KR101602952B1 - Manufacturing equipment of electrolyte for redox flow battery comprising punched electrode with lattice structure - Google Patents

Abstract

The present invention provides an apparatus of preparing an electrolytic solution for a redox flow battery including: an electrolyzer in which a positive electrode solution chamber and a negative electrode solution chamber are separated from each other by a separator unit; a power unit sequentially and repeatedly supplying a constant voltage and a constant current through electrodes respectively installed in the positive electrode solution chamber and the negative electrode solution chamber; a positive electrode electrolytic solution tank piped to the positive electrode solution chamber to store a positive electrode solution electrolyzed in the positive electrode solution chamber; and a negative electrode electrolytic solution tank piped to the negative electrode solution chamber to store a negative electrode solution electrolyzed in the negative electrode solution chamber. The power unit includes electrodes including: lattice units formed by intersecting plural metal wires with each other; and plural perforated units in which perforated holes are formed, and which are disposed between the lattice units. An apparatus of preparing an electrolytic solution for a redox flow battery according to the present invention is capable of improving the mobility of electrons and effectively supplying a constant current by including latticed and perforated electrodes. Further, the apparatus according to the present invention is capable of reducing the electrolysis time as much as 50% or more such that the electrolytic solution for the redox flow battery can be effectively prepared, by suppressing overvoltage phenomena caused by the concentration of ions on the electrode surface such that a constant voltage and a constant current of a limiting current value can be effectively supplied, thereby reducing the initial vanadium ionizing time through repeated electrolysis.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an apparatus for manufacturing an electrolyte for redox flow cells,

The present invention relates to an apparatus for manufacturing an electrolyte for a redox-flow battery, and a method of manufacturing an electrolyte for a redox-flow battery using the same.

Recently, interest in renewable energy has been increasing in order to reduce the adverse effects caused by the use of fossil fuels. Research on energy storage system (ESS), which stores generated renewable energy, is actively being carried out.

The redox flow battery is a battery in which a cathode electrolyte containing a cathode and a cathode active material and a cathode electrolyte containing a cathode and a cathode active material are charged and discharged using a redox reaction of the two active materials, A technology for producing and storing current by circulating an electrolytic solution contained in a tank from a stock tank to an electrolytic cell and storing a large amount of energy.

Particularly, the vanadium redox flow cell has various advantages such as simple electrode reaction, high electromotive force, fast ion electrode reaction, and excellent durability, so that the development is proceeding in earnest.

The vanadium redox flow cell has a redox reaction of vanadium divalent (V ²⁺ ) / trivalent (V ³⁺ ) in the cathode cell and a redox reaction of vanadium tetravalent (V ⁴⁺ ) / ^{5 +} ), And the electrolytic solution of the positive electrode and the negative electrode has the same kind of metal ion species, and even when the electrolytic solution is mixed through the diaphragm, it is normally regenerated by charging. Therefore, even when using the same active material, The amount of hydrogen generated as a side reaction is small, and it exhibits superior properties to a redox flow cell using other metal species.

In order to effectively utilize the vanadium redox flow cell as described above, various studies for producing an electrolytic solution containing vanadium ion have been conducted.

For example, in Patent Document 1, V ²⁺ , V ³⁺ , V ^4+, and V ⁵⁺ can be prepared from vanadyl sulfate (VOSO ₄ ) to produce electrolytes of both electrodes containing vanadium, And a method of manufacturing an electrolytic solution for VRB using electrolysis which does not require a second step for manufacturing the electrolytic solution.

However, in the method disclosed in Document 1, in order to prepare a vanadium electrolytic solution, the electrolytic solution is separated into a tertiary electrolytic step to electrolyze the vanadium electrolytic solution. In order to remove the salt generated after the first electrolytic electrolysis, And a third electrolytic step of separating the electrolytic solution into a cation and an anion, and then electrolyzing the electrolytic solution to form a vanadium electrolytic solution. Therefore, there is a disadvantage in that it takes a long time and an apparatus and a method for manufacturing an electrolytic solution of vanadium redox battery Research is needed.

