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WO2016128038A1 - Système électrochimique bipolaire - Google Patents

Système électrochimique bipolaire Download PDF

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Publication number
WO2016128038A1
WO2016128038A1 PCT/EP2015/052860 EP2015052860W WO2016128038A1 WO 2016128038 A1 WO2016128038 A1 WO 2016128038A1 EP 2015052860 W EP2015052860 W EP 2015052860W WO 2016128038 A1 WO2016128038 A1 WO 2016128038A1
Authority
WO
WIPO (PCT)
Prior art keywords
perforated plate
electrolyte
electrochemical system
bipolar electrochemical
bipolar
Prior art date
Application number
PCT/EP2015/052860
Other languages
English (en)
Inventor
Michael STRÖDER
Markus Schuster
Thomas Kania
Original Assignee
Outotec (Finland) Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Outotec (Finland) Oy filed Critical Outotec (Finland) Oy
Priority to PCT/EP2015/052860 priority Critical patent/WO2016128038A1/fr
Publication of WO2016128038A1 publication Critical patent/WO2016128038A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • H01M10/0418—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes with bipolar electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention is directed to a bipolar electrochemical system according to the preamble of claim 1 comprising at least one bipolar stack consisting of a plurality of cells each having an anode, a separator, a cathode, an electrically conductive liquid as the electrolyte, an electrolyte inlet and an electrolyte outlet; at least one electrolyte supply circuit and at least one shunt current interrupter.
  • Bipolar electrochemical systems like redox flow batteries or alkaline electrolyz- ers usually comprise at least one bipolar stack with multiple single cells.
  • a bipolar stack 1 consists of multiple single cells 2 with anode 3, separator 4, cathode 5, electrolyte inlet 6 and outlet 7 for each cell 2.
  • a liquid electrolyte is supplied to the at least one bipolar stack through at least one electrolyte supply circuit 8, including pipe connections, storage tanks 9 and active or passive fluid conveying systems 10 such as natural circulation or a pump.
  • the electrolyte is withdrawn from the cells through an electrolyte withdrawal circuit (lines) 1 1 and recirculated to the storage tanks 9.
  • a Vanadium Redox Flow Battery using two different liquid electrolytes is shown as an example, but the invention applies to all bipolar electrochemical systems which use at least one liquid electrolyte
  • the coupling of the regarded system to an electric energy system or to the grid can be realized by a transformer and a rectifier, a converter or an inverter and a transformer, depending on the direction of the flow of the electric energy.
  • the voltage of a bipolar stack is the sum of all cell voltages.
  • the electrolyte feed to every single cell is realized by a stack internal distribution system whereby an electrical connection of each cell of the stack across the electrolyte is given. The same is true for the electrolyte withdrawal from the cells. If at least two stacks are used, there exist electrical connections between the stacks via the electrolyte supply circuit and via the electrolyte withdrawal circuit as well. Result is the formation of shunt currents 13a between the single cells of each stack across the electrolyte and shunt currents 13b between the stacks of the bipolar electrical system.
  • shunt currents in electro- chemical systems reduce the efficiency factor significantly and thus its economic feasibility.
  • Preconditions for the formation of shunt currents are differences of the electric potential and electrically conductive fluid phases (electrolyte solutions). Both preconditions are given in a typical bipolar electrochemical system using liquid electrolytes.
  • Fig. 1 shows the state of the art configuration of a Vanadium Redox Flow Battery, which uses two different liquid electrolytes, without any measures to reduce shunt currents as well as a schematic description of arising shunt currents within the system. To facilitate the understanding, only some exemplary shunt currents are shown in the figure. Other bipolar electrochemical systems need one liquid electrolyte only, but the principle of shunt current remains the same. The magnitude of the shunt currents depends on the differences of the electric potential as well as on conductivity properties of the electrolyte and on the geometrical dimensions of the electrolyte lines. Characteristic is the ohmic resistance that is dependent on cross section and length of the electrolyte chan- nels.
  • shunt currents are essential for the efficiency increase of the system.
  • Higher ohmic resistances within the electrolyte channels reduce the shunt currents and therefore increase the electrochemical efficien- cy.
  • smaller cross-sections and longer lengths of the electrolyte lines also increase the pressure drop in the electrolyte system and hence the necessary pump power, which in turn decreases the overall energy efficiency of the bipolar system.
  • Two main approaches are known to minimize or to avoid shunt currents: Manipulation of the electrolyte flow through the electrochemical system to increase the ohmic resistances and reducing the differences of potential by choice of an alternative electrical connection. The reduction of shunt currents within a stack 13a and between several stacks 13b must be considered separately.
