graphene in negative electrode of lithium ion battery preparation |
| CN109179403A (en) * | 2018-11-20 | 2019-01-11 | 运城学院 | A kind of preparation method of graphite oxide |
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Application publication date: 20150603 |