WO2013147380A1 - Électrode en carbone composite sélective pour un ion spécifique pour une désionisation capacitive et son procédé de préparation - Google Patents

Électrode en carbone composite sélective pour un ion spécifique pour une désionisation capacitive et son procédé de préparation Download PDF

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WO2013147380A1
WO2013147380A1 PCT/KR2012/008994 KR2012008994W WO2013147380A1 WO 2013147380 A1 WO2013147380 A1 WO 2013147380A1 KR 2012008994 W KR2012008994 W KR 2012008994W WO 2013147380 A1 WO2013147380 A1 WO 2013147380A1
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carbon electrode
selective
ion
group
composite carbon
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PCT/KR2012/008994
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Korean (ko)
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최재환
김유진
이재헌
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공주대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • 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
    • C02F1/4691—Capacitive deionisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/135—Carbon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • 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
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material

Definitions

  • the present invention relates to a capacitive desalination composite carbon electrode capable of exhibiting selectivity to a specific ion, a method for preparing the same, and an electrochemical cell including the composite carbon electrode.
  • the present invention relates to an electrode capable of efficiently separating and removing anions, a method for preparing the same, and an electrochemical cell.
  • nitrate (NO 3 -) in the ground water and surface water of the ion concentration is gradually increased.
  • Nitrate ions in drinking water are known to cause metahemoglobinemia in infants. Therefore, WHO recommends that concentrations of nitrate-nitrongen in drinking water be kept below 10 mg / L.
  • nitrate removal methods include ion exchange, biological treatment, reverse osmosis (RO), electrodialysis (ED), and the like.
  • Biological treatments are relatively inexpensive but require large scale bioreactors.
  • the water temperature is low in winter, there is a problem that the removal rate is lowered because the activity of the microorganisms.
  • the ion exchange method can remove nitrate ions by a simple method, but has a disadvantage in that a large amount of secondary pollutants are discharged in the process of regenerating the resin in which the ion exchange is completed.
  • Reverse osmosis and electrodialysis can also effectively remove nitrate, but they have a disadvantage in that the economy is poor because the membrane must be replaced periodically and high pressure or voltage must be applied during operation.
  • CDI capacitive deionization
  • the CDI technology removes ions by adsorbing ions having opposite charges on the electrodes when an electric potential is applied to the porous carbon electrode. Therefore, in order to increase the desalination rate, it is important to increase the adsorption capacity of the carbon electrode itself.
  • carbon electrodes for CDI using many kinds of carbon bodies have been developed. In the early 2000s, Andelman was able to dramatically improve the desalination efficiency of the CDI process by using membrane capacitive deionization (MCDI), which combines an ion exchange membrane with a carbon electrode [Canada Patent 2,444,390].
  • MCDI membrane capacitive deionization
  • Korean Patent Publication No. 10-2010-0082977 discloses the preparation of a CDI electrode prepared by coating an electrode active material with a functional additive providing an ionic group reacting with a hydrophilic polymer and a hydrophilic polymer, followed by heat and light treatment to react the CDI electrode.
  • the CDI electrode adsorbs all anions or all cations present in the solution according to the type of the ionic group, and selectively adsorbs only specific ions in a solution containing various kinds of ions having the same charge. There is a drawback to not doing it.
  • the ion-selective electrode developed to date serves to selectively adsorb cations or anions. That is, the anion-selective electrode can adsorb all the anions present in the solution regardless of the kind of anion, but serves to prevent the cation from adsorbing. If a specific anion can be selectively adsorbed in a mixed solution of various anions, it is the most preferable selective carbon electrode. For example, it is the ideal desalination if only nitrate ions can be selectively removed while leaving chloride ions in ground water mixed with nitrate (NO 3 ⁇ ) and chloride (Cl ⁇ ). In the case of using a carbon electrode having a selectivity to the specific ions, only the necessary ions are removed, thereby significantly reducing energy costs during operation. It also has the advantage of increasing throughput with carbon electrodes of the same size.
