WO2018048180A1 - Electrochemical cell including channel-type flow electrode unit structure - Google Patents

Abstract

The present invention relates to an electrochemical cell including a channel-type flow electrode unit. A channel-type flow electrode unit structure including at least two channel-type flow electrode units according to the present invention has an electrode capacity expanded to be suitable for use in large-scale plants for electricity generation, energy storage, desalting and the like, includes a reduced number of components, which bring about a significant reduction in production cost and installation space, and finds applications in capacitive flow-electrode devices and/or redox flow-electrode devices and even in any device that uses the migration of ions or protons in electricity generation, energy storage, or desalting.

Description

Electrochemical Cells with Channel Flow Electrode Unit Structures

The present invention relates to an electrochemical cell having a channel flow electrode unit structure.

Recently, countries around the world are making efforts to develop clean alternative energy to solve the air pollution and global warming problem. Especially, recently, marine power generation using electrolyte concentration difference is emerging as a new topic.

In addition, the development of large-capacity power storage technology that can store electric energy generated through various alternative energy is emerging as the core of the future green industry foundation. Most of these future power storage technologies, such as Li-ion battery method or super capacitor using the adsorption (charge) and desorption (discharge) principle of ions, the world around the world to improve the charge and discharge characteristics of the material parts Many R & D efforts are underway for high efficiency compactness and high capacity.

Recently, the same principle is used in water treatment fields such as water purification or wastewater treatment and seawater desalination in preparation for water pollution and water shortage, and the water treatment is performed at a much lower energy cost than conventional evaporation or reverse osmosis (RO) methods. A possible process is being developed, namely Capacitive Deionization (CDI).

The biggest problem in the power storage and water treatment system using the same principle is the efficiency reduction and the high cost of the device at the time of large capacity. That is, the large area of the electrode for scale-up, the nonuniformity of the electric field distribution in the electrode, the limited amount of active material of the thin film electrode coated on the current collector, the contact area between the active material and the electrolyte by the binder during the coating process, and the charge and discharge efficiency decrease, etc. As a result, a large number of unit cell stacks are required, and accordingly, the high cost of the device, and in particular, in the case of CDI (Capacitive Deionization) process, increases in operating costs due to pressure loss of the water (electrolyte) flow in the stack are pointed out as a problem. .

In order to solve the above problems, the present applicant has developed a capacitive electrode flow device (Korean Patent No. 10-1233295), and developed it (Korea Patent No. 10-1318331), energy storage (Korean Patent No. 10-1210525) ), Water treatment (Korean Patent No. 10-1221562) and the like.

Although it was possible to supply the electrode having infinite electrode capacity to the unit cell as the flow electrode proposed in the above invention, the prior art such as a redox flow battery including devices using the flow electrode increases the electrode area to increase the capacity. In this case, in the prior art, the unit components including the positive electrode current collector and the negative electrode current collector are infinitely stacked.

As a result, the stacking of the unit cells not only greatly increases the volume, but also has a large problem that the number of parts increases due to the large flow path, thereby increasing the cost for manufacturing the device.

An object of the present invention is to configure the flow electrode unit as a channel defined by a liquid-permeable wall or separator in order to reduce the device cost and increase the capacity while applying to a large-scale plant such as power generation, energy storage, and desalination. The present invention provides a flow electrode structure in which a plurality of channel type flow electrode units are arranged in a high density such as a lattice, while a skeleton is formed of a support for supplying an electrolyte.

A first aspect of the invention is a channel flow electrode unit defined by a liquid penetrating wall, wherein an ion exchange current collector that passes through cations or anions and is electrically conductive is located on the inner surface of the channel wall and has a channel inlet. An electrode flow path through which an electrode active material-containing fluid introduced from the outlet and discharged to a channel outlet flows is spaced apart from the wall through an ion exchange current collector.

A second aspect of the invention is a channel flow electrode unit defined by a liquid penetrating wall, wherein the ion exchange material passes through the channeled wall inner surface, outer surface, wall itself, or a combination thereof to allow passage of cations or anions. The electrode flow path is applied to the inner surface of the channel-like wall to which the ion exchange material is applied, and the electrode flow path through which the electrode active material-containing fluid flowing from the channel inlet and discharged to the channel outlet flows. It provides a channel flow electrode unit, characterized in that spaced from the wall.

The third aspect of the present invention provides a channel flow electrode structure having two or more channel flow electrode units of the first or second aspect.

A fourth aspect of the present invention provides a method for producing a channel flow electrode unit of the first or second aspect, comprising the steps of: preparing a channel defined by a liquid-permeable wall; A second step of applying an ion exchange material through which a cation or anion passes through the inner surface, the outer surface, the wall itself, or a combination thereof; And a third step of applying the porous current collector to the inner surface of the channel-shaped wall to which the ion exchange material is applied.

A fifth aspect of the present invention provides a method for producing a channel flow electrode unit of the first aspect, comprising: preparing a channel defined by a liquid-permeable wall; A second step of applying the porous current collector to the inner surface of the channel-shaped wall; And a third step of applying an ion exchange membrane through which a cation or anion passes to the inner surface of the channel wall to which the porous current collector is applied.

A sixth aspect of the present invention is a method of manufacturing a channel flow electrode structure of the third aspect, the first step of preparing a liquid-permeable wall to form a basic skeleton having a plurality of channels in which fluid is introduced to the inlet and discharged to the outlet ; Apply the selected channel (s) to the channel-like wall inner surface with an ion exchange material through the cation, the wall itself or a combination thereof, and select the other channel (s) to the channel-wall wall with an ion exchange material passing the anions, A second step of applying to the wall itself or a combination thereof; And a third step of applying the porous current collector to an inner surface of the channel-shaped wall to which the ion exchange material is applied.

