WO2018091070A1 - Système électrochimique bipolaire - Google Patents

Système électrochimique bipolaire Download PDF

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Publication number
WO2018091070A1
WO2018091070A1 PCT/EP2016/077688 EP2016077688W WO2018091070A1 WO 2018091070 A1 WO2018091070 A1 WO 2018091070A1 EP 2016077688 W EP2016077688 W EP 2016077688W WO 2018091070 A1 WO2018091070 A1 WO 2018091070A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
electrochemical system
stacks
bipolar electrochemical
bipolar
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2016/077688
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English (en)
Inventor
Thomas Danko
Thomas Kania
Markus Schuster
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Outotec Finland Oy
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/EP2016/077688 priority Critical patent/WO2018091070A1/fr
Publication of WO2018091070A1 publication Critical patent/WO2018091070A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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 invention relates to a bipolar electrochemical system comprising at least one module with at least two bipolar stacks wherein each stack consists of at least two cells each having an anode, a separator, a cathode, at least one electrolyte inlet and at least one electrolyte outlet opposed to the respective electrolyte inlet, wherein there is a serial electrical connection between the stacks in the respective module, and wherein there is a fluidic connection directed from one electrolyte inlet to the respective electrolyte outlet for the electrolyte in at least one stack of at least one module.
  • 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.
  • An example is a Vanadium Redox Flow Battery using two different liquid electrolytes, but the invention applies to all bipolar electrochemical systems which use at least one liquid electrolyte
  • shunt currents 13a be- tween the single cells of each stack across the electrolyte and also shunt currents between the stacks of the bipolar electrical system. Shunt currents in electrochemical systems leads to high current losses and thus lower their economic feasibility.
  • Preconditions for the formation of shunt currents are differences of the electric potential and electrically conductive fluid phases (electro- lyte 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 re- sistance that is dependent on cross section and length of the electrolyte channels.
  • 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 efficiency.
  • 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.
  • 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.
  • a simple but expensive way to reduce shunt currents between two stacks is the choice of a parallel electrical connection of each stack to avoid the high potential differences generated by an electric series connection of the stacks.
  • Figure 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 simple way to increase the electric resistance is to extend the length of the ducts or to reduce the duct diameter.
  • a bipolar electrochemical system comprising the features of claim 1 .
  • a bipolar electrochemical system comprising at least one module with at least two bipolar stacks.
  • Each stack consists of at least two cells.
  • Each cell in turn features an anode, a separator, a cathode, at least one electrolyte inlet and at least electrolyte outlet opposed to the respec- tive electrolyte inlet.
  • a serial electrical connection is provided between all stacks of one module. Further a fluidic connection directed from one electrolyte inlet to the respective electrolyte outlet for the electrolyte is established in at least one stack of at least one module.
  • this fluid connection is formed as a straight line between is the electrolyte inlet to the respective electrolyte outlet.
  • the essential feature of the invention is that the serial electrical connection is arranged perpendicular to the fluidic connection.
  • the fluidic connection and the electrical connection form two straight lines. Where these two lines intersect at a point, four angles are formed. Perpendicularly in the sense of the invention means, that two angles opposite each other are between 75 and 90 °, preferably 85 and 90 °, most preferably all four angles are 90 °.
  • the bipolar electrochemical system according to the invention is very simple in its set-up and obviates the need to include additional, complicated and expensive equipment like shunt current interrupters or converters.
  • This design prevents a fluid connection between stacks of extensively different elec- trie potential levels, resulting in the avoidance of shunt currents since these require a fluidic connection between different stacks.
  • the electrolyte inlets of two adjacent stacks in at least one module are fluidically connected in a parallel connection.
  • the number pumping system including an electrolyte storage tank, a pump and a tank for spent electrolyte is reduced.
  • a further embodiment of the invention there is a first electrolyte inlet (6) and a first electrolyte outlet opposed to the first electrolyte inlet for the anolyte and a second electrolyte inlet and a second electrolyte outlet opposed to the second electrolyte inlet for the catholyte.
  • the inventive system can be used for cells with different catholyte and anolyte.
  • a first fluid connection between the first electrolyte inlet and the first electrolyte outlet and a second fluid connection between the second electrolyte inlet and the second electrolyte outlet have preferably the same flow direction to adjust the electrical connection.
  • the separator is a membrane.
  • a membrane is a selective barrier, whereby ions are delivered selectively from the anodic part comprising the anode and a cathodic part comprising the cathode.
  • each cell in is divided liquid-impermeably into an anodic part comprising the anode and a cathodic part comprising the cathode.
  • each module comprises 4 to 100, preferably 4 to 20 stacks and/or each stack comprises 10 to 200, preferably 20 to 100.
  • a preferred system contains at least one electrolyte cycle comprising a reservoir of electrolyte, at least one pumping mechanism and a tank for spent electrolyte as well as corresponding fluid lines to ensure a steady electrolyte concentration.
  • such a system contains one electrolyte cycle for the anolyte and one electrolyte cycle for the catholyte.
  • each module is connected to a DC/DC converter.
  • a DC-to-DC converter is an electronic circuit which converts a source of direct current (DC) from one voltage level to another direct current (DC).
  • Linear DC/DC converter can only output at lower voltages from the input. Elec- tronic switch-mode DC to DC converters convert one DC voltage level to another, by storing the input energy temporarily and then releasing that energy to the output at a different voltage.
  • the storage may be in either magnetic field storage components (inductors, transformers) or electric field storage components (capacitors). This conversion method is more power efficient (often 75% to 98%) than linear voltage regulation.
  • Switched capacitor converters rely on alternately connecting capacitors to the input and output in differing topologies. For example, a switched-capacitor re- ducing converter might charge two capacitors in series and then discharge them in parallel. This would produce an output voltage of half the input voltage, but at twice the current (minus various inefficiencies).
  • DC-to-DC converters are designed to move power in only one direction, from the input to the output.
  • all switching regulator topologies can be made bi-directional by replacing all diodes with independently controlled active rectification.
  • a bi-directional converter can move power in either direction, which is useful in applications requiring regenerative braking.
  • 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 schematically depicts a design of an electrochemical system according to the invention applied to one module
  • Fig. 6 schematically depicts a design of an electrochemical system according to the invention applied to multiple modules
  • Fig. 7 shows an alternative design of an electrochemical system according to the invention applied to multiple modules
  • Fig. 8 shows cumulative shunt currents as function of stack number
  • the design of the bipolar electrochemical system according to the invention can be applied to one module Mi as shown in figure 5.
  • Each bipolar stack 1 comprises at least two cells. All bipolar stacks 1 are electri- cally connected which is depicted with line X.
  • the electrically connected stacks 1 form a module Miwhereby the stacks in the modules have an equal or very similar electric potential with a difference ox macimum 10 V.
  • the electrical connection X is fed with the converter 15, prefer- ably a DC/DC converter.
  • the stack shows one electrolyte inlet 6 for the anolyte and one electrolyte inlet 6' for the catholyte as well as the corresponding electrolyte outlet 7 and 7'.
  • a fluid connection Y is established between the anolytic electrolyte inlet 6 and the anolytic electrolyte outlet 7 as well as between the catholytic electrolyte inlet 6' and the catholytic electrolyte outlet 7 .
  • the 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.
  • This fluid connection Y is positioned such that it is perpendicular to the electric connection X.
  • the invention also covers multiple modules as shown in figure 6.
  • the electrical connection X is done perpendicularly in series according to the usual approach in the state of the art, while the respec- tive fluidic stack connection Y is done perpendicularly, connecting stacks of different electrical strings.
  • the perpendicular fluidic stack connection Y exclusively links stacks 1 which are of the same electric potential level, thereby eliminating shunt currents due to a lack of potential difference between fluidically connected stacks.
  • Figure 8 shows the maximum loss caused by shunt currents relating to the overall voltage of all stack. It is obviously, that with increasing stack number, plotted on the X-axis, the maximum loss increases nearly linear. For a system featuring 12 stacks, the overall loss is about 24 %.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne un système électrochimique bipolaire comprenant au moins un module (M1 - Mn) avec au moins deux empilements bipolaires (1). Chaque empilement (1) est constitué d'au moins deux cellules (2) ayant chacune une anode (3), un séparateur (4), une cathode (5), au moins une entrée d'électrolyte (6) et au moins une sortie d'électrolyte (7) opposée à l'entrée d'électrolyte respective (6). Il y a une connexion électrique en serie (X) entre les empilements (1) dans le module respectif (Mi - Mn) avec une connexion fluidique (Y) dirigée d'une entrée d'électrolyte (6) à la sortie d'électrolyte respective (7) pour l'électrolyte dans au moins un empilement (1) d'au moins un module (M1 - Mn). La connexion électrique en série (X) est perpendiculaire à la connexion fluidique (X).
PCT/EP2016/077688 2016-11-15 2016-11-15 Système électrochimique bipolaire Ceased WO2018091070A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2016/077688 WO2018091070A1 (fr) 2016-11-15 2016-11-15 Système électrochimique bipolaire

