CN104064375A - Method for compounding ternary composite membrane of cellulose, graphene oxide and carbon nano tube in ionic liquid - Google Patents
Method for compounding ternary composite membrane of cellulose, graphene oxide and carbon nano tube in ionic liquid Download PDFInfo
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Abstract
The invention relates to a preparing method of cellulose composite materials, and discloses a method for compounding a ternary composite membrane of cellulose, graphene oxide and a carbon nano tube in ionic liquid to solve the technical problem that cellulose composite aerogel prepared based on an existing method is low in strength and prone to collapsing and deforming. The method comprises the steps that the carbon nano tube and graphene oxide dispersion liquid dispersed into organic solvent are added into the ionic liquid solution of cellulose, temperature is increased, stirring is carried out, repeated washing and suction filtration forming are carried out, and after vacuum drying at the normal temperature, the cellulose/carbon nano tube/graphene oxide ternary composite membrane is obtained. The ternary composite membrane of the cellulose, the graphene oxide and the carbon nano tube can be used in a supercapacitor.
Description
Technical field
The invention belongs to material science, particularly relate to a kind of under ionic liquid the method for synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane.
Background technology
Natural plant cellulose is one of natural organic matter the abundantest on the earth, and the more than 50% of Ta Zhan plant kingdom carbon content, can synthesize approximately 1.5 * 10 by photosynthesis every year
12t.In recent years, along with the rapidly soaring and sustainable development of oil equal energy source price in the urgent need to, natural plant cellulose more and more comes into one's own as eco-friendly renewable resource.Cellulose has meticulous network structure, utilize cellulose as matrix, thereby replace relatively costly synthetic macromolecule, composite material concurrent has the wherein performance of every material simultaneously, the cellulose base graphene/carbon nanometer tube composite materials of preparing has good mechanical property and capacitive property, can make EMI shield, chemically modified electrode, ultracapacitor etc.The patent No. is that 201110274091.4 Chinese patent discloses a kind of method of preparing cellulose composite aerogel, first by cellulose dissolution in alkaline solution, dispersing Nano carbon tubes, graphene oxide or redox graphene in this solution system subsequently, then obtain cellulose composite aerogel by gelation, exchange of solvent, dry run.The method easily causes structure to cave in, be out of shape in exchange of solvent process because gel strength is low at gel.
Summary of the invention
The present invention will solve the technical problem that cellulose composite aerogel intensity prepared by existing method is low, easily cave in, be out of shape, and provide a kind of under ionic liquid the method for synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane.
Of the present invention a kind of under ionic liquid the method for synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane carry out according to the following steps:
One, the cellulose that takes 1～15 part of parts by weight adds in the ionic liquid of 100 parts of parts by weight, and at 60～100 ℃, stirring and dissolving 4～12h, to dissolving completely, obtains cellulose solution;
Two, graphene oxide and carbon nano-tube are added respectively in solvent, be uniformly dispersed, obtain graphene oxide dispersion liquid and carbon nano tube dispersion liquid;
Three, graphene oxide dispersion liquid step 2 being obtained and carbon nano tube dispersion liquid join in the cellulose solution that step 1 obtains, and at 70～100 ℃, stirring reaction 8～24h, obtains mixed solution;
Four, the mixed solution of step 3 gained is joined to cyclic washing in distilled water, then carry out filtration under diminished pressure, obtain wet film, then wet film is put into vacuum drying chamber, under vacuum condition, drying at room temperature, to constant weight, obtains cellulose/graphene oxide/carbon nanometer pipe ternary composite membrane.
The present invention is a kind of method at ionic liquid system synthetic cellulose and graphene oxide and carbon nano-tube compound film.First by graphene oxide and carbon nanotube dispersed to organic solvent, after carbon nano-tube and graphene oxide dispersion liquid are joined in cellulose ionic liquid solution, heating, utilize mechanical agitation to make graphene oxide, carbon nano-tube and cellulosic molecule interphase interaction, form the membrane material of composite construction, under preparation condition of the present invention, the active bond of cellulose surface and graphene oxide, carbon nano-tube combination are strong, the mechanical strength of the composite membrane that obtains is improved, and structural stability improves.It is simple that this method has process conditions, and stability is high, and reaction production safety degree is high, and raw material is easy to get, and reaction condition is gentle, and preparation cost is low, and products obtained therefrom is containing objectionable impurities, environmentally safe and the ionic liquid feature such as can be recycled.