According to a seventh aspect of the present invention, there is provided a method of manufacturing a channel flow electrode structure according to the third aspect, the first step of preparing a liquid-permeable wall that forms a basic skeleton having a plurality of channels through which fluid is introduced into and discharged from the outlet. ; A second step of applying the porous current collector to the inner surface of the channel-shaped wall; Coating the selected channel (s) of the porous current collector to the inner surface of the channel-like wall with an ion exchange material through which cations pass, and passing the negative ion through other selected channel (s) of the channels to which the porous current collector is applied. It provides a method for producing a channel-type flow electrode structure characterized in that it comprises a third step of coating the inner surface of the channel-like wall with an ion exchange material.

An eighth aspect of the present invention is a channel flow anode unit defined by a liquid penetrating wall, in which a channel flow anode in which an anode ion exchange current collector passing through cations and having electrical conductivity is located on an inner surface of the channel wall. monomer; And a channel type flow cathode unit defined by the liquid penetrating wall, the channel type flow cathode unit having a negative ion ion exchange current passing through the anion and having an electrical conductivity located on an inner surface of the channel wall. An electrode flow path through which an electrode active material-containing fluid flowing from an inlet and discharged to a channel outlet flows is separated from the wall through an ion exchange current collector.

A ninth aspect of the invention is a channel flow anode unit defined by a liquid penetrating wall, wherein the ion exchange material is applied to the channel wall inner wall, outer surface, wall itself, or a combination thereof to pass cations. A channel-type flow anode unit having a porous current collector applied to an inner surface of the channel-type wall to which the ion exchange material is applied; And a channel-type flow cathode unit defined by a liquid-permeable wall, wherein an ion exchange material is applied to the inner surface of the channeled wall, the outer surface, the wall itself, or a combination thereof so as to allow anions to pass therethrough. The channel flow cathode unit is applied to the inner surface of the channel-like wall to which the ion exchange material is applied, the electrode flow path flowing through the electrode active material-containing fluid introduced from the channel inlet and discharged to the channel outlet through the porous current collector It provides a cell with a channel flow electrode characterized in that it is spaced apart from the wall.

A tenth aspect of the present invention is a membrane support for forming a basic skeleton having a plurality of channels in which fluid is introduced into the inlet and discharged to the outlet; The porous current collector is disposed on the inner wall of the channel (s) selected in the membrane support, and an anode flow path through which the positive electrode active material-containing fluid flowing from the channel inlet and discharged to the channel outlet flows from the channel-type separator support. Spaced, channel-type flow anode units; And a negative electrode flow path having a porous current collector disposed on an inner wall surface of the other channel (s) selected from the membrane support, and flowing a negative electrode active material-containing fluid introduced from the channel inlet and discharged to the channel outlet through the channel-type separator. A channel flow electrode structure is provided that includes a channel flow cathode unit spaced from a support.

An eleventh aspect of the present invention provides a capacitive electrode flow device comprising the channel-type flow electrode structure of the third or tenth aspect.

A twelfth aspect of the present invention provides a redox flow cell device, characterized in that the channel type flow electrode structure of the third or tenth aspect is provided.

Hereinafter, the present invention will be described in detail.

In the present invention, the positive electrode means a cathode, and the negative electrode means an anode. In desalting or discharging, the polarity may change.

Although the principle of action is different, the four basic components common to secondary cells such as condenser, capacitor and battery are anode, cathode, separator and electrolyte. Redox reaction is applied to battery and ion adsorption (EDL) theory is applied to capacitor.

Redox flow cells, commonly known as flow cells, are the ones in which electrolytes (including reaction catalysts) flow.

In the flowable electrode (flow-electrode) according to the present invention, the electrode active material does not flow only in the fixed container, but in-out flow of the electrode active material through the channel. In the case of a "capacitive flow electrode", an electrode active material is used that can adsorb and desorb ions.

Accordingly, the FCDI to which the channel type flow electrode cell according to the present invention can be applied may be referred to as a "capacitive flow battery" in terms of the phenomenon, but it is a cathode active material and a cathode active material among four components. The materials are simultaneously introduced from the electrode flow path inlet and discharged to the electrode flow path outlet, wherein the electrolyte may or may not flow through the flow path having the inlet / outlet.

In the present invention, the channel type flow electrode unit and the unit structure have the same meaning.

Meanwhile, referring to FIG. 1, a capacitive flow electrode device 100 that can be used in a power generation device for producing electricity from an electrolyte is described with a plate-shaped flow anode 112 at both sides of the plate-shaped electrolyte flow path 102. A plate-shaped flow cathode 114 is disposed. A plate-shaped positive electrode ion exchange current collector is disposed between the electrolyte flow path 102 and the flow anode 112, and a plate-shaped negative electrode ion exchange current collector is disposed between the electrolyte flow path 102 and the flow cathode 114. In addition, closed plates 116 and 118 for forming a flow path outside the plate-shaped flow anode 112 and the plate-shaped flow cathode 114 are disposed.

As the cathode ion exchange current collector, as shown in FIG. 1, a cathode ion exchange membrane 104 and a porous cathode plate 106 may be stacked. The anode ion exchange membrane 104 is disposed on the electrolyte flow path 102 side, and the porous cathode plate 106 is disposed on the flow anode 112 side. On the contrary, the anode ion exchange membrane 104 may be disposed on the flow anode 112 side, and the porous cathode plate 106 may be disposed on the electrolyte flow path 102 side.

In addition, as shown in FIG. 1, the cathode ion exchange current collector may be formed by overlapping the cathode ion exchange membrane 108 and the porous cathode plate 110. The cathode ion exchange membrane 108 is disposed on the electrolyte flow path 102 side, and the porous cathode plate 110 is disposed on the flow cathode 114 side. In contrast, the cathode ion exchange membrane 108 may be disposed on the flow cathode 114 side, and the porous cathode plate 110 may be disposed on the electrolyte flow path 102 side.

The plate-shaped flow positive electrode 112 is a plate-shaped flow path flowing in a slurry state in which the positive electrode active material 111 is dispersed in an electrode solution. In addition, the plate-shaped flow cathode 114 is a plate-shaped flow path flowing in a slurry state in which the negative electrode active material 113 is dispersed in the electrode solution. The plate-shaped flow anode 112 and the plate-shaped flow cathode 114 need closed plates 116 and 118 on the outside and a plate-like support on the inside to form a plate-shaped flow path.

