• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention uses the principles of ion absorption (charge) and ion desorption (electrochemical discharge) and concerns an electrode system in continuous flow, a high capacity energy storage system and its use in a treatment method of water being that the aforementioned systems in which the high capacity energy is stored as active materials of the electrodes in the slurry phase, and the electrolytes flow simultaneously and successively within a dino flow channel disposed in the electrode. More specifically, the present invention relates to a continuous flow electrode system, an energy storage system and a water treatment method in which the electrode active materials flow consecutively in a slurry state through which high capacity is obtained without increasing or stacking the electrodes.
    公开号:BR112013003263B1
    申请号:R112013003263-4
    申请日:2011-08-16
    公开日:2020-12-08
    发明作者:Dong-kook Kim；Tae-hwan Kim；Churl-Hee Cho；Chong-Su Park；Ko-Yeon Choo；Jeong-Ku Yeo
    申请人:Korea Institute Of Energy Research；
    IPC主号:
    专利说明:

    Technical Field of the Invention
    [001] The present invention uses the principles of ion absorption (charge) and ion desorption (discharge) electrochemical and concerns a system of electrodes in continuous flow, a system of energy storage of high capacity and its use in a water treatment method in which the materials of the electrodes in the slurry phase and the electrolytes flow simultaneously and continuously within a fine flow channel disposed in an electrode, in order to store the high capacity electrical energy. More specifically, the present invention relates to a continuous flow electrode system, an energy storage system and a water treatment method in which the active electrode materials flow consecutively in a fluid paste state and through which high capacity is easily obtained without increasing or stacking the electrodes. Background of the Invention
    [002] In recent years, many countries in the world have devoted intense efforts to the research and development of clean alternative energies and energy storage techniques in order to solve problems of air pollution and / or global warming. More specifically, electric energy storage technologies, including, for example, a high capacity energy storage system for storing electrical energy generated by a variety of alternative sources, different types of mobile devices, an energy storage system high capacity but small size needed for future electric vehicles to reduce air pollution, or the like, were developed as the foundation of the future green industry. Most future energy storage technologies are based on the use of the principles of ion absorption (charge) and ion desorption (discharge) as in the case of lithium ion batteries or supercapacitors, which is why all countries in the world continue to dedicate significant research and development efforts to achieve high-efficiency densification and extension of capacity by improving the loading and unloading characteristics of materials and components.
    [003] However, recently, the same principles as described above have been used in water treatment applications, including in the treatment of purified water or wastewater, desalination of sea water, etc. a method of water treatment with a very low energy cost compared to existing methods of evaporation or reverse osmosis (OR), that is, a capacitive deionization process (DIC), is now in the development phase.
    [004] For an energy storage and water treatment system that uses the same principles as described above, the most significant problem is the high cost of equipment as well as the reduction of efficiency in the extension of capacity. In other words, due to the increase in the area of the electrode and the irregularity of the distribution of the electric field in the electrode because of this, the limited amount of active material in the thin film electrode coated in the collector, the increase in the contact area between the active material and the electrolyte by a binder during coating and the deterioration of the charge-discharge effectiveness and so on, a series of unit cells must be stacked, thereby increasing the cost of equipment that is already high, and especially the operational costs of the capacitive deionization process (DIC) due to the loss of water pressure (electrolyte) in the battery flow. Technical problem
    [005] Therefore, the aim of the present invention is to provide a continuous flow electrode system that can have an extended capacity without stacking or increasing the electrode area to which the capacity extension is applied.
    [006] Another objective of the present invention is to provide an energy storage system of high capacity economical and effective. Another objective of the present invention is to provide a water treatment method that makes it possible to treat water with low cost energy. Technical Solution
    [007] In a first aspect, the present invention discloses a system of electrodes in continuous flow, comprising: a flow anode that contains the active material of flowing anode; a flow cathode that contains the flowing cathode active material; and an electrolyte.
    [008] According to the electrode system in continuous flow of aspect 1, the active material of the anode and the active material of the cathode flow in a continuous way, being, thus, supplied consecutively to the system; therefore, the capacity can be easily extended without stacking and / or increasing the electrode area.
    [009] According to the second aspect of the present invention, in the continuous flow electrode system of the first aspect of the present invention, the anode comprises an anode collector; an anode separation layer; an anode flow channel disposed between the anode collector and the anode separation layer; and the active material of the anode flowing through the flow channel of the anode, and the cathode comprises a cathode collector; a cathode separation layer; a cathode flow channel disposed between the cathode collector and the cathode separation layer; and the cathode active material flowing through the cathode flow channel, the electrolyte flowing through an insulating spacer as an electrolyte flow channel disposed between the anode separation layer and the cathode separation layer.