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2016/077688 WO2018091070A1 (fr) 2016-11-15 2016-11-15 Système électrochimique bipolaire

Publications (1)

Publication Number Publication Date
WO2018091070A1 true WO2018091070A1 (fr) 2018-05-24

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Citations (10)

* 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"
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
WO2007131250A1 (fr) * 2006-05-15 2007-11-22 Cellstrom Gmbh Module de courant électrochimique avec un dispositif permettant de juguler un courant de dérivation
WO2014145844A1 (fr) * 2013-03-15 2014-09-18 Unienergy Technologies, Llc Systèmes et procédés d'atténuation du courant de dérivation et des pertes mécaniques dans les systèmes électrochimiques
US20140272484A1 (en) * 2013-03-15 2014-09-18 Unienergy Technologies, Llc Electrochemical cell stack having a protective flow channel
WO2016128038A1 (fr) * 2015-02-11 2016-08-18 Outotec (Finland) Oy Système électrochimique bipolaire

Patent Citations (10)

* 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"
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
WO2007131250A1 (fr) * 2006-05-15 2007-11-22 Cellstrom Gmbh Module de courant électrochimique avec un dispositif permettant de juguler un courant de dérivation
WO2014145844A1 (fr) * 2013-03-15 2014-09-18 Unienergy Technologies, Llc Systèmes et procédés d'atténuation du courant de dérivation et des pertes mécaniques dans les systèmes électrochimiques
US20140272484A1 (en) * 2013-03-15 2014-09-18 Unienergy Technologies, Llc Electrochemical cell stack having a protective flow channel
WO2016128038A1 (fr) * 2015-02-11 2016-08-18 Outotec (Finland) Oy Système électrochimique bipolaire

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