  • CDI uses the principle that when a potential is applied to a carbon electrode, ions in the solution are adsorbed on the electrode surface by electrostatic attraction. Therefore, when using a common carbon electrode, the amount of ions adsorbed may vary depending on the concentration of ions present in the solution or the mobility of each ion.
  • the present inventors apply ions adsorbed on the coating layer by applying a potential by coating a material capable of exhibiting selectivity for specific ions on the surface of the carbon electrode in order to give selectivity to specific ions among various kinds of ions having the same charge.
  • the present invention was completed by discovering that they preferentially move to the inside of the carbon electrode to effectively remove only desired ions.
  • An object of the present invention is to provide a specific ion-selective capacitive desalination composite carbon electrode and a method of manufacturing the same.
  • an object of the present invention is to provide a capacitive desalination electrochemical cell comprising a specific ion-selective capacitive desalination composite carbon electrode prepared by the above production method.
  • the present invention relates to a specific ion-selective capacitive desalination composite carbon electrode and a method for manufacturing the same, and more particularly, to give specific ion to a surface of a carbon electrode in order to give selectivity to a specific ion among various kinds of ions having the same charge. It provides a specific ion selective capacitive desalination composite carbon electrode and a method of manufacturing the same by coating a material that can show a selectivity for the ions adsorbed on the coating layer preferentially moves to the inside of the carbon electrode when the potential is applied to effectively remove only the desired specific ions do.
  • the present invention provides a specific ion-selective capacitive desalted composite carbon electrode in which an ion-selective resin powder is coated, coated or treated.
  • the present invention also provides a specific ion-selective capacitive desalination composite carbon electrode comprising a current collector, an activated carbon layer formed on the current collector, and an ion-selective resin powder coating layer formed on the active carbon layer.
  • the particle size of the ion-selective resin powder may be 100 ⁇ m or less.
  • the ion selective resin powder may be poorly soluble or insoluble that does not dissolve in an organic solvent.
  • the ion-selective resin powder may include one or two or more selected from a polymer resin having a cation exchange group, a polymer resin having an anion exchange group, and a chelate resin.
  • the present invention provides a capacitive desalination electrochemical cell including the specific ion-selective capacitive desalination composite carbon electrode.
  • the present invention also provides a water treatment method using the specific ion-selective capacitive desalination composite carbon electrode or a capacitive desalination electrochemical cell including the same.
  • the particular ion-selective capacitive desalination composite carbon electrode of the present invention or a capacitive desalination electrochemical cell comprising the same can be used to remove nitrate ions in groundwater, river water or drinking water.
  • the present invention also provides the use of the specific ion-selective capacitive desalination composite carbon electrode or a capacitive desalination electrochemical cell comprising the same for water treatment.
  • the present invention also provides the use of a specific ion selective capacitive desalination composite carbon electrode or a capacitive desalination electrochemical cell comprising the same for removing nitrate ions from groundwater, river water or drinking water.
  • the present invention 1) manufacturing an electrode slurry comprising a nonionic polymer binder, an organic solvent and an active carbon-based electrode active material, and then applying the electrode slurry to a current collector to produce a carbon electrode; And 2) coating a coating solution including a polymer binder, an ion selective resin powder, and an organic solvent on the carbon electrode of step 1) to prepare a specific ion selective composite carbon electrode having an ion selective resin coating layer formed thereon.
  • a method of manufacturing a selective capacitive desalination composite carbon electrode is provided.
  • the present invention also provides a method for producing a specific ion-selective capacitive desalination composite carbon electrode further comprising a drying step after step 1) or step 2).
  • the present invention also provides a polymer binder coating layer formed of an organic solution in which one or two or more polymer binders selected from cation exchange polymers and anion exchange polymers are formed in the ion selective resin coating layer of the specific ion selective composite carbon electrode prepared in step 2). After that, it provides a method for producing a specific ion-selective capacitive desalination composite carbon electrode further comprising the step of drying and pressing.
