CN109704443B - Capacitive deionization adsorption electrode and preparation method thereof - Google Patents
Capacitive deionization adsorption electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a capacitive deionization adsorption electrode and a preparation method thereof. The capacitive deionization adsorption electrode provided by the invention has the advantages of high desalination amount, high current efficiency, high desalination rate, strong electrode adhesion capacity, stable electrode structure, long service life, cheap and easily-obtained raw materials, simple process, easiness for large-scale production, low cost and environment-friendly preparation process.
Description
Technical Field
The invention relates to the technical field of capacitive deionization, in particular to a capacitive deionization adsorption electrode and a preparation method thereof.
Background
The earth has abundant water resources, but fresh water resources account for only 2.7%, and most of the fresh water is glacier water which is difficult to be utilized. In addition, the problem of uneven distribution of fresh water resources is serious, and the shortage of fresh water resources becomes a bottleneck for development of many countries. Because of the abundant seawater and brackish water resources on the earth, desalination becomes an effective way for solving the problem of shortage of fresh water resources. The capacitive deionization is a novel desalination technology based on a capacitive principle, has the advantages of low energy consumption, no secondary pollution and the like, and is particularly suitable for treating brackish water with the concentration of 500-5000 ppm. A typical capacitive deionization module consists of two electrodes placed opposite to each other, and a saline solution flows through a channel between the two electrodes, and when a voltage is applied between the two electrodes, ions in the saline solution are adsorbed to the electrodes, and after the adsorption equilibrium is reached, the electrodes can be regenerated by short-circuiting or reverse-connecting the voltage.
The main factors influencing the capacitive adsorption desalting effect are electrode materials, electrode plate voltage, solution concentration, solution surface flow velocity, the number of collector plates and the like, wherein the most important factor is the selection of the electrode materials. The pore size distribution, specific surface area, specific capacitance and resistance of the electrode material all have the most direct influence on the capacitance adsorption effect. Porous carbon having advantages of high specific surface area, excellent conductivity and chemical stability, such as activated carbon powder, carbon aerogel, carbon nanotube, carbon nanofiber, graphene and other materials, has become a research hotspot.
The electrode material used by the capacitive deionization module is mostly a carbon material with a developed pore structure, so that a certain amount of ions can be adsorbed by the electrode under the condition of no voltage application. When a voltage is applied, not only adsorption of ions (counterions) with opposite charges but also desorption of ions (ions of the same name) with the same charges occur at the electrodes. This repulsion of homonymous ions is known as the homonymous ion repulsion effect. The homonymous ion repulsion effect results in a decrease in current utilization efficiency and an increase in power consumption.
In the research of the polymeric ion membrane capacitive deionization adsorption electrode, for example, chinese patent publication No. CN 105540764 a discloses the preparation and application of an electrode of an asymmetric capacitive deionization module, wherein one of the electrodes uses activated carbon treated with nitric acid as an active substance, and the other electrode uses activated carbon coated with quaternized poly-tetraethyl pyridine as an active substance. After the treatment of nitric acid, the surface of the activated carbon has a large number of negative electric functional groups such as carboxyl and the like, and the surface of the activated carbon coated by the quaternized poly tetraethyl pyridine has positive charges. When the adsorption and desorption voltages of the asymmetric capacitive deionization module are both 1.2V, the desalting capacity of the capacitive deionization module can reach 15-24 mg/g; the raw material is commercial activated carbon, and the obtained electrode has poor adhesion capability; meanwhile, the used active carbon has the requirements of large specific surface area, small particle size, good conductivity and higher raw material cost; moreover, a large amount of nitric acid is needed for modification, nitric acid waste liquid is generated, and the method is not environment-friendly.
Therefore, it is urgently needed to develop a new capacitive deionization adsorption electrode which has strong adhesion capability, good desalination effect, low cost and environmental friendliness.
