CN102432088B - Method for preparing carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode - Google Patents
Method for preparing carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode Download PDFInfo
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Abstract
The invention relates to a method for preparing a carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode, which belongs to the field of the capacitance desalination electrode preparation. The method comprises the following steps that: firstly, graphite oxide/carbon nanometer tube high-stability dispersing liquid is obtained, and the graphite oxide/carbon nanometer tube compounds are fast peeled at a low temperature to obtain carbon nanometer tube/graphene three-dimensional nanometer compound materials. The carbon nanometer tube/graphene three-dimensional nanometer compound materials and polytetrafluoroethylene emulsion are uniformly mixed and coated on graphite paper, the carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode is prepared after being baked. The method has the advantages that the temperature is low, simplicity is realized, and the operation is easy. The obtained carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode has good conductivity and better desalination performance, and potential prospects are realized in the capacitance desalination aspect.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode, the desalination electrode of the present invention's preparation has efficiently, the desalting performance of less energy-consumption.Belong to electric desalting electrode manufacturing process technical field.The present invention can be used for can be applicable to the desalination of seawater and bitter alkali water, worker, agriculture production and domestic water (underground water) softening.
Background technology
Water resources crisis is one of maximum resource crisis that this century, the whole world faced, and seawater and brackish water desalting are the important channels that solves this crisis.Existing desalting method mainly contains distillation method and embrane method.The distillation method service temperature is high, and energy consumption is larger; Bird nest harm and seriously corroded; Embrane method is strict to film properties, the high and somewhat expensive of film spoilage.In addition, all there is the high shortcoming of energy consumption in these desalting method, even if consume energy minimum reverse osmosis membrane, its energy consumption also is about ten times of theoretical value.Therefore, research and development energy consumption desalting technology application prospect low, that cost is low is very bright.The structure capacitance desalination method be a kind of based on electric double layer capacitance away from brand-new desalting technology.The method energy consumption is low, desalting efficiency is high, and is environmentally friendly.Can be applicable to the aspect such as softening of the desalination of seawater and brackish water and worker, agriculture production and domestic water, its development space and having a extensive future.
Graphene is the elementary cell that consists of graphite as a kind of carbon material of emerging bi-dimensional cellular shape structure.It has good electroconductibility, wider electrochemical window, high chemical stability, and larger specific surface area.Although the theoretical specific surface area of Graphene is very large, because stronger Van der Waals force between sheet and the sheet, between layers lamination and the phenomenon such as reunion easily occur, so that the Graphene specific surface area reduces greatly, thereby reduced desalting performance.The people such as Pan (L i H.B, Zou L.D. Lu T A comparative study on electrosorptive behavior of carbon nanotubes and graphene for capacitive deionization Journal of Electroanalytical Chemistry 653 (2011) 40 – 44) prepared the Graphene desalination electrode, its Graphene is reunited serious, and specific surface area only has 77 m
2/ g, desalting performance is relatively poor.The people such as Zou (L i H.B, Zou L.D. Pan L.K. Novel Graphene-Like Electrodes for Capacitive Deionization Environ. Sci. Technol. 2010,44,8692 – 8697) prepare the Graphene desalination electrode and reunited more seriously, reduced its desalting performance.Therefore, how solving the reunion of Graphene, improve its effective ratio area, increase nano pore, strengthen its desalting performance, is a challenging job.
Summary of the invention
The objective of the invention is to overcome the shortcoming of Graphene electrodes, the carbon nanotube of high-specific surface area, high conductivity is inserted between graphene layer, make carbon nanotube be grafted on the Graphene surface, so that Graphene is separated from each other out between layers, prevent the Graphene reunion, to reach the purpose that improves the Graphene specific surface area.Can play bridge linking effect in the middle of carbon nanotube embeds Graphene separated from one another is coupled together, form three-dimensional conductive network structure, can introduce more nanometers duct simultaneously, be conducive to the ion diffusion, can greatly improve desalting performance.The carbon nanotube of special hollow structure, satisfactory electrical conductivity, low-resistivity is introduced a kind of novel carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode of preparation between graphene layer, have good electroconductibility and desalting performance preferably.