  • the nonionic polymer binder in step 1) is not limited thereto.
  • polyisulfone, polysulfone, polyvinylidene difluoride, polyacrylonitrile, cellulose acetate, polyimide and polyisimide One or two or more mixtures selected from the group consisting of may be used, and more preferably polyvinylidenedifluoride may be used.
  • the weight average molecular weight of the nonionic polymer binder is not limited, but is preferably 200,000 to 500,000, and when the polymer resin in the above range is used, the viscosity of the electrode slurry and the electrode active material are excellent.
  • the organic solvent may be determined by the type of the nonionic polymer binder, and any organic solvent in which the selected polymer binder is dissolved may be used.
  • the organic solvent of the preferred polymer binder may be dimethylacetamide, dimethylformamide, dimethylcarbonate, or ethylene. In the group consisting of carbonate, ethylmethyl carbonate, diethyl carbonate, propylene carbonate, acetonitrile, N-methyl-2-pyrrolidone, acetone, chloroform, dichloromethane, trichloroethylene, ethanol, methanol, isopropanol, propanol and hexane One or two or more mixtures selected are possible.
  • the active carbon-based electrode active material is an active carbon-based material having a high specific surface area, and may be used as an activated carbon powder, activated carbon fiber, carbon nanotube, carbon aerogel, graphene, or a mixture thereof, and may be used as a powder. It is desirable to.
  • the electrode active material may be used by adjusting the content range according to the required physical properties, and is not particularly limited, but the average particle diameter is 10 ⁇ m or less, more specifically 10 nm ⁇ 10 ⁇ m to use the carbon electrode It is desirable to increase the specific surface area and storage capacity.
  • the electrode slurry of step 1) preferably comprises 5 to 30 parts by weight of the nonionic polymer binder and 100 to 400 parts by weight of the organic solvent based on 100 parts by weight of the active carbon-based electrode active material.
  • the amount of the nonionic polymer binder is less than 5 parts by weight, the carbon electrode is brittle due to insufficient bonding with the active carbon-based electrode active material, and the electric conductivity of the carbon electrode may be lowered when used in excess of 30 parts by weight.
  • more preferably 8 to 15 parts by weight of the nonionic polymer binder is added to 100 parts by weight of the active carbon-based electrode active material.
  • the amount of the organic solvent for dissolving the nonionic polymer binder and the mixing of the electrode active material affects the viscosity of the electrode slurry and the formation of pores on the surface of the carbon electrode during the drying process, so that the amount of the organic solvent is less than 100 parts by weight of the electrode slurry. May not be uniformly mixed and if the content exceeds 400 parts by weight, the viscosity of the electrode slurry decreases, making it difficult to apply to the current collector, and the pore size increases on the surface of the carbon electrode, thereby reducing the capacitance of the carbon electrode. have.
  • the organic solvent is more preferably 200 to 300 parts by weight based on 100 parts by weight of the active carbon-based electrode active material.
  • the current collector When the current collector is supplied with an electric current to the electrode manufactured by the power supply device, it is preferable to use an excellent electrical conductivity so that the electric field can be uniformly distributed on the electrode surface.
  • Examples can be sheets, thin films or plain weave mesh forms comprising aluminum, nickel, copper, titanium, iron, stainless steel, graphite or mixtures thereof.
  • the coating method is not limited by spraying, dip coating, knife casting, doctor blade, spin coating, etc., and the coating thickness is in the range of 50 to 300 ⁇ m, which is desirable to increase the desalination efficiency while reducing the electrical resistance of the carbon electrode. Do.
  • a carbon electrode having a specific thickness to be manufactured may be manufactured by repeating the step of applying the electrode slurry to a current collector one or more times as necessary.
  • step 2) is to form an ion-selective resin powder coating layer on the carbon electrode prepared in step 1), and the coating method is not limited by spraying, dip coating, knife casting, doctor blade, spin coating, or the like. .