Korea Patent Publication No. 10-2013-0107845 (Publication Date: Oct. 20, 2013) Korean Registered Patent: No. 10-13167618 (Disclosure Date: March 13, 2014) Korean Patent Publication No. 10-2011-0064058 (published on June 15, 2011) Korean Patent Publication No. 10-2014-0017191 (Publication date: 2014.02.11)

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide an apparatus for manufacturing an electrolyte for a redox flow battery having improved productivity by reducing the number of times and time of electrolysis in producing an electrolyte for a vanadium- .

According to an aspect of the present invention, there is provided an electrolytic cell comprising: an electrolytic bath in which an anolyte chamber and a catholyte chamber are separated from each other by a diaphragm; A power supply unit for sequentially and repeatedly supplying a constant voltage and a constant current through electrodes provided respectively in the anolyte chamber and the catholyte chamber; A positive electrode electrolyte tank connected to the anolyte chamber and storing the anolyte solution electrolyzed in the anolyte chamber; And a negative electrode electrolyte tank connected to the negative electrode liquid chamber and storing the negative electrode liquid electrolyzed in the negative electrode liquid chamber,

The power supply unit may include: a grid unit having a plurality of metal lines intersecting with each other; And a plurality of troughs formed inside the pores and disposed between the lattice portions. The apparatus for manufacturing an electrolytic solution according to claim 1,

And a plurality of troughs having perforations formed therein and disposed between the grid portions,

The diaphragm portion may include a diaphragm and a cation exchange membrane adjacent to the diaphragm and disposed in the direction of the catholyte chamber.

In addition, a sulfuric acid solution in which vanadyl sulfate (VOSO ₄ ) is dissolved is supplied to the anolyte chamber and the catholyte chamber.

The anolyte chamber and the catholyte chamber are connected to a nitrogen supply device.

Further, the anolyte is an electrolytic solution containing a vanadium cation having a ^valence of (V ⁵⁺ ).

Further, the cathode liquid is an electrolytic solution containing vanadium cations of divalent (V ²⁺ ).

In addition, the power source unit is characterized by repeatedly supplying a constant voltage and a constant current at intervals of 20 to 40 minutes.

The power supply unit supplies a constant voltage of 3 to 24 V and a constant current of 1 to 5 A.

The anolyte chamber may further include at least one selected from the group consisting of citric acid, acetic acid, acetic acid, carbonic acid, and phosphoric acid.

The apparatus for manufacturing an electrolytic solution for a redox-flow battery according to the present invention comprises electrodes provided with a grid and perforations to improve the mobility of electrons and effectively supply a constant current, and a phenomenon in which ions are concentrated on an electrode surface to generate an overvoltage The electrolysis time can be shortened by 50% or more by reducing the ionization time of the initial vanadium through repetitive electrolysis, so that the electrolytic solution for the redox flow battery can be effectively produced, The electrolytic solution has a high purity because the mixing of the constant voltage and the constant current drastically reduces the occurrence of salt.

1 is a block diagram showing an apparatus for producing an electrolyte for a redox-flow battery according to the present invention.
2 is a schematic view showing an electrode used in an apparatus for producing an electrolyte for a redox-flowable battery.

Hereinafter, the present invention will be described in detail.

FIG. 1 is a configuration diagram showing an apparatus 100 for manufacturing an electrolyte for a redox-flow battery according to the present invention.

1, the present invention includes an electrolytic bath 130 in which an anolyte chamber 110 and a catholyte chamber 120 are separated from each other by a diaphragm 150; A power supply unit 140 for sequentially and repeatedly supplying a constant voltage and a constant current through electrodes provided respectively in the anolyte chamber 110 and the catholyte chamber 120; A positive electrode electrolyte tank 180 piped to the anolyte chamber 110 to store the anolyte solution electrolyzed in the anolyte chamber 110; And a negative electrode electrolyte tank 190 connected to the negative electrode liquid chamber 120 to store the negative electrode liquid electrolyzed in the negative electrode liquid chamber 120,

The power supply unit 140 includes a grid 143 formed by intersecting a plurality of metal lines; And a plurality of troughs formed inside the pores and disposed between the lattice portions. The apparatus for manufacturing an electrolytic solution according to claim 1,

The electrolytic bath 130 is piped to a raw material supply unit 170 including a sulfuric acid solution containing vanadyl sulfate (VOSO ₄ ), which is a raw material for producing an electrolytic solution for a redox flow battery, and is connected to the anolyte chamber 110 and a solution of sulfuric acid in which raw material vanadyl sulfate (VOSO ₄ ) is dissolved in the cathode liquid chamber 120.

