KR20150118771A - Capacitive Deionization Composited Electrode, Capacitive Deionization Composited Electrode Cell and Capacitive Deionization Composited Electrode Manufacturing Method - Google Patents

Abstract

The present invention relates to a capacitive deionization electrode (CDI electrode) utilizing a non-conductive porous support.
More particularly, the electrode material layer is formed on both sides of a non-conductive porous support such as a woven fabric, a nonwoven fabric and a porous film which are not electrically conductive current collectors, and then, a cation-selective coating layer is formed on one side and a depolarizing composite Electrodes were prepared and laminated so as to have a plurality of layers facing each other with the cation-selective layer and the anion-selective layer. The potential was varied depending on the number of laminations at the inner and outer sides of the laminate, Which is capable of operating in a bi-polar type with different applied electric potentials depending on the number of turns and the number of turns wound on the inside and outside of the battery.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite desalination composite electrode, a capacitor type desalination composite electrode cell, and a capacitor type composite desalination electrode,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite electrode and module for groundwater, tap water, brackish water, heavy water and industrial wastewater, and CDI (Capacitive deionization) for soft water.

That is, the present invention relates to a method for manufacturing a charge-coupled desalination composite electrode utilizing a non-conductive porous support such as a non-conductive woven fabric, a non-woven fabric and a porous film without using a conductive current collector.

That is, in the present invention, first, an electrode material such as an electrode active material such as a carbon-based material is coated on both sides of a non-conductive porous support, or a sheet of electrode active material is attached to a carbon electrode (electrode material layer) The present invention relates to a method for producing a composite composite desalination electrode having a different ion selective layer on a carbon electrode layer of a carbonaceous electrode, and a novel composite electrolytic desalination composite electrode obtained thereby.

According to one embodiment of the present invention, first, an electrode active material is coated on both sides of a non-conductive porous support, or a sheet of electrode active material is attached to form a carbon electrode (electrode active material layer). Then, a cation-selective layer or anion-selective layer is formed on one side of the carbon electrode using an ion-exchange membrane, an ion-exchange solution, or an ion-exchange resin powder. On the other side of the carbon electrode, ion- And a stratified layer (the cation-selective layer in the above case, the other is an anion-selective layer). Also, a capacitive complex desalination apparatus manufactured using the above-described composite desalination composite electrode is manufactured.

In addition, the present invention provides a new battery separator composite desalination composite electrode having the structure in which the cation-selective layer and the anion-selective layer face each other at least two

The present invention also provides a composite composite desalination electrode laminate which is prepared by laminating the cationic selective layer and the anion selective layer so as to face each other using two or more new composite desalination composite electrodes prepared above.

In addition, the present invention is characterized in that the above-described electrodeposited composite desalination composite electrode laminate is applied at different ends according to the number of laminated layers, or the laminated depolarized composite electrode laminate of the present invention is rolled by a roll, And a method for producing the same, a CDI composite electrode module using the same, a storage type composite desalination device, and a manufacturing method therefor will be.

In the production of domestic water or industrial water, desalination technology plays a very important role in determining human health, process efficiency, and product performance.

Water containing heavy metals, nitrate nitrogen, and fluoride ions can have a serious health impact when people drink for a long time. In addition, hard water, such as the number of boilers containing hard materials, can scale the boiler or heat exchanger, which can significantly reduce the efficiency of the process. In the electronic and pharmaceutical industries, manufacturing and using ultrapure water that completely eliminates ions is an important factor in determining product performance.

Recently, due to lack of water in the world, studies on seawater desalination methods, wastewater and brine treatment methods have been actively conducted. Among the above methods, a method using an ion exchange resin is widely used, but the use thereof is still limited due to problems such as the use of a compound during the regeneration of the resin and an expensive operation cost.

To solve such a problem, a condensation desalination process (CDI process) like the present invention has been studied.

The CDI process is based on the electric double layer theory used in the capacitor process and utilizes the property that relatively polar ions in the water quality are adsorbed on the electrode surface when electricity is applied to the electrode surface. That is, when a solution containing a cation and an anion is passed between two porous carbon electrode layers, an electrostatic force is applied to remove ions contained in the aqueous solution. Such an elimination principle is that by applying an electrostatic force, negative ions such as Cl- migrate to the anode by electrostatic force, and positive ions such as Na + migrate to the cathode, and ionic substances contained in the aqueous solution are removed, The waste water solution is purified.

The CDI process can be exemplified by a CDI electrode and a CDI module fabricated using the same. CDI electrodes using porous carbon materials must rapidly penetrate and diffuse ions. It also has selectivity for ions and should be able to prevent re-adsorption to the opposite electrode due to inversion during the regeneration. Durability is also required for industrial applications.

However, since the conventional CDI electrode is made of a conductive graphite foil that can directly apply electricity as a current collector, it is difficult to handle due to its weak mechanical strength and its performance Degradation and defective rate are high.

In addition, the laminated module manufactured using the conductive current collector such as the graphite foil is required to cut the electrode, and the electrode terminal capable of providing electricity can be cut into a predetermined length on one side, There is a difficulty to connect with. This is because when the graphite is assembled into a double pole, the current efficiency is reduced due to the current, so that it can only be assembled into a single pole. In order to assemble the single pole, a certain shape must be formed for applying electricity from the outside. Therefore, in order to assemble into a single pole, electrode terminals must be designed so that they are cut and processed, resulting in a large loss of the current collector. Particularly, in order to connect the terminal block so as to be able to apply electricity to the stacked electrodes, it is necessary to have a sufficiently large space, so that the external volume becomes large and the CIP (Cleaned in place) cleaning liquid must be used more.

Korean Patent No. 10-1022257 discloses a method of manufacturing an ion-selective storage desalination composite electrode and a module.

Korean Registered Patent [10-1022257] (Registered on Mar 08, 2011)

The present invention utilizes a non-conductive support such as woven fabric, nonwoven fabric, or porous film to improve the disadvantage of a conventional electroconductive current collector, for example, a graphite foil, , And a laminated structure thereof.

In the present invention, the non-conductive support is more preferably porous but is not limited thereto. Examples of the non-conductive support include woven fabric, nonwoven fabric, perforated film, and porous film. However, the non-conductive support is not limited thereto.

In the present invention, an electrode layer (electrode material layer) is formed by coating an electrode active material on both sides of the non-conductive support or by attaching an electrode active material sheet, and then using an ion exchange membrane, an ion exchange solution, or an ion exchange resin powder (CDI) electrode having a novel structure, which is produced by forming a cation-selective layer on one side and an anion-selective layer on the other side, and a method for producing the same.

In addition, the present invention provides a non-conductive support such as a woven fabric, a nonwoven fabric and a porous film having excellent mechanical strength in place of the graphite foil current collector, which is easy to handle and can reduce the performance deterioration and defective rate It is an object of the present invention to provide a method for manufacturing a composite desalination composite electrode (CDI Composite Electrode), a CDI Composite Electrode Cell, and a storage type desalination composite electrode.

In addition, if a non-conductive support is used to form an electrode material layer on both sides (usually, but not limited to, a carbon electrode layer) and then a cation-selective layer is formed on one of the electrode material layers, (CDI electrode) of a new structure is prepared by having a layer having opposite ion selectivity (in this case, an anion-selective layer opposite to the cation selective layer) on the layer.