Disclosure of Invention
The invention provides the capacitive deionization adsorption electrode for overcoming the defects of poor adhesion capability, high cost and unfriendly environment in the prior art, and the provided electrode has the advantages of high desalination amount, high current efficiency, high desalination rate, strong electrode adhesion capability, stable electrode structure, long service life, cheap and easily-obtained raw materials, simple process, easiness in large-scale production, low cost and environment-friendly preparation process.
Another object of the present invention is to provide a method for preparing the capacitive deionization adsorption electrode.
In order to solve the technical problems, the invention adopts the technical scheme that:
a capacitive deionization adsorption electrode comprises a first working electrode taking polyethyleneimine coated carbonized bacterial cellulose as an active substance and a second working electrode taking sulfosuccinic acid coated carbonized bacterial cellulose as an active substance.
In the capacitive deionization adsorption electrode provided by the invention, a first working electrode taking polyethyleneimine coated carbonized bacterial cellulose as an active substance is a biological carbon electrode modified by a positively charged polymer, and a second working electrode taking sulfosuccinic acid coated carbonized bacterial cellulose as an active substance is a biological carbon electrode modified by a negatively charged functional group. The capacitive deionization adsorption electrode is used for a capacitive deionization technology, improves the adhesion capacity of the electrode, improves the desalting capacity, the current efficiency and the desalting rate, reduces the environmental pollution, and achieves the purpose of recycling saline-alkali water.
Therefore, the capacitive deionization adsorption electrode has the advantages of high desalination amount, high current efficiency, high desalination rate, strong electrode adhesion capacity, stable electrode structure, long service life, cheap and easily-obtained raw materials, simple process, easiness in large-scale production, low cost and environment-friendly preparation process.
Preferably, the first working electrode is prepared from polyethyleneimine, bacterial cellulose carbide, polyvinyl alcohol, carbon black and a conductive substrate; the mass ratio of the polyethyleneimine to the carbonized bacterial cellulose is 12.5% -37.5%. The polyvinyl alcohol and carbon black may be added in amounts conventionally used in the art.
Preferably, the mass ratio of the polyethyleneimine to the carbonized bacterial cellulose is 18.75%.
Preferably, the second working electrode is prepared from sulfosuccinic acid, carbonized bacterial cellulose, polyvinyl alcohol, carbon black and a conductive substrate; the mass ratio of the sulfosuccinic acid to the carbonized bacterial cellulose is 12.5-37.5%. The polyvinyl alcohol and carbon black may be added in amounts conventionally used in the art.
Preferably, the mass ratio of the sulfosuccinic acid to the carbonized bacterial cellulose is 25%.
The invention also provides a preparation method of the capacitive deionization adsorption electrode, which comprises the following steps:
s1, preparing a first mixed slurry of polyethyleneimine, carbonized bacterial cellulose, polyvinyl alcohol and carbon black by using a solvent;
s2, preparing an active film on the conductive substrate by using the first mixed slurry, and drying to obtain a first working electrode;
s3, preparing a second mixed slurry of sulfosuccinic acid, carbonized bacterial cellulose, polyvinyl alcohol and carbon black by using a solvent;
and S4, preparing an active film on the conductive substrate by using the second mixed slurry, and drying to obtain a second working electrode.
And S1 and S3, the mass ratio of the carbonized bacterial cellulose to the polyvinyl alcohol to the carbon black can be (6-8) to 1: 1. Preferably, the mass ratio of the carbonized bacterial cellulose, the polyvinyl alcohol and the carbon black in the steps S1. and S3. is 8: 1.
Preferably, in the steps s1. and s3. the solvent is water, and the polyvinyl alcohol is dissolved by water to obtain a 10g/L polyvinyl alcohol solution.
Specifically, the preparation method of the first working electrode comprises the following steps:
dissolving polyvinyl alcohol in deionized water at 90 ℃ and stirring for 6h to prepare 10g/L polyvinyl alcohol solution; mixing polyethyleneimine (100-300 mg) with a polyvinyl alcohol solution, and stirring for 12 hours, wherein the mass ratio of the polyethyleneimine to the carbonized bacterial cellulose is 12.5% -37.5%, and the mass ratio of the carbonized bacterial cellulose to the polyvinyl alcohol to the carbon black is 8: 1; coating the titanium mesh with a coating film thickness of 100-500 mu m, drying the coated titanium mesh at 45 ℃ for 2h, and then drying at 110 ℃ for 1 h; and obtaining the electrode which takes the polyethyleneimine coated carbonized bacterial cellulose as an active substance, namely the first working electrode.
