CN102157728A - Method of preparing graphene in-situ modified graphite carbon electrode material for lithium-ion battery - Google Patents
Method of preparing graphene in-situ modified graphite carbon electrode material for lithium-ion battery Download PDFInfo
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- CN102157728A CN102157728A CN2011100677808A CN201110067780A CN102157728A CN 102157728 A CN102157728 A CN 102157728A CN 2011100677808 A CN2011100677808 A CN 2011100677808A CN 201110067780 A CN201110067780 A CN 201110067780A CN 102157728 A CN102157728 A CN 102157728A
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- 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 a graphene-based graphite carbon composite electrode material for a lithium-ion battery, which comprises the steps of: in a sealed reactor, carrying out pyrolysis expansion on graphite oxide at a temperature of 200-300 DEG C to obtain a graphene in-situ modified graphite carbon material, wherein the graphite oxide is obtained by preferably using a Hummers method; and mixing and prefroming the graphene in-situ modified graphite carbon material, acetylene black and binder to obtain the graphene-based graphite carbon composite electrode material. In the invention, graphite carbon is in-situ modified by grapheme such that graphene is distributed more evenly in the material by contrast of physical doping; by using a sealed reactor expansion technology, experiment cost is decreased and process flow is simplified; and the graphene in-situ modified graphite carbon composite electrode material combines respective advantages of the graphene and the graphite carbon so as to increase lithium storage capability remarkably, cycle life and coulombic efficiency, and charge and discharge plateaus are remarkable.
Description
Technical field
The present invention relates to the preparation method of lithium ion battery with the in-situ modified graphitic carbon electrode material of Graphene, specifically, relate to and use the method that in-situ modified technology prepares graphene-based graphitic carbon electrode material, belong to lithium ion battery graphite electrode material preparing technical field.
Background technology
Lithium rechargeable battery is as a kind of novel high energy secondary power supply, have that specific energy is big, discharging voltage balance, voltage high and low temperature performance is good, environmentally friendly, security performance is superior, memory-less effect and advantage such as have extended cycle life, and is considered to 21 century to national economy and the significant new high-tech industry of people's lives.Yet along with the development of battery miniaturization, more the exploitation of height ratio capacity and Geng Duo cycle-index lithium ion battery becomes more and more urgent.Graphite is as the negative material of lithium ion battery, and in use main problem is that specific capacity is low and loop attenuation is fast at present.Therefore, need carry out modification to graphite material and handle, to promote its specific capacity and cycle life.
The research of Graphene becomes the new direction that improves the research of carbon negative pole material lithium reserves, and Graphene is owing to have high conductivity, big specific area, and advantages such as chemical inertness are considered to have future the electrode material of development potentiality.Yoo etc. (E. J. Yoo, J. Kim, E. Hosono, H. S. Zhou, T. Kudo, I. Honma,
Nano. Lett.2008,8,2277) prepare the grapheme material of the different numbers of plies by chemical oxidization method, it is carried out electrochemical property test find that such material has good storage lithium ability (the initial charge capacity can reach 540 mAh/g), (D. Pan such as Pan, S. Wang, B. Zhao, M. Wu, H. Zhang, Y. Wang, Z. Jiao
Chem. Mater.2009,21,3136) further increase the randomness and the defective of grapheme material by chemical method, with the storage lithium ability of such material get a promotion (the initial charge capacity can reach 1054 mAh/g).As seen, grapheme material is having very big effect aspect the storage lithium ability that improves lithium ion battery.Yet when at present Graphene was as the negative material of lithium ion battery, have following deficiency: the first charge-discharge coulombic efficiency was low, and the charging voltage hysteresis is obvious, did not have defectives such as obvious voltage platform and loop attenuation be too fast, and these are the notable feature of hard carbon material.Therefore, grapheme material can not need to form combination electrode material with other material and just can be expected to overcome itself defective separately as electrode material, brings into play the storage lithium ability of its excellence.
Summary of the invention
The preparation method who the purpose of this invention is to provide the in-situ modified graphitic carbon electrode material of Graphene that a kind of cost is low, specific capacity is high, cycle performance is excellent.
Implementation procedure of the present invention is as follows:
It consists of the in-situ modified graphitic carbon electrode material of Graphene: Graphene/Graphite, and Graphene represents Graphene, and Graphite represents graphitic carbon.