    [010] According to the electrode system in continuous flow of the second aspect, ion adsorption (charge) and / or ion desorption (discharge) occurs by the exchange of ions between the active material of the anode and the electrolyte or material cathode and electrolyte in order to store and / or generate energy.
    [011] According to the third aspect of the present invention, in the continuous flow electrode system of the second aspect of the present invention, the anode separation layer is a microporous insulating separation membrane or anion exchange (conductive) membrane and the cathode separation layer is a microporous insulating separation membrane or a cation exchange (conductive) membrane.
    [012] According to the electrode system in continuous flow of the third aspect, ions can be transferred or exchanged from the active material to the electrolyte by the microporous insulating separation membrane or ion exchange membrane to store and / or generate energy.
    [013] According to the fourth aspect of the present invention, in the electrode system in continuous flow of the second aspect of the present invention, the active material of the anode or the active material of the cathode is mixed with the electrolyte to form an active material in the phase of slurry.
    [014] According to the electrode system in continuous flow of the fourth aspect, it is easy to control the flow rate and supply the active material to the electrode system unit in continuous flow in a constant and consecutive manner, thereby storing and / or generating energy steadily.
    [015] According to the fifth aspect of the present invention, in the electrode system in continuous flow of the second aspect of the present invention, the active material of the anode or the active material of the cathode comprises the same material. According to the fifth aspect continuous flow electrode system, both anode and cathode materials can be stored and supplied using only one device to reduce the inconvenience caused by separate storage and management of the active materials mentioned above as well as to reduce the expense of providing the respective devices.
    [016] According to the sixth aspect of the present invention, in the continuous flow electrode system of the second aspect of the present invention, the separation layer is a microporous insulating separation membrane and the active material of the anode or the active material of the cathode it is microencapsulated.
    [017] According to the electrode system in continuous flow of the sixth aspect, the active material of the microencapsulated electrode allows the area of contact with the electrolyte to increase, thereby improving reactivity. According to the seventh aspect of the present invention, the direction of flow of the electrolyte is opposite to the direction of flow of the active material of the flow anode and the active material of the flow cathode with these two active materials flowing in the same direction.
    [018] It is possible to design a continuous flow electrode system based on the above technical configurations.
    [019] According to the eighth aspect of the present invention, the flow anode active material has a different flow rate than the flow cathode active material to obtain an asymmetric electrode. That is, since their flow rates are different, the absolute values of the flow rates may be different or the flow directions may be opposite from each other. Therefore, it is possible to design electrode systems in continuous flow in several ways.
    [020] According to the ninth aspect of the present invention, the system does not have the separation layer. Thus, the system has a simple structure. However, in order to avoid mixing the active material of the anode and the active material of the cathode, the active material of the anode or the active material of the cathode is microencapsulated.
    [021] According to the tenth aspect of the present invention, in the continuous flow electrode system of any of aspects 1 to 9, the continuous flow electrode system is a second battery or a double layer electrical capacitor (CEDC ).
    [022] According to the tenth aspect continuous flow electrode system, the system can be used in various ways depending on your objectives.
    [023] In the twelfth aspect, the present invention discloses a high capacity energy storage system, comprising: the electrode system in continuous flow according to any one of aspects 1 to 9; a feeding device for supplying the active material of the anode, the active material of the cathode and the electrolyte, respectively; a power supply to supply power to the electrode system in continuous flow; a switching switch to control the potential difference that occurs in the power supply; and storage tanks for storing the active material of the anode, the active material of the cathode and the electrolyte.
    [024] According to the eleventh aspect energy storage system, the active material of the anode, the active material of the cathode and the electrolyte are not stored in the electrode system in continuous flow, but are stored in a storage tank additional supplied separately and arranged in the system, the high energy capacity can be stored without having to increase the electrode area or stack it. Therefore, increasing the proportion suitable for different capacities can easily be done with a significant reduction in manufacturing and operating costs, the above system being able to be used advantageously by the energy industries in the future.
    [025] In accordance with the twelfth aspect of the present invention, in the eleventh aspect high capacity energy storage system, the system further comprises a resistor connected to the switching switch.