Specifically, the preparation method of the second working electrode comprises the following steps:
dissolving polyvinyl alcohol in deionized water at 90 ℃ and stirring for 6h to prepare 10g/L polyvinyl alcohol solution; mixing and stirring 100-300 mg of sulfosuccinic acid with polyvinyl alcohol for 12 hours, wherein the mass ratio of the sulfosuccinic acid to the carbonized bacterial cellulose is 12.5-37.5%, and the mass ratio of the carbonized bacterial cellulose to the polyvinyl alcohol to the carbon black is 8: 1; coating the titanium mesh with a coating film thickness of 100-500 mu m, drying the coated titanium mesh at 45 ℃ for 2h, and then drying at 110 ℃ for 1 h; the electrode with the sulfosuccinic acid-coated carbonized bacterial cellulose electrode as an active material, namely a second working electrode, is obtained.
Compared with the prior art, the invention has the beneficial effects that:
the capacitive deionization adsorption electrode provided by the invention has the advantages of high desalination amount, high current efficiency, high desalination rate, strong electrode adhesion capacity, stable electrode structure, long service life, cheap and easily-obtained raw materials, simple process, easiness for large-scale production, low cost and environment-friendly preparation process.
Drawings
Fig. 1 is a schematic structural view of a capacitive deionization module of experimental example 1.
Fig. 2 is a schematic view of the capacitive deionization apparatus of experimental example 1.
FIG. 3 is a diagram of a bacterial cellulose.
FIG. 4 is a scanning electron micrograph of carbonized bacterial cellulose.
FIG. 5 is a scanning electron micrograph of the first working electrode.
FIG. 6 is a scanning electron micrograph of the second working electrode.
FIG. 7 is a Zeta potential diagram for polyethyleneimine and sulfosuccinic acid.
FIG. 8 is a graph showing the desalting performance in the capacitive deionization processes in test examples 1 to 4.
Fig. 9 shows the performance stability of the capacitive deionization process in experimental example 1.
Fig. 10 shows the performance stability of the capacitive deionization process in experimental example 1.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The same or similar reference numerals in the drawings of the embodiments of the present invention correspond to the same or similar components; in the description of the present invention, it is to be understood that the terms "upper", "lower", "left", "right", "top", "bottom", "inner", "outer", and the like, if any, are used in the orientations and positional relationships indicated in the drawings only for the convenience of describing the present invention and simplifying the description, but not for indicating or implying that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and therefore the terms describing the positional relationships in the drawings are used for illustrative purposes only and are not to be construed as limiting the present patent.
Furthermore, if the terms "first," "second," and the like are used for descriptive purposes only, they are used for mainly distinguishing different devices, elements or components (the specific types and configurations may be the same or different), and they are not used for indicating or implying relative importance or quantity among the devices, elements or components, but are not to be construed as indicating or implying relative importance.
In the present application, PEI refers to polyethyleneimine; SSA refers to sulfosuccinic acid.
The raw materials in the examples are all commercially available;
reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
A capacitive deionization adsorption electrode comprises a first working electrode and a second working electrode;
the method for preparing the first working electrode comprises the following steps: dissolving polyvinyl alcohol in deionized water at 90 ℃ and stirring for 6h to prepare 10g/L polyvinyl alcohol solution; stirring 300mg of mixed polyvinyl alcohol solution of polyethyleneimine for 12 hours, wherein the mass ratio of the polyethyleneimine to the carbonized bacterial cellulose is 18.75%, and the mass ratio of the carbonized bacterial cellulose to the polyvinyl alcohol to the carbon black is 8: 1; coating the titanium mesh (TA1,100 meshes, 0.1mm of wire diameter/0.15 mm of pore diameter, 3 multiplied by 3cm) with a film thickness of 100-500 mu m, drying the coated titanium mesh at 45 ℃ for 2h, and then drying at 110 ℃ for 1 h; and obtaining the electrode which takes the polyethyleneimine coated carbonized bacterial cellulose as an active substance, namely the first working electrode. The total loading of the first working electrode was 100 mg.