The operating principle of the capacitive electrode flow device 100 when used as a power generation device, when the electrolyte having a cation and an anion flows into the plate-shaped electrolyte flow path 102, the cation that has passed through the plate-shaped positive electrode ion exchange current collector is the plate-shaped When the negative ions move to the flow anode 112 and pass through the cathode ion exchange current collector to the plate-shaped flow cathode 114, a potential difference is generated between the flow anode 112 and the flow cathode 114. . When the potential difference is electrically connected to the outside through the porous positive electrode plate 106 and the porous negative electrode plate 110, the capacitive electrode flow device 100 may be utilized as a power generation unit.

On the contrary, when a current flows from the outside to generate a potential difference between the porous positive electrode plate 106 and the porous negative electrode plate 110, the electrolyte flows through the electrolyte flow path 102 to the flow positive electrode 112 and the flow negative electrode 114. Forcing cations and anions to move, desalting the electrolyte.

In addition, since the charge is filled in the slurry flowing through the flow anode 112 and the flow cathode 114 at the same time, it is also possible to store the slurry to use as an electrical storage device.

The closing plates 116 and 118 may use a non-electrically conductive plate, or may use an electrically conductive metal plate. In the case of using an electrically conductive metal plate, it can be utilized as an additional current collector.

In order to reduce the device cost and take up a small space when applied to large-scale plants such as power generation, energy storage, and desalination, the present inventors apply the plate-shaped flow electrode flow path configuration shown in FIG. The flow-type flow electrode channel can be designed as a channel surrounded by a liquid-permeable wall or separator, and can provide a channel-type flow electrode structure in which a plurality of channel-type flow electrode units are arranged highly densely, such as a lattice, and a liquid-permeable wall. Or it was found that the separator can serve as a support for supplying the electrolyte while forming a basic skeleton. The present invention is based on this.

Accordingly, the present invention forms a basic skeleton having a plurality of channels into which the fluid is introduced into the outlet and discharged to the outlet as an integral liquid-permeable wall or separator, and then some or all of the defined channels are surrounded by the liquid-permeable wall or separator. It is one feature to provide a channel flow electrode structure that constitutes an electrode unit (FIG. 3). In this case, two channel-type flow electrode units adjacent to each other may share a liquid penetrating wall or a separator (FIG. 2).

In addition, the present invention is designed to assemble the channel flow electrode unit (unit) in the form of a block (Fig. 3), it is another feature to provide a channel flow electrode structure having two or more channel flow electrode units. (FIG. 4).

Furthermore, in the channel type flow electrode structure according to the present invention, unlike the capacitive flow electrode device having the plate-shaped electrode flow path shown in FIG. 1, the electrolyte may be supplied through the liquid penetrating wall of the channel type electrode unit even without a separate electrolyte flow path. It is another feature that it can therefore act as an electrochemical cell.

The present invention provides an anode / cathode / separator / electrolyte of the capacitive flow electrode device as a channel flow electrode structure according to the third or tenth aspect of the present invention. The channel flow electrode structure according to the third aspect of the present invention includes two or more channel flow electrode units according to the first or second aspect of the present invention.

The channel flow electrode unit according to the first aspect of the present invention is a channel flow electrode unit defined by a liquid penetrating wall,

An ion exchange current collector having only a cation or an anion, preferably a cation and an anion and having electrical conductivity is located on the inner surface of the channel wall,

The electrode flow path through which the electrode active material-containing fluid introduced from the channel inlet and discharged to the channel outlet flows may be spaced apart from the wall through the ion exchange current collector.

In this case, when the positive ion ion current collector having a positive electrode and passing through the cation may be a channel flow positive electrode unit, and the negative ion ion current collector having a negative ion passing through the negative electrode and having an electrical conductivity, the channel flow negative electrode It may be a monomer (Fig. 5).

In this case, the ion exchange current collector may be made of a material that is electrically conductive while transmitting only ions, and the ion exchange membrane and the porous current collector (for example, carbon, a metal material, and a conductive polymer) may be stacked. In this case, the stacking order is not important as long as it serves as an ion exchange collector.

The cation exchange membrane may be a dense membrane that prevents the flow of electrolyte liquid and selectively passes only cations, and the anion exchange membrane may be a dense membrane that prevents the flow of electrolyte liquid and selectively passes only anions. A well-known ion separation membrane can be used for a cation exchange membrane and an anion exchange membrane.

The channel flow electrode unit according to the second aspect of the present invention is a channel flow electrode unit defined by a liquid penetrating wall,

The ion exchange material is applied (e.g., coated) at the inner surface of the channeled wall, the outer surface, the wall itself or a combination thereof so as to pass only one of the cations or anions, preferably cations and anions,

The porous current collector is applied to the inner surface of the channel-shaped wall to which the ion exchange material is applied,

The electrode flow path through which the electrode active material-containing fluid introduced from the channel inlet and discharged to the channel outlet flows may be spaced apart from the wall through the porous current collector.

When an ion exchange material through which a cation is applied may be a channel flow cathode unit, and when an ion exchange material through which an anion is applied may be a channel flow cathode unit.

In the present invention, the positive electrode active material and the negative electrode active material may be different materials, but the same material may be used. In this case, the electrode active material is collectively named as the electrode active material. The cathode active material and the anode active material may be porous carbon (activated carbon, carbon fiber, carbon aerogel, carbon nanotube, etc.), graphite powder, metal oxide powder, or the like.

In addition, the electrode solution is a water-soluble electrolyte solution such as NaCl, H ₂ SO ₄ , HCl, NaOH, KOH, Na ₂ NO ₃ , propylene carbonate (Propylene Carbonate, PC), diethyl carbonate (DEC), tetrahydro It may include an organic electrolyte solution such as furan (Tetrahydrofuran, THF). In particular, it is possible to use brine containing a large amount of salt (especially NaCl) or fresh water containing a small amount of salt as the electrode solution.