Cellulose/graphene oxide/carbon nanometer pipe ternary composite membrane can obtain by different processing modes different forms.This composite membrane has many good performances, toughness as good in cellulose, and the mechanical performance that graphene oxide and carbon nano-tube are good and electric conductivity, can be used in ultracapacitor.
Accompanying drawing explanation
Fig. 1 is the cellulosic X-ray diffraction spectrogram of test 1;
Fig. 2 is the X-ray diffraction spectrogram of the carbon nano-tube of test 1.
Fig. 3 is the X-ray diffraction spectrogram of the graphene oxide of test 1.
Fig. 4 is the cellulose of test 1 preparation and the X-ray diffraction spectrogram of carbon nano-tube and graphene oxide composite membrane.
Fig. 5 is the cellulose of test 1 preparation and the cyclic voltammogram of carbon nano-tube and graphene oxide composite membrane.
Fig. 6 is cellulose in test 1, the Fourier transform infrared spectroscopy figure of graphene oxide, cellulose and carbon nano-tube and graphene oxide composite membrane.
Fig. 7 is the sectional view of the cellulose of test 1 and the scanning electron microscopy (SEM) of carbon nano-tube and graphene oxide composite membrane.
Fig. 8 is cellulose in test 2, the Fourier transform infrared spectroscopy figure of graphene oxide, cellulose and carbon nano-tube and graphene oxide composite membrane.
Fig. 9 is the plane graph of the cellulose of test 3 and the scanning electron microscopy (SEM) of carbon nano-tube and graphene oxide composite membrane.
Figure 10 is the sectional view of the cellulose of test 3 and the scanning electron microscopy (SEM) of carbon nano-tube and graphene oxide composite membrane.
Embodiment
Embodiment one: a kind of present embodiment method of synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane under ionic liquid is carried out according to the following steps:
One, the cellulose that takes 1～15 part of parts by weight adds in the ionic liquid of 100 parts of parts by weight, at 60～100 ℃, stirs 4～12h, obtains cellulose solution;
Two, graphene oxide and carbon nano-tube are added respectively in solvent, be uniformly dispersed, obtain graphene oxide dispersion liquid and carbon nano tube dispersion liquid;
Three, graphene oxide dispersion liquid step 2 being obtained and carbon nano tube dispersion liquid join in the cellulose solution that step 1 obtains, and at 70～100 ℃, stirring reaction 8～24h, obtains mixed solution;
Four, the mixed solution of step 3 gained is joined to cyclic washing in distilled water, then carry out filtration under diminished pressure, obtain wet film, then wet film is put into vacuum drying chamber, under vacuum condition, drying at room temperature, to constant weight, obtains cellulose/graphene oxide/carbon nanometer pipe ternary composite membrane.
Embodiment two: what present embodiment was different from embodiment one is that the cellulose described in step 1 is chemical cellulose.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one or two is that step 1 intermediate ion liquid is 1-butyl-3-methylimidazole villaumite.Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three is that in step 1, the mass ratio of cellulose and ionic liquid is (1～15): 100.Other is identical with one of embodiment one to three.
The full execution mode five of tool; What present embodiment was different from one of embodiment one to four is at 80 ℃, to stir 8h in step 1.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is that the carbon nano-tube described in step 2 is surface treated carbon nano-tube, surface-treated process is: the volume ratio of the concentrated sulfuric acid that the red fuming nitric acid (RFNA) that is 70% by mass concentration and mass concentration are 98% is 1:3, red fuming nitric acid (RFNA) is mixed with the concentrated sulfuric acid, obtain nitration mixture, by carbon nanotube dispersed in nitration mixture, in temperature, be the 2h that refluxes under the condition of 70 ℃, then with watery hydrochloric acid and deionized water, clean successively, vacuumize again, completes the surface treatment of carbon nano-tube.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is that the solvent described in step 2 is DMF (DMF), DMA (DMAc) or dimethyl sulfoxide (DMSO) (DMSO).Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven is that in step 3, graphene oxide and the gross mass of carbon nano-tube and the ratio of cellulosic quality are (0.5～10): 100, the mass ratio of graphene oxide and carbon nano-tube is (0.1～10): 1.Other is identical with one of embodiment one to seven.