The present invention also relates to a storage-type desalination composite electrode having two or more laminated surfaces laminated so that the cationic selective layer and the anionic selective layer are laminated so as to face each other using at least one of the above-described storage type desalination electrodes, Layer separator and the anion-selective layer are opposed to each other, a plurality of two or more storage-type desalination electrodes of the present invention are laminated to fabricate a new type of storage desalination composite electrode.

According to the present invention, it is possible to apply a potential different depending on the number of laminations at both ends of the above-described composite desalination composite electrode, or wrap the rolled composite electrolytic desalination composite electrode so as to roll the inside and outside of the roll, The present invention also provides a method of manufacturing the same, and a method of manufacturing the same. Herein, the capacitor-type desalination composite electrode unit cell means that a module is constituted by a minimum unit. That is, the unit cell of the electrolytic desalination composite electrode means a module composed of a cathode composite electrode (one composite electrode) and a cathode. In addition, the storage type desalination composite electrode cell means a module of more than a unit cell of a storage type desalination composite electrode, and includes a wider meaning than a storage type composite electrode unit cell.

Further, the present invention may further comprise a channel pattern for allowing the fluid to flow through the storage desalination electrode and the storage desalination composite electrode. In the case of having a flow pattern, there is an advantage that a module can be easily produced by stacking the cation-selective layer and the anion-selective layer so as to face each other without using a separate spacer.

Accordingly, the present invention provides a bipolar cell including a single cell of a storage desalination electrode having a flow path pattern, a storage desalination composite electrode, a single cell of a storage desalination composite electrode, a CDI composite electrode module having the same, Of the present invention.

In addition, the present invention does not require processing to connect with a terminal block like all existing electrodes in a sheet form, and there is no difficulty in making a large number of electrode terminals capable of providing electricity, And to provide a manufacturing method of a CDI (Capacitive Deionization) composite electrode module which can be easily applied to commercial applications because the design and size can be varied.

According to an aspect of the present invention, there is provided a storage desalination composite electrode comprising a non-conductive porous support on which an electrode material layer is formed, a cation-selective coating layer on one surface, and an anion- Characterized in that it has at least one or more storage desalination electrodes formed thereon and has at least two structures in which the cation-selective layer and the anion-selective layer face each other.

The storage desalination composite electrode is characterized in that a flow path pattern or a diaphragm is formed on the ion selective layer in the ion selective layer to have a flow path pattern.

In addition, the non-conductive porous support may be any one selected from a porous polymer sheet, a thin film, a porous ceramic, a woven fabric, a nonwoven fabric, a porous polymer film, and a porous polymer foam.

The composite desalination composite electrode cell according to an embodiment of the present invention includes a non-conductive porous support on which an electrode material layer is formed, a cationic selective coating layer formed on one surface, and an anion selective coating layer formed on the other surface, And an external current collecting electrode is laminated on both sides of the electrodeposited composite desalination composite electrode, and the electrodeposited desalination composite electrode is formed so as to have at least two structures in which the cation-selective layer and the anion-selective layer face each other, And is operated in the form of a bipolar electrode by varying the applied electric potential according to the number of layers of the desalted composite electrode.

In addition, the storage desalination composite electrode is wound in rolls and is operated in a bi-polar manner by varying the application potential according to the number of turns and the number of windings wound by collector electrodes on the inside and outside of the roll.

In addition, the present invention is characterized in that two or more of the above-described storage desalination composite electrodes are laminated.

The storage desalination composite electrode has a channel pattern in the ion selective layer.

A method of manufacturing a composite desalination composite electrode according to an embodiment of the present invention includes the steps of applying a slurry containing an electrode active material and a binder on both surfaces of a non-conductive porous support or calendering the slurry to form a sheet, To form an electrode material layer; Forming a different ion selective layer on each side of the electrode material layer using an ion exchange membrane, an ion exchange solution coating, and an ion exchange resin powder slurry to produce a storage desalination electrode; The ion selective layer of the storage type desalination electrode is laminated so as to include at least two structures in which one or more ion selective layers are stacked so as to face different ion selective layers.

The method may further comprise forming a flow path pattern at the same time or after the ion selective layer formation step.

The flow path pattern is obtained by forming a diaphragm on the ion selective layer.

The electrocatalytic desalination composite electrode manufactured according to the present invention is easy to handle because it uses a non-conductive porous support having excellent mechanical strength and can be prevented from being degraded by by current when it is operated in a bi-polar type.

In addition, since a channel pattern is included on the electrode including the ion selective layer, a separate spacer for providing a flow path is not required, automation of module assembly can be achieved, and mass production can be enhanced .

The square and cylindrical module manufactured using the charge and discharge electrode fabricated according to the present invention can easily assemble the module and minimize the volume of the module in the form of a bipolar electrode that does not apply electricity directly to the electrode. In addition, it can be used safely at high water pressure, and various types of cylindrical modules of high voltage and low current can be manufactured according to the number of electrodes of the adsorption electrode, and the capacity and working voltage of the module can be freely designed according to the system scale.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a composite electrolytic desalination composite electrode according to an embodiment of the present invention; FIG.
2 is a view showing a composite electrolytic desalination composite electrode cell according to an embodiment of the present invention.
3 is an exploded view of a CDI composite electrode module utilizing a porous support member using FIG.
FIG. 4 is a view showing the structure of a capacitively desalinated composite electrode in FIG. 3 and the configuration of a capacitively desalinated composite electrode roll. FIG.
5 is a view showing a method of making a composite desalination composite electrode roll in FIG.
FIG. 6 is a view showing a composite desalination composite electrode roll of FIG. 4;
7 is a view showing an assembling process of FIG. 3;
8 is a view showing the assembly diagram of Fig.

Hereinafter, the present invention will be described in more detail with reference to the drawings. The following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms. In addition, like reference numerals designate like elements throughout the specification. It is to be noted that the same elements among the drawings are denoted by the same reference numerals whenever possible. Further, it is to be understood that, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.

FIG. 1 is a view showing a composite electrodeless desalination composite electrode according to an embodiment of the present invention, FIG. 2 is a view showing a composite electrodeless desalination composite electrode cell according to an embodiment of the present invention, FIG. FIG. 4 is a view showing the structure of a composite electrodeless desalination composite electrode and the structure of a composite electrodeposited desalination electrode roll in FIG. 3, and FIG. FIG. 6 is a view showing a composite desalination composite electrode roll of FIG. 4, FIG. 7 is a view showing an assembling process of FIG. 3, and FIG. Fig.

Hereinafter, the present invention will be described in more detail in the following examples, but the present invention is by no means limited thereto. It will be apparent to those skilled in the art that the present invention is not limited to the process conditions set forth in the following examples, and can be arbitrarily selected within the range necessary for achieving the object of the present invention.

Hereinafter, the manufacturing steps of the present invention will be described.

One embodiment of the present invention is a method for manufacturing a non-conductive porous support, comprising applying a slurry containing an electrode active material and a binder on both sides of a non-conductive porous support such as a woven fabric, a nonwoven fabric and a porous film, or by calendaring the slurry to form a sheet, Thereby forming an electrode material layer (which may be referred to as a carbon electrode (layer) when a carbon material is used); Forming a different ion selective layer on each side of the electrode material layer using an ion exchange membrane, an ion exchange solution coating, and an ion exchange resin powder slurry; and a method for manufacturing the same .