    [026] In accordance with the high capacity energy storage system of the twelfth aspect of the present invention, the switching switch is transformed from the power supply into the resistor allowing the energy of adsorbed (charged) ions stored in the storage tank. is the exit.
    [027] In accordance with the thirteenth aspect of the present invention, in the eleventh aspect high capacity energy storage system, the feed device comprises a feed tank and a feed pump to supply the anode's active material, the active material of the cathode and the electrolyte, respectively.
    [028] According to the high capacity energy storage system of the thirteenth aspect, the supply tank can be supplied independently of the electrode system in continuous flow, thus obtaining the extension of the capacity with reduced cost regardless of size of the electrode system in continuous flow.
    [029] In accordance with the fourteenth aspect of the present invention, in the high quality energy storage system of the thirteenth aspect, a single feed tank acts as the feed tank for the active material of the anode to supply the active material of the anode simultaneously with the cathode active material feed tank to supply the cathode active material.
    [030] According to the fourteenth aspect high capacity energy storage system, the active materials can be supplied in sufficient quantity using only a single feed tank when the active material of the anode is identical to the active material of the cathode, thereby reducing equipment costs.
    [031] According to the fifteenth aspect of the present invention, in the high quality energy storage system of the thirteenth aspect, two continuous flow electrode systems are provided, a part of the continuous flow electrode systems being used as the charging device while the rest is used as the discharge device, and the active material of the anode and the active material of the cathode flowing from the energy storage device for the discharge are again recycled in the feed tank of the active material of the anode and in the feed tank of the active material of the cathode, respectively.
    [032] According to the fifteenth aspect high-capacity energy storage system, loading / unloading can be done consecutively and simultaneously and there is no need to additionally fill the feed tank with active material from the anode and the tank of feeding the active material of the cathode, thereby reducing equipment costs.
    [033] According to the sixteenth aspect of the present invention, in the eleventh aspect high capacity energy storage system, the storage tank is an electrically insulated storage container.
    [034] According to the sixteenth aspect high capacity energy storage system, the energy stored in the storage tank is kept stable without leaks.
    [035] According to the seventeenth aspect of the present invention, in the eleventh aspect high capacity energy storage system, the electrolyte comprises sea water or industrial waste water.
    [036] According to the seventeenth aspect high capacity energy storage system, considering that seawater and wastewater are used as electrolyte, expenses can be reduced and the above system can be applied in the desalination of water. sea water and wastewater purification.
    [038] In the eighteenth aspect, the present invention discloses a method of treating water by means of capacitive deionization, using the high capacity energy storage system according to the eleventh aspect.
    [039] The use of the eighteenth aspect water treatment method makes it possible to treat water on a large scale with equipment costs and reduced operating costs.
    [040] In the nineteenth aspect, the present invention discloses a method of desalination of sea water by means of capacitive deionization, using the high capacity energy storage system according to the eleventh aspect in which the electrolyte comprises sea water .
    [041] According to the nineteenth aspect seawater desalination method, it is possible to carry out seawater desalination on a large scale with equipment costs and reduced operating costs.
    [042] In the twentieth aspect, the present invention discloses a method of purifying residual water by means of capacitive deionization, using the high capacity energy storage system according to the eleventh aspect in which the electrolyte comprises industrial waste water.
    [043] According to the twentieth aspect industrial wastewater purification method, it is possible to purify wastewater on a large scale with reduced equipment costs and operating costs. Advantageous Effects
    [044] Contrary to the electrode of the active material of stationary phase, coated in the existing collector, the active material of microfine electrode with the size of several tens of nm to several tens of μm, and separated from the collector, flows continuously in a state of slurry mixed with the electrolyte, therefore, high capacity can be obtained easily, using only an insulated storage container as well as a unit cell with the microfine flow channel as an energy storage device, and it is easy to increase the size of the deionization device (DIC), adapting it to different capacities and the costs of manufacturing and operating the device can be considerably reduced. Description of the drawings
    [045] Figure 1 is a schematic view showing the electrode system in continuous flow according to an embodiment of the present invention. Figure 2 is a cross-sectional view showing the microcapsule containing the electrode material according to an embodiment of the present invention. Figure 3 is a schematic view showing the high capacity electrode system according to an embodiment of the present invention. Figure 4 is a schematic view showing the electrode system in continuous flow according to another embodiment of the present invention. Figure 5 is a schematic view showing the electrode system in continuous flow according to another embodiment of the present invention. Best Form of Execution of the Invention
    [046] The present invention will be described in more detail below. However, the following description is provided to more specifically explain the present invention and its design can be appropriately altered or modified by professionals in the field.
