WO2022033750A1 - Système de batterie à flux rédox et procédé de fonctionnement - Google Patents

Système de batterie à flux rédox et procédé de fonctionnement Download PDF

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Publication number
WO2022033750A1
WO2022033750A1 PCT/EP2021/066399 EP2021066399W WO2022033750A1 WO 2022033750 A1 WO2022033750 A1 WO 2022033750A1 EP 2021066399 W EP2021066399 W EP 2021066399W WO 2022033750 A1 WO2022033750 A1 WO 2022033750A1
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WO
WIPO (PCT)
Prior art keywords
battery
battery module
converter
switch
electrolyte
Prior art date
Application number
PCT/EP2021/066399
Other languages
German (de)
English (en)
Inventor
Thomas LÜTH
Original Assignee
Voith Patent Gmbh
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 Voith Patent Gmbh filed Critical Voith Patent Gmbh
Priority to EP21739263.8A priority Critical patent/EP4193408A1/fr
Publication of WO2022033750A1 publication Critical patent/WO2022033750A1/fr

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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type 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

Definitions

  • the invention relates to a vanadium redox flow battery system and a method for operating such a system.
  • the invention particularly relates to redox flow battery systems with a high output voltage.
  • the operating procedure mainly concerns the conditioning of the battery system.
  • the invention thus relates to a battery system which comprises a plurality of battery modules, the battery system being designed in such a way that the battery modules are connected in series during the charging and discharging of the system, i.e. they form a string.
  • WO 2012/020277 A1 discloses such a method on page 5.
  • both tanks ie the tank for the negative electrolyte and the tank for the positive electrolyte
  • a solution which contains V 3+ and V 4+ ions in a ratio of approximately 1:1 are filled with a solution which contains V 3+ and V 4+ ions in a ratio of approximately 1:1.
  • the solutions from the two tanks are circulated through the respective chambers of the cells, at the same time as an electric current is passed through the cells.
  • the negative electrolyte contain only trivalent vanadium and the positive electrolyte only tetravalent vanadium.
  • the inventor has set himself the task of specifying an operating method, i.e. primarily a conditioning method, for a battery system with a number of battery modules which can be connected in series. Furthermore, the inventor has set himself the task of specifying battery systems which are designed in such a way that the operating method according to the invention can be carried out advantageously.
  • an operating method i.e. primarily a conditioning method
  • FIG. 4 battery system in a further embodiment
  • FIG. 5 battery module in a further embodiment
  • FIG. 1 shows a battery module on the left side in a schematic representation.
  • the battery module is denoted by 1.
  • the battery module includes a cell arrangement, which is denoted by 2, and a tank device, which is denoted by 3.
  • the cell arrangement 2 is an arrangement of a large number of redox flow cells, which can be arranged in any way. For example, it could be a single cell stack, a series connection of several stacks, a parallel connection of several stacks, or a combination of series and parallel connection of several stacks. In any case, all cells of the cell arrangement 2 contribute to storing electrical energy when charging in the battery module 1 or to supplying electrical energy when discharging the battery module 1 .
  • the tank device 3 is used to store the electrolyte and to supply the Cell arrangement 2 with electrolyte.
  • the tank device 3 comprises at least two tanks, a pipe system for connecting the tanks to the cell arrangement 2 and pumps for conveying the electrolyte.
  • Figure 1 shows two separate pumps.
  • the electrolyte could just as well be conveyed with a double-head pump, ie with two pumps which are driven by a common motor.
  • the tank device 3 is designed in such a way that it can supply all cells of the cell arrangement 2 with electrolyte.
  • All cells in cell arrangement 2 therefore always contribute to charging the electrolyte in tank device 3, and all cells in cell arrangement 2 always contribute to discharging the electrolyte in tank device 3 when battery module 1 is charged or discharged.
  • the battery module 1 shown in FIG. 1 includes two measuring devices, which are labeled 4 and 5 .
  • the measuring device which is denoted by 4, is a measuring device for providing the so-called open circuit voltage (OCV).
  • OCV value is a measure of the state of charge of the battery module (SoC).
  • the measuring device which is denoted by 5 , is a measuring device for providing the terminal voltage of the cell arrangement 2 and thus also of the battery module 1 .
  • the terminal voltage differs from the no-load voltage by the voltage that drops across the internal resistance of the cell arrangement 3.
  • a symbolic representation of the battery module 1 is shown on the right-hand side of FIG. This symbolic representation is used below.
  • FIG. 2 shows a schematic representation of a battery system in a first embodiment.
  • the battery system comprises at least two battery modules, one of which is denoted by 1, a bidirectional converter (engl. bidirectional power conversion system - PCS), which is denoted by 6, and a controller, which is denoted by 8.
  • the battery modules 1 are connected in series and connected to the converter 6 .
  • Four battery modules are shown in FIG Number of other modules should indicate.
  • the converter 6 takes over the connection of the battery system to the grid or to a higher-level electrical system.
  • the battery system also includes for each battery module 1 a first switch, one of which is labeled 9 , and a second switch, one of which is labeled 10 .