Another embodiment of the present invention is a method for manufacturing a non-conductive porous support, comprising applying a slurry containing an electrode active material and a binder on both sides of a non-conductive porous support such as a woven fabric, a nonwoven fabric and a porous film or by calendaring the slurry to form a sheet, Thereby producing an electrode active material layer; Forming ion-selective layers different from each other by using an ion exchange membrane, an ion exchange solution coating, and an ion exchange resin powder slurry on each surface of the electrode active material layer (usually, but not limited to, a carbon electrode layer); Forming a flow path pattern in the ion selective layer; And a method for producing the same.

Another embodiment of the present invention may be a capacitor-type desalination composite electrode manufactured by laminating or laminating two or more layers of the electrostatic desalination electrode manufactured in the aspects of the present invention described above, and then rolling, and a method for manufacturing the same.

The electrodeposited desalination composite electrode is formed by applying a slurry containing an electrode active material and a binder on both surfaces of a non-conductive porous support or by calendaring the slurry to form a sheet and then pressing the non-conductive porous support onto the non-conductive porous support to form an electrode material layer ;

Forming a different ion selective layer on each side of the electrode material layer using an ion exchange membrane, an ion exchange solution coating, and an ion exchange resin powder slurry to produce a storage desalination electrode;

Laminating the ion selective layer of the storage type desalination electrode so as to include at least two structures stacked so that at least one ion selective layer is different from each other;

. ≪ / RTI >

The electrode layer and the ion selective layer are formed on the laminated surface of the outermost layer of the storage type desalination composite electrode so that the ion selective layer is stacked with other ion selective layers of the charge storage type desalination electrode, The surface may be the surface of the non-conductive porous sheet itself on which the electrode material or the ion selective layer is not coated.

According to another aspect of the present invention, there is provided an electrochemical device, comprising at least two layers of the electrochemical desalination electrodes manufactured in the aspects of the present invention described above, which are stacked or laminated, rolled and laminated with an external electrode of current collector A bipolar cell of a CDI electrode and a method of manufacturing the same.

Wherein the electrode material layer and the ion selective layer are formed on the laminated surface of the outermost layer of the charge coupled desalination composite electrode in contact with the collector electrode so that the ion selective layer is stacked with other ion selective layers of the charge storage type desalination electrode, The other surface to be laminated with the external applied electrode layer may be the surface of the non-conductive porous sheet itself on which the electrode material or the ion selective layer is not coated.

Another embodiment of the present invention may be a CDI composite electrode module schematically illustrated in FIG. 3, which is manufactured using the above-described battery cell for a storage and desalination electrode, and a method of manufacturing the same.

The non-conductive porous support according to the present invention can be applied to a non-conductive porous support such as a porous polymer, a ceramic woven fabric, a nonwoven fabric, a porous film, a porous foam, a porous sheet, Materials can be used. The non-conductive porous support of the present invention is preferably a non-conductive porous support made of a polymer, but is not limited thereto. The non-conductive porous support may be formed by forming an electrode active material layer (for example, a carbon electrode) Any support that can be used is not limited.

The non-conductive porous support may be used without pretreatment, and may be washed using a solvent that does not deform the support or the support to remove impurities.

The non-conductive porous support of the present invention may be characterized in that it is surface-treated with an ion exchange resin. That is, although it may be used without any separate pretreatment, it may be used by pretreatment. In the case of pretreatment, it is better to coat with a polymer resin solution (ion exchange solution) having an ion exchanger, which is another characteristic of the present invention. This is because when the electrode active material layer (for example, carbon electrode layer) is formed on one side of the porous nonwoven fabric and the electrode active material slurry is coated on the opposite side, the nonporous porous support is directly absorbed by the solvent, Carbon electrode layer), it is very preferable in the present invention to previously coat the non-conductive porous support with an ion exchange resin.

When the electrode active material layer according to the present invention is formed, the electrode active material and the binder may be coated with a slurry for lowering the active material. The binder includes all materials that can be applied or pressed by forming an electrode active material and a slurry on a non-conductive porous support. For example, the binder may be a non-ionic, cationic, or anionic Exchange resin, and can be used without limitation as long as it is a conventional one used in this technical field. The content of the binder resin is usually from 1 to 50% by weight, preferably from 2 to 15% by weight.

The cation or anion exchanger contained in the material used for the cation exchange layer, the anion exchange layer or the binder of the present invention may be a sulfonic acid group (-SO ₃ H), a carboxyl group (-COOH), a phosphonic group -PO ₃ H _2), may be a polymer resin having a cation exchange group such as Phosphinicosuccinic nikgi (-HPO ₂ H), oh sonic group (-AsO ₃ H _2), cell Reno nikgi (-SeO ₃ H). As a non-limiting example, a quaternary ammonium salt (-NH ₃ ), a primary to tertiary amine (-NH ₂ , -NHR, -NR ₂ ), a quaternary phosphonium group (-PR ₄ ), a tertiary sulfonium group -SR < ₃ >), and the like, but is not limited thereto.

Examples of the polymer resin that can have the ion exchanger include polystyrene, polysulfone, polyisocyanurate, polyamide, polyester, polyimide, polyether, polyethylene, polytetrafluoroethylene, polyglycidyl methacrylate, , But the present invention is not limited thereto. The ion exchanger can be produced by employing a comonomer having an ion-exchange group in polymerization or by modifying the polymer after polymerization.

The electrode coated with the polymer resin having the cation exchanger according to the present invention can be used as a negative electrode, and the electrode coated with a polymer resin having an anion exchanger can be used as a positive electrode.

The nonionic binder solution may include all the polymer resins that can be applied or pressed onto the electrode by forming the slurry with the electrode active material. Examples of the nonionic binder solution include polyvinylidenefluoride (PVDF), polystyrene butadiene rubber (SBR), polytetrafluoroethylene (PTFE), and polyurethane (PU). However, it is not limited to these, and any resin that is in the form of an organic solvent or an emulsion solution can be used without limitation .

 The weight average molecular weight of the polymer resin or nonionic polymer resin having the ion exchanger is not limited in order to achieve the object of the present invention, but is preferably 20,000 to 4,000,000, more preferably 50,000 to 1,500,000 When the polymer resin having the above range is used, the viscosity of the electrode slurry and the property of bonding the electrode active material are excellent.

The organic solvent may be selected according to the kind of the polymer resin. For example, the organic solvent in which the polymer resin is dissolved includes dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone acetone, chloroform, The solvent may be any one or a mixture of two or more selected from dichloromethane, trichlorethylene, ethanol, methanol and n-hexane, but is not limited thereto and may include all organic solvents capable of dissolving the polymer resin.

The electrode active material according to the present invention can be used without limitation as long as it is an active carbon based material having a high specific surface area. As a non-limiting example, activated carbon powder, activated carbon fiber, carbon nanotube, carbon airgel, And it is preferable to use it as a powder.

Also, RuO ₂ , Ni (OH) ₂ , MnO ₂ , PbO ₂ , TiO _2, or a mixture thereof may be used as the metal oxide based material, but the present invention is not limited thereto.

