CN103771394A - Graphene material and preparation method thereof - Google Patents
Graphene material and preparation method thereof Download PDFInfo
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- CN103771394A CN103771394A CN201210406014.4A CN201210406014A CN103771394A CN 103771394 A CN103771394 A CN 103771394A CN 201210406014 A CN201210406014 A CN 201210406014A CN 103771394 A CN103771394 A CN 103771394A
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Abstract
The invention provides a preparation method for a graphene material. The preparation method comprises the following steps: (1) taking a graphene oxide suspension with a concentration of 0.1 to 2 mg/L, adding nitric acid according to a solid-liquid ratio of graphene oxide to nitric acid of 1 mg: 1-10 mL with stirring and carrying out an ultrasonic reaction at a temperature of 20 to 50 DEG C for 0.5 to 2 h so as to obtain a graphene oxide-nitric acid mixed solution; and (2) washing the graphene oxide-nitric acid mixed solution with deionized water, then drying the mixed solution, putting obtained dried graphene oxide-nitric acid powder in a muffle furnace and carrying out a reduction reaction in an inert gas atmosphere at a temperature of 500 to 700 DEG C for 0.5 to 3 h so as to finally obtain the graphene material. The invention further provides the graphene material prepared by using the method. According to the invention, a lot of oxygen-containing function groups--carbonyl groups are introduced through addition of nitric acid, so the electrochemical performance of the graphene material is substantially improved; moreover, the preparation method is simple to operate and easy to industrialize.
Description
Technical field
The present invention relates to the synthetic field of grapheme material, especially a kind of grapheme material and preparation method thereof.
Background technology
Along with the development of various new forms of energy, the miniaturization development of portable electric appts and the widespread demand of electromobile to large-capacity high-power chemical power source.Current commercial lithium ion battery adopts inorganic positive pole/graphite system mostly, although the chemical property excellence of this class system, due to itself capacity lower (as the theoretical 170mAh/g of iron lithium phosphate), complicated process of preparation, cost is high.So the electrode materials of other kind of development of new has been subject to people's attention widely.
Grapheme material is as a kind of carbon material with advantages such as high-specific surface area, electroconductibility are strong, it is the ideal material of preparing the electrode materials of lithium ion battery, the electrochemical reaction mechanism of grapheme material is: Sauerstoffatom when electric discharge on each carbonyl obtains an electronics, embeds lithium ion simultaneously and generates enol lithium salts; When charging, lithium ion is deviate from, and carbonyl reduction is realized lithium ion by the conversion between carbonyl and enol structure and reversibly embedded and deviate from.But it is lower to prepare at present Graphene carbonyl content, greatly limit the application of grapheme material in lithium ion battery.
Summary of the invention
The object of the present invention is to provide a kind of convenient and simple, be easy to realize industrialized graphene preparation method, simultaneously for overcoming the lower problem of carbonyl content in grapheme material, provide a kind of containing the high grapheme material of carbonyl content.
The present invention solves the problems of the technologies described above adopted scheme:
First aspect, the invention provides a kind of preparation method of grapheme material, comprises the following steps:
(1) get the graphene oxide suspension that concentration is 0.1 ~ 2mg/L, the ratio that is 1mg:1～10mL in graphene oxide and nitric acid solid-to-liquid ratio stirs and adds nitric acid, ultrasonic reaction 0.5 ~ 2 hour under 20～50 ℃ of conditions, makes graphene oxide-nitric acid mixing solutions;
(2) by graphene oxide-nitric acid mixing solutions with dry after deionized water wash, then the dry graphene oxide-nitric acid powder obtaining is put into retort furnace, under atmosphere of inert gases, 500 ~ 700 ℃ of reduction reactions 0.5 ~ 3 hour, finally obtain grapheme material.