The circulation pump may further include a control unit for controlling the flow rate of the electrolytic solution. The control unit may further include a pressure gauge (not shown) and a control valve (not shown) .

A nitrogen supply device 160 may be connected to the anolyte chamber 110 and the catholyte chamber 120 so that the electrolysis reaction proceeds in a reducing atmosphere in which a nitrogen gas flows. (Not shown) so as to discharge the exhaust gas.

In addition, the anolyte chamber 110 may be configured to include a weak acid composed of citric acid, acetic acid, acetic acid, carbonic acid, phosphoric acid, or a mixture thereof to effectively prevent the salt formation that may occur during the electrolysis process described below.

The power supply unit 140 may include an electrode including an anode 141a and a cathode 141b and may sequentially and repeatedly supply a constant voltage and a constant current to the electrolytic bath 130. The electrode may be configured such that a plurality of metal wires cross each other And a plurality of ridges 147 formed inside the grid portion 143 and a plurality of ridges 147 formed inside the grid portion 143. [

Conventionally, when an electrolytic solution is prepared by electrolyzing vanadyl sulfate, when a lattice formed on a surface electrode is clogged with vanadyl sulfate particles, the current flow due to the movement of ions is changed into an electron flow in the particle, And the overvoltage was generated.

In the present invention, as shown in FIG. 2, an electrode including a grid 143 formed by intersecting a plurality of metal lines in parallel with each other, and a trough 147 formed by perforating the grid between the grid 143 and the grid 147 The mobility of electrons is improved through the ridge 147 formed to be used for the electrolytic solution so that the flow of electrons is smooth as compared with the grid electrode which was conventionally used in the production of electrolytic solution and the metal wire of the grid portion 143, As the electricity flows, the constant voltage and constant current can be supplied with a high output, so that the electrolysis time can be effectively shortened.

The electrode may be formed by forming a grid pattern 143 and a hole pattern 147 on the nonconductor through holes and then supplying platinum Pt, It is possible to use an electrode in which a metal wire is formed by coating titanium (Ti), gold (Au), silver (Ag) or a mixture thereof, but not limited thereto, And a surface electrode including a trench 143 is formed on the surface of the substrate.

The power supply unit 140 can be used without limitation as long as it can repeatedly supply constant voltage and constant current repeatedly at intervals of 20 to 40 minutes. Preferably, the power supply unit 140 supplies a constant voltage of 3 to 24 V and a constant current of 1 to 5 A It is possible to configure the power supply unit 140 as a power supply unit that can supply the power.

The diaphragm unit 150 includes a diaphragm 151 fixedly installed between the anolyte chamber 110 and the catholyte chamber 120 of the electrolytic bath 130 and a diaphragm 151 adjacent to the diaphragm 151, And a cation exchange membrane 153 disposed in the direction of the membrane.

When only the diaphragm 151 is provided between the anolyte chamber 110 and the catholyte chamber 120, the catholyte chamber (or the catholyte chamber) is formed by the constant voltage formed by the vanadium cations (VO ₂ ⁺ ) and hydrogen contained in the anolyte 120, and a salt may be formed in the cathode solution containing V ₂ (SO ₄ ) ₃ .

Thus, the present invention can be configured to arrange the cation exchange membrane 153 in the direction of the catholyte chamber 120 in the formed diaphragm 151.

The cation exchange membrane 153 serves to prevent permeation of hydrogen ions and cations. The cation exchange membrane 153 suppresses the inflow of hydrogen ions and vanadium cations by the cation exchange membrane 153, increases the anion concentration in the catholyte chamber 120, The purity of the catholyte can be increased.

At this time, the cation exchange membrane 153 may be formed of various known materials capable of preventing permeation of hydrogen ions and cations.