  • FIG. 2 shows the state of the art arrangement of such a system, including measures to reduce shunt currents within a stack but without any measures to reduce shunt currents between several stacks.
  • each electrolyte channel has a meander structure 14.
  • FIG. 3 shows the principle of this alternative electrical connection arrangement, which requires the usage of a transformer and rectifier, a converter or an inverter and transformer 15 for each stack to couple the bipolar electrochemical system to the electrical energy system or to the grid. It sets all stacks of the system to the same defined electrical potential level. This arrangement decreases shunt currents significantly due to a lack of potential difference.
  • a second approach manipulates the electrolyte flow.
  • a bipolar electrochemical system comprising the fea- tures of claim 1 , wherein according to the invention the shunt current interrupter comprises a perforated plate having boreholes penetrating the perforated plate, wherein electrolyte is guided to an upper surface of the perforated plate to flow through the boreholes, and wherein on a lower surface of the perforated plate, facing a collecting section, grooves are provided between adjacent boreholes. There is a drop height h d between the lower surface of the perforated plate and the electrolyte level within the collecting section.
  • the invention shows a very simple shunt current interrupter apparatus that is able to reliably create discontinuous electrolyte flows. The shunt current across the apparatus is totally avoided, because the space between the droplets is filled with an non-conductive gas which does not allow the shunt current to flow.
  • the cross section of said grooves is rectangular, triangular, trapezoidal or circular. This design has proven to be particularly effective in forming droplets and preventing the formation of a fluid film.
  • the angle between the inner edge of the groove and the lower surface of the perforated plate is between 30° and 120°, more preferably between 45° and 90° and most preferably between 45° and 75°.
  • the width w w of the wall between the borehole and the adjacent groove is between 0.0 and 3.0 mm, preferably between 0.1 and 1 .0 mm.
  • the invention preferably provides a circumventing groove between the outermost boreholes and the outer circumference of the perforated plate.
  • the perforated plate may have a circular or rectangular shape when viewed from above.
  • the drop height h d between the lower surface of the perforated plate and the fluid level F within the collecting section is between 5 and 400 mm, more preferably between 12 and 200 mm.
  • the invention also is directed to a method for operating a bipolar electrochemical system as described above, wherein the following relation is fulfilled
  • Pg gas phase (around the droplets) density (kg/m 3 )
  • the Weber number (We) is a dimensionless number in fluid mechanics that describes the ratio between inertia and surface forces.
  • Fig. 4 shows the arrangement of the shunt current interrupters 16 in the electrolyte supply lines 8 and the electrolyte withdrawal lines 1 1 to and from each stack of a Vanadium Redox Flow Battery as an example of a bipolar electrochemical system, whereby the shunt currents 13b between stacks are avoided. It is within this invention to also apply the shunt current interrupters within a stack. In this case the shunt current interrupters are applied in the electrolyte inlets 6 and electrolyte outlets 7 to of each cell and replace the meander structures 14. This avoids the shunt currents 13a within the stack.
  • Fig. 1 schematically depicts a bipolar electrochemical system wherein shunt currents are formed
  • Fig. 2 shows a state of the art arrangement of the bipolar electrochemical system
  • Fig. 3 schematically shows the reduction of shunt currents by choice of an alternative electrical connection
  • Fig. 4 schematically shows shunt current reduction by fluid interruption
  • Fig. 5 shows cumulative shunt currents as function of stack number
  • Fig. 6 schematically depicts a shunt current interrupter according to the present invention
  • Fig. 7 shows alternative embodiments of the cross section of the grooves in the shunt current interrupter according to the present invention
  • Fig. 8 shows a shunt current interrupter plate from below
  • Fig. 9 shows a cross section of the shunt current interrupter plate along line
  • the bipolar electrochemical system includes a shunt current interrupter 16 as schematically shown in Fig. 6.
  • the shunt cur- rent interrupter 16 consists of a perforated plate 17, a drum section 18 and a collecting section 19.
  • the system interrupts the continuous electrolyte flow by creating droplets with the maximum droplet diameter c/ d under the perforated plate 17. This causes a significant reduction of the shunt currents. If the drop height h d between the lower surface of the perforated plate and the liquid level F in the collecting section is sufficiently high, the shunt current across the shunt current interrupter is decreased to zero and thereby completely avoided.
