CN103741264A - Method for preparing graphene fibers through self-assembly of large lamellar graphene oxide - Google Patents
Method for preparing graphene fibers through self-assembly of large lamellar graphene oxide Download PDFInfo
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Abstract
The present invention discloses a method for preparing graphene fibers through self-assembly of large lamellar graphene oxide. The technical scheme comprises that: graphite is adopted as a base material to prepare large lamellar graphene oxide, and the graphene fibers are formed through self-assembly of the graphene oxide in a solidification solution. According to the present invention, the type of the solidification solution and the concentration of the graphene oxide are adjusted to prepare the graphene fibers with different types; and the prepared graphene fibers can be widely used in the fields of supercapacitors, aerospace, new energy sources, and civil construction and the like.
Description
Technical field
The invention belongs to graphene nano material technology field, relate in particular to a kind of preparation method of graphene fiber.
Background technology
Material is the material base that the mankind depend on for existence, is also the basic industry of the national economic development.Along with the development of new technology, new material is constantly proposed to new demand, this has also impelled the development of new material.This that is to say, the demand in market is the driving force of new material development, and graphene fiber and composite thereof are exactly the new material growing up under new technology drives.Graphene fiber, as its name suggests, has the soft machinability that the intrinsic intrinsic property of carbon graphite material has both again spinning fibre, is enhancement fiber of new generation.Graphene is since the scientist of 2004 Nian Bei University of Manchester finds, with its excellent mechanical performance, physics and chemistry performance has become the focus of research, Graphene two-dimension plane structure can be made the quantum dot of zero dimension, the fiber of one dimension, the film of two dimension, 3-D solid structure, its superpower plasticity makes Graphene all be widely used in a plurality of fields.
At present, the most widely used fiber in market is glass fibre and carbon fiber, 2005 years, Global Carbon fiber market is only 900,000,000 dollars, and within 2013, be expected to meet or exceed 10,000,000,000 dollars, and expecting 2022 and be expected to reach 40,000,000,000 dollars, the application of carbon fibre composite also will enter the brand-new epoch.Current, Global Carbon fiber core technology is firmly controlled in minority developed country hand.On the one hand, with the developed country headed by America and Japan, remaining the strict blockade on new techniques of Chinese carbon fiber industry; On the other hand, the enterprise of carbon fiber industry-leading abroad starts to enter Chinese market, and the pressure of China domestic carbon fiber industry increases.Although the Chinese government has strengthened guiding and support dynamics to domestic carbon fiber local enterprise, under larger technological gap, the road of the breakthrough of domestic carbon fibre enterprise is still bumpy.
At present, graphene fiber is in laboratory development, and superb seminar of Zhejiang University has delivered one piece of Graphene chiral liquid crystals and macroscopic assembled fibers by name on Nature Communication periodical article in 2011 has proposed Graphene liquid phase spinning graphene fiber; The Shi Gaoquan professor of Tsing-Hua University delivers one piece of Facile fabrication of light by name on Advance Materiels magazine, the article of flexible and multifunctional graphene fibers, is coated in graphene oxide the intensity that has improved graphene fiber on glass fibre.But the graphite fibre method of being prepared by large stretch of graphite oxide of mentioning in a lot of documents now, just after graphite oxide reaches certain concentration, simple physical crosslinking in solidification liquid, the mechanical strength of the fiber of preparation a little less than.And in the present invention by utilizing the difference of solidification liquid kind, by the effect of chemical bond, utilize graphite oxide self assembly in solidification liquid to form fiber.Under scientists is constantly made great efforts, the quality of graphene fiber is in continuous lifting, and be expected in the future make TENSILE STRENGTH reach 10GPa and elongation at break reaches 5% left and right, fragility improves, toughness is increased, to having better application in Aero-Space and most advanced and sophisticated war industry and civil area.
Summary of the invention
The object of the invention is to solve the shortcoming and defect of prior art, a kind of preparation method of graphene fiber is provided, and by regulating the type of solidification liquid and the concentration of Graphene to prepare dissimilar graphene fiber.