With following verification experimental verification beneficial effect of the present invention:
Test 1: a kind of this test method of synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane under ionic liquid is carried out according to the following steps:
One, 0.4g cellulose joins in 1-butyl-3-methylimidazole villaumite of 15g, and at 80 ℃, stirring and dissolving 10h, to dissolving completely, obtains cellulose solution;
Two, graphene oxide, surface-treated carbon nano-tube are joined respectively and in DMF (DMF), be mixed with suspension that concentration is 20mg/ml and ultrasonic it be uniformly dispersed, obtain graphene oxide dispersion liquid and carbon nano tube dispersion liquid; Wherein the surface treatment process of carbon nano-tube is specially: the volume ratio of the concentrated sulfuric acid that the red fuming nitric acid (RFNA) that is 70% by mass concentration and mass concentration are 98% is 1:3, red fuming nitric acid (RFNA) is mixed with the concentrated sulfuric acid, obtain nitration mixture, by carbon nanotube dispersed in nitration mixture, in temperature, be the 2h that refluxes under the condition of 70 ℃, then with watery hydrochloric acid and deionized water, clean successively, then vacuumize, the surface treatment of carbon nano-tube completed;
Three, graphene oxide dispersion liquid step 2 being obtained and carbon nano tube dispersion liquid join in the cellulose solution that step 1 obtains, and at 80 ℃, stirring reaction 12h, obtains mixed solution; Wherein, the mass ratio of graphene oxide and carbon nano-tube is 1:1, and the quality sum of graphene oxide and carbon nano-tube is 1:25 with the ratio of cellulose quality;
Four, the mixed solution of step 3 gained is joined in distilled water to cyclic washing 3 times, then carry out filtration under diminished pressure, obtain wet film, then wet film is put into vacuum drying chamber, under vacuum condition, drying at room temperature, to constant weight, obtains cellulose/graphene oxide/carbon nanometer pipe ternary composite membrane.
Cellulosic X-ray diffraction spectrogram described in step 1 as shown in Figure 1, the X-ray diffraction spectrogram of the carbon nano-tube described in step 2 as shown in Figure 2, the X-ray diffraction spectrogram of the graphene oxide described in step 2 as shown in Figure 3, the X-ray diffraction spectrogram of cellulose/graphene oxide that this test one obtains/carbon nanometer pipe ternary composite membrane as shown in Figure 4, comparison diagram 1～4 is known, Fig. 1, 2, on 3, X-ray diffraction peak can find corresponding peak on Fig. 4, illustrate that plural gel is by cellulose, carbon nano-tube, graphene oxide tri compound forms, wherein only containing these three kinds of compositions.
Cellulose/graphene oxide that this test is obtained/carbon nanometer pipe ternary composite membrane is put into inherent 700 ℃ of Muffle furnace, N
2under protection, carry out calcination 6 hours, obtain powder, with this powder, carry out capacity measurement, (by electrochemical workstation, carry out cyclic voltammetry, calomel electrode is as reference electrode, platinum electrode is as to electrode, sample is work electrode, electronegative potential is-0.2V, high potential is 0.6V, 6 sections of scanning hop counts, sensitivity is 1.e-002), the cyclic voltammetry curve obtaining as shown in Figure 5, wherein a is that sweep speed is the cyclic voltammetry curve under 100mv/s condition, b is that sweep speed is the cyclic voltammetry curve under 20mv/s condition, c is that sweep speed is the cyclic voltammetry curve under 5mv/s condition, as can be seen from Figure 5, the electrical property of the powder that this test obtains is better.
Fig. 6 is the Fourier transform infrared spectroscopy of material in this test, wherein a is cellulose Fourier transform infrared spectroscopy, the Fourier transform infrared spectroscopy of b graphene oxide, c is the cellulose of this test preparation and the Fourier transform infrared spectroscopy figure of carbon nano-tube and graphene oxide composite membrane.Known from infrared figure, along with adding of graphene oxide and carbon nano-tube, cellulosic absorption peak strength significantly reduces.