  • the particle size of the ion-selective resin powder used for coating plays a very important role in making the coating layer and the solution reach the adsorption equilibrium. The smaller the particle size of the ion-selective resin powder, the larger the contact area with the solution, which is advantageous for selectively adsorbing specific ions.
  • the particle size of the ion-selective resin powder used for coating is 100 ⁇ m or less, preferably 50 nm to 30 ⁇ m in size.
  • the coating thickness is preferably in the range of 10 to 300 ⁇ m, but preferably in the range of 20 to 100 ⁇ m is preferred to increase the desalination efficiency while reducing the electrical resistance of the electrode.
  • the ion-selective resin is coated with a carbon electrode with ion-selective resin powder having high selectivity for specific ions among various kinds of ions of the same charge to secure the contact time with the desalting solution passing through the electrode surface due to the large contact area of the coating layer. As the ion-selective resin powder reaches the adsorption equilibrium with the specific ion, it shows an excellent effect to selectively remove the specific ion.
  • the ion-selective resin powder of step 2) is typically crosslinked to use poorly soluble or insoluble in organic solvents.
  • Poorly soluble generally means a solubility of 10 wt% or less, preferably 5 wt% or less, more preferably 1 wt% or less.
  • the polymer binder of step 2) may use one or two or more of a nonionic polymer, a cation exchange polymer, and an anion exchange polymer, and the polymer binder should not be crosslinked and can be dissolved in an organic solvent.
  • the coating solution of step 2) is 5 to 30 parts by weight when the polymer binder is a nonionic polymer, 100 to 10 parts by weight and 10 to 500 parts by weight of the organic solvent 150 to 100 parts by weight of the ion-selective resin powder It is preferable to include 800 parts by weight.
  • the polymer binder is a nonionic polymer
  • the amount is less than 5 parts by weight, the ion-selective resin powder may fall off due to insufficient bonding with the ion-selective resin powder, and when used in excess of 30 parts by weight, the electrical resistance of the coating layer may increase. Can be.
  • the ion-selective resin powder may be impregnated into the polymer binder to decrease the selectivity to a specific ion.
  • 100 to 200 parts by weight of the ion exchange polymer is added to the polymer binder with respect to 100 parts by weight of the ion selective resin powder in terms of bonding and selectivity of the ion selective resin powder.
  • the coating solution may not be uniformly mixed. If it exceeds 800 parts by weight, the viscosity of the coating solution is reduced. There is a problem that the coating on the carbon electrode prepared in step is not easy. More preferably, in view of uniform mixing of the coating solution and ease of coating, the organic solvent is more preferably 300 to 500 parts by weight based on 100 parts by weight of the ion exchange resin powder of the coating solution.
  • ion selective resin one or two or more selected from a polymer resin having a cation exchange group, a polymer resin having an anion exchange group, and a chelate resin can be used.
  • the cation exchange resin may be a sulfonic acid group (-SO 3 H), a carboxyl group (-COOH), a phosphonic group (-PO 3 H 2 ), a phosphonic group (-HPO 2 H), an asonic group (-AsO 3 H 2 ) And a cation exchange group such as a selenic group (-SeO 3 H), and the anion exchange resin is quaternary ammonium salt (-NH 3 ), primary to tertiary amine (-NH 2 , -NHR, -NR 2 ), A quaternary phosphonium group (-PR 4 ), a tertiary sulfonium group (-SR 3 ) and the like having an anion exchange group.
  • the ion exchange resin is cross-linked and insoluble in an organic solvent.
  • Poly styrene-divinylbenzene
  • polystyrene polystyrene
  • polysulfone polyisulfone
  • polyamide polyester
  • polyimide polyether
  • polyethylene polytetrafluoroethylene
  • polyglycidyl methacrylate any one or a mixture of two or more selected may be used, and any resin that may have a cation exchange group or an anion exchange group without being limited thereto may be used without limitation.