    [047] According to an embodiment of the present invention, the electrode system in continuous flow comprises a flow anode that contains the active material of the flowing anode; a flow cathode that contains the active material of the flowing cathode; and a fluent electrolyte.
    [048] The active material of the anode, the active material of the cathode and the electrolyte can comprise any material used in a typical electrode system in continuous flow, that is, a battery or a storage battery that can be properly selected by the professionals of the branch, considering the purposes and / or circumstances of their use.
    [049] According to an embodiment of the present invention, the active material of the anode and the active material of the cathode can comprise different materials or, otherwise, the same material.
    [050] According to an embodiment of the present invention, the electrode material such as the active material of the anode and / or the active material of the cathode may comprise porous carbon (activated carbon, carbon aerosol, carbon nanotube, etc.) , graphite powder, metal oxide powder and the like, which can be mixed with the electrolyte to be used in a fluidized state.
    [051] According to an embodiment of the present invention, the electrolyte comprises a water soluble electrolyte such as NaCl, H2SO4, HCl, NaOH, KOH, Na2NO3, etc. and an organic electrolyte such as propylene carbonate (CP), diethyl carbonate (CDE), tetrahydrofuran (THF), etc.
    [052] According to one embodiment of the present invention, the active material of the electrode flows alone while the electrolyte can be a solid or stationary phase electrolyte.
    [053] According to an embodiment of the present invention, the anode comprises an anode collector; an anode separation layer, an anode flow channel arranged between the anode collector and the anode separation layer, and the anode active material flowing through the anode flow channel, and the cathode comprises a cathode, a cathode separation layer, a cathode flow channel arranged between the cathode collector and the cathode separation layer, and the cathode active material flowing through the cathode flow channel, the electrolyte flowing through the flow channel disposed between the anode separation layer and the cathode separation layer.
    [054] The electrode collector and the electrode separation layer can comprise any one used in conventional electrode systems in continuous flow (battery, storage battery, etc.) that can be properly selected or adopted by professionals in the field, considering the purposes and conditions of use thereof.
    [055] The width of the anode flow channel or the cathode flow channel can be the same size or smaller than the space between the electrode collector and the separation layer in a conventional continuous flow electrode system. Since the active material of the electrode is fixed in a conventional manner, it causes a problem: the size of the electrode system in continuous flow increases when trying to obtain the desired capacity of the active material necessary for loading / unloading in order to limit the space between the electrode collector and separation layer. On the other hand, according to the present invention, considering that the active material of the electrode can be supplied continuously, the design can be freely changed or modified, depending on the objectives, the active materials of the electrolyte to be used, etc. without limitations. According to an embodiment of the present invention, the width and height of the flow channel used can vary from tens of μm to several mm.
    [056] Likewise, the width of the insulating spacer can be appropriately changed without limitations caused by the size of the electrode system in continuous flow as the electrolyte can be supplied continuously.
    [057] However, to increase the loading / unloading efficiency, the speeds of the electrolyte and the active material may be different from each other, or, otherwise, the ratio of the widths between the active material and the insulating spacer may be restricted.
    [058] According to an embodiment of the present invention, the anode separation layer can be a microporous insulating separation membrane or anion exchange (conductive) membrane while the cathode separation layer can be a microporous insulating separation membrane. or a cation exchange membrane (conductive).
    [059] The separation layer is used for electrical and physical separation and the microporous insulating membrane allows the transfer of ions only when the ion exchange (conductive) membrane can selectively transfer either cations or anions.
    [060] In addition, according to an embodiment of the present invention, the active material of the anode and the active material of the cathode can comprise the active material in the slurry phase, including the active material of the anode or the active material of the cathode mixed with the electrolyte.
    [061] However, according to yet another embodiment of the present invention, the electrolyte can flow in the opposite direction to that of the active material of the anode and the active material of the cathode. Therefore, it is possible to assemble a system of electrodes in continuous flow in several ways.
    [062] Furthermore, the adoption of different flow rates of the active material of the anode in the anode and the active material of the cathode in the cathode can induce different reaction times of the active material of the anode and the active material of the cathode with the electrolyte, respectively . Therefore, a variety of design modifications can be made.
    [063] The preferred embodiments of the present invention will be described in more detail below with reference to the accompanying drawings.
