CN105712448B - A kind of preparation method of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/ - Google Patents
A kind of preparation method of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/ Download PDFInfo
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- CN105712448B CN105712448B CN201610107667.0A CN201610107667A CN105712448B CN 105712448 B CN105712448 B CN 105712448B CN 201610107667 A CN201610107667 A CN 201610107667A CN 105712448 B CN105712448 B CN 105712448B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/4604—Treatment of water, waste water, or sewage by electrochemical methods for desalination of seawater or brackish water
Abstract
The present invention provides a kind of preparation methods of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/, which is characterized in that including step a：By porous carbon materials, ultrasonic disperse, addition Nafion solution and binder, mechanical agitation blending prepare slurries in water, slurries are stood overnight, and after removing supernatant, drying forms cloud mixture, mixture is obtained into the porous carbon composite electrodes of Nafion/ with ethanol wet roll-in on inert conductor；Alternatively, including step b：By porous carbon materials ultrasonic disperse in water, binder is added, mechanical agitation blending prepares slurries, slurries are stood overnight, after removing supernatant, drying forms cloud mixture, and mixture is formed porous carbon electrodes with ethanol wet roll-in on inert conductor, Nafion solution is sprayed at porous carbon electrodes surface using high voltage electric field, obtains the porous carbon composite electrodes of Nafion/.The present invention can be effectively improved the repelling effect of same ion during capacitive desalination, improve current efficiency, reduce energy consumption.
Description
Technical field
The invention belongs to the preparation method of capacitive adsorption desalination electrode, Nafion/ porous carbons prepared by the present invention are compound
Electrode can effectively reduce same ion repulsive interaction, improve current efficiency, have efficient desalting effect.
Background technology
Capacitive adsorption desalting technology is a kind of technology with efficient, energy saving and environmentally friendly outstanding advantage, this technology base
In double layer capacity principle, under external power supply effect, soluble salt ion is adsorbed under electrostatic field and carries in solution
On opposite charged electrode, to which removal achievees the purpose that desalinating saline water from water；In discharge process, by electric pole short circuit or instead
It connects, ion desorption electrode regeneration energy also can be recycled further.It can be applied to desalination and the hard water of seawater and bitter
Softening etc..Porous carbon materials have good chemical stability, abundant pore structure, higher reference area etc. excellent
Gesture, thus the porous carbon materials such as activated carbon, carbon nano-fiber, carbon nanotube, graphene, carbon aerogels, mesoporous carbon are extensive
It is prepared by the research and development for electrode material.But in practical desalination processes, when applying power source charges to electrode, electrode adsorption is opposite
While charged ion, it can also consume electric energy and repel same ion into solution, eventually lead to energy consumption increase, current efficiency drop
It is low.
At present both at home and abroad mostly by porous carbon materials surface modified active functional group, increasing the modes such as amberplex
To prepare the selectivity for improving electrode, the current efficiency and desalination rate of raising capacitive desalination device.Yu-Jin Kim et al.
(Yu-Jin Kim, Jae-Hwan Choi.Enhanced desalination efficiency in capacitive
deionizationwith an ion-selective membrane.Separation and Purification
Technology 71 (2010) 70-75) by increasing cation-exchange membrane in the capacitor membrane capacitance is prepared, it is effectively improved
The ion selectivity of desalter, current efficiency are promoted from 35.5%~43.1% to 83.9%~91.3%.
Nafion is a kind of cation-exchanger being made of perfluorinated sulfonic acid ester, and the end of the chain is hydrophilic ionization sulfonic acid
The Nafion of base, ionization is negatively charged, electrical charge rejection can be leaned on to obstruct anion, therefore have good selection to penetrate cation
Property.
The present invention is basic raw material using porous carbon materials electrode, by Nafion components on electrode interior or surface pair
It is modified.Using the abundant sulfonic acid group of the unique ion selectivity of Nafion molecules and its end of the chain by modified electrode group
Asymmetric capacitive desalination device is dressed up, the ion selectivity of electrode on the one hand can be improved, reduces coion repelling effect, it is another
The abundant sulfonic acid group in its surface of aspect can be effectively improved its hydrophily, promote ion in the transmission of electrode surface.
Invention content
The purpose of the present invention is being directed in capacitive adsorption desalination processes, the repulsive interaction of coion leads to the drop of current efficiency
It is low, desalting performance decline the problem of, a kind of preparation method of the porous carbon composite electrode materials of Nafion/ is provided.