The porous current collector may be a material, such as porous carbon or a conductive polymer, through which fluid can pass while electricity is passed through. The porous carbon may be made of graphite, graphene, carbon fiber, activated carbon, carbon nanotubes, and the like.

As the electrolyte, a water-soluble electrolyte solution such as NaCl, H ₂ SO ₄ , HCl, NaOH, KOH, Na ₂ NO ₃ , propylene carbonate (PC), diethyl carbonate (DEC), It may include an organic electrolyte solution such as tetrahydrofuran (THF). In particular, it is possible to use brine containing a large amount of salt (especially NaCl) or fresh water containing a small amount of salt as the electrolyte.

The liquid penetrating wall can serve as a skeletal support. The channel defined surrounded by the liquid-penetrating wall may be a polygonal column, such as a square pillar, as shown in FIG. 3, or may be a cylinder.

The liquid penetrating wall is preferably electrically insulating. The material of the liquid penetrating wall may contain zeolite, ceramic, or high molecular material. It is preferable that the electrolyte is made of a fibrous structure to facilitate movement.

In the present invention, the ion exchange membrane formed on the liquid permeable wall may be a pore filling membrane coated with a material that transmits ions to the porous support.

As illustrated in FIG. 8, the channel type flow electrode unit of the present invention is

A first step of preparing a channel defined by the liquid penetrating wall;

A second step of applying an ion exchange material passing only one of a cation or an anion, preferably a cation and an anion, to an inner surface, an outer surface, the wall itself, or a combination thereof; And

Step 3a of applying the porous current collector to the inner surface of the channel-shaped wall to which the ion exchange material is applied

It may be provided by a manufacturing method comprising a.

In addition, the channel type flow electrode unit of the present invention

Step 1b of preparing a channel defined by the liquid-penetrating wall;

A second step of applying the porous current collector to the inner surface of the channel-shaped wall; And

A third step of applying an ion exchange membrane through which only one of a cation and an anion, preferably a cation or an anion, is applied to the inner surface of the channel-type wall to which the porous current collector is applied;

It may be provided by a manufacturing method comprising a.

Meanwhile, the channel type flow electrode structure according to the third aspect of the present invention may be an assembly of the channel type flow electrode units in the form of an assembleable block. In addition, the channel flow electrode structure according to the third aspect of the present invention is formed of a liquid-permeable wall having a basic skeleton for forming a plurality of channels into which the fluid is introduced into the inlet and discharged to the outlet, and among the channels defined by the liquid-permeable wall. Some or all may be configured as a flow electrode unit.

The channel flow electrode structure according to the present invention may further include a channel electrolyte flow path. The electrolyte passage may serve to continuously supply the electrolyte. In this case, the electrolyte flow path may be surrounded by a liquid penetrating wall and may have a defined channel shape. The channel electrolyte flow path is not limited in shape and position as long as the electrolyte can be supplied adjacent to the at least one channel flow anode unit and the at least one channel flow cathode unit (empty space in FIG. 9, hatched in FIG. 10). , Black circle in Fig. 11).

If there is a separate electrolyte flow path, the liquid-penetrating wall mainly serves as a movement of the ions and the structure, the movement of the electrolyte may be mainly by the electrolyte flow path.

In the channel electrolyte flow path, the moving direction of the electrolyte and the moving direction of the fluid in the channel flow cathode unit and the channel flow cathode unit may be the same or opposite to each other.

When there is no electrolyte flow path, the channel flow electrode structure according to the present invention may be formed only by the channel flow anode unit and the channel flow cathode unit.

The electrolyte is supplied through a separate channel-like flow path, through the liquid penetrating wall, or both, and based on the channel, the electrolyte can be supplied in the longitudinal direction of the channel, in the lateral direction of the channel, or both.

The liquid-permeable wall may be partially contained in the electrolyte solution to allow the electrolyte to move naturally by gravity or capillary action, or may be flowed while the electrolyte forced by the electrolyte flow path penetrates into the liquid-permeable wall.

In the channel flow electrode structure according to the present invention, the channel flow anode unit, the channel flow cathode unit, and the channel electrolyte channel unit can be arranged in various forms according to the designer's intention, and thus supply of the flow electrode active material is continued. If desired, it can be continuously desalted / generated by infinite adsorption capacity (FIGS. 9 and 10).

For example, the channel flow anode unit and the channel flow cathode unit face each other around the channel electrolyte flow path, and at the same time, the channel flow anode unit and the channel flow cathode unit may be disposed in a diagonal direction. The channel electrolyte flow path may be arranged in a diagonal direction.

The channel flow electrode structure according to the present invention may include at least one channel flow anode unit and at least one channel flow cathode unit, and may be supplied with an electrolyte through a liquid penetrating wall to form an electrochemical cell.

In the present invention, the electrochemical includes not only a redox reaction but also a desorption reaction of ions.

In order to form the electrochemical cell, the channel flow electrode structure according to the present invention preferably has at least one relationship between the channel flow anode unit and the channel flow cathode unit adjacent to each other. The relationship between the channel flow anode unit and the channel flow cathode unit close to each other includes not only a case where the channel flow anode unit and the channel flow cathode unit are directly adjacent to each other, but also a case where the channel flow anode unit and the channel flow cathode unit are adjacent to each other.

The principle of operation of the electrochemical cell in the channeled flow electrode structure according to the invention is shown in FIGS. 5 and 6.