    [064] Figure 1 is a schematic view, demonstrating a continuous flow electrode system according to one embodiment of the present invention. According to Figure 1, the system comprises an anode 10 which includes an anode collector 11, an anode separating layer 13 and anode 12 active material flowing through the anode 14 flow channel disposed between the anode collector. anode 11 and the separation layer of anode 13; a cathode 20 that includes a cathode 21 collector, a cathode 23 separation layer and the active material of cathode 22 flowing through the cathode 24 flow channel disposed between cathode 21 collector and cathode 23 separation layer ; and an electrolyte 13 and the cathode separation layer 23.
    [065] The electrode system in continuous flow can be a unit cell in which two or more unit cells can be arranged consecutively and in which the electrode material as well as the electrolyte can flow simultaneously and continuously.
    [066] In addition, as shown in Figure 4, it is possible to direct the movement of electrolyte 30 in the opposite direction to that of the active material of anode 12 and the active material of cathode 22.
    [067] According to Figure 2, the electrode material can be microencapsulated to increase the contact area between the electrolyte and the electrode material. More specifically, an anion separation layer (a dense layer that selectively passes the anions, while blocking the flow of liquid electrolyte) is used, and a cation separation layer (a dense layer that selectively passes only cations). However, if the active material of the encapsulated electrode is used for each ion selective layer (see Fig.2), it is not necessary to provide the conductive dense ion layers between the two electrodes. Alternatively, if the microporous insulating separation membrane is used, which allows the flow of electrolyte as well as ions to flow, the contact area between the electrolyte and the particles of the active electrode material is increased.
    [068] The microencapsulated electrode comprises a core in the center and a shell around the periphery of the core, the shell material having the property of exchanging ions present in the electrolyte. According to an embodiment of the present invention, the shell material can comprise a polymeric membrane containing a sulfonic acid group (SO3-), a carboxylic group (COO-) or a phosphoric acid group (PO4-), etc. , which is capable of exchanging cations; or a polymeric membrane that contains a group of primary, secondary, tertiary, quaternary ammonium attached to it, which is capable of exchanging anions. The microcapsule can be prepared using a solid or liquid phase method. In particular, in the liquid phase method, the core / shell structure can be formed by, for example, an emulsion method, using a surfactant, a polymerization method, polymerizing the monomers to prepare the shell material or a method of injection or extrusion of the core and the shell, simultaneously or separately, in order to obtain a microencapsulated electrode. Since the micro-encapsulated electrode comprises a single granule or individual granules agglomerated together and the wrapper covers them, its advantage is that the electrode area per unit of weight or volume is larger than that of the static electrode formed by all agglomerated granules.
    [069] In particular, as shown in Figure 5, when the electrode system in continuous flow 60 without the separation layer is manufactured, it is possible to avoid direct mixing of the active material of the anode and the active material of the cathode with the electrolyte.
    [070] Figure 3 demonstrates an energy storage system 100 according to one embodiment of the present invention, comprising a continuous flow electrode system 1 in the form of a single cell, a feed tank for cathode 2a active material and a feed pump 41 to supply the cathode active material that was prepared in the slurry phase, mixing the cathode 22 active material with electrolyte 30, an anode 2b active material feed tank and a feed pump 42 to provide the anode active material that was prepared in the slurry phase, mixing the anode 12 active material with the electrolyte 30, an electrolyte feed tank and a feed pump 43 to supply the electrolyte 30, a power source 7 for apply direct current to the electrode system in continuous flow 1, a switching switch 9 to control the potential difference that occurs in the power supply 7, an air tank anion storage 3 in which the active material of the anode containing adsorbed (charged) ions is stored while passing through the electrode system in continuous flow 1 applied to the potential, a cation storage tank 4 in which the active material of the anode is stored cathode containing adsorbed (charged) ions, and a storage tank for deionized electrolyte 6.
    [071] The energy storage system 100 has the following technical functions.
    [072] When applying the potential difference that occurs in the supply of direct current 7, for example, in the range of 0.5 to 2.0v, to the electrode system in continuous flow 1 using the switching switch 9, the active material of anode 12, the active material of cathode 22 and electrolyte 30 in the slurry phases, the active material of anode 12, the active material of cathode 22 and electrolyte 30 in the slurry phases pass simultaneously and continuously through the continuous flow electrodes 1.