Technical scheme provided by the invention comprises following concrete steps:
1. the preparation of large lamella graphene oxide
(1) get a certain amount of graphite powder, add the concentrated sulfuric acid/red fuming nitric acid (RFNA) mixed liquor that the volume ratio with respect to graphite powder consumption 300 wt% ~ 1000 wt% is 1:1 ~ 10:1, the deionized water filtration, the wash solution that add afterwards 600 ~ 1000ml, putting into 40 ℃ ~ 100 ℃ baking ovens dries, 5 ~ the 50s that expands under 500 ~ 2000 ℃ of high temperature again, obtains expanded graphite.
(2) in the expanded graphite of preparing in step (1), add the 180-1300ml concentrated sulfuric acid, slowly add the oxidant with respect to graphite powder consumption 500 wt% ~ 2000 wt%, at 60 ~ 200 ℃, carry out pre-oxidation, to be cooled to after room temperature with deionized water washing, in 30 ~ 80 ℃ of baking ovens, dry.Under ice bath, slowly add the 100-1500ml concentrated sulfuric acid and 9-25g potassium permanganate, after fully stirring, in oil bath pan, react 1 ~ 5 h, with deionized water, slowly dilute mixed liquor, adding appropriate hydrogenperoxide steam generator to remove excessive potassium permanganate to solution becomes light yellow again, with a certain amount of 1mol/L watery hydrochloric acid and deionized water washing, centrifugal pale yellow solution, make solution be neutral, it is that the bag filter of 8000-14000Da is dialysed that GO is placed in to molecular cut off, again solution is placed on to freeze-drying in freeze dryer, obtain large lamella with the Graphene (GGO) of oxide group.
Oxidant in above-mentioned steps (2) is one or more mixtures in the concentrated sulfuric acid, phosphorus pentoxide, potassium peroxydisulfate, phosphoric acid, red fuming nitric acid (RFNA), ammonium persulfate, sodium dichromate, sodium perborate, potassium perborate, clorox, Na2Fe04.
2. the preparation of graphene fiber
A certain amount of large lamella graphene oxide (GGO) is dissolved in deionized water, the ultrasonic GGO of making is dispersed in the aqueous solution, being made into concentration is the graphene oxide solution of 5 mg/ml ~ 50 mg/ml, and compound concentration is the solidification liquid of 5 wt% ~ 80 wt%, by syringe, graphene oxide solution is injected in solidification liquid, then Graphene forms graphene oxide fiber with self assembly form, then with teflon rod, roll the graphene fiber in solidification liquid, dry at normal temperatures, again the graphene oxide fiber after drying is reduced and obtains graphene fiber under 100 ~ 800 ℃ of vacuum high-temperatures.
Above-mentioned coagulating agent is any one or the multiple mixture in alcohol organic solvent, bases solvent (NaOH, KOH, CaCl2), acids solvent (dilute sulfuric acid, watery hydrochloric acid, acetic acid, tartaric acid), amine organic solvent, dimethyl sulfoxide (DMSO), dodecyl sodium sulfate, enuatrol, oxolane and N-methylpyrrole alkane, and the temperature of solidification liquid is 10 ℃ ~ 120 ℃.
Above-mentioned graphene oxide self assembly forms the chemical bond comprising in graphene oxide and is not limited to covalent bond, ionic bond, hydrogen bond.
The present invention is the graphite fibre method of preparing by large stretch of graphite oxide, improved in the past Graphene and prepared in spinning with graphene oxide simple physical crosslinking in solidification liquid, the mechanical strength of the fiber of preparation a little less than.And in the present invention by utilizing the difference of solidification liquid kind, by the effect of chemical bond, utilize graphite oxide self assembly in solidification liquid to form fiber.Graphene fiber prepared by the present invention can be widely used in the fields such as ultracapacitor, Aero-Space, new forms of energy and civil construction.
Accompanying drawing explanation
Fig. 1 is the TEM(a of graphene oxide of preparation in embodiment 1) and SEM(b) figure.
Fig. 2 is the graphene fiber pictorial diagram (a, b) prepared in aniline solidification liquid in embodiment 1 and the elasticity photo (c, d) of graphene fiber.