Fig. 7 is the scanning electron microscope (SEM) photograph (SEM) of composite membrane section, the linear structure of the lamellar structure of obvious Graphene, and carbon nano-tube as we can see from the figure, and its carbon nano-tube plays longitudinal phase and supports, and Graphene plays the effect that improves mechanical strength.By one dimension material with carbon element carbon nano-tube and Two-dimensional Carbon material oxidation Graphene, thereby form 3-D solid structure under cellulosic effect, improve mechanical property.By calcining, cellulose is transformed into material with carbon element, integral body is had how empty, the material with carbon element that specific area is large, is extremely applicable to doing capacitor.
A kind of test 2, this test method of synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane under ionic liquid is carried out according to the following steps:
One, 2g cellulose joins in 1-butyl-3-methylimidazole villaumite of 50g, and at 70 ℃, stirring and dissolving 12h, to dissolving completely, obtains cellulose solution;
Two,, by graphene oxide, carbon nano-tube joins respectively and in DMF (DMF), is mixed with suspension that concentration is 50mg/ml and ultrasonic it is uniformly dispersed, and obtains graphene oxide dispersion liquid and carbon nano tube dispersion liquid;
Three, graphene oxide dispersion liquid step 2 being obtained and carbon nano tube dispersion liquid join in the cellulose solution that step 1 obtains, and at 80 ℃, stirring reaction 12h, obtains mixed solution; Wherein, the mass ratio of graphene oxide and carbon nano-tube is 1:1, and the quality sum of graphene oxide and carbon nano-tube is 1:5 with the ratio of cellulose quality;
Four, the mixed solution of step 3 gained is joined in distilled water to cyclic washing 3 times, then carry out filtration under diminished pressure, obtain wet film, then wet film is put into vacuum drying chamber, under vacuum condition, drying at room temperature, to constant weight, obtains cellulose/graphene oxide/carbon nanometer pipe ternary composite membrane.
Fig. 8 is the Fourier transform infrared spectroscopy of material in this test, wherein a is cellulose Fourier transform infrared spectroscopy, the Fourier transform infrared spectroscopy of b graphene oxide, c is the cellulose of this test preparation and the Fourier transform infrared spectroscopy figure of carbon nano-tube and graphene oxide composite membrane.More known, along with adding of graphene oxide and carbon nano-tube, cellulosic absorption peak strength significantly reduces.
A kind of test 3, this test method of synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane under ionic liquid is carried out according to the following steps:
One, take in 1-butyl-3-methylimidazole villaumite that 0.5g cellulose joins 20g, at 80 ℃, stirring and dissolving 12h, to dissolving completely, obtains cellulose solution;
Two,, by graphene oxide, carbon nano-tube joins respectively and in DMF (DMF), is mixed with suspension that concentration is 20mg/ml and ultrasonic it is uniformly dispersed, and obtains graphene oxide dispersion liquid and carbon nano tube dispersion liquid;
Three, graphene oxide dispersion liquid step 2 being obtained and carbon nano tube dispersion liquid join in the cellulose solution that step 1 obtains, and at 80 ℃, stirring reaction 12h, obtains mixed solution; Wherein, the mass ratio of graphene oxide and carbon nano-tube is 1:1, and the quality sum of graphene oxide and carbon nano-tube is 1:5 with the ratio of cellulose quality;
Four, the mixed solution of step 3 gained is joined in distilled water to cyclic washing 3 times, then carry out filtration under diminished pressure, obtain wet film, then wet film is put into vacuum drying chamber, under vacuum condition, drying at room temperature, to constant weight, obtains cellulose/graphene oxide/carbon nanometer pipe ternary composite membrane.
The plane graph of the scanning electron microscopy (SEM) of cellulose/graphene oxide that this test obtains/carbon nanometer pipe ternary composite membrane as shown in Figure 9.As can be seen from Figure 9, the lamellar structure of Graphene in material, and in lamella, be to be supported by carbon nano-tube, Graphene covering forms, and has cellulose to link together.Stereochemical structure is obvious.
The sectional view of the scanning electron microscopy (SEM) of cellulose/graphene oxide that this test obtains/carbon nanometer pipe ternary composite membrane as shown in figure 10.Material is that Graphene covers its surface by piling up and form from level to level, can clearly see the structure that carbon nano-tube is interweaved in section as can be seen from Figure 10, by cellulose, is connected together, forms layered laminate.