  • poly (styrene-divinylbenzene) having a phosphoric acid group, an aminophosphate group or an aminodiacetic acid group can be used.
  • the polymer binder is not cross-linked so that it may be dissolved in an organic solvent and present in a solution state, the nonionic polymer used in step 1); Sulfonic acid group (-SO 3 H), carboxyl group (-COOH), phosphonic group (-PO 3 H 2 ), phosphonic group (-HPO 2 H), asonic group (-AsO 3 H 2 ), selenic group Polymers having a cation exchange group such as (-SeO 3 H); Quaternary ammonium salts (-NH 3 ), primary to tertiary amines (-NH 2 , -NHR, -NR 2 ), quaternary phosphonium groups (-PR 4 ), tertiary sulfonium groups (-SR 3 ), and the like.
  • Sulfonic acid group (-SO 3 H), carboxyl group (-COOH), phosphonic group (-PO 3 H 2 ), phosphonic group (-HPO 2 H), asonic group (-As
  • One or two or more selected from polymers having an anion exchange group may be used. Specifically, for example, at least one selected from polystyrene, polysulfone, polyisulfone, polyamide, polyester, polyimide, polyether, polyethylene, polytetrafluoroethylene and polyglycidyl methacrylate. Mixtures may be used, and any polymer may be used without limitation, and any polymer may have a cation exchange group or an anion exchange group.
  • the weight average molecular weight of the polymer having a cation exchange group and the polymer having an anion exchange group is not limited, but is preferably 50,000 to 4,000,000, but more preferably 300,000 to 1,500,000.
  • the organic solvent may be appropriately selected and used according to the type of the polymer binder, and as the organic solvent in which the polymer binder is dissolved, dimethyl acetamide, dimethyl formamide, dimethyl carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate
  • dimethyl acetamide, dimethyl formamide, dimethyl carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate One or more mixtures selected from the group consisting of propylene carbonate, acetonitrile, N-methyl-2-pyrrolidone, acetone, chloroform, dichloromethane, trichloroethylene, ethanol, methanol, isopropanol, propanol and hexane It is possible, but not limited to these.
  • step 1) or step 2) may further comprise a drying step, the organic solvent used in each step by removing the organic solvent in a normal pressure, vacuum drying in a temperature atmosphere of room temperature ⁇ 200 °C.
  • the polymer binder coating layer is formed of an organic solution in which one or two or more polymer binders selected from a cation exchange polymer and an anion exchange polymer are dissolved in the ion selective resin coating layer of the specific ion selective composite carbon electrode prepared in step 2), Drying and pressing may be further included.
  • Electrochemical cells using a specific ion-selective composite carbon electrode produced by the production method of the present invention only for one electrode selected from the positive electrode or the negative electrode, or both the positive electrode and the negative electrode are included in the scope of the present invention.
  • the electrochemical cell forms an electrode by applying electricity, and refers to a form composed of an anode, a cathode, and a spacer.
  • Such electrochemical cells include capacitive desalination cells, capacitors and the like.
  • Electrochemical cells also include those in which two or more layers of anodes and cathodes are alternately stacked. The number of laminations is related to the capacity, and is produced by laminating appropriately as necessary.
  • the specific ion-selective composite carbon electrode is used for only one electrode selected from the positive electrode or the negative electrode, the other electrode is an ion exchanger Using a carbon electrode that does not have, even in this case it is possible to achieve excellent adsorption and desorption of specific ions.
  • the specific ion selective composite carbon electrode has a high capacitance, and facilitates adsorption and desorption of specific ions during the operation of the process.
  • the electrode coated with cation exchange resin powder may be used as a cathode, and the electrode coated with anion exchange resin powder may be used as an anode.
  • the method of manufacturing a specific ion-selective capacitive desalination composite carbon electrode according to the present invention may provide selectivity to specific ions on a surface of a carbon electrode in order to give selectivity to specific ions among various kinds of ions having the same charge.