Fig. 3 is the microscope picture of the graphene fiber prepared in KOH solidification liquid in embodiment 2.
Fig. 4 be the graphene fiber prepared in 1,8-octamethylenediamine solidification liquid in embodiment 3 SEM figure.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
embodiment 1
1, the preparation of large lamella graphene oxide
Take 5g graphite powder as raw material, add the 650 mL concentrated sulfuric acids and 100 mL red fuming nitric acid (RFNA)s, stir at normal temperatures 24h, mixture imports in 2L water, filters, and washs latter 60 ℃ and dries 24h.The 10s that expands under 1500 ℃ of high temperature, obtains expanded graphite.Add the 1000 mL concentrated sulfuric acids, slowly add 13.2g K
2s
2o
8with 16.2g P
2o stirs 2h at 80 ℃ of constant temperature, to be cooledly after room temperature, washes with water, dries 24h for 45 ℃.In the GO after drying, add the 1200mL concentrated sulfuric acid again, under ice bath, stir 1.5h, slowly add again 15g potassium permanganate, after fully stirring, in 35 ℃ of oil bath pans, react 2h, with deionized water, slowly dilute mixed liquor, wait solution to be cooled to 60 ℃ of hydrogenperoxide steam generators that add 15mL 30%, become shallow yellow transparent solution to solution.Centrifuge washing, then the solution that adds the quantitative 1mol/L watery hydrochloric acid washing of 80 mL to obtain, remove metal ion, and standing 3h pours out supernatant; Use again the unnecessary acid of deionized water centrifuge washing, until solution is neutral; Centrifugal GO is placed in to the bag filter that molecular cut off is 8000-14000Da, in deionized water, dialyses 7 days, every 12 hours, change one time deionized water.Again solution is put in to temperature and is-48 ℃, pressure, lower than freeze-drying in the freeze dryer of 18 Pa, obtains large lamella with the Graphene (GGO) of oxidation group.
2, utilize aniline solidification liquid to produce graphene fiber
By in the water-soluble solution of large lamella graphene oxide (GGO) of 450 mg, ultrasonic 2 h are dispersed in the aqueous solution GO, be made into the graphene oxide that concentration is 20 mg/ml (GGO) solution, preparing mass fraction is 5%(7%, 10% again) aniline solution as solidification liquid, by syringe, graphene oxide solution is injected in solidification liquid to self assembly and forms graphene oxide fiber.With the fiber that teflon rod is rolled in solidification liquid, dry at normal temperatures, then the graphene oxide fiber drying is reduced and obtains graphene fiber at 220 ℃.
embodiment 2
In step 1, prepare GGO method with embodiment 1, by the water-soluble solution of large lamella graphene oxide (GGO) of 400 mg, ultrasonic 3 h are dispersed in the aqueous solution GO, are made into graphene oxide (GGO) solution of 5 mg/ml.Prepare again the KOH solution of mass fraction 15% as solidification liquid, by syringe, graphene oxide solution is injected into self assembly in solidification liquid and forms graphene oxide fiber.With the fiber that teflon rod is rolled in solidification liquid, dry at normal temperatures, then the graphene oxide fiber drying is reduced and obtains graphene fiber at 400 ℃.
The preparation GGO method of step 1 is with embodiment 1, and by the water-soluble solution of large lamella graphene oxide (GGO) of 350 mg, ultrasonic 4 h are dispersed in the aqueous solution GO, are made into graphene oxide (GGO) solution of 30 mg/ml.Prepare 1 of mass fraction 15%, 8-octamethylenediamine solution, as solidification liquid, is injected into self assembly in solidification liquid by syringe by graphene oxide solution and forms graphene oxide fiber again.With the fiber that teflon rod is rolled in solidification liquid, dry at normal temperatures.The graphene oxide fiber drying is reduced and obtains graphene fiber at 550 ℃.