As shown in FIG. 5A, the same principle of operation as in FIG. 1 applies to the channel type flow electrode structure according to the present invention. However, in the channel type flow electrode structure according to the present invention, unlike the capacitive flow electrode device having the plate-shaped electric flow path shown in FIG. 1, the electrolyte may be supplied by the liquid penetrable wall of the channel type electrode unit even without a separate electrolyte flow path. And thus can act as an electrochemical cell (FIG. 7). In addition, in the channel flow electrode structure according to the present invention, since the movement of the anions and cations occurs on the entire wall of the channel-type liquid penetrating wall surrounding the electrode flow path, unlike the plate flow electrode, the movement distance of the anions and the cations in the electrode flow path is short. In addition to the high adsorption / desorption speed on the electrode active material, the charge and discharge efficiency is high, and the capacity of the flow electrode device 200 may be greatly increased.

When voltage is applied to the porous current collector, charges are formed in the positive electrode active material and the negative electrode active material flowing through the channel, so that desalination occurs as the positive and negative ions in the electrolyte are adsorbed and escaped through the membrane and the channel wall. Electricity can be collected when electricity is generated through ion adsorption or desorption from the electrode active material.

As shown in FIG. 7, the channel type flow electrode structure according to the present invention may not have a separate electrolyte flow path, and a liquid permeable wall may replace it. Therefore, there is an advantage that the size of the capacitive electrode flow device can be further reduced.

The channel flow electrode structure of the present invention

Preparing a liquid-permeable wall that forms a basic skeleton having a plurality of channels through which fluid is introduced into the inlet and discharged to the outlet;

Apply the selected channel (s) to the channel-like wall inner surface with an ion exchange material through the cation, the wall itself or a combination thereof, and select the other channel (s) to the channel-wall wall with an ion exchange material passing the anions, A second step of applying to the wall itself or a combination thereof; And

Step 3c, applying the porous current collector to the inner surface of the channel type wall to which the ion exchange material is applied

It may be provided by a manufacturing method comprising a.

In addition, the channel flow electrode structure of the present invention

Preparing a liquid-permeable wall that forms a basic skeleton having a plurality of channels through which fluid is introduced into the inlet and discharged to the outlet;

A second step of applying the porous current collector to the inner surface of the channel-shaped wall;

Coating the selected channel (s) of the porous current collector to the inner surface of the channel-like wall with an ion exchange material through which cations pass, and passing the negative ion through other selected channel (s) of the channels to which the porous current collector is applied. A third step of coating the inner surface of the channel wall with an ion exchange material;

It may be provided by a manufacturing method comprising a.

On the other hand, the cell with a channel flow electrode according to an eighth aspect of the present invention

A channel flow anode unit defined by a liquid penetrating wall, comprising: a channel flow anode unit in which an anode ion exchange current collector passing through cations and having electrical conductivity is located on an inner surface of the channel wall; And

A channel flow cathode unit defined by a liquid-permeable wall, comprising a channel flow cathode unit in which a negative ion ion current collector passing through an anion and having electrical conductivity is located on an inner surface of the channel wall,

The electrode flow path through which the electrode active material-containing fluid introduced from the channel inlet and discharged to the channel outlet flows may be spaced apart from the wall through the ion exchange current collector.

In addition, the cell with a channel flow electrode according to the ninth aspect of the present invention

A channel flow anode unit defined by a liquid-permeable wall, in which an ion exchange material is applied to the inside of the channel wall, the outer surface, the wall itself, or a combination thereof to pass cations and the porous current collector is ionized. A channel flow anode unit applied to the inner surface of the channel wall to which the exchange material is applied; And

A channel flow cathode unit defined by a liquid penetrating wall, wherein an ion exchange material is applied to the inner surface, the outer surface, the wall itself, or a combination thereof to pass an anion and the porous current collector is ionized. A channel flow cathode unit is applied to the inner surface of the channel wall to which the exchange material is applied,

The electrode flow path through which the electrode active material-containing fluid introduced from the channel inlet and discharged to the channel outlet flows may be spaced apart from the wall through the porous current collector.

A cell with a channel flow electrode according to an eighth or ninth aspect of the present invention has at least one channel flow anode unit and at least one channel flow cathode unit and is supplied with an electrolyte through a liquid penetrating wall to provide electrochemical Form a cell. In this case, the channel type flow anode unit and the channel type flow cathode unit may share adjacent walls (FIG. 7).

As shown in FIG. 12, in the redox flow electrode device 120, an anode flow path 126 and a cathode flow path 128 in which electrode solutions flow on both sides of the separator 130 are formed, and the anode flow path 126 is formed. ) And the negative electrode flow path 128 are disposed in each of the positive electrode collector 122 and the negative electrode collector 124 for collecting electricity.

The positive electrode solution 126 is circulated by the positive electrode solution tank 132 by the positive electrode pump 134, and the negative electrode solution 128 is stored in the negative electrode solution tank 136 by the negative electrode pump ( 138). The positive electrode solution and the negative electrode solution generally use an electrolyte solution containing zinc ions and bromine ions.

Accordingly, the redox reaction occurs in the positive electrode channel 126 and the negative electrode channel 128 based on the separator 130, thereby releasing or accumulating electricity.

The present invention is characterized in that the anode / cathode / separation membrane / electrolyte of the redox flow electrode device is provided as a channel flow electrode structure according to the third or tenth aspect of the present invention.

The channel flow electrode structure according to the tenth aspect of the present invention partially modifies the channel flow electrode unit according to the first or second aspect of the present invention to apply a separator instead of the liquid penetrating wall as a function of the channel skeleton support. It is.

Here, the separator is an electrically insulating membrane through which ions can pass freely, and physically separates the positive electrode and the negative electrode.

The channel flow electrode structure according to the tenth aspect of the present invention,

A separator support for forming a basic skeleton having a plurality of channels through which fluid is introduced into the inlet and discharged to the outlet;

The porous current collector is disposed on the inner wall of the channel (s) selected in the membrane support, and an anode flow path through which the positive electrode active material-containing fluid flowing from the channel inlet and discharged to the channel outlet flows from the channel-type separator support. Spaced, channel-type flow anode units; And

The porous current collector is disposed on the inner wall surface of the other channel (s) selected from the membrane support, and a cathode flow path through which the negative active material-containing fluid flowing from the channel inlet and discharged to the channel outlet flows through the porous current collector. It may comprise a channel flow cathode unit, spaced from the.

