CN102153074A - Method for preparing graphene with high specific surface area through low-temperature pyrolysis and expansion - Google Patents
Method for preparing graphene with high specific surface area through low-temperature pyrolysis and expansion Download PDFInfo
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- CN102153074A CN102153074A CN 201110067779 CN201110067779A CN102153074A CN 102153074 A CN102153074 A CN 102153074A CN 201110067779 CN201110067779 CN 201110067779 CN 201110067779 A CN201110067779 A CN 201110067779A CN 102153074 A CN102153074 A CN 102153074A
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Abstract
The invention discloses a method for preparing graphene with high specific surface area through low-temperature pyrolysis and expansion. The method has the technical key that under the protection of an inert gas, graphite oxide is pyrolyzed and expanded at 260-800 DEG C, and the specific surface area of the obtained graphene is greater than 380 m<2>/g. At low temperature, the obtained graphene has high specific surface area, uniform dimension distribution and a controllable structure; and the obtained graphene with high specific surface area is applied to a lithium battery cathode material so that the specific capacity of the battery is greatly increased; and after the lithium battery is circularly used 100 times, and the specific capacity is stabilized at more than 500 mA.h/g.
Description
Technical field
The present invention relates to a kind of method of peeling off method acquisition Graphene by expansion, particularly a kind of the expansion by low temperature pyrogenation peeled off the method that graphite oxide prepares the high-specific surface area Graphene, the Graphene for preparing can be used for lithium ion battery negative material, belongs to the Graphene preparing technical field.
Background technology
2004, the A.K. Geim of Britain Manchester university group (
Science2004,
306(5696), 666-9.) prepare Graphene (Graphene) material with the mechanics stripping means, found afterwards that excellent performances such as its big specific surface area, high electronic mobility, less mass density, high thermostability and unreactiveness can bring into play good effect in nano electron device and machinofacture.Yet, at present the bibliographical information common method for preparing Graphene but exist yield poorly, length consuming time, as the micromechanics disintegrating method; Big to equipment requirements height, energy consumption, as reduction SiC method (
Science2006,
312(5777), 1191-1196.).
Graphene is at the green high-capacity rechargeable battery of latest generation---and the application in the lithium ion battery has become the new direction of lithium cell researchdevelopment gradually, also becomes the new direction that Graphene has the value utilized most.In the developing history of lithium ion battery negative material, metallic lithium as the first negative material of lithium ion battery bring in use form Li dendrite and cause safety problem (
Science,1995,
270, 590.), graphite substituted metal lithium be used to lithium ion battery but greatly reduce energy capacity of battery density (
J Power Sources, 2003,119-121,528-537), the tubular structure of carbon nanotube uniqueness is expected to improve the battery specific storage in the modified graphite electrode material, feasible irreversible first specific storage increase (
Battery, 2006,1,53), and Graphene is in the negative material as lithium ion battery, not only can solve low, the defective such as irreversible specific storage height first of potential safety hazard, energy capacity of battery density that Li dendrite causes, can also improve the specific storage of lithium ion battery.
The method that the present invention utilizes low temperature pyrogenation to expand to peel off graphite oxide to prepare Graphene has not only avoided power consumption big, to the high deficiency of equipment requirements, and can also obtain the specific surface area height, even size distribution, the grapheme material of controllable structure.In the present invention, by measuring the battery performance index of Graphene, detect performance difference by the Graphene of the controlled pyrolysis expanding method preparation of low temperature as lithium ion battery negative material.
Summary of the invention
The purpose of this invention is to provide a kind of low cost, low power consuming, mass preparation high-specific surface area; even size distribution; the method of the Graphene of controllable structure; this method utilizes graphite oxide that the Hummers method obtains at a lower temperature; pyrolysis is expanded and is prepared Graphene under the protection of inert gas, and this Graphene can improve the specific storage of lithium ion battery greatly as electrode materials.
Implementation procedure of the present invention is as follows:
A kind of low temperature pyrogenation expands and prepares the method for high-specific surface area Graphene, and its key problem in technology is: under the protection of inert gas, graphite oxide is expanded 260～800 ℃ of pyrolysis, the Graphene specific surface area for preparing is greater than 380m
2/ g; Preferably graphite oxide is expanded 260～500 ℃ of pyrolysis, can prepare specific surface area greater than 420m
2/ g Graphene; Described rare gas element is argon gas or nitrogen.