embodiment 4
The preparation GGO method of step 1 is with embodiment 1, and by the water-soluble solution of the 200 large lamella graphene oxide of mg (GGO), ultrasonic 2 h are dispersed in the aqueous solution GO, are made into graphene oxide (GGO) solution of 13 mg/ml.Prepare again the propane diamine solution of mass fraction 9% as solidification liquid, by syringe, graphene oxide solution is injected into self assembly in solidification liquid and forms graphene oxide fiber, with the fiber that teflon rod is rolled in solidification liquid, dry at normal temperatures, then the graphene oxide fiber after drying is reduced and obtains graphene fiber at 600 ℃.
embodiment 5
The preparation GGO method of step 1 is with embodiment 1, and by the water-soluble solution of the 580 large lamella graphene oxide of mg (GGO), ultrasonic 2.5 h are dispersed in the aqueous solution GO, are made into the graphene oxide solution of 18mg/ml.Prepare again softex kw (CTAB) solution of mass fraction 20% as solidification liquid, by syringe, graphene oxide solution is injected into self assembly in solidification liquid and forms graphene oxide fiber.With the fiber that teflon rod is rolled in solidification liquid, dry at normal temperatures, then the graphene oxide fiber after drying is reduced and obtains graphene fiber at 750 ℃.
Claims (10)
1. by the self assembly of large lamella graphene oxide, prepare a method for graphene fiber, preparation process comprises the following steps:
(1) preparation of large lamella graphene oxide (Giant Graphene Oxide (GGO))
Take graphite powder as raw material, with a certain amount of sulfuric acid/nitric acid mixed liquor, graphite powder is carried out to preliminary treatment, after pretreated graphite powder expands at high temperature 500-2000 ℃, add a certain amount of oxidant at a certain temperature graphite to be carried out to pre-oxidation, under condition of ice bath, add a certain amount of KMnO
4/ H
2sO
4solution, after reaction finishes, adds appropriate hydrogen peroxide in solution, remove excessive KMnO
4, obtain shallow yellow transparent solution, then freeze-drying obtains large lamella with the Graphene (GGO) of oxide group;
(2) preparation of graphene fiber
Be dispersed in the aqueous solution the graphene oxide of freeze-drying is ultrasonic, in order to reach into the viscosity requirement of fiber, need the certain density graphene oxide solution of configuration and certain density solidification liquid, by syringe, graphene oxide solution is injected to solidification liquid, graphene oxide forms graphene oxide fiber in self assembly mode, then with teflon rod, roll the fiber in solidification liquid, be put under normal temperature and dry, by the high temperature reduction under vacuum environment of the graphene oxide fiber after drying, obtain graphene fiber again.
2. the preparation method of graphene fiber according to claim 1, is characterized in that: the large lamella graphene oxide described in step (1), its diameter is 20-80 um.
3. the preparation method of graphene fiber according to claim 1, it is characterized in that: in the preliminary treatment graphite powder process described in step (1), the volume ratio of the concentrated sulfuric acid/red fuming nitric acid (RFNA) is 1:1 ~ 10:1, and the consumption of mixed liquor is 300 wt% ~ 1000 wt% of graphite powder consumption.
4. the preparation method of graphene fiber according to claim 1, it is characterized in that: the oxidant described in step (1) is one or more mixtures in the concentrated sulfuric acid, phosphorus pentoxide, potassium peroxydisulfate, phosphoric acid, red fuming nitric acid (RFNA), ammonium persulfate, sodium dichromate, sodium perborate, potassium perborate, clorox, Na2Fe04, the consumption of oxidant is 500 wt% ~ 2000 wt% of graphite powder consumption.
5. the preparation method of graphene fiber according to claim 1, is characterized in that: the temperature of the graphite powder pre-oxidation that step (1) is described is 60 ~ 200 ℃.
6. the preparation method of graphene fiber according to claim 1, is characterized in that: the concentration of the graphene oxide solution described in step (2) is 5mg/ml ~ 50 mg/ml, and the concentration of solidification liquid is 5 wt% ~ 80 wt%.
7. the preparation method of graphene fiber according to claim 1, is characterized in that: the solidification liquid described in step (2) is alcohol organic solvent, bases solvent (NaOH, KOH, CaCl
2), any one or multiple mixture in acids solvent (dilute sulfuric acid, watery hydrochloric acid, acetic acid, tartaric acid), amine organic solvent, dimethyl sulfoxide (DMSO), dodecyl sodium sulfate, enuatrol, oxolane and N-methylpyrrole alkane.