  • the ions adsorbed on the coating layer preferentially move to the inside of the carbon electrode when potential is applied, thereby selectively removing only a specific desired ion.
  • CMPS chloromethylated polystyrene
  • the activated carbon powder was mixed with a polymer to prepare a carbon electrode to be used to prepare a composite carbon electrode.
  • PVdF polyvinylidenedifluoride
  • DMAc dimethylacetamide
  • activated carbon powder specific surface area 1400 m 2 / g, average particle diameter 4 ⁇ m, PCT) , Power Carbon Technology Co., Korea
  • the electrode slurry was cast on a conductive graphite sheet (thickness: 250 ⁇ m, Dongbu Carbon Co., Ltd., Cat.No. F02511C) as a current collector with a doctor blade and then dried at 50 ° C. Dried at 1 h. The electrode was again dried in a vacuum oven at 50 ° C. for 2 hours to remove all of the dimethylacetamide remaining on the electrode.
  • the content ratio of polyvinylidene difluoride as a polymer binder in the prepared carbon electrode was 10% by weight.
  • the thickness of the carbon layer on the graphite sheet after drying was 150 ⁇ m.
  • the anion exchange polymer prepared in Preparation Example 1 was used as a binder.
  • the weight ratio of the anion exchange polymer and BHP55 anion exchange resin powder of Preparation Example 1 as a binder was mixed to be 1: 1.
  • the uniformly mixed coating solution was coated on the surface of the carbon electrode prepared in step 1) using a doctor blade, and dried in a drying oven at 50 ° C. for 12 hours to prepare a composite carbon electrode.
  • the average thickness of the coating layer was 50 ⁇ m.
  • a scanning electron microscope (SEM) image is shown in FIG. 1 to observe the surface structure of the manufactured composite carbon electrode.
  • the size of BHP55 anion exchange resin powder coated on the surface of the composite carbon electrode is variously distributed from several micro to up to 60 ⁇ m.
  • the size of the BHP55 anion exchange resin powder coated is relatively large compared to the size of activated carbon particles of about 4 ⁇ m, the surface shows a relatively rough structure, but it is combined with the anion exchange polymer binder as a whole to form a uniform coating layer on the surface of the carbon electrode.
  • the composite carbon electrode of Example 1 was found to have a large surface area that the ions in the solution can contact the resin particles and the solution.
  • Example 1 In order to confirm whether the composite carbon electrode prepared in Example 1 is selective for nitrate ions, two types of capacitive desalting unit cells were manufactured and desalting experiments were performed.
  • the "BHP55 cell” using the composite carbon electrode prepared in Example 1 and the "MCDI cell” consisting of a known ion exchange membrane and a carbon electrode were prepared to compare the degree of desalination.
  • the MCDI cell includes a cation exchange membrane (Neosepta CMX, Astom Corp., Japan), a 100 ⁇ m thick spacer (nylon, 20mesh), and an anion exchange membrane (Neosepta AMX, Astom Corp., Japan) between the two carbon electrodes as shown in FIG. 2. Were arranged in order and bolted to each side with a plexiglass plate.
  • the BHP55 cell was prepared by replacing the anion exchange membrane and the carbon electrode (+) with the composite carbon electrode prepared in Example 1 in the MCDI cell. All carbon electrodes and composite carbon electrodes were cut into 10 x 10 cm in size.
  • a rubber gasket was placed on the outside of the carbon electrode, and the influent was supplied using a peristaltic pump.
  • a 1 cm size hole was drilled in the center of the cation exchange membrane and the carbon electrode (-) to allow the influent to enter the edge of the electrode and pass through the spacer to exit through the center hole.
  • Influent was prepared by mixing NaCl and NaNO 3 so that the concentrations of chloride (Cl ⁇ ) and nitrate (NO 3 ⁇ ) ions were 5.0 mM and 2.0 mM, respectively, and 300 mL of the influent was used for the desalination experiment.