  • Centerpiece of the invented shunt current interrupter 16 is the perforated plate 17. It can have either an angled or a circular base. As shown in Fig. 6 to 9, the plate 17 contains penetrating boreholes 20 with the diameter d h and grooves or slots 21 with the groove or slot width w s . As shown in Fig. 8, an additional circumventing groove 23 is provided between the outermost boreholes 20 and the outer circumference of the perforated plate 17. The grooves 21 , 23 are provided on the lower surface 25 of the perforated plate 17. The cross section of the grooves 21 , 23 can be rectangular as well as triangular, trapezoidal or circular as shown in Fig. 7. It is within the invention to provide other suitable shapes, such as polygonal forms.
  • the angle a s between the inner edge 21 i of groove 21 , 23 and the lower surface 25 of the perforated plate 17 is between 30° and 120°, preferably between 45° and 90° and most preferably between 45° and 75°.
  • a further characteristic of the perforated shunt current interrupter plate 17 is the web width w w between the boreholes 20 and the grooves 21 corresponding to the width of the walls 22 between the boreholes 20 and the grooves 21 .
  • the web works as tearing edge for the droplets and avoids the formation of a current conductive fluid coat due to agglomerating droplets as well as the formation of a fluid jet. If the equation d. + 2 - w ⁇ d . (0.1 ) is fulfilled, the web width between the borehole 20 and the groove 21 is primarily decisive for the droplet size and not the physical properties of the fluid. Furthermore, the drop height of the droplets h d is decisive for the shunt current interrupting properties. As shown as an example in Fig 8, the perforated shunt cur- rent interrupter plate 17 has a circular base. Other shapes, such as a rectangular or polygonal base are also possible within the invention.
  • electrolyte will be introduced via the electrolyte supply circuit 8 into the shunt current interrupter 16 and is collected above the upper surface 24 of the perforated plate 17 forming an upper fluid level F u above said plate 17 (see Fig. 6).
  • the electrolyte then flows through the boreholes 20 wherein on the lower surface 25 of the plate 17 droplets 26 are generated and drip into the collecting section 19 without the formation of a fluid film on the lower surface 25 of the plate 17.
  • the Weber number for the operation range of the shunt current interrupter according to the invention preferably is between 0.001 and 2.0, more preferably between 0.002 and 1 .0.
  • the minimal web width w w between the boreholes 20 and the grooves 21 is between 0.0 mm and 3.0 mm, preferably between 0.0 mm and 1 .0 mm.
  • within the collecting section 19 is between 5 mm and 400 mm, preferably between 12 mm and 200 mm.
  • the local interruption of the electrolyte flow preferably is controlled and adjusted to the working flow rate. Additionally, the invention leads to minor efficiency losses so that the electrochemical system can run within the designed and defined working range. This ensures the efficient mini- mization of the shunt currents at the design point as well as in defined part-load or overload operation points.
  • the present invention ensures a controlled and defined fluid flow interruption. It also enables tailor made droplet generation adapted to the regarded electro- chemical system and working parameters. This ensures a firm and wideband shunt current interruption in a given and defined operating range. This operation range is dependent on the borehole diameter d h , the web width w w between the boreholes 20 and the grooves 21 and the angle a s between the groove edge 21 i and the plate 17. It can be predefined and adapted to the requirements of the system. The defined web width w w between the boreholes 20 and the grooves 21 provides an immediate droplet break-off and consequently ensures a minimum size of the drop height of the droplets h d and consequently of the shunt current interruption apparatus. List of reference numbers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne un système électrochimique bipolaire qui comprend au moins un empilement bipolaire (1) constitué d'une pluralité de cellules (2) ayant chacune une anode (3), un séparateur (4), une cathode (5), un orifice d'admission d'électrolyte (6) et un orifice de sortie d'électrolyte (7); au moins un circuit d'alimentation en électrolyte (8) et un interrupteur de courant de dérivation (16). L'interrupteur de courant de dérivation (16) comprend une plaque perforée (17) ayant des trous de sonde (20) pénétrant dans la plaque perforée (17), l'électrolyte étant guidé vers une surface supérieure (24) de la plaque perforée (17) de sorte à s'écouler à travers les trous de sonde (20). Sur une surface inférieure (25) de la plaque perforée (17) faisant face à une section de collecte (19), des rainures (21) sont formées entre des trous de sonde adjacents (21).
PCT/EP2015/052860 2015-02-11 2015-02-11 Système électrochimique bipolaire WO2016128038A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2015/052860 WO2016128038A1 (fr) 2015-02-11 2015-02-11 Système électrochimique bipolaire