    [073] The active material of anode 12 and the active material of cathode 22 can be mixed with electrolyte 30 beforehand, then flow from the feed tank of cathode 2a active material, from the feed tank of active material of cathode anode 2b and electrolyte supply tank 5, respectively, and be fed into the electrode system in continuous flow 1 by means of supply pumps 41, 42 and 43, respectively. In this case, if the anode 12 active material and cathode 22 active material used are the same, it is not necessary to provide both pumps 2b and 2a, respectively, instead, preferably, only one feed tank 2 is used. The electrolyte in the electrolyte feed tank 5 is supplied from seawater or sewage via the feed pump 44 and the control valve 45.
    [074] As mentioned above, the active material of anode 12, the active material of cathode 22 and electrolyte 20 flow through the electrode system in continuous flow 1 applied to the potential (in the direction of the solid line), the active materials of electrodes 12 and 22 with ion absorption (charged) as they pass through the system and ion-free electrolyte 30 are stored in storage tanks 3,4 and 6, respectively. According to an embodiment, the storage tank is preferably an electrically insulated storage tank.
    [075] As for the conventional electrode of active material of stationary phase, it is impossible to continue charging it after the ions are charged in the active material of the electrode. Therefore, in order to obtain high capacity, the electrode must have a large area or several electrodes must be stacked, thus causing the problem of significant increase in the manufacturing and operating costs of the device. However, according to the present invention, it is possible to supply the active material continuously and store the active material for adsorption of ions in an additionally supplied storage tank, therefore, high capacity can be obtained without increasing the size of the electrodes in continuous flow 1 or stack it. In addition, since the electrode system in continuous flow 1 can be changed if necessary, it can be adjusted to various capacities.
    [076] However, the method of emission (application) of energy adsorbed by ions (charged) to the active material of the electrode stored in each storage tank can be the opposite of the ion adsorption process (charge) and comprise: shutdown power supply 7; conversion of the communication switch 9 to connect the power supply to resistor 8 and simultaneously allow the active material of the anode, the active material of the cathode and the electrolyte stored in storage tanks 3, 4 and 6 to flow in reverse order through of the electrode system in continuous flow 1 (in the direction of the dotted line so that, in this way, the ion desorption (discharge) continues while passing through the electrode system in continuous flow 1.
    [077] In this sense, if it is necessary to carry out the charging and discharging simultaneously and continuously for a long period of time, it is possible to use two or more electrode systems in continuous flow 1 to obtain the final system, with part of the The system can function as the loading device while the rest can function as the discharge device. According to the present invention, without the need for additional storage tanks 3 and 4 for the active material of anode 12 and the active material of cathode 22, the active materials of the electrodes absorbed by ions (charged) in the flow electrode system Continuous 1 in the discharge process can be recycled directly into the feed tanks 2b and 2a without passing through the storage tanks described above.
    [078] More specifically, the continuous flow electrode system 1 additionally installed for the discharge may comprise a separation layer with conductive ion properties or use the microencapsulated electrode material to prevent contamination of the electrode material, the rapid desorption of stored ions and electrolyte concentration by reversing polarity.
    [079] The energy storage system 100 according to the present invention can be applied to capacitive deionization type water treatment techniques. For example, when sea water or industrial wastewater flows into the electrolyte feed tank 5 and passes through the electrode system in continuous flow 1 where the potential difference occurs, the water is desalinated (deionized) and stored in the electrolyte storage tank 6, thus making it possible to desalinate sea water and purify industrial waste water.
    [080] Therefore, when compared with existing evaporation or OR methods, water treatment can be carried out with low energy cost. It is possible to obtain the high capacity of water treatment. EXAMPLE
    [081] The present invention will be described in more detail below by way of examples. However, the following examples are provided by way of description of the present invention and are not to be considered as limiting the scope of the present invention.
    [082] Fluidized deionization properties of activated carbon powder slurry from NaCl electrolyte
    [083] A unitary cell (continuous flow electrode system) was made with a microfine flow channel in which the cation exchange membrane (-SO3-), the anion exchange membrane (R3N + -) and the spacer they are isolated between the cathode and anode collectors (SUS316, 95x52 mm, 22.4 cm2 contact area). As shown in Table 2, the aqueous NaCl electrolyte with electrical conductivity (concentration) in the range of 1,030 μs to 11,000 μs passed through the unit cell at a flow rate of 3 to 5 cc / mm using a measuring micro pump (Japan Fine Chemicals Co. Ltd., Minichemi Pump).