The objective of the invention is to reach by following technique means and measure.
The present invention also provides a kind of carbon nanotube/Graphene three-dimensional manometer composite capacitance-type desalting electrode and preparation method thereof, may further comprise the steps:
(1) preparation of electrode materials: under the ice-water bath condition, graphite is under agitation slowly joined in the vitriol oil of massfraction 98%, slowly add potassium permanganate, its graphite: the vitriol oil: the mass ratio of potassium permanganate is 1:40～100:2 ~ 8, at 32-38 again
oIn the C water bath with thermostatic control, stir lower insulation 1-6 h, after reaction finishes, slowly add the deionized water dilution, stir several minutes, press graphite: H
2O
2Mass ratio be the H that 1:7 ~ 10 adds massfractions 30%
2O
2, leave standstill rear filtration, fully washing leaching cake washs to neutral, and drying obtains graphite oxide under the room temperature; By graphite oxide: the mass ratio of carbon nanotube is 99:1～4:1, and graphite oxide and carbon nanotube ultra-sonic dispersion in deionized water, after being uniformly dispersed, are detached drying; The mixture of above-mentioned gained is placed pre-warmed tube furnace, and insulation for some time can obtain carbon nanotube/Graphene three-dimensional manometer matrix material.
(2) preparation of carbon nanotube/Graphene three-dimensional manometer composite capacitance-type desalting electrode: the adding massfraction is that the ptfe emulsion of 5-15% is binding agent in the carbon nanotube/Graphene of step (1) gained, be applied to after mixing on the Graphite Electrodes paper, subsequently at 100-110
oThe C oven dry is spent the night, and finally makes the compound desalination electrode of carbon nanotube/Graphene.
Above-mentioned graphite oxide graphene/carbon nanotube uniform dispersion, this dispersion liquid can be stablized more than the week, illustrate that carbon nanotube fully is inserted in the graphite oxide, graphite oxide and carbon nanotube combine by П-П conjugation, graphite oxide and nanotube can reach nano level to be disperseed, increase the dispersiveness of carbon nanotube in water, be conducive to the preparation of electrode.
Above-mentioned pre-warmed silica tube is 200-500
oC, soaking time is 5-20 min, low temperature of the present invention can make carbon nanotube/graphite oxide body volume rapid expansion peel off.The oxidized burning of carbon material during the protection of excess Temperature inert-free gas is crossed to hang down and can not be played the effect of peeling off fast.
Above-mentioned carbon nanotube is many walls nanotube, and diameter is 5-50 nm.Agglomeration is stronger between the single-walled nanotube, and the reactive force between nanotube and the Graphene is weak can't the dispersion it, and Single Walled Carbon Nanotube can not be separated graphene sheet layer.
Above-mentioned graphite oxide: when the mass ratio of carbon nanotube is 99:1～4:1, the gained Graphene is separated from each other, contacting between carbon nanotube and the Graphene is better, playing the conducting bridge continuous cropping uses, the electrode nano pore structure increases, so that salt ion can pass in and out electrode interior more fast, and internal resistance is less, electroconductibility is better, and desalting performance is better; Along with the increase of content of carbon nanotubes, the sheet structure of Graphene is easy to be surrounded by carbon nanotube, has caused the internal resistance of electrode to begin to increase, and reduces its desalting performance.
Preparation process of the present invention is simple, and energy consumption is little, easy handling.The prepared carbon nanotube of the inventive method/Graphene three-dimensional manometer combined electrode has good electroconductibility and desalting performance preferably, has potential application prospect aspect structure capacitance desalination.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
Under the ice-water bath condition 3 g graphite are under agitation slowly joined in the vitriol oil of 120 mL massfractions 98%, slowly add 14 g potassium permanganate, its graphite: the vitriol oil: the mass ratio of potassium permanganate is 1:40:4.7,35 again
oIn the C water bath with thermostatic control, stir lower insulation 2 h, after reaction finishes, slowly add the dilution of 500 mL deionized waters, stir several minutes, press graphite: H
2O
2Mass ratio be the H that 1:7.5 adds 22.5 mL massfractions 30%
2O
2, leave standstill rear filtration, fully washing leaching cake washs to neutral, and drying obtains graphite oxide under the room temperature.With the multi-walled carbon nano-tubes of diameter 10 ~ 30 nm, press graphite oxide: carbon nanotube mass ratio 9:1, mix ultrasonic 2 h, after being uniformly dispersed, detach drying.The mixture of above-mentioned gained placed preheat to 300
oIn the tube furnace of C, be incubated 10 min, can obtain carbon nanotube/Graphene three-dimensional manometer matrix material.Be that 10% ptfe emulsion is binding agent with adding massfraction in the carbon nanotube/Graphene of gained, be applied to after mixing on the Graphite Electrodes paper, subsequently at 100-110
oThe C oven dry is spent the night.Finally make the compound desalination electrode of carbon nanotube/Graphene.