8. the preparation method of graphene fiber according to claim 1, is characterized in that: the temperature of the solidification liquid described in step (2) is 10 ℃ ~ 120 ℃.
9. the preparation method of graphene fiber according to claim 1, is characterized in that: the graphene oxide self assembly described in step (2) forms the chemical bond comprising in graphene oxide and is not limited to covalent bond, ionic bond, hydrogen bond.
10. the preparation method of graphene fiber according to claim 1, is characterized in that: the temperature of high temperature reduction graphene oxide under vacuum environment described in step (2) is 100 ℃ ~ 800 ℃.
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| CN105293477A (en) * | 2015-11-13 | 2016-02-03 | 安徽易能新材料科技有限公司 | Preparation method for large lamellar graphene oxide |
| CN105603580A (en) * | 2015-12-31 | 2016-05-25 | 盐城增材科技有限公司 | Preparing method for oriented graphene oxide fibers |
| CN105937066A (en) * | 2015-12-27 | 2016-09-14 | 南京新月材料科技有限公司 | Preparation method of highly oriented graphene oxide fiber |
| CN106752116A (en) * | 2016-11-15 | 2017-05-31 | 吉林省云亭节能技术有限公司 | The preparation method and modified graphene oxide EPS of modified graphene oxide mold the preparation method of styrofoam |
| CN106865526A (en) * | 2017-02-21 | 2017-06-20 | 四川大学 | β graphite alkenes and its synthetic method and the application in energy storage field |
| CN106894113A (en) * | 2017-02-21 | 2017-06-27 | 东华大学 | A kind of graphene oxide dry-jet wet-spinning spinning process |
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| CN105937066A (en) * | 2015-12-27 | 2016-09-14 | 南京新月材料科技有限公司 | Preparation method of highly oriented graphene oxide fiber |
| CN105603580A (en) * | 2015-12-31 | 2016-05-25 | 盐城增材科技有限公司 | Preparing method for oriented graphene oxide fibers |
| CN106752116A (en) * | 2016-11-15 | 2017-05-31 | 吉林省云亭节能技术有限公司 | The preparation method and modified graphene oxide EPS of modified graphene oxide mold the preparation method of styrofoam |
| CN106865526A (en) * | 2017-02-21 | 2017-06-20 | 四川大学 | β graphite alkenes and its synthetic method and the application in energy storage field |
| CN106894113A (en) * | 2017-02-21 | 2017-06-27 | 东华大学 | A kind of graphene oxide dry-jet wet-spinning spinning process |
| CN109950479A (en) * | 2017-12-21 | 2019-06-28 | 中国科学院上海硅酸盐研究所 | A kind of three-dimensional porous structure graphene/sulfur composite positive electrode material and preparation method thereof |
| CN109322009A (en) * | 2018-08-24 | 2019-02-12 | 宿迁南航新材料与装备制造研究院有限公司 | A kind of graphene fiber and preparation method thereof of wet spinning preparation |
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| CN111013540A (en) * | 2019-12-30 | 2020-04-17 | 西北工业大学 | Preparation method of graphene magnetic aerogel with high adsorption performance |
| CN111223688A (en) * | 2020-01-13 | 2020-06-02 | 北京化工大学 | Preparation method of nitrogen and sulfur co-doped graphene fiber supercapacitor electrode material |
| CN112999415A (en) * | 2021-03-24 | 2021-06-22 | 兰州大学 | Graphene-based polymer composite nerve conduit and preparation method thereof |
| CN112999415B (en) * | 2021-03-24 | 2022-05-24 | 兰州大学 | Graphene-based polymer composite nerve conduit and preparation method thereof |
| WO2023155282A1 (en) * | 2022-02-16 | 2023-08-24 | 浙江大学 | Preparation method for large crystal region high crystallinity carbonaceous fiber |
| WO2023236351A1 (en) * | 2022-06-07 | 2023-12-14 | 苏州大学 | Graphene assembly fiber, and preparation method therefor and use thereof |
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Application publication date: 20140423 |