In order to achieve the above object, the present invention provides a kind of capacitive adsorption desalination porous carbon composite electrodes of Nafion/
The preparation method of material, which is characterized in that including
Step a：By porous carbon materials, ultrasonic disperse, addition Nafion solution and binder, mechanical agitation are blended in water
Slurries are prepared, slurries are stood overnight, and after removing supernatant, drying forms cloud mixture, by mixture ethanol wet roller
It is pressed on inert conductor, obtains the porous carbon composite electrodes of Nafion/；
Alternatively, including step b：By porous carbon materials, preparation is blended in ultrasonic disperse, addition binder, mechanical agitation in water
Slurries, slurries are stood overnight, and after removing supernatant, drying forms cloud mixture, and mixture ethanol wet roll-in is existed
Porous carbon electrodes are formed on inert conductor, and Nafion solution is sprayed at porous carbon electrodes surface using high voltage electric field, is obtained
The porous carbon composite electrodes of Nafion/.
Preferably, the porous carbon materials in the step a and step b are activated carbon, electrically conductive graphite, carbon nanotube, carbon
One or more of fiber and carbon aerogels.
Preferably, the water in the step a and step b is pure water.
Preferably, the mass fraction of the step a and the Nafion solution in step b is 5%, and solvent is water and volatilization
The mixture of property organic matter.
Preferably, the Nafion solution in the step a and step b is Du Pont's Nafion5% coating solutions.
Preferably, the binder in the step a and step b is the polytetrafluoroethyl-ne that mass percentage concentration is 6~10%
Polyvinylidene fluoride lotion that alkene (PTFE) lotion, mass percentage concentration are 6~10%, mass percentage concentration are 6~10%
One or more of the polypropylene lotion that polyethylene emulsion and mass percentage concentration are 6~10%.
Preferably, the inert conductor is one or more of titanium net, graphite paper and nickel foam.
Preferably, the amount of every gram of porous carbon materials addition Nafion solution is 0.2~2.5ml in the step a, will be more
Hole carbon material in water in the dispersion liquid obtained by ultrasonic disperse porous carbon materials a concentration of 20~80mg/mL.
Preferably, Nafion solution is sprayed in the step b using high voltage electric field the behaviour on porous carbon electrodes surface
It is as condition：Voltage be 15~25kV direct currents, syringe pump spray flow be 0.8~1.2ml/h, needle diameter be 0.8~
1.5mm, syringe needle and porous carbon electrodes surface distance are 10~30cm, and spray time is 0.5~4h, control environment temperature is 20~
30 DEG C, relative humidity is 20~40%.
Preferably, the mechanical agitation in the step a and step b carries out under room temperature, normal pressure, and stir speed (S.S.) is
600r/min, mixing time are 2~4h.
Preferably, the thickness of the porous carbon composite electrodes of Nafion/ in the step a and step b is 0.2-2mm.
The present invention prepares the porous carbon composite electrode materials of Nafion/ using Du Pont's Nafion5% coating solutions as modifying agent.One
Aspect Nafion molecules can improve the ion selectivity of electrode, coion repelling effect be reduced, to improve the electricity of capacitor
Stream efficiency, another aspect Nafion molecular surfaces, which contain abundant sulfonic acid group, can be effectively improved its hydrophily, promotion ion
In the transmission of electrode surface.The porous carbon composite electrodes of Nafion/ are assembled into asymmetric capacitive desalination for cathode by studying
Device can improve the adsorptive selectivity to ion, improve its desalting performance.
Compared with prior art, the beneficial effects of the invention are as follows：
1. the electrode preparation method of the present invention carries out at normal temperatures and pressures, easy to operate.
2. molten using Nafion since Nafion molecules have excellent ion selectivity and abundant sulfonic acid group
Liquid is modified porous carbon materials, can improve the ion selectivity of electrode simultaneously, promotes ion in the diffusion of electrode surface
And absorption.The combination electrode used prepared of the invention can assemble asymmetric capacitive desalination dress as the cathode of capacitive desalination device
Carry out desalination is set, the repulsion of electrode surface coion can be reduced.The current efficiency for being effectively improved common porous carbon electrode is low, energy consumption
High problem.
Description of the drawings：
Fig. 1 is the SEM shape appearance figures of the Nafion/AC electrodes prepared in embodiment 1.