Above-mentioned graphite oxide obtains by the Hummers method, and concrete preparation method comprises the steps:
(1) graphite is dissolved in the mixing solutions of the vitriol oil and concentrated nitric acid;
(2) potassium permanganate is added in the above-mentioned solution;
(3) reacted respectively 0.5-2.5 hour-10-10 ℃, 30-40 ℃ and 85-95 ℃ successively, add graphite quality 80-200 deionized water doubly then;
(4), add graphite quality 10-30 superoxol washing doubly with above-mentioned solution cool to room temperature;
(5) centrifugal, dry, grind, sieve, obtain the graphite oxide powder;
Above-mentioned reactant quality volume ratio is: graphite: potassium permanganate: the vitriol oil: concentrated nitric acid=
(0.5～1.5): (5～7): (85～95): (20～30), wherein graphite and potassium permanganate are in gram, and the vitriol oil and concentrated nitric acid are in milliliter.
Experiment finds, the solution that adds behind the potassium permanganate can reach the high specific surface-area in 2 hours in-10-10 ℃ a reaction.
Above-mentioned graphite is analytical pure, and particle diameter is 4～25 μ m.
Advantage of the present invention and positively effect: (1) under lower temperature, the Graphene specific surface area height for preparing, even size distribution, controllable structure; (2) the inventive method power consumption is low, and cost is low, can be used for scale operation; (3) Graphene of high-specific surface area is used for lithium ion battery negative material, has improved the specific storage of battery greatly, and after recycling 100 times, specific storage is stabilized in more than the 500mAh/g.
Description of drawings
Thermogravimetric of Fig. 1 graphite oxide (TGA) and differential scanning calorimetric (DSC) curve;
The stereoscan photograph of Fig. 2 graphite oxide and the Graphene that under differing temps, prepares, wherein a, b, c, d are respectively the SEM photo of the Graphene under the expansion temperature of graphite oxide and 300 ℃, 600 ℃, 800 ℃;
The transmission electron microscope photo of Graphene under Fig. 3 differing temps, wherein a, b, c are respectively the TEM photo of the Graphene under 300 ℃, 600 ℃, 800 ℃ the expansion temperature;
The first charge-discharge specific storage of Graphene and the relation of voltage under the different expansion temperatures of Fig. 4;
The specific discharge capacity of Graphene and the relation of cycle index under the different expansion temperatures of Fig. 5.
Embodiment
The violent phenomenon of thermogravimetric (TGA), differential scanning calorimetric (DSC) curve and the reaction process of the graphite oxide by Fig. 1 can analyze, and from room temperature to 100 ℃ this stage, 15% weight loss is arranged.Graphite oxide is a hydroaropic substance, and this moment, the weight of loss should be adsorbed moisture of graphite oxide and gas.In 185 ~ 255 ℃ of these scopes, weight is loss fast again, probably is 30%, and this process is the stage important in the low temperature pyrogenation expansion process, and in this stage, the main component of loss is CO, CO
2And other oxygen-containing functional groups.Under this temperature, because violent expansion reaction power, graphite oxide moment has generated fluffy, the Graphene of bigger serface.
When graphite oxide was heated, the surperficial epoxy group(ing) of its lamella and hydroxyl decomposed generation CO, CO
2With water vapour etc., when gas generating rate during greater than its rate of release, the interlayer pressure of generation has surpassed the Van der Waals force between graphene film, thereby graphite oxide being produced expand peels off.In this process, the volume of material is inflatable tens of to hundreds of times of (M.J. McAllister, J.-L. Li, D.H. Adamson, H.C. Schniepp, A.A Abdala, J. Liu, M. Herrera-Alonso, D.L. Milius, R. Car, R.K. Prud ' homme, I.A. Aksay, Chem.Mater. 19 (2007) 4396.).Simultaneously, because expansion stripping reaction process can be emitted a large amount of heats, so the expansible generating process also can be reflected synchronously by the DSC curve.As seen from the figure, the DSC curve has violent fluctuation 185 ~ 255 ° of C scopes, can judge that this is to expand to peel off the main temperature range of generation.