A kind of lithium ion battery in closed reactor, obtains the in-situ modified graphitic carbon material of Graphene with graphite oxide 200-300 ℃ of pyrolysis expansion with the preparation method of graphene-based graphitic carbon combination electrode material, and graphite oxide pyrolysis at least expanded 30 minutes; Graphite oxide is preferably in 250 ℃ and carries out the pyrolysis expansion.
Described graphite oxide preferably prepares by the Hummers method, and the preparation method comprises the steps:
(1) graphite is dissolved in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), stirs adding potassium permanganate down;
(2) obtain oxidation intercalated graphite material with carbon element more than 30 minutes-10-95 ℃ of reaction;
(3) use H
2O
2Wash the above-mentioned oxidation intercalated graphite material with carbon element for preparing;
(4) 50～70 ℃ of following vacuumizes obtain oxidation intercalated graphite material with carbon element powder;
Above-mentioned graphite and KMnO
4, H
2SO
4And HNO
3Mass volume ratio be (1-2): (3-6): (85-95): (20-40), wherein graphite and KMnO
4In gram, H
2SO
4And HNO
3In milliliter.
In closed reactor, oxidation intercalated graphite material with carbon element powder expanded in 200-300 ℃ promptly obtained the in-situ modified graphitic carbon material of Graphene at least in 30 minutes, and the graphite expansion temperature is preferably 250 ℃.
Graphitic carbon material that Graphene is in-situ modified and acetylene black, binding agent mix, compressing tablet promptly gets graphene-based graphitic carbon combination electrode material.
In the above-mentioned steps (2), react the graphitic carbon material that obtains the oxidation intercalation more than 30 minutes respectively-10-10 ℃, 30-40 ℃ and 85-95 ℃ successively.
The present invention is different from prior art: 1) adopting Graphene modified graphite carbon negative pole material is by in-situ modified realization, partly change graphite into Graphene through chemical reaction process, reach the purpose of Graphene modified graphite, rather than by Graphene is blended in method in the graphite equably as a kind of additive.2) Graphene is that the pressure reaction obtains in the low temperature (200-300 ℃) by taking place in reactor, produces but not utilize the high temperature (1000 ℃) that generally uses at present to react, and such research is at international, the domestic bibliographical information that there is no.
Advantage of the present invention is as follows: 1) by the in-situ modified graphitic carbon of Graphene, Graphene distributes even than physical doping in the product; 2) use reactor pyrolysis expansion technique to help reducing the pyrolysis expansion temperature, reduced experimental cost and simplified technological process; 3) the in-situ modified graphitic carbon combination electrode material of Graphene combines Graphene and graphitic carbon advantage separately, and storage lithium ability, cycle life and coulombic efficiency significantly improve, and charge and discharge platform is obvious.
Description of drawings
Fig. 1. the SEM of differential responses stage material with carbon element and TEM photo.(a) graphitic carbon former state; (b) material behind the oxidation intercalation; (c) and (d) the Graphene modified graphite material with carbon element that obtains after the compression swelling in the low temperature in the hydro-thermal jar; (e) and (f) TEM of Graphene and HRTEM figure shows that the Graphene number of plies is about 5 ~ 10 layers in the Graphene modified graphite material with carbon element.
Fig. 2. graphitic carbon former state, Graphene modified graphite material with carbon element and pure Graphene are as the charge-discharge performance curve chart of the lithium ion battery of negative pole.(a) graphitic carbon former state; (b) Graphene modified graphite material with carbon element; (c) pure Graphene.
Fig. 3. graphitic carbon former state, Graphene modified graphite material with carbon element and pure Graphene are as the cycle life and the coulombic efficiency figure of the lithium ion battery of negative pole.(a) graphitic carbon former state; (b) Graphene modified graphite material with carbon element; (c) pure Graphene.