Fig. 2 is asymmetric capacitor (AC||) and symmetric capacitor (AC| Nafion/AC;|AC) in constant current charge-discharge pattern
Lower conductivity versus time curve.
Fig. 3 is asymmetric capacitor (AC||) and symmetric capacitor (AC| Nafion/AC-b;|AC) in constant current charge-discharge mould
Conductivity versus time curve under formula.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Comparative example
The preparation and symmetric capacitor desalination of pure activated carbon electrodes are tested：(check experiment)
It takes activated carbon 2g ultrasonic disperses in 100ml pure water, Du Pont 60%wt PTFE emulsion 0.24g, normal temperature and pressure is added
Under with rotating speed 600r/min mechanical agitations be blended 2h prepare slurries, slurries are stood overnight, remove supernatant after, in 95 DEG C of baking ovens
Drying obtains mixture.A small amount of ethyl alcohol 0.5mL wettings are added into gained mixture, roll-in is in blocks and is pressed in titanium net, obtains
Pure activated carbon (AC) electrode.
The pure activated carbon electrodes of two panels are taken to be assembled into symmetric capacitor (AC||AC), in the NaCl solution of 500mg/L, setting
By voltage 1.2V, constant current charge-discharge test is carried out.The single cycle desalination amount of the pure activated carbon AC electrodes of experiment test is 4.4mg/
G, current efficiency 38%.
Embodiment 1
It takes activated carbon 2g ultrasonic disperses in 100ml pure water, 2ml Nafion5% solution (Du Pont is added thereto
Nafion5% coating solutions), Du Pont 60%wt PTFE emulsion 0.24g are total with rotating speed 600r/min mechanical agitations under normal temperature and pressure
Mixed 2h prepares slurries, and slurries are stood overnight, and after removing supernatant, is dried in 95 DEG C of baking ovens and obtains cotton-shaped Nafion/ activated carbons
Mixture.Ethyl alcohol 0.5mL wettings are added into gained mixture, roll-in is in blocks and is pressed in titanium net, and it is 0.3mm's to obtain thickness
Nafion/ activated carbons (Nafion/AC-a) electrode.Fig. 1 is the SEM shape appearance figures of Nafion/AC-a electrodes.
Using Nafion/AC-a electrodes as cathode, pure activated carbon electrodes are that anode is assembled into asymmetric capacitive desalination device (AC
||Nafion/AC-a), in the NaCl solution of 500mg/L, setting carries out constant current charge-discharge test by voltage 1.2V.Fig. 2
For asymmetric capacitor (AC||) and symmetric capacitor (AC| Nafion/AC-a;|AC) under constant current charge-discharge pattern conductivity with
The change curve of time.AC||The single cycle desalination amount of Nafion/AC-a electrodes is 8.2mg/g, current efficiency 58.8%.
Embodiment 2
It takes activated carbon 2g ultrasonic disperses in 100ml pure water, Du Pont 60%wt PTFE emulsion 0.24g is added thereto, often
2h is blended with rotating speed 600r/min mechanical agitations under normal temperature and pressure and prepares slurries, slurries are stood overnight, after removing supernatant, at 95 DEG C
Drying obtains cotton-shaped Nafion/ Mixture of Activated Carbon in baking oven.Ethyl alcohol 0.5mL wettings are added into gained mixture, are rolled into
Piece is simultaneously pressed in titanium net and forms porous carbon electrodes, and electrode slice thickness is 0.3mm, is sprayed at Nafion solution using high voltage electric field
Porous carbon electrodes surface, voltage are 18kV direct currents, and it is 1.0ml/h, needle diameter 0.8mm, syringe needle that syringe pump, which sprays flow,
It is 20cm, spray time 2h with porous carbon electrodes surface distance, control environment temperature is 25 DEG C, and relative humidity 35% obtains
To Nafion/ activated carbons (Nafion/AC-b) electrode that thickness is 0.3mm.
Using Nafion/AC-b electrodes as cathode, pure activated carbon electrodes are that anode is assembled into asymmetric capacitive desalination device (AC
||Nafion/AC-b), in the NaCl solution of 500mg/L, setting carries out constant current charge-discharge test by voltage 1.2V.Fig. 3
For asymmetric capacitor (AC||) and symmetric capacitor (AC| Nafion/AC-b;|AC) under constant current charge-discharge pattern conductivity with
The change curve of time.