The electrochemical reaction mechanism of carbonyl is: Sauerstoffatom when electric discharge on each carbonyl obtains an electronics, embeds lithium ion simultaneously and generates enol lithium salts; When charging, lithium ion is deviate from, and carbonyl reduction is realized lithium ion by the conversion between carbonyl and enol structure and reversibly embedded and deviate from.Preparation method of the present invention introduces a large amount of oxygen-containing functional group carbonyls by adding nitric acid, and more carbonyl can be participated in the redox reaction of lithium cell directly, improved the electrochemistry capacitance of lithium cell, and preparation technology is simple, and cost is low.
Preferably, the concentration of described nitric acid is 50%～70%.
Preferably, the described rare gas element of step (2) is argon gas, nitrogen, helium or neon.
Preferably, the preparation method of described graphene oxide suspension is: first, by improved Hummers legal system for graphite oxide; Then,, by graphite oxide vacuum-drying 24 hours under 120 ℃ of conditions, obtain dehydration graphite oxide; Finally, dehydration graphite oxide is put into water, ultrasonic formation graphene oxide suspension;
Wherein, prepare graphite oxide step by improved Hummers method as follows:
In mass ratio the ratio of 2:1:1 get the vitriol oil that Graphite Powder 99, Potassium Persulphate and Vanadium Pentoxide in FLAKES add 80 ℃ and stir after cooling 6～10 hours, filtration drying, then filter residue is joined in the vitriol oil of 0 ℃, add again potassium permanganate, after mixing, keeping the temperature of mixed solution is 0～10 ℃, then 35～40 ℃ of oil baths 2～3 hours; Add deionized water, after 15～30 minutes, add hydrogen peroxide suction filtration while hot again in mixed solution, with dilute hydrochloric acid and deionized water, solids is washed successively, suction filtration drying solid thing, obtain graphite oxide; The solid-to-liquid ratio of the vitriol oil of described Graphite Powder 99 and described 0 ℃ is 1g:10～15mL; The mass ratio of described Graphite Powder 99 and described potassium permanganate is 1:3～5; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g:40～50mL.
Preferably, the purity of described Graphite Powder 99 is 90%～99.5%.
Preparation method of the present invention introduces a large amount of oxygen-containing functional group carbonyls by adding nitric acid, in battery charge and discharge process, carbonyl functional group directly carries out redox reaction, improve the capacity of battery, improved the chemical property of grapheme material, be a kind of convenient and simple, be easy to realize industrialized grapheme material preparation method.
Second aspect, the invention provides a kind of grapheme material, and described grapheme material makes by above-mentioned preparation method.
Preparation method of the present invention introduces a large amount of oxygen-containing functional group carbonyls by adding nitric acid, the content of carbonyl is 5% ~ 15%, and carbonyl content < 2% in grapheme material prepared by general method, therefore, the grapheme material that the present invention prepares has higher carbonyl content, has better chemical property.
Compare and prior art, the present invention has following beneficial effect:
Preparation method of the present invention introduces a large amount of oxygen-containing functional group carbonyls by adding nitric acid, makes grapheme material have good chemical property, and preparation method of the present invention is simple simultaneously, and raw material is cheap and easy to get, is applicable to large-scale industrial production.
Embodiment
The following stated is the preferred embodiment of the present invention.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvement and adjustment, these improvement and adjustment are also considered as in protection scope of the present invention.
Embodiment mono-
A preparation method for grapheme material, comprises the following steps:
(1) Graphite Powder 99 that is 90% by purity prepares graphite oxide by improved Hummers method, concrete grammar is: 2:1 in mass ratio: 1 ratio get the vitriol oil that Graphite Powder 99, Potassium Persulphate and Vanadium Pentoxide in FLAKES add 80 ℃ and stir after cooling 6 hours, filtration drying, then filter residue is joined in the vitriol oil of 0 ℃, add again potassium permanganate, after mixing, keeping the temperature of mixed solution is 0 ℃, then 35 ℃ of oil baths 2 hours; Add deionized water, after 15 minutes, in mixed solution, add hydrogen peroxide suction filtration while hot again, with dilute hydrochloric acid and deionized water, solids is washed successively, after drying solid thing, obtain graphite oxide.The solid-to-liquid ratio of the vitriol oil of described Graphite Powder 99 and described 0 ℃ is 1g:10mL; The mass ratio of described Graphite Powder 99 and described potassium permanganate is 1:3; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g:40mL.