Such an electrode active material can be used by adjusting its content range according to the required physical properties. For example, it is preferred that the average particle size is 5 nm to 50 탆 or less, preferably 20 탆 or less, more preferably 10 탆 or less And more preferably 10 nm to 10 탆 is preferably used because it can increase the specific surface area of the electrode and the electric storage capacity.

The method of forming the electrode material layer on the non-conductive porous support using the slurry including the polymer solution (binder solution) and the electrode active material may include all the methods for producing the storage desalination electrode according to the present invention For example, by coating on a support, or by calendering the slurry by moderately kneading it to form a sheet, followed by pressing with the support.

The method of applying the slurry according to the present invention to a non-conductive porous support may be spraying, dip coating, knife casting, doctor blade, spin coating and the like, but not limited thereto, Preferably in the range of 20 to 300 mu m, is effective in increasing the desalting efficiency while reducing the electrical resistance of the electrode. The slurry applying method may also produce an electrode having a specific thickness desired to be repeated one or more times.

Also, in the method of pressurizing after forming the sheet by calendering the slurry appropriately, the temperature of the roll surface of the calender is determined according to the type of the polymer resin, The reason is that if the temperature of the roll surface of the calender becomes higher than the melting temperature, the softening of the resin becomes more vigorous and the sheet on the surface of the roll becomes thicker than the glass transition temperature of the roll surface It is difficult to wind the sheet due to the phenomenon that the sheet is cut due to the sticking and weakening of tension in the production of the roll, so that it may be difficult to manufacture the sheet in a roll form. If the roll surface temperature of the calender is lower than the glass transition temperature Since the resin is not softened, the surface of the sheet becomes uneven and it may be difficult to produce a sheet having a thickness of 200 탆 or less to be.

The surface temperature of the roll press varies depending on the type of the polymer resin when the electrode manufactured by pressing the sheet produced through the calender process is pressed on the non-conductive porous support using a roll press. Preferably, The glass transition temperature is preferably higher than the glass transition temperature and lower than the melting temperature, but is preferably 20 ° C higher than the glass transition temperature, but is not limited thereto.

Next, a method of forming an ion selective layer according to the present invention will be described.

The formation of the ion selective layer on the electrode (electrode material layer) manufactured by the above-described method according to the present invention is intended to increase the adsorption efficiency by completely desorbing ions adsorbed on the electric double layer, which is a problem of the desalination technique.

Examples of the method of forming the ion selective layer include laminating an ion exchange membrane, forming by ion exchange solution coating, and coating with a mixture of an ion exchange resin powder and a binder to form an ion selective layer. That is, in the method for producing a storage type desalination electrode or a storage type desalination composite electrode according to the present invention, the ion selective layer may be a layer formed by adhering a cation exchange membrane and an anion exchange membrane, and may be a cation exchange solution and an anion exchange solution And may be a layer formed by applying a cation exchange resin powder or an anion exchange resin powder and a slurry of a binder mixture, and the formation method thereof is not limited.

A method of roll pressing as one of the methods of attaching the cation exchange membrane and the anion exchange membrane will be described. A cation exchange membrane is attached to one side of a carbon electrode made of a nonporous porous support, and an anion exchange membrane is rolled to the other side. . The surface temperature of the roll press in the above-mentioned roll pressing is different depending on the type of the ion exchange membrane. It is preferable that the surface temperature is lower than the temperature at which the ion exchange function is not decomposed, but it is preferably 80 deg.

The method of applying the ion exchange solution includes, but is not limited to, spray coating, dip coating, knife casting, doctor blade, spin coating and the like. The coating thickness of the ion selective layer applied in the present invention is preferably in the range of 2 to 1,000 μm, but preferably in the range of 10 to 100 μm, in order to improve the desalination efficiency while reducing the electrical resistance of the electrode. The ion exchange solution may include a solution of the polymer resin having a cation or anion exchanger dissolved in an organic solvent and present in the form of a solution.

Examples of the ion exchange resin constituting the ionic crosslinking layer include a sulfonic acid group (-SO ₃ H), a carboxyl group (-COOH), a phosphonic group (-PO ₃ H ₂ ), a phosphonic group (-HPO ₂ H) , Abu sonic group (-AsO ₃ H _2), cell Reno nikgi (-SeO ₃ H), such as a polymer resin or a quaternary ammonium salt having a cation-exchange group (-NH _3), 1 ~ ₃ primary amine (-NH _2, in - NHR, -NR ₂ ), a quaternary phosphonium group (-PR ₄ ), and a tertiary sulfonium group (-SR ₃ ), but the present invention is not limited thereto. More specifically, the ion-exchangeable polymer resin may be selected from the group consisting of a polystyrene resin having the ion exchange group, a polysulfone, a polyisocyanate (PES), a polyphenylene oxide (PPO), a polyetheretherketone (PEEK), a polyamide, , Polyimide, polyether, polyethylene, polytetrafluoroethylene, polyglycidyl methacrylate, and the like, but is not limited thereto.

The ion selective layer may be formed by a mixture of the ion exchange resin powder and the binder described above. In this case, examples of the coating method include, but are not limited to, extrusion melt coating, calendering coating, spray coating, dip coating, knife casting, doctor blade, spin coating and the like. The thickness of the coating of the present invention is preferably in the range of 2 to 1,000 μm, but preferably in the range of 10 to 100 μm, in order to improve the desalination efficiency while reducing the electrical resistance of the electrode.

In the mixture of the ion exchange resin powder and the binder, the binder is a polymer material having a low glass transition temperature and stable at room temperature and water. The binder is uniformly mixed with the ion exchange resin powder and can form a coating layer. If possible, a polymer material can be used. More specifically, any one or a mixture of two or more selected from linear low density polyethylene (LLDPE), low density polyethylene (LDPE), polyethylene (PE), ethylene vinyl acetate (EVA), polyolefin, polyamide, polyester and polyurethane But is not limited thereto. In the preparation of the mixture of the ion exchange resin powder and the binder, the composition of the ion exchange resin powder is preferably 20 to 80% by weight, more preferably 40 to 60% by weight. If the composition is less than 20% by weight or more than 80% by weight, the electric resistance may be high, so that the adsorption characteristics of the ions may deteriorate or the flowability may be deteriorated, so that the melt coating or the calibration coating may not be easy.

It is preferable that the ion exchange resin powder is 60 to 40 parts by weight based on 40 to 60 parts by weight of the polymeric binder material to make a charge storage type desalting electrode having excellent ion absorption / desorption properties. In the case of calendering, it is recommended to make a dough mass and cut it into a certain size and make it into a pellet.

The kneading step of uniformly mixing the ion-exchange resin powder with a binder to knead a kneaded mass is performed by kneading the ion-exchange resin powder and an ion-exchange polymer solution using a pressure dispersion kneader, The kneading temperature and time may be varied depending on the type of the exchange polymer solution. At this time, after kneading at room temperature for about 2 hours, the temperature of the kneader is made to be higher than the softening point of the ion-exchange polymer. If the temperature is too low, the viscosity of the polymer becomes high and mixing becomes difficult. More preferably 20 ° C or higher than the softening point. At this time, if the heating temperature is too high, the kneading mass for the galvanizing process is not well formed by the decomposition of the binder, and if it is too low, the kneading time becomes long.