Embodiment 1:
Raw materials used as follows:
Graphite 1g
The vitriol oil (H
2SO
4) 92ml
Concentrated nitric acid (HNO
3) 24ml
Potassium permanganate (KMnO
4) 6g
Hydrogen peroxide (H
2O
2) 20ml
Deionized water (H
2O) 100ml
Preparation process is as follows:
(1) with the 1g carbon dust under the ice-water bath condition with the dense H of 92ml
2SO
4(massfraction is 98%) and the dense HNO of 24ml
3After (massfraction is 67-70%) stirs, slowly add 6g KMnO
4
(2) will be warming up to 35 ℃ behind the above-mentioned solution stirring reaction 2h, reaction 1h is warming up to 85 ℃ of reaction 30min, suspends heating, after reducing to 50 ℃, slowly splash into the 100ml deionized water, be warming up to 85 ℃ of reaction 30min again, finish heating, reduce to 40 ℃ after, add superoxol 10ml;
(3) with the power ultrasonic dispersion 2h of (2) reacted solution, obtain graphite oxide solution with 60KHz and 800W;
(4) with the solution centrifugal in (3), to the pH to 6, remove moisture with deionized water wash, dry in loft drier, grind, obtain the graphite oxide powder, recording its specific surface area is 59.93 m
2/ g;
(5) the graphite oxide powder is placed in the tube furnace, under the argon gas atmosphere protection, be warming up to 300 ℃ with the speed of 10 ℃/min, finish reaction, obtain grapheme material, the specific surface area that records Graphene is 559.3 m
2/ g, product pattern such as Fig. 2 b are shown in Fig. 3 a.
(6) product and tackiness agent are mixed, promptly get the Graphene electrodes material.
Embodiment 2:
Similar to Example 1, different is that expansion temperature is respectively 600 ℃ (Fig. 2 c, Fig. 3 b) and 800 ℃ (2d, Fig. 3 c), records the Graphene specific surface area for preparing and is respectively: 412.1m
2/ g and 380m
2/ g.
From Fig. 2, Fig. 3 as seen, when expansion temperature was 300 ℃, the Graphene number of plies that obtains was few, and thickness is 1.62nm, approximately the 4-6 layer; When expansion temperature was 600 ℃, the Graphene thickness that obtains was 2.7nm, approximately the 7-9 layer; When expansion temperature was 800 ℃, the Graphene thickness that obtains was 4.32nm, approximately the 11-13 layer.Temperature is high more, and the Graphene number of plies that obtains is many more.Graphite oxide expansible optimum temps of the present invention is 260～500 ℃.
From scanning electron microscope and transmission electron microscope photo (Fig. 2, Fig. 3) as seen, analytically pure graphite flake layer structure is tight, interfloor distance is little, in oxidising process, concentrated nitric acid, the vitriol oil by strong oxidizing property, under the potassium permanganate effect, the graphite oxide of acquisition is under the effect of oxygenant intercalation, and it is big that interfloor distance becomes.
Embodiment 3:
Similar to Example 1, different is that expansion temperature is 450 ℃, and the Graphene specific surface area for preparing is respectively: 465m
2/ g.
Embodiment 4:
Similar to Example 1, different is with the 1g carbon dust under the ice-water bath condition with 92ml H
2SO
4(massfraction is 98%) and 24ml HNO
3After (massfraction is 67-70%) stirs, slowly add 6g KMnO
4, with above-mentioned solution stirring reaction 4h, the specific surface area of the Graphene for preparing is 260 m
2/ g.
Embodiment 5:
Discharge and recharge instrument with LAND CT2001A type, come the charge-discharge performance of the sample of test implementation example 1,2 preparations, concrete steps are as follows:
(1) mixes (weight ratio: 1:2 ~ 4) with pulverous negative electrode active material with binding agent, after evenly stirring, make the negative material of pulpous state.
(2) slurry of making is rolled repeatedly through three grades roll, make the uniform thin slice of thickness, be placed on the surface of Copper Foil, compressing tablet, cathode pole piece is made in oven dry.