  • the BHP55 cell when looking at the electrical conductivity change of the two cell structure, it can be seen that when the adsorption potential is applied, the BHP55 cell has a lower electrical conductivity than the MCDI cell.
  • the conductivity was reduced to 670 ⁇ S / cm while operating in MCDI cell, while it was reduced to 640 ⁇ S / cm in BHP55 cell.
  • the conductivity results indicate that the BHP55 cell adsorbs more ions than the MCDI cell when the same potential is applied.
  • the average amount of adsorbed total ions was 0.336 mmol for BHP55 cells.
  • the nitrate ion in the adsorbed ions was 0.193 mmol, which was 57.3% of the total adsorption amount.
  • the total adsorption amount was increased by 35% compared to the MCDI cell.
  • nitrate ions were found to increase 2.3-fold from 0.083 mmol to 0.193 mmol.
  • nitrate ions can be selectively adsorbed by coating the surface of the carbon electrode with BHP55 anion exchange resin, an ion selective resin known to be selective for nitrate ions.
  • the present invention provides an ion selective number having selectivity for a particular ion.
  • coating the paper on the surface of the carbon electrode has the effect of selectively adsorbing only specific ions in a mixed solution of various ions having the same charge.
  • FIG. 5 and 6 are graphs showing the result of measuring the ion concentration change in the solution according to the time when the third adsorption potential is applied to the BHP55 cell and the MCDI cell, respectively.
  • the results of the BHP55 cell of FIG. 5 are similar to those of the MCDI cell of FIG. In comparison, it was found that there was a difference in the change of ion concentration in solution.
  • the MCDI cell as the adsorption potential is applied, nitrate and chloride ions start to be adsorbed, thereby decreasing the ion concentration in the solution, but as the adsorption capacity of the electrode saturates after 5 minutes, a constant concentration is maintained. ]. That is, since the adsorption was completed within 5 minutes after the adsorption potential was applied to the MCDI cell as shown in the electrical conductivity results of FIG.
  • the amount of chloride adsorption decreased from 0.174 mmol to 0.138 mmol after 15 minutes when the adsorption potential was applied, whereas nitrate ions decreased from 0.153 mmol to 15 minutes after 5 minutes. Then increased to 0.192 mmol. From this, it was confirmed that the ion exchange reaction occurred in the resin after the adsorption time had elapsed for 5 minutes. The sum of the two ions adsorbed increases until 5 minutes and then shows a constant value, which indicates that the adsorption on the carbon electrode is completed in 5 minutes and then the ion exchange reaction takes place.
  • the mole fraction of initially adsorbed nitrate ions increased from 30% to 58% after 15 minutes.
  • the mole fraction of adsorbed nitrate ions was 46.8%. This is because the BHP55 anion exchange resin in the coating layer exhibits selectivity for nitrate ions.

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Abstract

La présente invention concerne un procédé de préparation d'une électrode en carbone composite pour une désionisation capacitive apte à présenter une sélectivité pour un ion spécifique, et de façon plus spécifique, l'invention concerne un procédé de préparation d'une électrode en carbone composite sélective pour un ion spécifique pour une désionisation capacitive, procédé suivant lequel une matière apte à présenter une sélectivité pour un ion spécifique est appliquée en revêtement sur une surface d'une électrode en carbone pour donner une sélectivité pour l'ion spécifique parmi divers types d'ions ayant la même charge, et les ions adsorbés sur la couche de revêtement lorsqu'une tension est appliquée se déplacent de façon préférentielle dans l'électrode en carbone, permettant ainsi une élimination efficace de seulement un ion spécifique désiré. De plus, la présente invention concerne une cellule électrochimique pour une désionisation capacitive comprenant une électrode en carbone composite sélective pour un ion spécifique pour une désionisation capacitive préparée par le procédé de préparation.
PCT/KR2012/008994 2012-03-29 2012-10-30 Électrode en carbone composite sélective pour un ion spécifique pour une désionisation capacitive et son procédé de préparation WO2013147380A1 (fr)

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