The kneader is preferably a type having a stirring blade or a roll kneader, but is not limited thereto as long as it can be uniformly kneaded. The amount of the feedstock to be added to the kneading machine is preferably 10 vol% or more, more preferably 15 to 50 vol%, of the volume of the mixer. The kneading time is preferably from 5 minutes to 5 hours, more preferably from 30 to 120 minutes until the time when the viscosity changes. The obtained kneaded product may be used as it is for extrusion coating or calendering. Preferably, the kneaded product is cut to a predetermined size so as to be easily handled, and the molding method is not limited as long as the shape is maintained.

 The film of the ion exchange resin powder and the polyolefin binder kneaded product of the present invention can be formed by a conventionally known melt extrusion method. Examples of the melt extrusion method include a T-die casting method and an inflation method, but a T-die casting method is preferable in order to form an ion selective layer of a charge storage type desalting electrode. As a device for melting the ion exchange resin powder and the polyolefin binder kneaded material, a commonly used extruder may be used, and a single-screw extruder or a multi-screw extruder may be used. The extruder may have one or more vents, and the gas may be removed from the solution of the ion exchange resin powder and the olefin binder mixture by reducing the pressure of the vent. Further, a wire mesh filter or sintering filter may be provided at the front end or the downstream side of the extruder, if necessary. The die may be a T-die, a coat hanger die, a fish tail die, a stock plate die, or the like. The extrusion temperature is preferably 100 to 300 ° C, more preferably 120 to 180 ° C, and particularly preferably 120 to 150 ° C. When the extrusion temperature is in the above range, the ion-selective layer of the obtained electrostatic desalination electrode has excellent balance of density, adhesion, adsorption / desorption characteristics, and the like. The air gap (the distance from when the molten coating layer is discharged from the die to contact with the cooling roll) is preferably 0.1 to 100 mm, more preferably 1 to 50 mm, and still more preferably 3 to 30 mm, It is not. When the air gap is in the above range, the orientation relaxation deviations due to the heat of the resin during the slow cooling process between the air gaps (influences of the ambient environment of the air gap, The effect of the difference) can be suppressed to be small, and further, it is possible to suppress an abrupt increase in the film thickness of the ion selective layer end due to the neck phosphorus.

The method of cooling the molten mixture of the ion-exchange resin powder and the olefin binder mixture extruded from the die may be a conventionally known method and is generally cooled with a cooling roll. The number of the cooling rolls may be two or more depending on the discharge amount of the molten material or the drawing speed of the molten material. Preferably, the plurality of cooling rolls are used to cool both surfaces of the electrode coated with the molten material therebetween. Since the polyester used in the present invention is a substantially amorphous resin, the temperature of the cooling roll can be set to a wide range. It is preferable that the temperature of the cooling roll is in the range of the glass transition temperature of the polyester-30 ° C to the glass transition temperature of the polyester + 30 ° C. The drawing speed is preferably from 0.2 to 100 m / min, more preferably from 0.5 to 95 m / min, and still more preferably from 1 to 90 m / min, although it varies depending on the apparatus such as the extruded amount of the molten metal or the width of the die. It is not. When the draw speed is in the above range, an ion selective layer having a desired thickness can be obtained. It is preferable to adjust the rotation speed of the cooling roll, the pinch roll, the winding roll, and the like so as not to be substantially stretched.

An ion-exchange sheet can be formed by calendaring the ion-exchange resin powder and the polyolefin binder kneaded material to form an ion selective layer by roll pressing at a temperature lower than the melting temperature of the polyolefin by 20 ° C. During the calendering, the surface temperature of the roll is determined according to the type of the binder, but preferably the melting temperature is higher than the glass transition temperature of the binder. When the temperature of the roll surface of the calender exceeds the melting temperature, the softening of the resin becomes active, the sheet on the roll surface becomes sticky, and the tension is weakened during the roll production, so that the sheet is cut. . On the other hand, when the roll surface temperature of the caliper is lower than the glass transition temperature, the resin is not softened and the surface of the sheet becomes uneven, making it difficult to produce a sheet having a uniform thickness.

In the present invention, the ion selective layer can form a flow path pattern after or simultaneously with formation. That is, as one example, a method for manufacturing a storage type desalination electrode according to the present invention includes the steps of applying a slurry containing a polymer solution and an electrode active material to a non-conductive porous support, calendering the slurry, The method further comprises a step of forming an ion selective layer on the electrode manufactured by pressing on the porous porous support and patterning the flow path thereby to fabricate a storage desalination electrode capable of easily fabricating a module by laminating it without the need of a separate spacer .

A method of patterning a channel on the storage type desalination electrode can form a channel by a printing method such as a printing method or a lithography method, - A flow path can be formed by using a die, and a flow path pattern is formed on a cooling roll of melted compression or calendered roll to form a flow path pattern on the storage desalination electrode. As another method of forming the flow path pattern, when the electrode is completely dried, that is, when the ion exchange solution is coated, that is, when the electrode is slightly tacky, the spacer is continuously blown onto the electrode roll and dried, It is also possible to produce an integral type electrolytic desalination electrode having a pattern.

    As another method for forming the flow path pattern, a method may be used in which a material is coated on the patterned dense portion on the storage type desalting electrode, or after forming a flow path pattern by curing or the like. As a non-limiting example of the material capable of patterning the flow path on the storage desalination composite electrode according to the present invention, any one or two or more of organic / inorganic hardeners, polymeric hardeners, It is not. As an example of a specific method of patterning using these materials, screening printing will be described as follows. This is a method of putting a silk cloth or other screen on a frame and pressing the screen image of a portion other than the image by a manual operation or a method of a photographic principle, and extruding the ink by screen printing with a squeegee. Lay the netting made of silk, nylon, deadron fiber or stainless steel into the frame, and fix the four corners tightly. Subsequently, a valve is formed on the mesh to form a flow path by forming a printing frame so that only a flow pattern or a coating pattern can be printed or coated.

When a flow path is formed by using a T-die having a flow path pattern in the melt extrusion coating of the ion exchange resin powder and the olefin binder mixture, the shape of the T-die to form a concave surface and a convex surface in the coating layer To form a stripe flow path by controlling the thickness of the coating layer and to form a flow path by forming a flow path pattern on a melt compression cooling roll and a calender roll to form a flow path by compressing the ion selective coating layer, Do not.

In addition, the pattern of the flow path can change the direction of the flow and enlarge the length of the flow path or adjust the flow path according to the flow rate. The flow path can be formed into various shapes such as combs, wavy patterns, stripes, grid patterns, and dot patterns, and the flow path is not limited thereto. It may also be formed in various shapes such as triangular, semi-elliptical, semicircular, trapezoidal, square, conical, and cylindrical shapes depending on the convex shape of the channel, but is not limited thereto.

The size and the shape of the flow path formed in the electrode according to the present invention are not limited within the scope of achieving the object of the present invention. However, the depth of the flow path is preferably in the range of 5 to 300 mu m, more preferably in the range of 30 to 100 mu m, When the depth is less than 5 탆, if the positive electrode and the negative electrode are stacked, the distance between the positive electrode and the negative electrode is too short to allow the fluid to flow, which may cause high pressure or frequent clogging. The ion-selective layer can not be formed in the concave portion of the electrode, so that the ions adsorbed during the regeneration are adsorbed on the opposite electrode to lower the removal efficiency, and the electrode adsorption layer may be exposed, resulting in electrode damage due to the side reaction.