Test the ratio electric capacity of the compound desalination electrode of above-mentioned carbon nanotube/Graphene.Use CHI 660D type electrochemical workstation, electrolytic solution is 0.5 M NaCl solution, and scanning speed is 5 mv; Voltage range is-0.4-0.6 V; The specific capacitance that records this electrode is 216.6 F/g.Its desalting performance of the electrode test of above-mentioned preparation, in the salt solution of 1000 mg/L, two ends apply the voltage of 2.0 V, and its desalting efficiency is greater than 80%.
Embodiment 2
Under the ice-water bath condition 3 g graphite are under agitation slowly joined in the vitriol oil of 150 mL massfractions 98%, slowly add 21 g potassium permanganate, its graphite: the vitriol oil: the mass ratio of potassium permanganate is 1:50:7,35 again
oIn the C water bath with thermostatic control, stir lower insulation 3 h, after reaction finishes, slowly add the dilution of 500 mL deionized waters, stir several minutes, press graphite: H
2O
2Mass ratio be the H that 1:8.3 adds 25 mL massfractions 30%
2O
2, leave standstill rear filtration, fully washing leaching cake washs to neutral, and drying obtains graphite oxide under the room temperature.Diameter is about the multi-walled carbon nano-tubes of 20 ~ 40 nm, presses graphite oxide: carbon nanotube mass ratio 17:3, mix ultrasonic 1.5 h, after being uniformly dispersed, detach drying.The mixture of above-mentioned gained placed preheat to 200
oIn the tube furnace of C, be incubated 8 min, can obtain carbon nanotube/Graphene three-dimensional manometer matrix material.Be that 8% ptfe emulsion is binding agent with adding massfraction in the carbon nanotube/Graphene of gained, be applied to after mixing on the Graphite Electrodes paper, subsequently at 100-110
oThe C oven dry is spent the night.Finally make the compound desalination electrode of carbon nanotube/Graphene.
Test the ratio electric capacity of the compound desalination electrode of above-mentioned carbon nanotube/Graphene.Use CHI 660D type electrochemical workstation, electrolytic solution is 0.5 M NaCl solution, and scanning speed is 10 mv; Voltage range is-0.4-0.6 V; The specific capacitance that records this electrode is 100 F/g.Its desalting performance of the electrode test of above-mentioned preparation, in the salt solution of 1200 mg/L, two ends apply the voltage of 2.0 V, and its desalting efficiency is greater than 70%.
Embodiment 3
Under the ice-water bath condition 4 g graphite are under agitation slowly joined in the vitriol oil of 240 mL massfractions 98%, slowly add 24g potassium permanganate, its graphite: the vitriol oil: the mass ratio of potassium permanganate is 1:60:6,35 again
oIn the C water bath with thermostatic control, stir lower insulation 2 h, after reaction finishes, slowly add the dilution of 500 mL deionized waters, stir several minutes, press graphite: H
2O
2Mass ratio be the H that 1:9 adds 36 mL massfractions 30%
2O
2, leave standstill rear filtration, fully washing leaching cake washs to neutral, and drying obtains graphite oxide under the room temperature.Diameter is about the multi-walled carbon nano-tubes of 30 ~ 50 nm, presses graphite oxide: carbon nanotube mass ratio 19:1, mix ultrasonic 1.5 h, after being uniformly dispersed, detach drying.The mixture of above-mentioned gained placed preheat to 300
oIn the tube furnace of C, be incubated 10 min, can obtain carbon nanotube/Graphene three-dimensional manometer matrix material.Be that 12% ptfe emulsion is binding agent with adding massfraction in the carbon nanotube/Graphene of gained, be applied to after mixing on the Graphite Electrodes paper, subsequently at 100-110
oThe C oven dry is spent the night.Finally make the compound desalination electrode of carbon nanotube/Graphene.