In addition, the diaphragm 151 is a beta-it is preferred to use a porous ceramic material comprising alumina _{(β alumina, β-Al 2} O 3). For reference, the beta-alumina (β alumina, β-Al ₂ O _3), a diaphragm 151 made of a porous ceramic material containing the nano-sized beta-configured to include alumina excellent in electrolyte retention, and electrolyte wettability And thermal stability, and is excellent in flexibility, and thus can be efficiently used for the production of electrolytes for redox flow cells.

An electrolytic solution containing vanadium ions having a valence of (V ⁵⁺ ) is generated in the anolyte chamber 110 that has been electrolyzed by the electrolytic solution producing apparatus 100 for the doffing current battery. In the catholyte chamber 120, An electrolytic solution containing a vanadium ion of the formula (V ²⁺ ) is generated. In the apparatus 100 for producing an electrolyte for a redox flow battery according to the present invention, the anolyte chamber 110 has a cathode solution And a cathode electrolyte tank 190 for storing a cathode solution electrolyzed from the cathode 141b so that a ^pentavalent V ⁵⁺ ) Of vanadium ions and a negative electrode solution containing vanadium ions of a dihydric (V ²⁺ ) state can be separately stored.

Hereinafter, a process for manufacturing an electrolyte using the apparatus 100 for manufacturing an electrolyte for a redox-flow battery according to the present invention will be described in detail.

A sulfuric acid solution in which vanadyl sulfate (VOSO ₄ ) is dissolved is supplied to the anolyte chamber 110 and the catholyte chamber 120 of the electrolytic bath 130 and a constant voltage and a constant current are supplied to the anolyte chamber 110 and the catholyte chamber 120 by 20 to 40 Minute, the VO ₂ ⁺ ions are first produced in the anolyte chamber 110 through the reaction shown in the formula (1).

The limit current value of the constant current is preferably set such that the area of the sulfuric acid solution used for electrolysis contacting the diaphragm 151 and the area of the diaphragm 151 Can be calculated as a product of current values.

≪ Formula 1 >

Then, the generated VO ₂ ⁺ ions are reacted as shown in the following formula ( ₂ ) by constant voltage and constant current supplied repeatedly to produce (VO ₂ ) ₂ SO ₄ , and a pentavalent vanadium ion VO ₂ ^{+ 5 +} is formed in the anolyte chamber 110.

(2)

Also, in the catholyte chamber 120, V ₂ (SO ₄ ) ₃ is firstly produced through the reaction shown in the following Chemical Formula 3 by repeatedly being electrolyzed by the supplied constant voltage and constant current.

(3)

At this time, when only the diaphragm 151 is installed between the common anolyte chamber 110 and the catholyte chamber 120, the catholyte chamber 120 (120) is formed by the constant voltage in which the vanadium cations (VO ₂ ⁺ ), And a salt may be formed in the cathode solution containing V ₂ (SO ₄ ) ₃ .

Therefore, the present invention can prevent the introduction of hydrogen ions and vanadium cations by the cation exchange membrane 153 installed in the direction of the cathode 141b of the diaphragm 151 formed in the catholyte chamber 120, The purity of the catholyte can be increased by increasing the anion concentration in the cation exchange membrane 153, and the cation exchange membrane 153 can prevent permeation of hydrogen ions and cations.

Then, the V ₂ (SO _{4) 3} produced as described above is repeated to by the constant voltage and constant current is supplied through a reaction such as the formula (4) is 2VSO ₄ is generated may be a divalent vanadium ions are generated.

Formula 4 is a formula showing that a solution containing V ^{2 +} is formed through the second electrolytic apparatus 200 according to the present invention.

≪ Formula 4 >

The repeated electrolysis is performed by setting the constant voltage of the power supply unit 140 in a predetermined order and delivering the constant current until the supplied current reaches the limit current value of the electrolytic bath 130. After reaching the limit current value, And the constant current is supplied in the range of 1 to 5 A while the temperature of the electrolytic bath 130 is kept constant in the range of 18 to 25 DEG C while the hydrogen ion concentration It is preferable to carry out the oxidation reduction potential (ORP) measurement in parallel.

The use of the apparatus 100 for producing an electrolyte for a redox flow battery according to the present invention can reduce the number of electrolysis and reduce the generation of salt due to mixing of a constant voltage and a constant current.