Embodiment
Embodiment 1:
The key step of the in-situ modified graphitic carbon electrode material preparation of Graphene is as follows:
(1) low-temp reaction, in 500 ml beakers, under the ice-water bath condition, add 1 g raw material graphite (microstructure is shown in Fig. 1 (a)), the 90 ml concentrated sulfuric acids and 25 ml red fuming nitric acid (RFNA)s, slowly add 3 g potassium permanganate after stirring 15 min, stir reaction 60 min in ice-water bath;
(2) temperature reaction in slowly is warming up to 35 ℃ with (1) step solution, reacts 30 min;
(3) pyroreaction slowly adds 350 ml distilled water in (2) step solution, be warming up to the graphitic carbon material (microstructure is shown in Fig. 1 (b)) that 90 ℃ of reaction 30 min obtain the oxidation intercalation simultaneously;
(4) washing suction filtration treats that the hydrogen peroxide that adds 18 ml 30% behind (3) step solution cool to room temperature reacts 10 min.Subsequently with distilled water washing and suction filtration,, stop suction filtration when detecting with barium chloride when the sulfate radical-free ion exists;
Dry 24 h in (5) 60 ℃ of following vacuum drying ovens;
(6) expansion reaction, take by weighing 0.5 g(5) step gained material with carbon element, insert in the reactor that volume is 25 ml, insert immediately after the sealing in 250 ℃ the baking oven, slowly reduce to room temperature after reacting 60 min, product is the in-situ modified graphitic carbon material of Graphene (microstructure is shown in Fig. 1 (c)-(f)), and specific area is 424 m
2/ g discharges and recharges reaction through 50 times, and cycle life is stabilized in 430 mAh/g.
Embodiment 2:
Discharge and recharge instrument with LAND CT2001A type, come the charge-discharge performance of the sample of preparation in the test implementation example 1, concrete steps are as follows:
(1) mixes (weight ratio: 5:10:85), after stirring, make the negative material of pulpous state with pulverous negative electrode active material with acetylene black, binding agent PTFE.
(2) with twin rollers the slurry of making is rolled even back pressure with 20 MPa and be pressed on the copper mesh, oven dry is cathode pole piece.
(3) put well by positive plate (lithium metal)-top-down order stack of barrier film-negative plate, inject electrolyte (1 mol/l LiPF
6EC/DMC/EMC (volume ratio is 1:1:1) solution) after through buckle closure with the assembling process that technology is promptly finished button cell such as seal.
(4) with battery charging/discharging apparatus LAND CT2001A the button cell that assembles in (3) is carried out the constant current charge-discharge test, current density is 0.25 mA/cm
2
As shown in Figure 2, measured graphitic carbon former state, Graphene modified graphite material with carbon element and pure Graphene charge-discharge performance as the lithium ion battery of negative pole, the result shows that the modified graphite electrode material that the present invention prepares has height ratio capacity, be stabilized in 430 mAh/g, graphite capacity 320 mAh/g far above non-modified, and at 0.2V obvious voltage platform is arranged, and pure Graphene there is not charge and discharge platform under the same test condition.As shown in Figure 3, coulombic efficiency and cycle life compared to find that Graphene modified graphite material with carbon element has higher coulombic efficiency (the first charge-discharge coulombic efficiency is up to 85%, and other circulations coulombic efficiencies down maintain 99%) and longer life-span (50 circulation volume decay＜5%) than graphite and pure Graphene.
Embodiment 3: similar to Example 1, different is only to react 30 minutes down at 90 ℃, after washing, drying and expansion obtain the in-situ modified graphitic carbon material of Graphene, the material specific area that this process obtains is 200 m
2/ g, cycle life is 320 mAh/g.
Embodiment 4: similar to Example 1, different is to get 2 g material carbons, 6 g potassium permanganate, and the 95 ml concentrated sulfuric acids and 35ml red fuming nitric acid (RFNA) react, and all the other processes are identical with embodiment 1, and the specific area of the in-situ modified graphitic carbon material of the Graphene that obtains is 405 m
2/ g discharges and recharges reaction through 50 times, and cycle life is stabilized in 425 mAh/g.
Embodiment 5: similar to Example 1, different is in closed reactor expanded 1 hour in 275 ℃, and the specific area of the in-situ modified graphitic carbon material of the Graphene that obtains is 440 m
2/ g discharges and recharges reaction through 50 times, and cycle life is stabilized in 435 mAh/g.
Embodiment 6: adopt the graphite oxide be purchased to expand 2 hours in 225 ℃ in closed reactor, the specific area of the in-situ modified graphitic carbon material of the Graphene that obtains is 400 m
2/ g discharges and recharges reaction through 50 times, and cycle life is stabilized in 410 mAh/g.
Claims (9)
1. a lithium ion battery is characterized in that with the preparation method of graphene-based graphitic carbon combination electrode material: in closed reactor, graphite oxide expanded 200-300 ℃ of pyrolysis obtains the in-situ modified graphitic carbon material of Graphene.