Test the ratio electric capacity of the compound desalination electrode of above-mentioned carbon nanotube/Graphene.Use CHI 660D type electrochemical workstation, electrolytic solution is 0.5 M NaCl solution, and scanning speed is 10 mv; Voltage range is-0.4-0.6V; The specific capacitance that records this electrode is 114.6 F/g.Its desalting performance of the electrode test of above-mentioned preparation, in the salt solution of 500 mg/L, two ends apply the voltage of 2.0 V, and its desalting efficiency is greater than 90%.
Claims (2)
1. the preparation method of a carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode is characterized in that may further comprise the steps:
(1) preparation of electrode materials: under the ice-water bath condition, graphite is under agitation slowly joined in massfraction 98% vitriol oil, slowly add potassium permanganate, wherein graphite: the vitriol oil: the mass ratio of potassium permanganate is 1:40～100:2 ~ 8, at 32-38 again
oIn the C water bath with thermostatic control, stir lower insulation 1-6 h, after reaction finishes, slowly add the deionized water dilution, stir several minutes, press graphite: H
2O
2Mass ratio be the H that 1:7 ~ 10 adds massfractions 30%
2O
2, leave standstill rear filtration, fully washing leaching cake washs to neutral, and drying obtains graphite oxide under the room temperature; By graphite oxide: the mass ratio of carbon nanotube is 99:1～4:1, and graphite oxide and carbon nanotube ultra-sonic dispersion in deionized water, after being uniformly dispersed, are detached drying; The mixture of above-mentioned gained is placed pre-warmed tube furnace, and insulation for some time can obtain carbon nanotube/Graphene three-dimensional manometer matrix material;
(2) preparation of carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode: the adding massfraction is that the ptfe emulsion of 5-15% is binding agent in the carbon nanotube/Graphene of step (1) gained, be applied to after mixing on the Graphite Electrodes paper, subsequently at 100-110
oThe C oven dry is spent the night, and makes carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode; Carbon nanotube is multi-walled carbon nano-tubes in this carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode, and diameter is 5-50 nm.
2. the preparation method of carbon nanometer tube/graphene three-dimensional nanometer structure capacitance desalination electrode according to claim 1 is characterized in that carbon nanotube/graphite oxide pre-heating temperature is 200-500
oC, soaking time is 5-20 min.
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| CN103794379A (en) * | 2012-11-02 | 2014-05-14 | 海洋王照明科技股份有限公司 | Graphene/carbon nano-tube composite material, and preparation method and application thereof |
| CN103626172B (en) * | 2013-11-29 | 2015-10-07 | 上海利物盛企业集团有限公司 | A kind of preparation method of high conductive graphite paper |
| CN104140144B (en) * | 2014-08-03 | 2015-10-28 | 大连理工大学 | A kind of preparation method of the desalination graphene oxide crystalline emulsion that flows |
| CN105461022A (en) * | 2014-09-12 | 2016-04-06 | 南京大学 | Flake graphite doped binary carbon material composite electrode, and preparation thereof, and applications of flake graphite doped binary carbon material composite electrode in electroadsorption desalination |
| CN105129927B (en) * | 2015-09-10 | 2017-08-11 | 上海大学 | The preparation method of graphene/carbon nano-tube aeroge composite capacitance-type desalting electrode |
| CN107089707B (en) * | 2017-03-20 | 2021-08-10 | 上海大学 | Core-shell structure three-dimensional graphene composite material for capacitive desalination electrode and preparation method thereof |
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Non-Patent Citations (4)
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|---|
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| Shin-Yi Yang etal.Design and tailoring of a hierarchical graphene-carbon nanotube architecture for supercapacitors.《Journal of Materials Chemistry》.2010,第21卷(第7期),第2374-2380页. |
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