Claims (9)
1. a kind of preparation method of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/, which is characterized in that including step
Rapid a：By porous carbon materials, ultrasonic disperse, addition Nafion solution and binder, mechanical agitation blending prepare slurries in water, starch
Liquid is stood overnight, and after removing supernatant, drying forms cloud mixture, by mixture with ethanol wet roll-in in inert conductor
On, obtain the porous carbon composite electrodes of Nafion/；Alternatively, including step b：By porous carbon materials, ultrasonic disperse, addition are viscous in water
Agent is tied, mechanical agitation blending prepares slurries, and slurries are stood overnight, and after removing supernatant, drying forms cloud mixture, will mix
It closes object and forms porous carbon electrodes on inert conductor with ethanol wet roll-in, be sprayed at Nafion solution using high voltage electric field more
Hole carbon electrodes obtain the porous carbon composite electrodes of Nafion/；Binder in the step a and step b is quality percentage
A concentration of 6 ~ 10% ptfe emulsion, the polyvinylidene fluoride lotion that mass percentage concentration is 6 ~ 10%, quality percentage are dense
One or more of the polypropylene lotion that the polyethylene emulsion and mass percentage concentration that degree is 6 ~ 10% are 6 ~ 10%.
2. the preparation method of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/ as described in claim 1, special
Sign is that the porous carbon materials in the step a and step b are activated carbon, electrically conductive graphite, carbon nanotube, carbon fiber and carbon
One or more of aeroge.
3. the preparation method of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/ as described in claim 1, special
Sign is that the water in the step a and step b is pure water.
4. the preparation method of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/ as described in claim 1, special
Sign is that the mass fraction of the step a and the Nafion solution in step b is 5%, and solvent is water and volatile organic matter
Mixture.
5. the preparation method of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/ as described in claim 1, special
Sign is that the Nafion solution in the step a and step b is Du Pont's Nafion5% coating solutions.
6. the preparation method of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/ as described in claim 1, special
Sign is that the inert conductor is one or more of titanium net, graphite paper and nickel foam.
7. the preparation method of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/ as described in claim 1, special
Sign is that the amount of every gram of porous carbon materials addition Nafion solution is 0.2 ~ 2.5ml in the step a, by porous carbon materials
In water in the dispersion liquid obtained by ultrasonic disperse porous carbon materials a concentration of 20 ~ 80 mg/mL.
8. the preparation method of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/ as described in claim 1, special
Sign is that the operating condition that Nafion solution is sprayed in the step b using high voltage electric field porous carbon electrodes surface is：
Voltage be 15 ~ 25kV direct currents, syringe pump spray flow be 0.8 ~ 1.2ml/h, needle diameter be 0.8 ~ 1.5mm, syringe needle with it is more
Hole carbon electrodes distance is 10 ~ 30cm, and spray time is 0.5 ~ 4h, and control environment temperature is 20 ~ 30 DEG C, relative humidity 20
~40%。
9. the preparation method of the capacitive adsorption desalination porous carbon composite electrode materials of Nafion/ as described in claim 1, special
Sign is that the mechanical agitation in the step a and step b carries out under room temperature, normal pressure, and stir speed (S.S.) is 600 r/min, is stirred
It is 2 ~ 4 h to mix the time.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101122575A (en) * | 2007-09-13 | 2008-02-13 | 山西大学 | Complex film modified nickel electrode preparation method |
| CN101576530A (en) * | 2009-05-21 | 2009-11-11 | 北京化工大学 | Method for measuring dopamine by utilizing graphite nano-sheet/Nafion composite film to modify electrode |
| CN104817144A (en) * | 2015-04-13 | 2015-08-05 | 东华大学 | Preparation method of polydopamine modified porous carbon electrode for capacitive deionization |
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| CN103563027B (en) * | 2011-03-23 | 2018-09-21 | 梅斯皮鲁斯股份有限公司 | Polarizing electrode for flowing through the deionization of formula capacitive character |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101122575A (en) * | 2007-09-13 | 2008-02-13 | 山西大学 | Complex film modified nickel electrode preparation method |
| CN101576530A (en) * | 2009-05-21 | 2009-11-11 | 北京化工大学 | Method for measuring dopamine by utilizing graphite nano-sheet/Nafion composite film to modify electrode |
| CN104817144A (en) * | 2015-04-13 | 2015-08-05 | 东华大学 | Preparation method of polydopamine modified porous carbon electrode for capacitive deionization |
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