  • the first switches 9 are each arranged in series with the battery modules 1, whereby it is of course irrelevant on which side of the respective battery module the associated switch 9 is arranged.
  • the second switches 10 are each arranged in a bypass line around a respective battery module 1 and the associated first switch 9 .
  • all switches 9 and 10 are shown in the open state. This operating state, ie that both switches of a switch pair 9 and 10 are open at the same time, can be assumed in the method according to the invention in the embodiment associated with FIG. In most other operating states, however, the switches are controlled by the control device 8 in such a way that exactly one switch of each switch pair of a first and second switch is closed and one switch is open (alternately open and closed).
  • a pair of switches has exactly two switch positions, with the associated battery module 1 being in the series connection of the battery system in the first switch position (first switch 9 closed and second switch 10 open), and in the second switch position (first switch 9 open and second switch 10 closed) the associated battery module 1 is separated from the series connection of the battery system by the bypass line.
  • the opening of the first switch 9 with the switch 10 closed prevents the module from being discharged via the bypass line.
  • the control device 8 is connected to each battery module in such a way that it can record the measured values of the measuring devices 4 and 5, respectively.
  • the control device 8 is connected to each of the switches 9 and 10 in such a way that it can determine the respective switch position in order to switch the battery modules 1 into or out of the Senen circuit. These connections can also be wireless.
  • FIG. 2 represents the minimum configuration for executing the operating method according to the invention. It should be mentioned here that when executing the operating method according to the invention in its most general form only the terminal voltage of the battery modules 1 must be measured. This means that it is not necessary for the battery modules 1 to also include a measuring device for detecting the OCV.
  • the method according to the invention is described below in a first embodiment based on the configuration of FIG.
  • This is a method for conditioning all battery modules 1 of the battery system. This procedure is therefore carried out in any case when such a battery system is put into operation for the first time. However, it is also possible that this method is carried out after a battery system has been in operation for a long time, for example if the battery system is to be regenerated because undesirable imbalances or capacity losses have occurred. It is therefore assumed that there is electrolyte in all the tanks of the battery modules 1, which consists of a mixture of V 3+ and V 4+ ions, which are contained in approximately equal proportions. This can be realized by external filling or mixing of the existing tank contents. In addition, it is assumed that all cells of a cell arrangement 2 of each battery module 1 are completely filled with electrolyte before a current flows through the corresponding battery module 1 .
  • the method according to the invention comprises the following steps:
  • step S2 Feeding a current into the battery module 1, which has been connected to the converter 6 in step S1, until the electrolyte in the cells of the cell arrangement 2 of the same battery module 1 reaches a state of charge that is at least as high as a predefined threshold value ;
  • Step S4 feeding a current into the series circuit from step S3; Steps S1 and S2 are repeated successively in this order, with a different battery module 1 always being connected to the converter 6 in the respective execution of step S1 and in the subsequent Execution of S2 is supplied with a current until all battery modules 1 meet the condition mentioned in the definition of step S2, which is then followed by execution of steps S3 and S4 in this order.
  • the respective battery module 1 initially has no counter-voltage and a very high internal resistance. It is clear that the converter 6 supplying the current must be able to deal with this situation.
  • the injected current may be reduced compared to the current injected in step S4.
  • the direction in which the current is fed in in step S2 is arbitrary. Since the direction in which the current is fed in in step S2 determines the charging current direction, all battery modules must of course be fed with the same current direction in step S2. In practice, however, there is a design-related preferred direction for the charging current in the battery modules and thus for the current in step S2.
  • step S2 So that the condition specified in step S2 can be met in a sufficiently short time interval, the rate at which electrolyte is conveyed during step S2 must not be too high.
  • the relevant limit for this is the so-called stoichiometric flow rate. More information can be found, for example, in the document "Model-based Design and Optimization of Vanadium Redox Flow Batteries” - DISSERTATION by Dipl.-Ing. Sebastian König at the Faculty of Electrical Engineering and Information Technology of the Düsseldorf Institute of Technology in Chapter 8 "Flow rate optimization”. If a delivery rate were set in step S2 that exceeds the stoichiometric flow rate, step S2 would last at least until the electrolyte contained in the tank device has been completely circulated once.
  • the process according to the invention can be carried out particularly advantageously in the embodiment described above, ie in a short time, if the delivery rate in steps S2 is set to be less than the stoichiometric delivery rate.