    [084] At the same time, the micro-pulverized active material of the electrode with an average particle size of about 95nm with fine pore properties shown in Table 1, that is, the activated carbon powder was mixed with the same electrolyte in the concentrations indicated in Table 2, respectively. Then, while the mixture passed through a part of the electrode material from the cathode flow channel and the anode flow channel in the unit cell at a flow rate of the slurry phase of about 20 to 25 cc / min, the DC potential difference of about 1.2 to 1.5v was applied to the cathode and anode terminals. In the present example, the active material from the slurry phase electrode that was absorbed by ions (charged), was no longer stored as it passed through the two collectors, but recycled in a feed and storage container and, at the same time, and subjected to the measurement of the variation of the collector current and the concentration (electrical conductivity) of the electrolyte with an interval of about 30 minutes. The measurement results are shown in Table 2. Table 1.
    Table 2.

    [085] According to the measured results shown in Table 2, the existing stationary phase electrode revealed that the current flow abruptly decreases when the electrode's active material was saturated with absorbed (charged) ions over a period of time (for example , Korean patent No. 2002-0076629). On the other hand, the continuous flow electrode system of the present invention demonstrated constant current flow when the electrolyte concentration was kept constant. Based on the fact that the concentration of active material recycled from the slurry phase electrode increased when the concentration (electrical conductivity) of the electrolyte that passed through the collector, it decreased by about 30 to 40%, depending on the concentration of a given solution of feeding (electrolyte), it was identified that possibly the electrolyte ions are adsorbed and stored by the electrode material in continuous flow of the present invention. Therefore, the present invention easily solved the problems of existing stationary phase electrode systems involving limitations in the extension of the electrode material coating of the DIC energy storage and desalination technologies, thereby significantly improving the high equipment costs. and operational due to high capacity. Description of drawing reference numbers
    [086] 1, 60: electrode system in continuous flow 2: feed tank for active material 3: anion storage tank 4: cation storage tank 5: electrolyte feed tank 6: electrolyte storage tank 7 : power supply 8: resistor 9: switching switch 10: anode 11: anode collector 12: anode active material 13: anode separation layer 14: anode flow channel 20: cathode 21: cathode 22 collector: cathode 23 active material: cathode separation layer 24: cathode 30 flow channel: electrolyte 34: insulating spacer 41, 42, 43, 44: feed pump 50: capsule membrane (ionic membrane).
    权利要求:
    Claims (19)
    [0001]
    1. “System of electrodes in continuous flow (1)”, in which said system comprises: - a flow anode (10) containing active material from the flowing anode (12); - a flow cathode (20) containing active material from the flowing cathode (22); and an electrolyte (30), characterized by the fact that the anode (10) comprises: an anode collector (11), an anode separation layer (13), an anode flow channel (14) disposed between the collector of the anode (11) and the separation layer of the anode (13), and the active material of the anode (12) flowing through the flow channel of the anode (14), and the cathode (20) comprises a cathode collector ( 21), a cathode separation layer (23), a cathode flow channel (24) disposed between the cathode collector (21) and the cathode separation layer (23), and the cathode active material (22 ) flowing through the cathode flow channel (24), the electrolyte (30) flowing through an insulating spacer (34) disposed between the anode separation layer (13) and the cathode separation layer (23 ).
    [0002]
    2. “Continuous flow electrode system (1)” according to claim 1, characterized by the fact that the anode separation layer (13) is a microporous insulating separation membrane or an anion exchange membrane ( 50), and the cathode separation layer (23) is a microporous insulating separation membrane or a cation exchange membrane (50).
    [0003]
    3. “Continuous flow electrode system (1)”, according to claim 1, characterized by the fact that the active material of the anode (12) or the active material of the cathode (22) is mixed with the electrolyte (30 ) to obtain the active material in the slurry phase.
    [0004]
    4. "Electrode system in continuous flow (1)", according to claim 1, characterized by the fact that the active material of the anode (12) or the active material of the cathode (22) comprises the same material.
    [0005]
    5. “Continuous flow electrode system (1)”, according to claim 1, characterized by the fact that the separation layer is a microporous insulating separation membrane (50), and the active material of the anode (12) or the cathode active material (22) is microencapsulated.
    [0006]
    6. “Continuous flow electrode system (1)”, according to claim 1, characterized by the fact that the flow direction of the electrolyte (30) is opposite to the flow direction of the active material from the anode (12) of flow and the active material of the flow cathode (22), with the two active materials mentioned flowing in the same direction.