The preparation method of the second working electrode comprises the following steps: dissolving polyvinyl alcohol in deionized water at 90 ℃ and stirring for 6h to prepare 10g/L polyvinyl alcohol solution; 300mg of sulfosuccinic acid is mixed with polyvinyl alcohol and stirred for 12h, the mass ratio of the sulfosuccinic acid to the carbonized bacterial cellulose is 25 percent, and the mass ratio of the carbonized bacterial cellulose to the polyvinyl alcohol to the carbon black is 8: 1; coating the titanium mesh with a coating film thickness of 100-500 mu m, drying the coated titanium mesh at 45 ℃ for 2h, and then drying at 110 ℃ for 1 h; the electrode with the sulfosuccinic acid-coated carbonized bacterial cellulose electrode as an active material, namely a second working electrode, is obtained. The total loading of the second working electrode was 100 mg.
Example 2
This example is a second example of the capacitive deionization adsorption electrode of the present invention, and differs from example 1 in that the mass ratio of polyethyleneimine to carbonized bacterial cellulose is 37.5%; the mass ratio of the sulfosuccinic acid to the carbonized bacterial cellulose is 37.5 percent;
other raw materials and operation steps were the same as in example 1.
Example 3
This example is a second example of the capacitive deionization adsorption electrode of the present invention, and differs from example 1 in that the mass ratio of polyethyleneimine to carbonized bacterial cellulose is 12.5%; the mass ratio of the sulfosuccinic acid to the carbonized bacterial cellulose is 12.5 percent;
other raw materials and operation steps were the same as in example 1.
Comparative example 1
This comparative example differs from example 1 in that no polyethyleneimine and sulfosuccinic acid were added and the other starting materials were added in the same amounts as in example 1.
Test example 1
Capacitive deionization test:
(1) assembled capacitive deionization module and capacitive deionization device
Assembling a capacitive deionization module: as shown in fig. 1, a first organic glass plate 11, a first working electrode 12, a non-woven fabric 13, a first silica gel gasket 14, a second silica gel gasket 15, a second working electrode 16 and a second organic glass plate 17 are assembled in sequence to obtain a capacitive deionization module. In this test example, the first working electrode and the second working electrode were both capacitive deionization electrodes prepared in example 1.
Assembling a capacitive deionization device: as shown in fig. 2, a water tank 1, a capacitive deionization module 2, a peristaltic pump 3, a direct current power supply 4, a conductivity meter 5 and a computer 6 are connected to obtain the capacitive deionization device.
(2) Capacitive deionization step:
(a) forming a closed loop by the asymmetric capacitive deionization module and a direct-current voltage circuit, wherein the voltage applied to the capacitive deionization module by the direct-current voltage circuit ranges from 1.2V to 2.0V; the voltage in this example is 1.2V;
(b) sending a NaCl solution with the concentration of 100-5000 mg/L into an asymmetric capacitive deionization module from a water tank by using a peristaltic pump, and finally flowing into the water tank, wherein the flow rate of the NaCl solution is 5-20 mL/min; in this embodiment, the concentration of the NaCl solution is 500mg/L, and the flow rate of the NaCl solution is 20 mL/min;
(c) firstly, a direct-current voltage circuit is utilized to apply voltage to a capacitive deionization module, an electrode which takes polyethyleneimine-coated carbonized bacterial cellulose as an active material is used as an anode, and an electrode which takes sulfosuccinic acid-coated carbonized bacterial cellulose as an active material is used as a cathode, so that ions are adsorbed;
(d) detecting the conductivity of the NaCl solution in real time at an outlet of the asymmetric capacitive deionization module by using a conductivity probe to determine the adsorption capacity;
(e) the adsorption time is 5-120 min, the electrode is desorbed by reverse voltage after reaching adsorption saturation, and the desorption time is 5-120 min; in this embodiment, the adsorption and desorption time is 30 min;
(f) repeating the steps (a) - (e) and performing the next capacitive deionization process.