(3) put well by the top-down order of positive plate (metallic lithium)---barrier film---negative plate, inject the electrolytic solution (LiPF of 1 mol/L
6), battery seal is made button cell, promptly finish the assembling process of battery.
(4) with the battery charging/discharging apparatus battery that assembles in (3) is carried out charge-discharge test, discharge and recharge constant current, electric current and voltage scope 5V/1mA.Fig. 4,5 is the charge-discharge performance graphic representation of prepared grapheme material as the lithium ion battery of negative electrode active material.
Experimental result shows that it is low to the invention provides a kind of power consumption, and the preparation method of graphene that cost is low has been prepared and had high-specific surface area, controllable structure, the Graphene electrodes material of heavy body (greater than 500mAh/g).
Claims (8)
1. a low temperature pyrogenation expands and prepares the method for high-specific surface area Graphene, it is characterized in that: under the protection of inert gas, graphite oxide is expanded 260～800 ℃ of pyrolysis.
2. low temperature pyrogenation according to claim 1 expands and prepares the method for high-specific surface area Graphene, and it is characterized in that: the Graphene specific surface area for preparing is greater than 380m
2/ g.
3. low temperature pyrogenation according to claim 1 expands and prepares the method for high-specific surface area Graphene, it is characterized in that: graphite oxide is expanded 260～500 ℃ of pyrolysis.
4. low temperature pyrogenation according to claim 3 expands and prepares the method for high-specific surface area Graphene, and it is characterized in that: the Graphene specific surface area for preparing is greater than 420m
2/ g.
5. low temperature pyrogenation according to claim 1 expands and prepares the method for high-specific surface area Graphene, and it is characterized in that: described rare gas element is argon gas or nitrogen.
6. expanding according to one of any described low temperature pyrogenation of claim 1 to 5 prepare the method for high-specific surface area Graphene, and it is characterized in that: described graphite oxide prepares by the Hummers method.
7. low temperature pyrogenation according to claim 6 expands and prepares the method for high-specific surface area Graphene, it is characterized in that the preparation method of graphite oxide comprises the steps:
(1) graphite is dissolved in the mixing solutions of the vitriol oil and concentrated nitric acid;
(2) potassium permanganate is added in the above-mentioned solution;
(3) reacted respectively 0.5-2.5 hour-10-10 ℃, 30-40 ℃ and 85-95 ℃ successively, add graphite quality 80-200 deionized water doubly then;
(4), add graphite quality 10-30 superoxol washing doubly with above-mentioned solution cool to room temperature;
(5) centrifugal, dry, grind, sieve, obtain the graphite oxide powder;
Above-mentioned reactant quality volume ratio is: graphite: potassium permanganate: the vitriol oil: concentrated nitric acid=
(0.5～1.5): (5～7): (85～95): (20～30), wherein graphite and potassium permanganate are in gram, and the vitriol oil and concentrated nitric acid are in milliliter.
8. low temperature pyrogenation according to claim 7 expands and prepare the method for high-specific surface area Graphene, it is characterized in that: the solution that adds behind the potassium permanganate reacted 2 hours at-10-10 ℃.
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| CN102424382A (en) * | 2011-09-16 | 2012-04-25 | 中国科学院宁波材料技术与工程研究所 | Method for preparing high-specific-surface-area graphene under conditions of normal pressure and low temperature |
| CN102769139A (en) * | 2012-08-10 | 2012-11-07 | 深圳市斯诺实业发展有限公司永丰县分公司 | Preparation method of high power capacity lithium ion battery cathode material |
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| CN102424382A (en) * | 2011-09-16 | 2012-04-25 | 中国科学院宁波材料技术与工程研究所 | Method for preparing high-specific-surface-area graphene under conditions of normal pressure and low temperature |
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| CN108033440A (en) * | 2018-01-16 | 2018-05-15 | 上海理工大学 | A kind of preparation method of high specific surface area porous fold graphene |
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| CN113131029A (en) * | 2019-12-30 | 2021-07-16 | 江苏天奈科技股份有限公司 | Method for recycling and regenerating graphene from graphite cathode of lithium ion battery |
| CN111591981A (en) * | 2020-04-21 | 2020-08-28 | 东北大学 | Preparation method of low-layer gauze-shaped nitrogen-doped graphene |
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Application publication date: 20110817 |