  • this restriction does not exist in other embodiments of the method according to the invention described below, so that the corresponding method can also be carried out in an advantageously short time when the delivery rate is greater than the stoichiometric delivery rate.
  • the inventor has recognized that the method according to the invention can be carried out advantageously if the threshold value is in a range of 2-8%.
  • the threshold value is particularly advantageously selected in a range of 3-7% or in a range of 4-6%.
  • the state of charge can be determined indirectly via the terminal voltage. That is, in practice, the termination criterion of step S2 is that the cell arrangement of the relevant battery module is supplied with current in step S2 until the terminal voltage exceeds a predefined threshold value.
  • the threshold value for the terminal voltage which corresponds to the threshold value for the state of charge, depends on various circumstances of the cell arrangement and the amperage of the supply current, as well as the voltage drop at the internal resistance of the cell arrangement. However, these relationships are fully known to a person skilled in the art, so that, instructed by the present application, he can easily define the required threshold value for the terminal voltage.
  • Step S4 is carried out until the entire volume of all tanks is conditioned.
  • step S4 merges seamlessly into a conventional charging process for the battery system. It can happen that the different battery modules have different OCV values and therefore different SoC values. This is particularly the case if there were deviations in the composition of the electrolyte filled in between the individual modules, ie if the associated vanadium fractions were different. All known methods can be used to equalize (the so-called “balancing”) such SoC variations of the battery modules. In this case, balancing can already begin towards the end of step S4 (see also below).
  • FIG. 3 shows a battery system according to the invention in a further embodiment.
  • the battery system includes another converter, which is denoted by 7 and is connected to the network or to a higher-level electrical system.
  • the battery system for each battery module additionally comprises a third and fourth switch, which are denoted by 11 and 12, and lines, the additional switches and lines being connected to one another and to the battery modules in such a way that each battery module 1 is connected separately to the further converter 7 can be connected.
  • all battery modules 1 can also be connected simultaneously to the additional converter 7 by closing all switches 11 and 12.
  • the battery modules and the further converter 7 are connected in parallel.
  • at least all the first switches 9 must be opened for this purpose.
  • any number of battery modules 1 and the further converter 7 can be connected in parallel with the aid of the switches 11 , 12 and 9 .
  • the additional switches 11 and 12 are also actuated by the control device, which is not shown in FIG. 3 for reasons of space.
  • FIG. 3 also shows other switches with which the converters 6 and 7 can each be electrically isolated from the rest of the arrangement. This can be an advantage. If necessary, only one isolating switch can be used per converter. Such switches can also be used in all other embodiments.
  • step S4 the battery modules 1 are supplied with power by the converter 6.
  • step S2 the battery modules 1 are supplied with power by the converter 6.
  • step S2 to be carried out separately for individual battery modules 1 or step S2 to be carried out simultaneously for two, three or more battery modules 1 S2, the further converter 7 only needs to be unidirectional.
  • a further embodiment results from the embodiment shown in FIG. 3, in which the converter 7 is omitted and the bidirectional converter 6 can be switched on both in the series connection and in the parallel connection.
  • the supply in step S2 can then take place in the parallel connection for more than one battery module, so that there is a time saving compared to the method according to the invention, which was described in connection with the arrangement of FIG.
  • a further embodiment results from the embodiment shown in FIG. 3, in which a further converter 7 is provided for each battery module 1, so that each battery module 1 is connected to its associated further converter 7 in step S1 and is fed with the same in step S2.
  • This embodiment results in the maximum possible time saving, since step S2 can be carried out in parallel for all battery modules.
  • this arrangement is of course correspondingly more expensive in comparison to the arrangement in FIG. 2, in which only one further converter 7 is provided.
  • a small saving results from the fact that one of the two switches 11 or 12 can be dispensed with for each battery module 1 if a separate further converter 7 is provided for each battery module 1 .
  • the method according to the invention generally comprises the following steps: S1: connecting at least one battery module 1 to a converter (6 or 7);
  • step S2 Feeding a current into the at least one battery module 1, which has been connected to the converter (6 or 7) in step S1, until the electrolyte in the cells of the cell arrangement 2 reaches a state of charge that is at least as high as a predefined threshold is;
  • step S4 feeding a current into the series circuit from step S3, electrolyte being conveyed in all battery modules 1; wherein in step S1, if more than one battery module 1 is connected to the converter (6 or 7), these battery modules 1 are connected in parallel to each other, and wherein steps S1 and S2 are successively repeated in this order until all battery modules 1 meet the condition mentioned in the definition of step S2, which is followed by the execution of steps S3 and S4 in this order.