2. lithium ion battery according to claim 1 is characterized in that with the preparation method of graphene-based graphitic carbon combination electrode material: graphite oxide pyrolysis at least expanded 30 minutes.
3. lithium ion battery according to claim 1 is characterized in that with the preparation method of graphene-based graphitic carbon combination electrode material: graphite oxide carries out pyrolysis at 250 ℃ and expands.
4. lithium ion battery according to claim 1 is characterized in that with the preparation method of graphene-based graphitic carbon combination electrode material: described graphite oxide obtains by the Hummers method.
5. lithium ion battery according to claim 4 is characterized in that with the preparation method of graphene-based graphitic carbon combination electrode material the preparation method of graphite oxide comprises the steps:
(1) graphite is dissolved in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), stirs adding potassium permanganate down;
(2) obtain oxidation intercalated graphite material with carbon element more than 30 minutes-10-95 ℃ of reaction;
(3) use H
2O
2Wash the above-mentioned oxidation intercalated graphite material with carbon element for preparing;
(4) 50～70 ℃ of following vacuumizes obtain oxidation intercalated graphite material with carbon element powder;
Above-mentioned graphite and KMnO
4, H
2SO
4And HNO
3Mass volume ratio be (1-2): (3-6): (85-95): (20-40), wherein graphite and KMnO
4In gram, H
2SO
4And HNO
3In milliliter.
6. lithium ion battery according to claim 5 is with the preparation method of graphene-based graphitic carbon combination electrode material, it is characterized in that: in closed reactor, oxidation intercalated graphite material with carbon element powder is carried out the pyrolysis expansion in 200-300 ℃ promptly obtained the in-situ modified graphitic carbon material of Graphene at least in 30 minutes.
7. lithium ion battery according to claim 6 is with the preparation method of graphene-based graphitic carbon combination electrode material, and it is characterized in that: graphite pyrolysis expansion temperature is 250 ℃.
8. lithium ion battery according to claim 6 is characterized in that with the preparation method of graphene-based graphitic carbon combination electrode material: graphitic carbon material that Graphene is in-situ modified and acetylene black, binding agent mix, compressing tablet promptly gets graphene-based graphitic carbon combination electrode material.
9. lithium ion battery according to claim 5 is with the preparation method of graphene-based graphitic carbon combination electrode material, it is characterized in that: in the step (2), react respectively-10-10 ℃, 30-40 ℃ and 85-95 ℃ successively and obtain oxidation intercalated graphite material with carbon element more than 30 minutes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2495752C1 (en) * | 2012-04-02 | 2013-10-20 | Федеральное государственное бюджетное учреждение науки Институт неорганической химии им. А.В. Николаева Сибирского отделения Российской академии наук (ИНХ СО РАН) | Method of producing composite including laminar graphite- and molybdenum sulphide-based materials |
| CN103387224A (en) * | 2012-05-07 | 2013-11-13 | 海洋王照明科技股份有限公司 | Preparation method of graphite |
| CN103839697A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/C60 composite material and preparation method and applications thereof |
| CN107579232A (en) * | 2017-09-08 | 2018-01-12 | 绵阳梨坪科技有限公司 | A kind of preparation method of graphene in-situ modified graphite carbon electrode material |
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2011
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| CN101367516A (en) * | 2008-09-26 | 2009-02-18 | 天津大学 | High electrochemistry capacitance oxidization plumbago alkene, low-temperature preparation method and uses |
| CN101969113A (en) * | 2010-09-21 | 2011-02-09 | 上海大学 | Preparation method of graphene-base tin dioxide composite anode material for lithium ion batteries |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2495752C1 (en) * | 2012-04-02 | 2013-10-20 | Федеральное государственное бюджетное учреждение науки Институт неорганической химии им. А.В. Николаева Сибирского отделения Российской академии наук (ИНХ СО РАН) | Method of producing composite including laminar graphite- and molybdenum sulphide-based materials |
| CN103387224A (en) * | 2012-05-07 | 2013-11-13 | 海洋王照明科技股份有限公司 | Preparation method of graphite |
| CN103839697A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/C60 composite material and preparation method and applications thereof |
| CN107579232A (en) * | 2017-09-08 | 2018-01-12 | 绵阳梨坪科技有限公司 | A kind of preparation method of graphene in-situ modified graphite carbon electrode material |
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Application publication date: 20110817 |