In this case, in order to operate as an electrochemical cell, the channel type flow cathode unit may be disposed adjacent to the channel type flow cathode unit.

The separator support may be in the form of a pore-filling membrane coated with a pore of the porous support with a material that selectively transmits protons to a porous support to form a structure.

The porous current collector may be disposed to abut the inner wall surface of the channel formed by the membrane support. Accordingly, the positive electrode flow path through which the positive electrode active material-containing fluid flows is spaced apart from the channel type separator support through the porous current collector, and the negative electrode flow path through which the negative electrode active material containing fluid flows is spaced apart from the channel type membrane support through the porous current collector.

In this case, although the different materials may be used for the positive electrode active material and the negative electrode active material, the same material may be used.

In addition, the channel type flow electrode structure according to the tenth aspect of the present invention may further include a channel type electrolyte flow path, and the electrolyte flow path may be a channel type defined by a separator.

As shown in FIG. 13, the redox flow electrode device 418 including the channel flow electrode structure according to the tenth aspect of the present invention includes a membrane support 402 for transmitting only protons, and the channel type membrane support. It may include a flow anode flow path 401 and the flow cathode flow path 403 formed inside the 402. As shown in FIG. 13, the channel type flow anode flow path 401 and the channel type flow cathode flow path 403 may be arranged to have a checkered pattern. As a result, redox reaction occurs in the positive electrode active material-containing fluid and the negative electrode active material-containing fluid in the channel flow anode flow channel 401 and the channel flow flow cathode flow path 403, respectively, while the proton moves through the membrane support 402. As this happens, it is charged or discharged.

The grid-type capacitive desalination cell according to one embodiment of the present invention may be operated in a batch mode as shown in FIG. 17 or in a continuous mode in which the supplied brine is desalted and drained out.

Desalting occurs mainly at the desalting site (center channel of 1 × 3 cells) between the cation and anion exchange membrane-coated channels. If the number of channels increases from three to nine, four separate sites can serve as desalination sites. That is, the volume of the entire system (3x3 cells) increased three times while the desalination site increased four times that of 1x3 cells. Thus, as cell size expands, the number of desalination sites increases dramatically, resulting in a significant increase in salt removal capacity. Moreover, in the case of lattice cells, even if the number of channels increases, the pressure increase, which is one of the problems of the series-type FCDI stack, does not occur.

According to the present invention, the channel type flow electrode structure including two or more channel type flow electrode units can reduce the number of parts while increasing the electrode capacity to be suitable for large-scale plants such as power generation, energy storage, and desalination. It can be reduced, and can be applied to capacitive flow electrode devices and / or redox flow electrode devices, and can be applied to devices for generating electricity, storing energy, and desalting electricity while ions or protons move.

1 is a schematic diagram of a plate-like capacitive flow electrode device from which the basic structure and operating principle of the present invention are derived.

2 is a schematic diagram of a channel flow electrode structure having two or more channel flow electrode units integrally formed according to one embodiment of the present invention.

3 is a schematic diagram of a channel-type flow anode unit and a channel-type flow anode unit according to one embodiment of the present invention.

4 is a schematic diagram of a channel flow electrode structure in which two or more channel flow electrode units are assembled according to one embodiment of the present invention.

5A illustrates distribution and flow of cations and anions on the electrode active material flow and the electrolyte flow in each channel when there is a separate electrolyte flow path between the channel flow anode unit and the channel flow cathode unit according to one embodiment of the present invention. It is a schematic diagram shown.

5B is a structural cross-sectional view of the channel flow electrode structure when there is a separate electrolyte flow path between the channel flow anode unit and the channel flow cathode unit according to one embodiment of the present invention.

FIG. 6 is a schematic diagram illustrating an operation principle of a channel flow electrode structure when an electrolyte flow path is disposed between the channel flow anode unit and the channel flow cathode unit according to one embodiment of the present invention.

7 is a schematic diagram illustrating the flow of an electrolyte through a liquid penetrating wall when there is no separate electrolyte flow path between the channel type flow anode unit and the channel type flow cathode unit according to one embodiment of the present invention.

FIG. 8 is a schematic view of a method of manufacturing the three channel flow electrode structure of Example 1. FIG.

9 is a layout view of a channel flow anode unit and a channel flow cathode unit in a channel flow electrode structure according to one embodiment of the present invention.

FIG. 10 is a layout view of each channel in a channel type flow electrode structure having a channel type electrolyte flow channel (indicated by hatching) according to one embodiment of the present invention.

11 is a schematic diagram of a channel flow electrode structure with an electrolyte flow path (indicated by black circles) in accordance with various embodiments of the invention.

12 is a schematic view showing the structure of a general redox flow battery.

13 is a schematic diagram of a redox flow electrode device according to an embodiment of the present invention.

FIG. 14 is a graph showing a change in current value according to a reaction time using the three-channel flow electrode structure manufactured in Example 1. FIG.

FIG. 15 is a graph showing a change in current value according to a reaction time using the nine-channel flow electrode structure manufactured in Example 2. FIG.

16 is a schematic diagram of a lattice capacitive desalination cell according to an embodiment of the present invention ((a): top view (1x3-channel cell), (b): 3x3-channel cell, (c): desalination process) .

FIG. 17 shows the configuration ((a)) and salt concentration change ((b)) of a lattice capacitive desalination cell operating in batch mode, according to one embodiment of the invention.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only intended to clearly illustrate the technical features of the present invention and do not limit the protection scope of the present invention.

Example 1: 3  Channel Flow Electrode Structure

As shown in FIG. 8, a channel type electrode structure having three channels was manufactured.

Specifically, three square pillar channel supports were molded to prepare a liquid-permeable microporous honeycomb structure. Subsequently, the first square column channel was coated with a cation separation membrane, and the third square column channel was coated with an anion separation membrane, and a cation exchange membrane and an anion exchange membrane were formed on the inner wall of the channel, respectively. Subsequently, graphene was coated on the inner wall surfaces of the first square pillar channel and the third square pillar channel coated with the ion exchange membrane to form a porous collector.