Then vacuum-drying 24 hours under 120 ℃ of conditions, obtains dehydration graphite oxide;
(2) dehydration graphite oxide is put into water, the graphene oxide suspension of ultrasonic formation 0.1mg/L, then stir the nitric acid (graphene oxide is 1mg:1mL with the solid-to-liquid ratio of the nitric acid adding) that adds 50%, ultrasonic reaction 0.5h under 20 ℃ of conditions, makes graphene oxide-nitric acid mixing solutions;
(3) be 7 after to put into baking oven with deionized water rinsing to the pH of elutant by graphene oxide-nitric acid mixing solutions, 60 ℃ are dried 2 hours, then the dry graphene oxide-nitric acid powder obtaining is put into retort furnace, under argon gas inert atmosphere, under 500 ℃ of high temperature, reduce 0.5h, obtain grapheme material.
Embodiment bis-
A preparation method for grapheme material, comprises the following steps:
(1) Graphite Powder 99 that is 99.5% by purity prepares graphite oxide by improved Hummers method, concrete grammar is: 2:1 in mass ratio: 1 ratio get the vitriol oil that Graphite Powder 99, Potassium Persulphate and Vanadium Pentoxide in FLAKES add 80 ℃ and stir after cooling 10 hours, filtration drying, then filter residue is joined in the vitriol oil of 0 ℃, add again potassium permanganate, after mixing, keeping the temperature of mixed solution is 20 ℃, then 40 ℃ of oil baths 3 hours; Add deionized water, after 30 minutes, in mixed solution, add hydrogen peroxide suction filtration while hot again, with dilute hydrochloric acid and deionized water, solids is washed successively, after drying solid thing, obtain graphite oxide.The solid-to-liquid ratio of the vitriol oil of described Graphite Powder 99 and described 0 ℃ is 1g:15mL; The mass ratio of described Graphite Powder 99 and described potassium permanganate is 1:5; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g:50mL.
Then vacuum-drying 24 hours under 120 ℃ of conditions, obtains dehydration graphite oxide;
(2) dehydration graphite oxide is put into water, the graphene oxide suspension of ultrasonic formation 2mg/L, then stir the nitric acid (graphene oxide is 1mg:10mL with the solid-to-liquid ratio of the nitric acid adding) that adds 70%, ultrasonic reaction 2h under 50 ℃ of conditions, makes graphene oxide-nitric acid mixing solutions;
(3) be to put into baking oven after 7 with deionized water rinsing to the pH of elutant, 80 ℃ dry 1 hour, then the dry graphene oxide-nitric acid powder obtaining is put into retort furnace, under nitrogen inert atmosphere, under 700 ℃ of high temperature, reduce 3h, obtain grapheme material.
Embodiment tri-
A preparation method for grapheme material, comprises the following steps:
(1) Graphite Powder 99 that is 94% by purity prepares graphite oxide by improved Hummers method, concrete grammar is: in mass ratio the ratio of 2:1:1 get the vitriol oil that Graphite Powder 99, Potassium Persulphate and Vanadium Pentoxide in FLAKES add 80 ℃ and stir after cooling but 8 hours, filtration drying, then filter residue is joined in the vitriol oil of 0 ℃, add again potassium permanganate, after mixing, keeping the temperature of mixed solution is 10 ℃, then 34 ℃ of oil baths 2.5 hours; Add deionized water, after 22 minutes, in mixed solution, add hydrogen peroxide suction filtration while hot again, with dilute hydrochloric acid and deionized water, solids is washed successively, after drying solid thing, obtain graphite oxide.The solid-to-liquid ratio of the vitriol oil of described Graphite Powder 99 and described 0 ℃ is 1g:12mL; The mass ratio of described Graphite Powder 99 and described potassium permanganate is 1:4; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g:42mL.