  • the additional converter 7 can be used for balancing during step S4 and when charging the battery system. So if there is a deviation in the SoC value for a battery module compared to the average SoC value of the other battery modules, the different SoC value can be adjusted by removing the battery module in question from the series connection of the string and connecting it to the additional converter 7, which then takes over the supply of the relevant battery module.
  • the switches 9, 10, 11 and 12 of the relevant battery module are switched as follows: switch 9 open, switches 10, 11 and 12 closed.
  • the further converter 7 feeds the battery module in question with a current which is greater than the current flowing through the other battery modules until the SoC value of the battery module in question corresponds to the average SoC value. If the SoC value of the battery module in question is too high, then it is obviously sufficient to remove the battery module in question from the series connection of the string for a while, ie switches 9, 10, 11 and 12 of the battery module in question During this time, the battery module is switched as follows: switches 9, 11 and 12 open, switch 10 closed. If the additional converter 7 is bidirectional, it can also be used for balancing when discharging the battery system, in that the battery module in question is discharged via the additional converter 7 faster than the rest of the string.
  • each of the resistors 13 shown in FIG. 4 can consist of a parallel connection of two switchable resistors. This arrangement has the advantage that resistances of different magnitudes can be used, with the low-impedance resistances being able to be used to discharge one or more battery modules 1 via the same. This process can be used for balancing.
  • the method according to the invention then comprises the following steps:
  • step S2 feeding a current into the battery module 1, which was connected to the further converter 7 in step S1, until the electrolyte of this battery module 1 reaches a state of charge which is at least as high as a predefined threshold value;
  • step S4 A current is fed into the series circuit from step S3, electrolyte being conveyed in all battery modules 1.
  • step S2 it is all about the electrolyte belonging to the battery module 1 in question, whereby the word “entire” should not be interpreted too narrowly here since there can always be local variations in the state of charge in the electrolyte of such a battery module.
  • the state of charge of the same can be determined in a conventional manner via the measuring device shown in FIG. 1 for providing the open circuit voltage (OCV).
  • OCV open circuit voltage
  • the predefined threshold value is the mean value of the state of charge of the remaining battery modules in the battery system.
  • the electrolyte in the relevant battery module 1 is delivered at a rate that is above the stoichiometric delivery rate.
  • FIG. 5 shows a battery module which is equipped with lines and a valve which enables the tanks to be mixed.
  • One of these lines is denoted by 14.
  • the line 14 branches off from a line that connects the cell arrangement to one of the tanks and opens into the tank that belongs to the other electrolyte circuit.
  • the valve which is denoted by 15, is arranged and designed so that it Electrolyte flow can deflect so that the contents of the left tank are conveyed via line 14 into the other tank.
  • a connecting line is arranged between the upper areas of the tanks. This allows electrolyte to leak from the right tank into the left tank when the right tank has more electrolyte than the right tank.
  • the arrangement shown in FIG. 5 represents only one of many possibilities for achieving the stated purpose, ie for mixing the contents of the two tanks.
  • the method according to the invention generally includes the following steps as common features:
  • step S2 Feeding a current into the at least one battery module 1, which was connected to the converter (6 or 7) in step S1, until at least part of the electrolyte belonging to this battery module 1 reaches a state of charge that is at least as high as is a predefined threshold;
  • step S4 A current is fed into the series circuit from step S3, electrolyte being conveyed in all battery modules 1.
  • the energy required for conditioning can be taken from the superordinate electrical system to which the converter 7 is connected.
  • the energy could just as well be taken from another battery system, which is operated in parallel with the battery system in question.
  • the additional converter 7 is used for balancing and, in doing so, dissipates electrical energy from the relevant battery system.
  • control device is designed in such a way that it can set the electrolyte delivery rate in the individual battery modules.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne un procédé pour faire fonctionner un système de batterie à flux redox au vanadium, le procédé comprenant les étapes suivantes : S1 : connecter au moins un module de batterie (1) à un convertisseur (6, 7) ; S2 : introduire un courant dans l'au moins un module de batterie (1) qui a été connecté au convertisseur (6, 7) à l'étape S1, jusqu'à ce qu'au moins une partie de l'électrolyte associé à ce module de batterie (1) atteigne un état de charge qui est au moins aussi élevé qu'un seuil prédéfini ; S3 : activer le premier et le second commutateur (9, 10) de sorte que tous les modules de batterie (1) se trouvent dans une connexion en série qui est connectée au convertisseur bidirectionnel (6) ; S4 : introduire un courant dans la connexion en série à partir de l'étape S3, l'électrolyte étant transporté dans tous les modules de batterie (1).
PCT/EP2021/066399 2020-08-10 2021-06-17 Système de batterie à flux rédox et procédé de fonctionnement WO2022033750A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP21739263.8A EP4193408A1 (fr) 2020-08-10 2021-06-17 Système de batterie à flux rédox et procédé de fonctionnement