The width of the flow path is preferably in the range of 10 to 5,000 mu m, more preferably 50 to 200 mu m, and when the flow path width is 10 mu m or less, the width of the flow path is too narrow, The pressure may be lowered. However, since the convex portions are overlapped on the concave portion of the flow path, it is difficult to form a uniform flow path.

Hereinafter, a CDI composite electrode utilizing a non-conductive porous support according to an embodiment of the present invention will be described with reference to the drawings.

3, a CDI composite electrode utilizing a non-conductive porous support according to an embodiment of the present invention includes a cation-selective adsorption electrode layer 102 and an anion (not shown) before and after one non-conductive porous support 101, Selective electrode layer 103 and the anion-selective adsorption electrode layer 103 at the same time as the storage-type desalination electrode 100 provided with the flow path patterns 104 and 105, One or more sheets are stacked so as to face each other. The plurality of stacked electrode units 100 may be wound in a roll shape with a predetermined pressure to allow water to pass through the porous tube 110. At this time, the woven fabric or the nonwoven fabric 120 can be used to fix the roll shape.

As shown in FIG. 4, one of the electrodes wound in a roll shape (see FIG. 5) has no holes and is brought into close contact with the module case to prevent an O-ring 131 from leaking out. (See FIG. 5) having a lid 130 provided with a lid 130 having a lid 130, and the other of which has a hole 142 through which water out of the porous tube can be discharged out, And a lid 140 provided with an O-ring 141 for the O-rings. As shown in FIG. 5, the electrodes and the lids 130 and 140 wound in the form of rolls are molded with an epoxy or urethane adhesive to form a laminated storage type desalination electrode The roll 300 can be formed.

The laminated battery separator electrode roll 300 can be assembled into the cylindrical module case 500 (see FIG. 7).

7, the module case 500 includes a channel 540 and a positive electrode 530 that include a negative electrode 531 on the inner side and can discharge treated water or concentrated water to the center, A case lid 550, an inlet 510 and a water outlet 520 are provided. At this time, electricity can be applied to the negative electrode 531 and the positive electrode 530.

The module case 500 and the module case lid 550 are combined so that the raw water and the process water are not mixed by the O-rings 131 and 141 Compartment is possible. Thus, a CDI composite electrode utilizing the non-conductive porous support according to an embodiment of the present invention can be formed so that fluid can flow in one direction inward from the outside of the laminated charge removing electrode roll 300.

Hereinafter, the CDI (Capacitive deionization) composite electrode, the cell for a bipolar electrode and the module and the method for manufacturing the same will be described in detail.

The following Production Example 1 of the present invention describes a carbon electrode on both sides of which a slurry containing a polymer solution and an electrode active material is applied on a non-woven fabric, which is a non-conductive nonporous porous support, and a method for producing the same.

In the following Production Examples 2 to 4 of the present invention, a cation exchange solution or an anion exchange solution or a cation exchange solution and an anion exchange solution are coated on a nonwoven fabric which is a nonporous porous support, and then a slurry containing a polymer solution and an electrode active material is applied Carbon electrode and a method for producing the same.

In Production Example 5 and Production Example 6 of the present invention, the carbon electrode made in Preparation Example 3 is exemplified by an ion selective layer, a cation exchange membrane on one side, and a storage type desalination electrode in which anion exchange membrane is attached on the other side.

In the following Production Example 7 of the present invention, the carbon electrode prepared in Preparation Example 3 was applied to the ion-selective layer, one of the cation exchange resin powder and the polyolefin-based binder mixture and the other was coated with the anion exchange resin powder and the polyolefin- Described below is a storage type desalination electrode, and the following Production Example 8 describes a storage type desalination electrode in which a flow path pattern is formed in the storage desalination electrode of Production Example 7 in which an ion exchange resin powder and a polyolefin type binder mixture are applied .

Comparative Example 1 is a comparative example for demonstrating the effects of the above production examples. In Comparative Example 1, a carbon electrode coated with a slurry containing a polymer solution and an electrode active material on a graphite current collector was charged with a cation exchange solution Comparative Example 2 is for evaluating the desalination efficiency by preparing a capacitively desalting electrode in which an anion exchange solution is coated on a carbon electrode coated with a slurry containing a polymer solution and an electrode active material on a graphite current collector .

The following Examples 1 and 2 illustrate the results of conducting desalination experiments using a cell for cathodic electrolytic desalting which comprises a cathode or a cathode prepared according to the [Preparation Example] and the [Comparative Example].

It is to be understood that the present invention is not limited to the above-described embodiments and examples, but is merely an example of the present invention.

[Production Example 1]

Electrode fabrication on both sides of a slurry containing a polymer solution and an electrode active material on a nonwoven fabric of non-conductive porous support

1.2 g of polyvinylidene diprolide (PVdF, Aldrich, Mw = 370,000) and 40 g of dimethylacetamide were mixed to prepare a polymer solution. To the polymer solution, activated carbon powder (P-60, Surface area = 1600 m 2 / g) were mixed to prepare an electrode slurry.

The prepared slurry was coated on a nonwoven fabric (thickness: 80 탆, PP, Hyosung Corp.) as a nonporous porous support with a doctor blade so that the coating layer had a thickness of 200 탆 and then dried at 70 캜 for 30 minutes Dried and coated on the backside with a Doctor blade to a coating layer thickness of 200 μm and dried at 70 ° C. for 30 minutes to prepare a carbon electrode having an active layer.

[Production Example 2]

Preparation of an electrode coated with a slurry containing a polymer solution and an electrode active material after coating a non-woven fabric having a non-conductive porous support with a cation exchange solution

1.2 g of polyvinylidene diprolide (PVdF, Aldrich, Mw = 370,000) and 40 g of dimethylacetamide were mixed to prepare a polymer solution. To the polymer solution, activated carbon powder (P-60, Surface area = 1600 m 2 / g) were mixed to prepare an electrode slurry.

The cation exchange solution was prepared by mixing 1.0 g of polystyrene (Mw = 270,000 Aldrich, cation exchange capacity = 1.5 meq / g) having a cation exchanger prepared through a sulfonation reaction and 20 g of dimethylacetamide (DMAc) And a non-woven fabric (thickness: 80 탆, PP, Hyosung Corporation) as a non-conductive porous support was dip-coated on the cation exchange solution and dried. The slurry thus prepared was applied to a nonwoven fabric Coated on one side with a doctor blade to a thickness of 200 μm, dried at 70 ° C. for 30 minutes, coated on the back side with a doctor blade to a coating layer thickness of 200 μm, and then coated with a doctor blade Lt; 0 > C for 30 minutes to prepare a carbon electrode having an active layer.

[Production Example 3]

Preparation of an electrode coated with a slurry containing a polymer solution and an electrode active material after coating an anion exchange solution on a nonwoven fabric having a non-conductive porous support

1.2 g of polyvinylidene diprolide (PVdF, Aldrich, Mw = 370,000) and 40 g of dimethylacetamide were mixed to prepare a polymer solution. To the polymer solution, activated carbon powder (P-60, Surface area = 1600 m 2 / g) were mixed to prepare an electrode slurry.