Then vacuum-drying 24 hours under 120 ℃ of conditions, obtains dehydration graphite oxide;
(2) dehydration graphite oxide is put into water, the graphene oxide suspension of ultrasonic formation 0.5mg/L, then stir the nitric acid (graphene oxide is 1mg:5mL with the solid-to-liquid ratio of the nitric acid adding) that adds 60%, ultrasonic reaction 1.5h under 35 ℃ of conditions, makes graphene oxide-nitric acid mixing solutions;
(3) be to put into vacuum drying oven after 7 with deionized water rinsing to the pH of elutant, 50 ℃ are dried 3 hours, then the dry graphene oxide-nitric acid powder obtaining is put into retort furnace, under nitrogen inert atmosphere, under 600 ℃ of high temperature, reduce 1h, obtain grapheme material.
Embodiment tetra-
A preparation method for grapheme material, comprises the following steps:
(1) Graphite Powder 99 that is 96% by purity prepares graphite oxide by improved Hummers method, concrete grammar is: 2:1 in mass ratio: 1 ratio get the vitriol oil that Graphite Powder 99, Potassium Persulphate and Vanadium Pentoxide in FLAKES add 80 ℃ and stir after cooling 9 hours, filtration drying, then filter residue is joined in the vitriol oil of 0 ℃, add again potassium permanganate, after mixing, keeping the temperature of mixed solution is 12 ℃, then 38 ℃ of oil baths 3 hours; Add deionized water, after 28 minutes, in mixed solution, add hydrogen peroxide suction filtration while hot again, with dilute hydrochloric acid and deionized water, solids is washed successively, after drying solid thing, obtain graphite oxide.The solid-to-liquid ratio of the vitriol oil of described Graphite Powder 99 and described 0 ℃ is 1g:14mL; The mass ratio of described Graphite Powder 99 and described potassium permanganate is 1:5; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g:49mL.
Then vacuum-drying 24 hours under 120 ℃ of conditions, obtains dehydration graphite oxide;
(2) dehydration graphite oxide is put into water, the graphene oxide suspension of ultrasonic formation 1mg/L, then stir the nitric acid (graphene oxide is 1mg:10mL with the solid-to-liquid ratio of the nitric acid adding) that adds 65%, ultrasonic reaction 2h under 40 ℃ of conditions, makes graphene oxide-nitric acid mixing solutions;
(3) be to put into baking oven after 7 with deionized water rinsing to the pH of elutant, 70 ℃ are dried 2 hours, then the dry graphene oxide-nitric acid powder obtaining is put into retort furnace, under nitrogen inert atmosphere, under 550 ℃ of high temperature, reduce 1.5h, obtain grapheme material.
Comparative example
A preparation method for grapheme material, comprises the following steps:
(1) Graphite Powder 99 that is 90% by purity prepares graphite oxide by improved Hummers method, concrete grammar is: in mass ratio the ratio of 2:1:1 get the vitriol oil that Graphite Powder 99, Potassium Persulphate and Vanadium Pentoxide in FLAKES add 80 ℃ and stir after cooling 6 hours, filtration drying, then filter residue is joined in the vitriol oil of 0 ℃, add again potassium permanganate, after mixing, keeping the temperature of mixed solution is 0 ℃, then 35 ℃ of oil baths 2 hours; Add deionized water, after 15 minutes, add hydrogen peroxide to remove potassium permanganate again in mixed solution, suction filtration while hot, washs solids with dilute hydrochloric acid and deionized water successively, after drying solid thing, obtains graphite oxide.The solid-to-liquid ratio of the vitriol oil of described Graphite Powder 99 and described 0 ℃ is 1g:10mL; The mass ratio of described Graphite Powder 99 and described potassium permanganate is 1:3; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g:40mL.
Then vacuum-drying 24 hours under 120 ℃ of conditions, obtains dehydration graphite oxide;
(2) dehydration graphite oxide is put into retort furnace, under nitrogen inert atmosphere, under 500 ℃ of high temperature, reduce 0.5h, obtain grapheme material.