Applications Claiming Priority (2)

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DE102020120984 2020-08-10
DE102020120984.3 2020-08-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024056281A1 (fr) 2022-09-16 2024-03-21 Voith Patent Gmbh Batterie redox et procédé de fonctionnement

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001292532A (ja) * 2000-04-05 2001-10-19 Nissin Electric Co Ltd 電池電力貯蔵システム
WO2012020277A1 (fr) 2010-08-13 2012-02-16 Krisada Kampanatsanyakorn Système batterie à flux redox qui utilise différentes cellules de charge et de décharge
DE102016125720A1 (de) * 2016-12-27 2018-06-28 Universität der Bundeswehr München Niedervoltauskopplung aus einem modularen Energiespeicher-Umrichtersystem
EP3790148A1 (fr) * 2019-09-03 2021-03-10 Universität der Bundeswehr München Système de charge pour véhicules électriques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001292532A (ja) * 2000-04-05 2001-10-19 Nissin Electric Co Ltd 電池電力貯蔵システム
WO2012020277A1 (fr) 2010-08-13 2012-02-16 Krisada Kampanatsanyakorn Système batterie à flux redox qui utilise différentes cellules de charge et de décharge
DE102016125720A1 (de) * 2016-12-27 2018-06-28 Universität der Bundeswehr München Niedervoltauskopplung aus einem modularen Energiespeicher-Umrichtersystem
EP3790148A1 (fr) * 2019-09-03 2021-03-10 Universität der Bundeswehr München Système de charge pour véhicules électriques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024056281A1 (fr) 2022-09-16 2024-03-21 Voith Patent Gmbh Batterie redox et procédé de fonctionnement

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