The anion exchange solution was prepared by mixing 1.0 g of polyether sulfone (Victrex, Mw = 80,000, anion exchange capacity = 1.2 meq / g) having an anion exchanger prepared through amination and 20 g of dimethylacetamide to prepare a polymer solution The non-woven fabric (thickness: 80 탆, PP, Hyosung Co.) as a non-conductive porous support was dip-coated on the anion exchange solution and dried. The prepared slurry was coated on a nonwoven fabric coated with an anion- Coated on one side with a doctor blade to a thickness of 200 탆, dried at 70 캜 for 30 minutes, coated on the back side with a doctor blade to a coating layer thickness of 200 탆, And dried for 30 minutes to prepare a carbon electrode having an active layer.

[Production Example 4]

Preparation of an electrode coated with a slurry containing a polymer solution and an electrode active material by coating a cation exchange solution and an anion exchange solution on a nonwoven fabric having a non-conductive porous support

1.2 g of polyvinylidene diprolide (PVdF, Aldrich, Mw = 370,000) and 40 g of dimethylacetamide were mixed to prepare a polymer solution. To the polymer solution, activated carbon powder (P-60, Surface area = 1600 m 2 / g) were mixed to prepare an electrode slurry.

Non-woven fabric (thickness: 80 탆, PP, Hyosung Co.) as a non-conductive porous support was dip-coated on the cation exchange solution of the above-mentioned [Preparation Example 2] and dried to prepare an anion exchange solution of [Preparation Example 3] The surface of the electrode slurry was coated with a cation exchange solution and a non-woven fabric coated with an anion exchange solution so as to have a coating layer thickness of 200 mu m on the surface of a doctor blade Dried at 70 ° C for 30 minutes, coated on the backside with a doctor blade to a coating layer thickness of 200 μm, and dried at 70 ° C for 30 minutes to prepare a carbon electrode having an active layer.

[Production Example 5]

The ion-selective layer used was an ion-exchange membrane,

In order to form an ion selective layer on the carbon electrodes of Production Examples 1 to 4, a cation exchange membrane (ASTOM Corp. CMX) was attached to one surface and an anion exchange membrane (AMX, ASTOM Corp.) was attached to the other surface. / min to prepare a charge storage type desalting electrode having an ion selective layer. (See Fig. 1)

[Production Example 6]

Ion-selective layer coated with ion exchange solution

In order to form an ion selective layer on the carbon electrode of [Manufacturing Example 3], the cation exchange solution of [Preparation Example 2] was coated on one side, dried at 70 ° C for 2 hours, Was coated and dried at 70 ° C for 2 hours to prepare a storage desalting electrode having an ion selective layer.

[Production Example 7]

Ion-selective layer was prepared by applying ion-exchange resin powder and a polyolefin-based binder mixture to a charge-

The cation exchange resin (Trilite CMP28, Samyang Corp.) and the anion exchange resin (Trilite AMP28, Samyang Corp.) were milled at 1700 rpm using an air jet mill (Model: NETSCH-CONDUX, Netsch) Mu m) and 2.0 mu m (maximum 5.5 mu m). The thus prepared cation exchange resin powder or anion exchange resin powder was mixed so as to have a linear low density polyethylene (LLDPE Lotte Chemical U8835) in an amount of 52 wt% and 48 wt%, respectively, relative to 100 wt% of the mixture, Korea M-Tech), rotated at 25 RPM for 1 hour, and sufficiently kneaded at 30 RPM for 1 hour to prepare uniform composition of cation exchange resin powder and linear low density polyethylene, uniform composition of anion exchange resin powder and linear low density polyethylene.

On both sides of the carbon electrode of [Manufacturing Example 3], the above-described two compositions were used to prepare a storage type desalination electrode in which different ion selective layers were formed on each surface. The layer was a leaf disk and a single-screw extruder with a vacuum vent (screw diameter of 32 mm) equipped with a coat hanger type T die having a width of 150 mm, a flat cooling compressing roll (Extruder cylinder temperature: 120 ° C, T-die temperature: 120 ° C, flat cooling roll temperature: 60 to 60 ° C) on a carbon electrode, 65 deg. C, a T-die lip opening of 0.1 mm, an air gap of 20 mm, and a discharge rate of 3 kg / h.

[Production Example 8]

The ion-selective layer and a channel-type desalination electrode

Except that a cold compression roll having a uniform flow pattern having a width of 70 mu m, a height of 40 mu m, and an interval of 200 mu m was used in place of the above-mentioned cooling roll of the above-mentioned production example 7, A cationic ion selective electrode having a stripe pattern was produced.

[Comparative Example 1]

1.2 g of polyvinylidene diprolide (PVdF, Aldrich, Mw = 370,000) and 40 g of dimethylacetamide were mixed to prepare a polymer solution. To the polymer solution, activated carbon powder (P-60, Surface area = 1600 m 2 / g) were mixed to prepare an electrode slurry.

The prepared slurry was coated on a conductive graphite sheet (130 占 퐉 thick, Dongfang Carbon Co., Ltd., Cat. No. F02511C) with a doctor blade so that the coating layer had a thickness of 200 占 퐉 and then dried at 70 占 폚 Dried for 30 minutes, coated on the backside with a doctor blade to a coating layer thickness of 200 μm, and dried at 70 ° C. for 30 minutes to prepare a carbon electrode having an active layer.

The cation exchange solution was prepared by mixing 1.0 g of polystyrene (Mw = 270,000, Aldrich, cation exchange capacity = 1.5 meq / g) having a cation exchanger prepared through a sulfonation reaction and 20 g of dimethylacetamide (DMAc) Solution, coating the carbon electrode with a cation exchange solution, and drying it at 70 ° C for 30 minutes to prepare a cathodic desalting electrode having cation selectivity and used as a cathode.

[Comparative Example 2]

1.2 g of polyvinylidene diprolide (PVdF, Aldrich, Mw = 370,000) and 40 g of dimethylacetamide were mixed to prepare a polymer solution. To the polymer solution, activated carbon powder (P-60, Surface area = 1600 m 2 / g) were mixed to prepare an electrode slurry.

The prepared slurry was coated on a conductive graphite sheet (130 占 퐉 thick, Dongfang Carbon Co., Ltd., Cat. No. F02511C) with a doctor blade so that the coating layer had a thickness of 200 占 퐉 and then dried at 70 占 폚 Dried for 30 minutes, coated on the backside with a doctor blade to a coating layer thickness of 200 μm, and dried at 70 ° C. for 30 minutes to prepare a carbon electrode having an active layer.

The anion exchange solution was prepared by mixing 1.0 g of polyether sulfone (anion exchange capacity = 1.2 meq / g) having an anion exchanger prepared through amination and 20 g of dimethylacetamide to prepare a polymer solution, Exchange solution was coated and dried at 70 ° C for 30 minutes to prepare a storage type desalting electrode having anion selectivity and used as a positive electrode.

[Examples 1 to 4]

Four kinds of ion-selective storage desalination composite electrodes prepared by using the carbon electrode of Production Example 1, the carbon electrode of Production Example 2, the carbon electrode of Production Example 3, and the carbon electrode of Production Example 4 were used in [Production Example 5] After cutting to 10 cm 2 x 10 cm, a 1 cm hole was made in the center so that the solution could pass from the slope of the electrode through the channel or spacer to the center.