As a result, a channel-type flow electrode structure was prepared in which the first square pillar channel provided the anode flow path through which the positive electrode active material-flowing fluid flowed, the second square pillar channel provided the electrolyte flow path, and the third square column channel provided the cathode flow path through which the negative electrode active material containing fluid flows. .

Meanwhile, the positive electrode active material and the negative electrode active material used activated carbon, and the positive electrode active material-containing fluid and the negative electrode active material-containing fluid were prepared by adding 10 wt% of activated carbon and 0.1 M NaCl to water.

The cell prepared as described above was placed in a vessel containing brine (35 g / L) to start the reaction. The amount of NaCl in brine can be inferred from the conductivity of the brine. The conductivity of the initial brine (35 g / L) without desalination was 55 mS / cm, whereas the conductivity after desalination decreased to 37 mS / cm. Through this, the concentration of saline was inferred to be 23.5 g / L.

As shown in Fig. 14, the three-channel flow electrode structure manufactured in Example 1 can be driven as a desalting apparatus with a Salt Removal Efficiency of ˜33%.

Example 2: 9  Channel Flow Electrode Structure

In the same manner as in Example 1, a nine channel flow electrode structure as shown in FIG. 5A was prepared.

In addition, the results of the experiment in the same manner as in Example 1 are shown in Table 1 and FIG.

The prepared cell was placed in a vessel containing brine (35 g / L) to start the reaction. The amount of NaCl in brine can be inferred from the conductivity of the brine. In the three-channel cell, the conductivity of the initial brine (35 g / L) without desalination was 62 mS / cm, but the conductivity decreased to 50 mS / cm after desalination. Through this, the concentration of brine was inferred to 28 g / L, and the salt removal efficiency was 20%. When the cell was expanded to nine channels, the conductivity was reduced to 8.15 mS / cm, with the brine concentration of 8.1 g / L and the salt removal efficiency of 87%.

	Conductivity (mS / cm)	Salt Concentration (g / L)	Salt Removal Efficiency (%)
Pristine	62	35
Desalinated (3 Cell Type)	50	28	20
Desalinated (9 Cell Type)	8.15	8.1	87

Operating Condition: @ 1.2 V for 90 min 3.5 mL

Example  3: placement In mode  Desalting Parameter Measurement of 1x3 and 3x3 Cells

As described in A novel three-dimensional desalination system utilizing honeycomb-shaped lattice structures for flow-electrode capacitive deionization, Energy Environ. Sci., 2017, 10, 1746-1750, desalting experiments were performed in the batch mode of FIG. 17. And the documents are included in the present invention.

The lattice structure was 3 mm wide, 0.5 mm thick and 120 mm high. Cordierite had a porous channel of 10-30 μm and an ion exchange membrane was coated on the surface. The graphene layer was coated at about 30 μm as a current collector thereon. Desalting experiments were performed in batch mode by immersing the prepared cells in a chamber containing 35 g / L saline. Salt removal efficiency was calculated by the following formula. The experimental results are shown in Table 2.

	Current after 100 min (mA)	Current density after 100 min (A / m 2 )	Salt removal capacity (μmol / min)	Desalination efficiency after 100 min (%)
1x3 cell	5.8	17.6	9	5.6
3x3 cell	21.1	15.9	33	18.3

As described above, it has been described with reference to the preferred embodiment of the present invention, but those skilled in the art various modifications and changes of the present invention without departing from the spirit and scope of the present invention described in the claims below I can understand that you can.

Explanation of the sign

100,200,418: flow electrode device

102,216,416: electrolyte flow path

104,204: anode ion exchange membrane

106,206 Porous Anode Plate

108,208: cathode ion exchange membrane

110,210: porous cathode plate

111: positive electrode active material

112,201,401: flow anode

113: positive electrode active material

114,203,403: flow cathode

116,118: closing plate

202,402 support

212,214,412,414: electrode solution

Claims (27)

1. A channel flow electrode unit defined by a liquid penetrating wall,

   An ion exchange current collector that passes through cations or anions and is electrically conductive is located inside the channel wall.

   The channel flow electrode unit, characterized in that the electrode flow path flowing through the electrode active material-containing fluid introduced from the channel inlet and discharged to the channel outlet is spaced apart from the wall through the ion exchange collector.
2. A channel flow electrode unit defined by a liquid penetrating wall,

   An ion exchange material is applied at the inner surface of the channeled wall, the outer surface, the wall itself, or a combination thereof to allow the passage of cations or anions,

   The porous current collector is applied to the inner surface of the channel-shaped wall to which the ion exchange material is applied,

   The channel flow electrode unit, characterized in that the electrode flow path flowing through the electrode active material-containing fluid introduced from the channel inlet and discharged to the channel outlet is spaced apart from the wall through the porous current collector.
3. The channel-type flow anode unit according to claim 1, wherein the ion exchange current collector is formed by stacking an ion exchange membrane and a porous current collector.
4. The channel type flow electrode unit according to claim 1 or 2, wherein the liquid-penetrating wall is electrically insulating.
5. The channel type flow electrode unit according to claim 1 or 2, wherein the electrode active material can adsorb and desorb ions.
6. A channel type flow electrode structure comprising at least two channel type flow electrode units according to any one of claims 1 to 3.
7. The channel type flow electrode structure of claim 6, wherein the channel type flow electrode units are assembleable in a block form.
8. 7. The channel flow electrode structure of claim 6, wherein two adjacent channel flow electrode units share a liquid permeable wall.
9. The method of claim 8, wherein after the fluid is introduced into the inlet and discharged to the outlet, a basic skeleton having a plurality of channels is formed as an integral liquid-permeable wall, and then some or all of the channels defined by the liquid-permeable wall are the flow electrode unit. Channel-type flow electrode structure characterized in that the unit.
10. 7. The channel type flow electrode structure according to claim 6, further comprising a channel type electrolyte flow path.
11. The channel type flow electrode structure according to claim 10, wherein the electrolyte flow path is channel type defined by the liquid penetrating wall.
12. 7. The channel flow electrode structure of claim 6, comprising at least one channel flow anode unit and at least one channel flow cathode unit, wherein an electrolyte is supplied through the liquid penetrating wall to form an electrochemical cell.
13. The channel of claim 6, wherein the channel flow anode unit is provided with at least one channel flow cathode unit and at least one channel flow cathode unit and the channel flow cathode unit is characterized in that at least one channel flow. Type flow electrode structure.
14. The electrolyte of claim 6 wherein the electrolyte is supplied through a separate channel-like flow path, through a liquid-permeable wall, or both, and based on the channel, the electrolyte is supplied in the longitudinal direction of the channel, in the lateral direction of the channel, or both. Channel-type flow electrode structure characterized in that.
15. A method for producing a channel flow electrode unit according to any one of claims 1 to 3,