Test example 2
The present test example differs from test example 1 in that the voltage applied to the capacitive deionization module by the dc voltage circuit was 1.6V;
the other steps and parameters were the same as in test example 1.
Test example 3
The present test example differs from test example 1 in that the voltage applied to the capacitive deionization module by the dc voltage circuit was 1.8V;
the other steps and parameters were the same as in test example 1.
Test example 4
The present test example differs from test example 1 in that the voltage applied to the capacitive deionization module by the dc voltage circuit was 2.0V;
the other steps and parameters were the same as in test example 1.
Comparative example 1
The present test example is different from test example 1 in that the capacitive deionization adsorption electrode used in the present comparative example was the electrode prepared in comparative example 1;
the other test procedures and parameters were the same as those in test example 1.
Comparative example 2
The present test example is different from test example 1 in that the capacitive deionization adsorption electrode used in the present comparative example was the electrode prepared in comparative example 1; when the capacitive deionization module is assembled, a corresponding ion exchange membrane is added in front of the electrode;
the other test procedures and parameters were the same as those in test example 1.
Characterization and Performance testing
(1) Morphology testing, model SEM of scanning electron microscope, Zeiss Merlin, GER;
(2) zeta potential test, the instrument adopted is Zeta, SurPASS, AT.
Test results
In the present invention, the bacterial cellulose is shown in fig. 3, the scanning electron microscope image of the carbonized bacterial cellulose is shown in fig. 4, the scanning electron microscope image of the first working electrode in example 1 is shown in fig. 5, and the scanning electron microscope image of the second working electrode is shown in fig. 6, and as can be seen from fig. 3 to 6, the raw bacterial cellulose is in a milk-white sheet shape, the carbonized bacterial cellulose is in a mesh shape, and the carbonized bacterial cellulose coated with polyethyleneimine and coated with sulfosuccinic acid does not significantly change the original appearance.
The Zeta potentials of the polyethyleneimine and the sulfosuccinic acid in example 1 are shown in fig. 7, and the Zeta potential of the sulfosuccinic acid-coated carbonized bacterial cellulose is negative in the range of pH 3-10, indicating that the surface is more negatively charged. The polyethyleneimine-coated carbonized bacterial cellulose has a zero charge point near pH 8.4, indicating that the surface thereof has a large amount of positive charges.
Therefore, in the module assembled by the capacitive deionization adsorption electrode, the surface of the sulfosuccinic acid coated carbonized bacterial cellulose is provided with a large number of negatively charged functional groups, and the surface of the polyethyleneimine coated carbonized bacterial cellulose is provided with a large number of positively charged functional groups. Meanwhile, the mesh structure of the bacterial cellulose enables the electrode structure to be more stable, and the service life of the electrode is prolonged. Meanwhile, the bacterial cellulose is waste in a bacterial culture stage, the waste can be utilized, and the raw materials are more environment-friendly than other types of carbon materials.
The desalting performance of the capacitive deionization adsorption electrode of example 1 is shown in FIG. 8, which is the test results of test examples 1 to 4. For the capacitive deionization process, the desalting capacity can reach 13.73mg/g under the voltage of 1.2V.
Performing a cycling stability test, as shown in fig. 9-10, fig. 9 is a graph of conductivity change of the device of test example 1 after 10 cycles, and it can be seen that the device has better cycling stability; fig. 10 shows the change in the amount of electric adsorption and the change in the amount of reduction in electric adsorption for 100 cycles of the apparatus of test example 1, and it can be seen from the graph that the reduction rate after 100 cycles of the apparatus is less than 17%, showing good recycling ability.