Furthermore, the redox flow battery electrolyte prepared in the manufacture of an electrolyte solution using the device 100, the concentration of the V ²⁺ ions in the catholyte produced may be reduced to the extent desired, but the anolyte V ⁵⁺ ions in accordance with the present invention It is difficult to secure the concentration. Since such a phenomenon may occur, the electrolysis step and the discharging step can be repeatedly performed in order to balance the charge (balance) of both polar ions.

The apparatus for manufacturing an electrolyte solution for a redox flow battery according to the present invention as described above has electrodes provided with gratings and perforations to improve the mobility of electrons and effectively supply a constant current, Can be effectively suppressed and the constant current of the constant voltage and the limiting current can be effectively supplied. As a result, the electrolysis time can be shortened by 50% or more by reducing the ionization time of the initial vanadium through repeated electrolysis, And the produced electrolytic solution has a high purity due to the remarkable reduction of the generation of salt due to the mixing of the constant voltage and the constant current.

100: electrolyte production apparatus 110: anolyte chamber
120: catholyte chamber 130: electrolytic chamber
140: power supply unit 141a: anode
141b: cathode 150: diaphragm
151: diaphragm 153: cation exchange membrane
160: nitrogen supply unit 170: raw material supply unit
180: positive electrode electrolyte tank 190: negative electrode electrolyte tank

Claims (9)

An electrolytic cell in which an anolyte chamber and a catholyte chamber are separated from each other by a diaphragm;
A power supply unit for sequentially and repeatedly supplying a constant voltage and a constant current through electrodes provided respectively in the anolyte chamber and the catholyte chamber;
A positive electrode electrolyte tank connected to the anolyte chamber and storing the anolyte solution electrolyzed in the anolyte chamber; And
And a catholyte tank connected to the catholyte chamber for storing catholyte solution electrolyzed in the catholyte chamber,
The diaphragm portion
A diaphragm fixedly installed between the anolyte chamber and the catholyte chamber; And
A cation exchange membrane disposed adjacent to the diaphragm and disposed in the direction of the catholyte chamber,
The electrode
A lattice portion formed by intersecting a plurality of metal lines in parallel with each other; And
And a plurality of troughs formed in the inside of the pores and disposed between the lattice portions,
The electrode is formed by forming a lattice pattern of the lattice pattern and the trough of the hole shape through the nonconductor,
The grid portion is coated with platinum (Pt), titanium (Ti), gold (Au), silver (Ag)
Wherein the electrode is provided with a perforation and a lattice formed thereon to improve the mobility of electrons through the trough and move the electricity through the metal line to supply a constant voltage and a constant current with a high output to shorten the electrolysis time An apparatus for producing electrolyte for redox flow battery. delete The method according to claim 1,
Wherein the anolyte chamber and the catholyte chamber are supplied with a solution of sulfuric acid in which vanadyl sulphate (VOSO ₄ ) is dissolved. The apparatus for manufacturing an electrolyte for a redox flow cell according to claim 1, The method according to claim 1,
Wherein the anolyte chamber and the catholyte chamber are connected to a nitrogen supply device. The apparatus for manufacturing an electrolyte solution for a redox flow cell according to claim 1, The method according to claim 1,
Wherein the anolyte is an electrolytic solution containing vanadium cations of ^pentavalent (V ⁵⁺ ). The apparatus for producing an electrolyte for a redox-flow battery according to claim 1, The method according to claim 1,
Wherein the catholyte is an electrolytic solution containing vanadium cations having a valence of (V ²⁺ ). The method according to claim 1,
Wherein the power supply unit sequentially and repeatedly supplies a constant voltage and a constant current at intervals of 20 to 40 minutes. The apparatus for manufacturing an electrolyte for a redox-flow battery according to claim 1, 8. The method of claim 7,
Wherein the power supply unit supplies a constant voltage of 3 to 24 V and supplies a constant current of 1 to 5 A. The apparatus for manufacturing an electrolyte for a redox flow battery according to claim 1, The method according to claim 1,
Wherein the anolyte chamber further comprises at least one electrode selected from the group consisting of citric acid, acetic acid, carbonic acid, and phosphoric acid.

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