    A first step of preparing a channel defined by the liquid penetrating wall;

    A second step of applying an ion exchange material through which a cation or anion passes through the inner surface, the outer surface, the wall itself, or a combination thereof; And

    Step 3a of applying the porous current collector to the inner surface of the channel-shaped wall to which the ion exchange material is applied

    Method of producing a channel-type flow electrode unit, characterized in that it comprises a.
16. A method for producing a channel flow electrode unit according to any one of claims 1 to 3,

    Step 1b of preparing a channel defined by the liquid-penetrating wall;

    A second step of applying the porous current collector to the inner surface of the channel-shaped wall; And

    A third step of applying an ion exchange membrane through which cations or anions pass through the inner surface of the channel wall to which the porous current collector is applied;

    Method of producing a channel-type flow electrode unit, characterized in that it comprises a.
17. A method for producing a channel type flow electrode structure according to claim 6,

    Preparing a liquid-permeable wall that forms a basic skeleton having a plurality of channels through which fluid is introduced into the inlet and discharged to the outlet;

    Apply the selected channel (s) to the channel-like wall inner surface with an ion exchange material through the cation, the wall itself or a combination thereof, and select the other channel (s) to the channel-wall wall with an ion exchange material passing the anions, A second step of applying to the wall itself or a combination thereof; And

    Step 3c, applying the porous current collector to the inner surface of the channel type wall to which the ion exchange material is applied

    Method of producing a channel-type flow electrode structure characterized in that it comprises a.
18. A method for producing a channel type flow electrode structure according to claim 6,

    Preparing a liquid-permeable wall that forms a basic skeleton having a plurality of channels through which fluid is introduced into the inlet and discharged to the outlet;

    A second step of applying the porous current collector to the inner surface of the channel-shaped wall;

    Coating the selected channel (s) of the porous current collector to the inner surface of the channel-like wall with an ion exchange material through which cations pass, and passing the negative ion through other selected channel (s) of the channels to which the porous current collector is applied. A third step of coating the inner surface of the channel wall with an ion exchange material;

    Method of producing a channel-type flow electrode structure characterized in that it comprises a.
19. A channel flow anode unit defined by a liquid penetrating wall, comprising: a channel flow anode unit in which an anode ion exchange current collector passing through cations and having electrical conductivity is located on an inner surface of the channel wall; And

    A channel flow cathode unit defined by a liquid-permeable wall, comprising a channel flow cathode unit in which a negative ion ion current collector passing through an anion and having electrical conductivity is located on an inner surface of the channel wall,

    A channel flow electrode cell, wherein an electrode flow path through which an electrode active material-containing fluid introduced from a channel inlet and discharged to a channel outlet flows is spaced apart from the wall through an ion exchange current collector.
20. A channel flow anode unit defined by a liquid-permeable wall, in which an ion exchange material is applied to the inside of the channel wall, the outer surface, the wall itself, or a combination thereof to pass cations and the porous current collector is ionized. A channel flow anode unit applied to the inner surface of the channel wall to which the exchange material is applied; And

    A channel flow cathode unit defined by a liquid penetrating wall, wherein an ion exchange material is applied to the inner surface, the outer surface, the wall itself, or a combination thereof to pass an anion and the porous current collector is ionized. A channel flow cathode unit is applied to the inner surface of the channel wall to which the exchange material is applied,

    And an electrode flow path through which an electrode active material-containing fluid introduced from a channel inlet and discharged to a channel outlet flows away from the wall through a porous current collector.
21. 21. The channel type according to claim 19 or 20, comprising at least one channel type flow anode unit and at least one channel type flow cathode unit, wherein the electrolyte is supplied through the liquid penetrating wall to form an electrochemical cell. Cell with flow electrode.
22. 21. A cell with a channel flow electrode as claimed in claim 19 or 20, wherein the channel flow anode unit and the channel flow cathode unit share adjacent walls.
23. A separator support for forming a basic skeleton having a plurality of channels through which fluid is introduced into the inlet and discharged to the outlet;

    A porous bipolar plate is disposed on the inner wall of the channel (s) selected in the membrane support, and a positive flow path through which a positive electrode active material containing fluid introduced from the channel inlet flows out to the channel outlet is spaced apart from the channel type membrane support through the porous bipolar plate. Channel-type flow anode units; And

    The negative electrode flow path is disposed on the inner wall surface of the other channel (s) selected in the separator support, and the negative flow path in which the negative active material-containing fluid flowing from the channel inlet and discharged to the channel outlet is spaced apart from the channel type separator support through the porous negative plate. And a channel type flow cathode unit.
24. 24. The channel flow electrode structure of claim 23, wherein the channel flow cathode unit is disposed adjacent to the channel flow anode unit.
25. 24. The channel flow electrode structure of claim 23, further comprising a channel electrolyte channel.
26. A capacitive electrode flow device comprising the channel-type flow electrode structure of claim 6 or 23.
27. A redox flow battery device comprising the channel type flow electrode structure of claim 6 or 23.

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