The electrode in test example 1 can adsorb more ions in the adsorption stage than the capacitive deionization module assembled with the carbonized bacterial cellulose alone, that is, compared to comparative example 1. As shown in test example 1 and test example 4, when the adsorption and desorption voltages are both 1.2V, the desalting capacity of the capacitive deionization module can reach 13.73mg/g, and the desalting capacity can reach 20.61mg/g when the voltage is 2.0V; under the same conditions, the desalination amount of the membrane capacitive deionization module of the comparative example 2, which is assembled by adding an ion exchange membrane before a pure carbonized bacterial cellulose electrode, is 12.31-19.01 mg/g. The asymmetric capacitive deionization module in test example 1 avoids the use of expensive ion exchange membranes, but can achieve a desalination effect similar to that of the membrane capacitive deionization module, thereby showing good industrial application prospects.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. A capacitive deionization adsorption electrode is characterized by comprising a first working electrode taking polyethyleneimine coated carbonized bacterial cellulose as an active substance and a second working electrode taking sulfosuccinic acid coated carbonized bacterial cellulose as an active substance; wherein the carbonized bacterial cellulose is in a shape of a net.
2. The capacitive deionization adsorption electrode according to claim 1, wherein said first working electrode is prepared from polyethyleneimine, bacterial cellulose carbide, polyvinyl alcohol, carbon black and a conductive substrate;
the mass ratio of the polyethyleneimine to the carbonized bacterial cellulose is 12.5% -37.5%.
3. The capacitive deionization adsorption electrode according to claim 2, wherein the mass ratio of polyethyleneimine to carbonized bacterial cellulose is 18.75%.
4. The capacitive deionization adsorption electrode according to claim 2 or 3, wherein said second working electrode is prepared from sulfosuccinic acid, carbonized bacterial cellulose, polyvinyl alcohol, carbon black and a conductive substrate;
the mass ratio of the sulfosuccinic acid to the carbonized bacterial cellulose is 12.5-37.5%.
5. The capacitive deionization adsorption electrode according to claim 4, wherein the mass ratio of sulfosuccinic acid to carbonized bacterial cellulose is 25%.
6. The method for preparing a capacitive deionization adsorption electrode according to any one of claims 4 or 5, comprising the steps of:
s1, preparing a first mixed slurry of polyethyleneimine, carbonized bacterial cellulose, polyvinyl alcohol and carbon black by using a solvent;
s2, preparing an active film on the conductive substrate by using the first mixed slurry, and drying to obtain a first working electrode;
s3, preparing a second mixed slurry of sulfosuccinic acid, carbonized bacterial cellulose, polyvinyl alcohol and carbon black by using a solvent;
and S4, preparing an active film on the conductive substrate by using the second mixed slurry, and drying to obtain a second working electrode.
7. The preparation method according to claim 6, wherein the mass ratio of the carbonized bacterial cellulose, the polyvinyl alcohol and the carbon black in the steps S1. and S3. is (6-8) to 1: 1.
8. The preparation method according to claim 7, wherein the mass ratio of the carbonized bacterial cellulose, the polyvinyl alcohol and the carbon black in steps S1. and S3. is 8: 1.
9. The preparation method according to claim 6, wherein in steps S1. and S3. the solvent is water, and the polyvinyl alcohol is dissolved by water to obtain a 10g/L polyvinyl alcohol solution.
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| CN105990043A (en) * | 2015-03-02 | 2016-10-05 | 江南石墨烯研究院 | Preparation method of efficient porous thin film electrode used for capacitive deionization |
| WO2016210419A1 (en) * | 2015-06-26 | 2016-12-29 | Florida State University Research Foundation, Inc. | Dry process method for producing electrodes for electrochemical devices and electrodes for electrochemical devices |
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| CN105990043A (en) * | 2015-03-02 | 2016-10-05 | 江南石墨烯研究院 | Preparation method of efficient porous thin film electrode used for capacitive deionization |
| WO2016210419A1 (en) * | 2015-06-26 | 2016-12-29 | Florida State University Research Foundation, Inc. | Dry process method for producing electrodes for electrochemical devices and electrodes for electrochemical devices |
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