Effect embodiment
By the grapheme material preparing in above-described embodiment one ~ tetra-and comparative example, by wherein carbonyl content of XPS measurements determination, measurement result is in table 1.
Carbonyl content in the prepared Graphene of table 1 embodiment of the present invention one ~ tetra-and comparative example
| Embodiment mono- | Embodiment bis- | Embodiment tri- | Embodiment tetra- | Comparative example | |
| Carbonyl content % | 15 | 8 | 9 | 5 | 1.3 |
As can be seen from Table 1, in embodiment mono-~ tetra-and prepared grapheme material, carbonyl content scope is 5%～15%, is far longer than the carbonyl content in grapheme material prepared by comparative example.Wherein embodiment mono-is identical with comparative example's raw material, proportioning, technique etc., just carry out a step nitric acid treatment more, therefore after nitric acid treatment, can effectively increase the carbonyl content in Graphene, improve the chemical property of grapheme material, make the application of Graphene more extensive.
The grapheme material preparing in above-described embodiment one ~ tetra-and comparative example is prepared into button cell and tests, test the capacity of its material.
The ratio of 2:10:88 is by conductive agent acetylene black in mass ratio, binding agent polyvinylidene difluoride (PVDF) and the prepared grapheme material of embodiment mono-~ tetra-mix and obtain slurry, then slurry is coated in aluminum foil current collector, put into vacuum drying oven dry, roll film with roll forming machine again, and carry out trimming processing, make the positive plate that contains grapheme material described in embodiment mono-~ tetra-, then using commercially available lithium sheet as negative pole, polypropylene diaphragm is as barrier film, be assembled into 2032 type button cells, then inject lithium hexafluoro phosphate/propylene carbonate of 1mol/L as electrolytic solution, after leaving standstill 24h, test.
Test condition: test respectively the loading capacity of prepared button cell under the electric current of 0.05C, voltage is 1.5 ~ 4.5V, and test result is as shown in table 2.
The prepared Graphene of table 2 embodiment of the present invention one ~ tetra-and comparative example is assembled into the loading capacity that button cell records
As can be seen from Table 2, grapheme material prepared by the embodiment of the present invention is suitable for preparing the positive pole of lithium ion exchanged battery very much, the lithium ion battery of preparing as anodal main material using this grapheme material, specific storage, up to 145 ~ 206mAh/g, is far longer than comparative example's loading capacity 30mAh/g.On grapheme material prepared by the present invention, increase carbonyl content, improved the chemical property of Graphene.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (6)
1. a preparation method for grapheme material, is characterized in that, comprises the following steps:
(1) get the graphene oxide suspension that concentration is 0.1 ~ 2mg/L, the ratio that is 1mg:1～10mL in graphene oxide and nitric acid solid-to-liquid ratio stirs and adds nitric acid, ultrasonic reaction 0.5 ~ 2 hour under 20～50 ℃ of conditions, makes graphene oxide-nitric acid mixing solutions;
(2) by graphene oxide-nitric acid mixing solutions with dry after deionized water wash, then the dry graphene oxide-nitric acid powder obtaining is put into retort furnace, under atmosphere of inert gases, 500 ~ 700 ℃ of reduction reactions 0.5 ~ 3 hour, finally obtain grapheme material.
2. the preparation method of a kind of grapheme material according to claim 1, is characterized in that, the concentration of described nitric acid is 50%～70%.
3. the preparation method of a kind of grapheme material according to claim 1, is characterized in that, the described rare gas element of step (2) is argon gas, nitrogen, helium or neon.