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2015/052860 WO2016128038A1 (fr) 2015-02-11 2015-02-11 Système électrochimique bipolaire

Publications (1)

Publication Number Publication Date
WO2016128038A1 true WO2016128038A1 (fr) 2016-08-18

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018091070A1 (fr) * 2016-11-15 2018-05-24 Outotec (Finland) Oy Système électrochimique bipolaire
WO2022269602A1 (fr) * 2021-06-21 2022-12-29 H2Pro Ltd Dispositif et procédé d'élimination de courant de dérivation ionique

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US679050A (en) 1899-05-11 1901-07-23 S D Warren & Company Liquid-feed device for electrolytic apparatus.
CH206960A (de) 1938-08-06 1939-09-15 Oerlikon Maschf Bipolarer Elektrolyseur.
US2673232A (en) 1950-01-24 1954-03-23 Diamond Alkali Co Feed device for electrolytic cells
DE3140347A1 (de) 1980-10-14 1982-09-02 General Electric Co., Schenectady, N.Y. "elektrochemische zellenbaugruppe und verfahren zur leckstromminimierung"
US4533455A (en) * 1980-10-14 1985-08-06 Oronzio De Nora Impianti Elettrochimici S.P.A. Bipolar separator plate for electrochemical cells
JPS62160664A (ja) 1986-01-07 1987-07-16 Sumitomo Electric Ind Ltd 電解液循環型２次電池
DE69916869T2 (de) 1998-09-29 2005-03-10 Regenesys Holding Ltd., Swindon Elektrochemische zelle
US20140065460A1 (en) * 2012-09-05 2014-03-06 Energy Storage Systems, Inc. Redox and plating electrode systems for an all-iron hybrid flow battery

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US679050A (en) 1899-05-11 1901-07-23 S D Warren & Company Liquid-feed device for electrolytic apparatus.
CH206960A (de) 1938-08-06 1939-09-15 Oerlikon Maschf Bipolarer Elektrolyseur.
US2673232A (en) 1950-01-24 1954-03-23 Diamond Alkali Co Feed device for electrolytic cells
DE3140347A1 (de) 1980-10-14 1982-09-02 General Electric Co., Schenectady, N.Y. "elektrochemische zellenbaugruppe und verfahren zur leckstromminimierung"
US4533455A (en) * 1980-10-14 1985-08-06 Oronzio De Nora Impianti Elettrochimici S.P.A. Bipolar separator plate for electrochemical cells
JPS62160664A (ja) 1986-01-07 1987-07-16 Sumitomo Electric Ind Ltd 電解液循環型２次電池
DE69916869T2 (de) 1998-09-29 2005-03-10 Regenesys Holding Ltd., Swindon Elektrochemische zelle
US20140065460A1 (en) * 2012-09-05 2014-03-06 Energy Storage Systems, Inc. Redox and plating electrode systems for an all-iron hybrid flow battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018091070A1 (fr) * 2016-11-15 2018-05-24 Outotec (Finland) Oy Système électrochimique bipolaire
WO2022269602A1 (fr) * 2021-06-21 2022-12-29 H2Pro Ltd Dispositif et procédé d'élimination de courant de dérivation ionique

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