    [0007]
    7. “Continuous flow electrode system (1)”, according to claim 1, characterized by the fact that the flow rate of the active material of the flow anode (12) is different from that of the active material of the cathode (22 ) flow.
    [0008]
    8. “Electrode system in continuous flow (1)”, according to claim 1, characterized by the fact that the anode (10) comprises: - an anode collector (11) and the active anode material (12) which flows near the anode collector (21) and the cathode (20) comprises: - the cathode collector (21) and the cathode active material (22) which flows near the cathode collector (21); - the electrolyte flows between the active material of the anode (12) and the active material of the cathode (22), and - the active material of the anode (12) or the active material of the cathode (22) is microencapsulated.
    [0009]
    9. "Continuous flow electrode system (1)", as defined in any one of claims 1 to 8, characterized by the fact that the continuous flow electrode system (1) is a secondary battery or an electrical layer capacitor double (CECD).
    [0010]
    10. "High capacity energy storage system", characterized by comprising: - the continuous flow electrode system (1), as defined in any one of claims 1 to 9; - a feed tank (2) to supply the active material of the anode (12), the active material of the cathode (22) and the electrolyte (30), respectively; - a power supply (7) to supply energy to the electrode system in continuous flow (1); - a switching switch (9) to control the potential difference that occurs in the power supply and - storage tanks (3,4 and 6) to store the active material of the anode (12), the active material of the cathode (22 ) and the electrolyte (30).
    [0011]
    11. "High capacity energy storage system" according to claim 10, characterized in that it comprises a resistor (8) connected to the switching switch (9).
    [0012]
    12. “High capacity energy storage system”, according to claims 10 and 11, characterized by the fact that it comprises: a supply tank (2) and supply pumps (41, 42, 43 and 44) for supply the active material of the anode (12), the active material of the cathode (22) and the electrolyte (30), respectively.
    [0013]
    13. “High capacity energy storage system” according to claim 12, characterized by the fact that a single feed tank (2) acts as the feed tank for the active material of the anode (12) to supply the anode active material (12) and simultaneously with the cathode active material feed tank to supply the cathode active material (22).
    [0014]
    14. "High capacity energy storage system", according to claim 13, characterized by the fact that two continuous flow electrode systems (1) are provided in which part of the continuous flow electrode systems (1 ) is used as the charging device while the rest is used as the discharge device, and the active material from the anode (12) and the active material from the cathode (22) that flow from the energy storage device to the discharge they are recycled again in the feed tank (3) of the active material of the anode (12) and in the feed tank (4) of the active material of the cathode (22), respectively.
    [0015]
    15. "High capacity energy storage system" according to claim 10, characterized by the fact that the storage tank is an electrically insulated storage container.
    [0016]
    16. "High capacity energy storage system" according to any one of claims 10 to 15, characterized by the fact that the electrolyte (30) comprises sea water or industrial waste water.
    [0017]
    17. "Use of the high-capacity energy storage system, as defined in any of claims 10 to 16, characterized by being for the treatment of water by means of capacitive deionization (DIC)".
    [0018]
    18. “Use of the high capacity energy storage system in the treatment of water by means of capacitive deionization (DIC)”, according to claim 17, characterized by the electrolyte comprising sea water.
    [0019]
    19. “Use of the high-capacity energy storage system in water treatment through capacitive deionization (DIC)”, according to claim 18, characterized by the electrolyte comprising industrial waste water.
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    同族专利:
    公开号 | 公开日
    CN103109336B|2015-12-16|
    JP2016115662A|2016-06-23|
    JP2013541407A|2013-11-14|
    EP2605326B1|2020-10-07|
    CN103109336A|2013-05-15|
    KR20120015964A|2012-02-22|
    BR112013003263A2|2017-02-21|
    JP6161667B2|2017-07-12|
    US9963363B2|2018-05-08|
    EP2605326A4|2017-01-25|
    EP2605326A2|2013-06-19|
    US20130209916A1|2013-08-15|
    WO2012021048A2|2012-02-16|
    WO2012021048A3|2012-05-10|
    KR101233295B1|2013-02-14|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-04-30| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-12-03| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-03-31| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-09-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/08/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
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    KR20100078543A|KR101233295B1|2010-08-13|2010-08-13|Flow-electrode device|
    KR10-2010-0078543|2010-08-13|
    PCT/KR2011/006010|WO2012021048A2|2010-08-13|2011-08-16|Fluidized-bed electrode system, and high-capacity power storage and water treatment method using same|
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