4. the preparation method of a kind of grapheme material according to claim 1, is characterized in that, the preparation method of described graphene oxide suspension is: first, by improved Hummers legal system for graphite oxide; Then,, by graphite oxide vacuum-drying 24 hours under 120 ℃ of conditions, obtain dehydration graphite oxide; Finally, dehydration graphite oxide is put into water, ultrasonic formation graphene oxide suspension;
Wherein, prepare graphite oxide step by improved Hummers method as follows:
In mass ratio the ratio of 2:1:1 get the vitriol oil that Graphite Powder 99, Potassium Persulphate and Vanadium Pentoxide in FLAKES add 80 ℃ and stir after cooling 6～10 hours, filtration drying, then filter residue is joined in the vitriol oil of 0 ℃, add again potassium permanganate, after mixing, keeping the temperature of mixed solution is 0～10 ℃, then 35～40 ℃ of oil baths 2～3 hours; Add deionized water, after 15～30 minutes, add hydrogen peroxide suction filtration while hot again in mixed solution, with dilute hydrochloric acid and deionized water, solids is washed successively, suction filtration drying solid thing, obtain graphite oxide; The solid-to-liquid ratio of the vitriol oil of described Graphite Powder 99 and described 0 ℃ is 1g:10～15mL; The mass ratio of described Graphite Powder 99 and described potassium permanganate is 1:3～5; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g:40～50mL.
5. the preparation method of a kind of grapheme material according to claim 4, is characterized in that, the purity of described Graphite Powder 99 is 90%～99.5%.
6. a grapheme material, is characterized in that, described grapheme material makes by the arbitrary described preparation method of claim 1～5.
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| CN106276868A (en) * | 2016-07-21 | 2017-01-04 | 东华大学 | A kind of preparation method based on graphene oxide antioxidant |
| CN107230558A (en) * | 2017-06-21 | 2017-10-03 | 太原理工大学 | A kind of Fe3O4The preparation method of/graphene composite material |
| CN110087773A (en) * | 2016-10-13 | 2019-08-02 | 托马仕有限责任公司 | Device and method for producing the thin two-dimensional material of the atom level including graphene in batches |
| CN110615970A (en) * | 2019-09-16 | 2019-12-27 | 海安南京大学高新技术研究院 | High-quality graphene, heat-conducting epoxy resin composite material thereof and preparation method thereof |
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| CN113941120A (en) * | 2021-12-20 | 2022-01-18 | 河北化工医药职业技术学院 | Digestion method of graphene material |
| CN114314794A (en) * | 2021-12-10 | 2022-04-12 | 哈尔滨工业大学 | Preparation method and application of graphene oxide based on high-salt spirulina residues |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104445168A (en) * | 2014-11-28 | 2015-03-25 | 张明 | Preparation method of graphene oxide |
| CN106276868A (en) * | 2016-07-21 | 2017-01-04 | 东华大学 | A kind of preparation method based on graphene oxide antioxidant |
| CN110087773A (en) * | 2016-10-13 | 2019-08-02 | 托马仕有限责任公司 | Device and method for producing the thin two-dimensional material of the atom level including graphene in batches |
| CN110087773B (en) * | 2016-10-13 | 2021-08-17 | 托马仕有限责任公司 | Apparatus and method for mass production of atomically thin two-dimensional materials including graphene |
| CN107230558A (en) * | 2017-06-21 | 2017-10-03 | 太原理工大学 | A kind of Fe3O4The preparation method of/graphene composite material |
| CN107230558B (en) * | 2017-06-21 | 2021-03-23 | 太原理工大学 | Fe3O4Preparation method of/graphene composite material |
| CN110615970A (en) * | 2019-09-16 | 2019-12-27 | 海安南京大学高新技术研究院 | High-quality graphene, heat-conducting epoxy resin composite material thereof and preparation method thereof |
| CN113772665A (en) * | 2021-07-06 | 2021-12-10 | 山东金利特新材料有限责任公司 | Method for preparing graphene on large scale by using high-solid-content filter cake |
| CN114314794A (en) * | 2021-12-10 | 2022-04-12 | 哈尔滨工业大学 | Preparation method and application of graphene oxide based on high-salt spirulina residues |
| CN113941120A (en) * | 2021-12-20 | 2022-01-18 | 河北化工医药职业技术学院 | Digestion method of graphene material |
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Application publication date: 20140507 |