Claims (8)
1. a method for synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane under ionic liquid, is characterized in that the method carries out according to the following steps:
One, the cellulose that takes 1～15 part of parts by weight adds in the ionic liquid of 100 parts of parts by weight, at 60～100 ℃, stirs 4～12h, obtains cellulose solution;
Two, graphene oxide and carbon nano-tube are added respectively in solvent, be uniformly dispersed, obtain graphene oxide dispersion liquid and carbon nano tube dispersion liquid;
Three, graphene oxide dispersion liquid step 2 being obtained and carbon nano tube dispersion liquid join in the cellulose solution that step 1 obtains, and at 70～100 ℃, stirring reaction 8～24h, obtains mixed solution;
Four, the mixed solution of step 3 gained is joined to cyclic washing in distilled water, then carry out filtration under diminished pressure, obtain wet film, then wet film is put into vacuum drying chamber, under vacuum condition, drying at room temperature, to constant weight, obtains cellulose/graphene oxide/carbon nanometer pipe ternary composite membrane.
According to claim 1 a kind of under ionic liquid the method for synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane, it is characterized in that the cellulose described in step 1 is chemical cellulose.
According to claim 1 and 2 a kind of under ionic liquid the method for synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane, it is characterized in that step 1 intermediate ion liquid is 1-butyl-3-methylimidazole villaumite.
According to claim 1 and 2 a kind of under ionic liquid the method for synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane, it is characterized in that in step 1, the mass ratio of cellulose and ionic liquid is (1～15): 100.
According to claim 1 and 2 a kind of under ionic liquid the method for synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane, it is characterized in that at 80 ℃, stirring 8h in step 1.
According to claim 1 and 2 a kind of under ionic liquid the method for synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane, it is characterized in that the carbon nano-tube described in step 2 is surface treated carbon nano-tube, surface-treated process is: the volume ratio of the concentrated sulfuric acid that the red fuming nitric acid (RFNA) that is 70% by mass concentration and mass concentration are 98% is 1:3, red fuming nitric acid (RFNA) is mixed with the concentrated sulfuric acid, obtain nitration mixture, by carbon nanotube dispersed in nitration mixture, in temperature, be the 2h that refluxes under the condition of 70 ℃, then with watery hydrochloric acid and deionized water, clean successively, vacuumize again, complete the surface treatment of carbon nano-tube.
According to claim 1 and 2 a kind of under ionic liquid the method for synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane, it is characterized in that the solvent described in step 2 is N, dinethylformamide, DMA or dimethyl sulfoxide (DMSO).
According to claim 1 and 2 a kind of under ionic liquid the method for synthetic cellulose and graphene oxide and carbon nanometer pipe ternary composite membrane, it is characterized in that in step 3 that graphene oxide and the gross mass of carbon nano-tube and the ratio of cellulosic quality are (0.5～10): 100, the mass ratio of graphene oxide and carbon nano-tube is (0.1～10): 1.
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| CN108521683A (en) * | 2018-05-15 | 2018-09-11 | 广西大学 | Nano-cellulose graphene oxide thermo electric material and preparation method thereof |
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| CN109596398A (en) * | 2018-11-20 | 2019-04-09 | 江苏科技大学 | A kind of preparation method of solid phase micro-extraction coat layer |
| CN109596398B (en) * | 2018-11-20 | 2020-12-25 | 江苏科技大学 | Preparation method of solid-phase microextraction coating |
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| CN111807809B (en) * | 2019-04-10 | 2021-12-28 | 盐城工业职业技术学院 | Preparation method of palm nanofiber-graphene-carbon nanotube composite aerogel |
| CN111785531A (en) * | 2020-06-12 | 2020-10-16 | 杭州电子科技大学 | Preparation method of carbon nanotube/bacterial cellulose aerogel material and super capacitor |
| CN113797767A (en) * | 2020-06-12 | 2021-12-17 | 四川大学 | Preparation method of carbon nanotube-ionic liquid-derived cellulose composite membrane and composite sheet |
| CN116535173A (en) * | 2023-05-10 | 2023-08-04 | 贵阳中建西部建设有限公司 | High-temperature-resistant concrete and preparation method thereof |
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