[Comparative Example 1] The cation-selective layer of the negative electrode and the negative electrode prepared in [Preparation Example 5] were opposed to each other. [Comparative Example 2] The anion-selective layer of the positive electrode and the cation-exchange membrane of [Preparation Example 5] Three layers were laminated to prepare a capacitor type desalination composite electrode, followed by lamination of external application current collector electrodes to form a composite desalting electrode cell. An acrylic plate having a size of 15 x 15 cm < 2 > was placed on the outside of the cathode of [Comparative Example 1] and the anode of [Comparative Example 2], and fixed with bolts to constitute a single cell for depolarization for storage of electricity [Fig. 2] Having a flow pattern requires no extra space in forming the cell, but a cell can be formed by adding "nylon 6, 100 mesh" between the electrodes to give a flow path without a flow pattern.

The single cell for the depolarization of the above-mentioned capacitive desalting was the same as in Example 1, Example 2 in Production Example 2, Example 3 in Production Example 3, and Carbon Electrode Was used as Example 4.

A 250 mg / L NaCl solution was supplied at a rate of 60 mL / min while applying an electrode potential constantly at 3.0 V to the collector electrode. The total dissolved solids (TDS) of the effluent was measured and the desalting efficiency was analyzed. After the adsorption for 3 minutes, the electrode potential was operated for 1 minute by short circuit and 50 seconds by reversing the reverse potential for 10 seconds.

The results of cell desalting experiments prepared in [Example 1] are shown in [Table 1].

[Production Example 4] (79.0? / Cm 2) [Manufacturing Example 1]> [Production Example 3] (1.5? / Cm 2)> [Production Example 2] (10.2? / Cm 2) The results show the salt removal efficiency of a single cell for a combined complex desalinization cell, which was fabricated using a composite electrode for a desalting membrane manufactured using carbon electrodes that were different from each other. This result is considered to be the highest in the case of [Preparation Example 1] because the electrode active material layer is formed directly on the porous nonwoven fabric without the ionic resin layer and the electrical resistance is the lowest in the aqueous solution. In addition, the salt removal efficiency of the single cell for a cathode for depolarization using the carbon electrode of [Manufacturing Example 4] is considered to be low because the support nonwoven fabric is coated with a cation and anion-selective solution, do. However, it can be seen that the salt removal efficiency as a whole is 70% or more, which is very excellent.

division Example 1 Example 2 Example 3 Example 4 Salt Removal Efficiency (%) 81.7 81.1 81.3 75.3

[Example 2]

Using the carbon electrode of [Manufacturing Example 3], a charge storage type desalting electrode was manufactured by the method of [Manufacturing Example 5], [Manufacturing Example 6], [Manufacturing Example 7], and [Manufacturing Example 8] A single cell for desalting was prepared by the same method as in Example 1 to evaluate the salt removal efficiency. The results are shown in Table 2. In the case of the preparation by the method of Production Example 5 above, the preparation by the method of Example 5, Production Example 6 was referred to as Example 6, and the production by the method of Production Example 7 was referred to as Example 8.

division Example 5 Example 6 Example 7 Example 8 Salt Removal Efficiency (%) 81.3 85.6 80.4 86.9

As shown in Table 2, it can be seen that Example 6 exhibits the best desalting efficiency and Example 7 is somewhat low, but all of them have an excellent salt removal efficiency of 80% or more. In the case of Example 6, the salt removal efficiency is considered to be highest because the contact resistance between the interface and the thickness of the ion selective layer is thin and the membrane resistance is low by coating the ion exchange solution. Example 7 shows that the ion exchange resin powder and the linear It is believed that the salt removal efficiency is lowered because of the high resistance of the ion selective layer coated with a mixture with a low density polyethylene binder. However, Example 8 in which a flow path pattern was formed after coating with a material having the same composition as in Example 7 shows higher salt removal efficiency.

[Example 3]

[Comparative Example 1] A cation-selective layer of the negative electrode and an anion-selective layer of the anion-selective layer prepared in [Preparation Example 6] were used in the same manner as in [Production Example 6] [Comparative Example 2] Anion-selective layer of the positive electrode and the anion-selective layer of the positive electrode of the [Preparation Example 6] were laminated successively so that the cation-selective layer and the anion- Nine sheets were laminated so that the cation exchange membranes of [Preparation Example 6] were opposed to each other to constitute a composite biodegradable cell for desalting.

Using this, a 250 mg / L NaCl solution was supplied at a rate of 240 mL / min while the electrode potential was constantly applied at 12.0 V in the same manner as in [Example 1]. The total dissolved solids (TDS) of the effluent was measured to be 90.1%.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

101: non-conductive porous support 102: cation-selective adsorption electrode layer
103: anion-selective adsorption electrode layer 104, 105: flow path pattern
110: Porous tube 120: Woven or nonwoven fabric
130, 140: Lid 131, 141: O-ring
142: hole 300: capacitive desalination electrode roll
500: Module case 510: Inlet port 520: Outlet
530: positive electrode 531 negative electrode 540:
550: Module case lid

Claims (10)

At least one charge storage type desalting electrode in which a cationic selective coating layer is formed on one surface of the non-conductive porous substrate on which the electrode material layer is formed and an anion selective coating layer is formed on the other surface thereof, A composite electrolytic desalination composite electrode fabricated to have at least two structures.
The method according to claim 1,
Wherein the ionic selective layer has a channel pattern or a diaphragm formed on the ion selective layer to have a flow path pattern in the ionic selective layer.
The method of claim 1, wherein
Wherein the non-conductive porous support is any one selected from a porous polymer sheet, a thin film, a porous ceramic, a woven fabric, a nonwoven fabric, a porous polymer film, and a porous polymer foam.
The non-conductive porous support on which the electrode material layer is formed is provided with at least one or more storage desalination electrodes having a cation-selective coating layer formed on one surface thereof and an anion-selective coating layer formed on the other surface thereof. And at least two externally applied current collector electrodes are laminated on both sides of the electrodeposited composite desalination composite electrode, and the electrodeposition type electrodeposited composite electrode is formed by applying a positive electrode The desalination composite electrode cell is operated as a condenser.
5. The method of claim 4,
Wherein the composite desalination composite electrode is wound in a roll and operated in the form of a bipolar electrode at different application potentials depending on the number of windings and the number of windings wound around the inner and outer collector electrodes of the roll.
5. The method of claim 4,
Wherein the composite desalination composite electrode is fabricated by laminating two or more of the composite desalination composite electrodes.
The method of claim 4, wherein
Wherein the ionic selectivity layer has a flow path pattern in the ionic selectivity layer.
Applying a slurry containing an electrode active material and a binder on both sides of a non-conductive porous support or calendering the slurry to form a sheet, and then pressing the non-conductive porous support onto the non-conductive porous support to form an electrode material layer;
Forming a different ion selective layer on each side of the electrode material layer using an ion exchange membrane, an ion exchange solution coating, and an ion exchange resin powder slurry to produce a storage desalination electrode;
Wherein the ion selective layer of the storage type desalination electrode is laminated so as to include at least two structures laminated so that at least one ion selective layer is different from each other.
The method of claim 8, wherein
And forming a flow path pattern at the same time as or after the ion selective layer formation step.
The method of claim 8, wherein
Wherein the flow path pattern is formed by forming a diaphragm on an ion selective layer.

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