CN107978775A - A kind of iron-based redox flow battery system - Google Patents
A kind of iron-based redox flow battery system Download PDFInfo
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- CN107978775A CN107978775A CN201711404347.2A CN201711404347A CN107978775A CN 107978775 A CN107978775 A CN 107978775A CN 201711404347 A CN201711404347 A CN 201711404347A CN 107978775 A CN107978775 A CN 107978775A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 76
- 239000003792 electrolyte Substances 0.000 claims abstract description 369
- 238000009713 electroplating Methods 0.000 claims abstract description 104
- 238000007747 plating Methods 0.000 claims abstract description 73
- 238000012806 monitoring device Methods 0.000 claims abstract description 20
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims description 99
- 239000000523 sample Substances 0.000 claims description 70
- 230000000996 additive effect Effects 0.000 claims description 60
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 33
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 30
- 230000003287 optical effect Effects 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 230000008859 change Effects 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 19
- 239000002000 Electrolyte additive Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 235000010323 ascorbic acid Nutrition 0.000 claims description 17
- 239000011668 ascorbic acid Substances 0.000 claims description 17
- 229960005070 ascorbic acid Drugs 0.000 claims description 17
- 150000007524 organic acids Chemical class 0.000 claims description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 14
- 235000010338 boric acid Nutrition 0.000 claims description 14
- 239000012530 fluid Substances 0.000 claims description 14
- 239000008151 electrolyte solution Substances 0.000 claims description 13
- 229910001447 ferric ion Inorganic materials 0.000 claims description 13
- 239000003014 ion exchange membrane Substances 0.000 claims description 13
- 239000012982 microporous membrane Substances 0.000 claims description 13
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 12
- 230000008878 coupling Effects 0.000 claims description 11
- 238000010168 coupling process Methods 0.000 claims description 11
- 238000005859 coupling reaction Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 9
- -1 iron ions Chemical class 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 230000008384 membrane barrier Effects 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 238000013494 PH determination Methods 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 230000002860 competitive effect Effects 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 6
- 238000001139 pH measurement Methods 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 231100000572 poisoning Toxicity 0.000 claims description 6
- 230000000607 poisoning effect Effects 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 238000007086 side reaction Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000001228 spectrum Methods 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 3
- 235000010350 erythorbic acid Nutrition 0.000 claims description 3
- 239000004318 erythorbic acid Substances 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 229940026239 isoascorbic acid Drugs 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 35
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000006479 redox reaction Methods 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000011263 electroactive material Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0444—Concentration; Density
- H01M8/04477—Concentration; Density of the electrolyte
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04791—Concentration; Density
- H01M8/0482—Concentration; Density of the electrolyte
-
- 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
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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)
- Fuel Cell (AREA)
Abstract
Present invention is disclosed a kind of iron-based redox flow battery system, including electroplated electrode, oxidation-reduction electrode, electroplating electrolytes storage tank, redox electrolyte storage tank, first reactor, second reactor, control system, monitoring device；The electroplating electrolytes storage tank is to store plating bath, and the redox electrolyte storage tank is storing redox electrolytes liquid；The oxidation-reduction electrode will be fluidly coupled to redox electrolyte storage tank, and the electroplated electrode will be fluidly coupled to electroplating electrolytes storage tank；The electroplating electrolytes storage tank connects first reactor by the first transfer pipeline, and redox electrolyte storage tank connects second reactor by the second transfer pipeline；The control system connects monitoring device.Iron-based redox flow battery system proposed by the present invention, can lift the performance of battery system, improve the efficiency of battery system.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to a battery system, and particularly relates to an iron-based redox flow battery system.
Background
A redox flow battery is an electrochemical storage device that stores energy in a chemical substance and converts the stored chemical energy into electrical energy through a spontaneous reverse redox reaction. The reaction in the flow battery is reversible, and conversely, the dispensed chemical energy can be recovered by inducing a current for the reverse redox reaction. A single redox flow battery generally includes a negative electrode, a membrane barrier layer, a positive electrode, and an electrolyte containing an electroactive material. Multiple cells may be connected in series or in parallel to produce a higher voltage or current in the flow cell. The electrolyte is typically stored in an external container and pumped through both sides of the cell. When a charge current is applied, the electrolyte loses electrons at the positive electrode and gains electrons at the negative electrode. The membrane barrier prevents mixing of the positive and negative electrolytes while allowing ionic conduction. When a discharge current is applied, a reverse redox reaction occurs at the electrode. The potential difference in the cell is maintained by the redox reaction in the electrolyte and current can be induced through the conductor as the reaction continues. The energy stored by a redox cell is limited by the amount of electroactive material available for discharge in the electrolyte, depending on the total volume of electrolyte and the solubility of the electroactive material.
Mixed flow batteries are distinguished by one or more solid layers of electroactive material deposited on the electrodes. For example, a mixed flow battery may include a chemical substance that acts as a solid on a substrate throughout the charging process, the discharged substance of which may be dissolved by the electrolyte throughout the discharging process. In a mixed liquor flow battery system, the energy stored by the redox cell may be limited by the amount of metallization during charging and therefore may depend on the efficiency of the plating system, as well as the volume and surface area available.
In a mixed liquor flow battery system, the negative electrode may be referred to as a plating electrode and the positive electrode may be referred to as a redox electrode. The electrolyte on the plating side of the cell may be referred to as the plating electrolyte and the electrolyte on the redox side of the cell may be referred to as the redox electrolyte.
Hybrid redox flow batteryOne example of (A) is iron as the electrolyte for the reaction, Fe on the negative electrode2+Two electrons are accepted during charging and deposit as metallic iron, which loses two electrons during discharge and resolubilizes to Fe2+. On the positive electrode, two Fe2+Two electrons are lost during charging to form two Fe3+During discharge, two Fe3+Two electrons are obtained to form two Fe2+：
The electrolyte used for this reaction is readily available and can be produced at low cost (e.g., ferrous chloride). It also has a high recovery value because the same electrolyte can be used for both the plating electrolyte and the redox electrolyte, thereby eliminating the possibility of cross-contamination. Unlike other compounds used in hybrid redox flow batteries, iron does not form dendrites during electroplating, thereby providing a stable electrode morphology. Furthermore, iron redox flow batteries do not require the use of toxic raw materials, operate at relatively neutral pH, unlike similar redox flow battery electrolytes. Therefore, it is the least environmentally hazardous product of all the advanced battery systems currently produced.
However, the disadvantages of the above system limit its utility in commercial applications. One of these disadvantages is the poor cycling performance and efficiency of these batteries due to the different pH ranges in which these negative electrodes and redox electrolytes tend to stabilize. In order to reduce the corrosion reaction of iron and improve the iron plating efficiency, the iron plating reaction needs a pH value of 3-4. However, the pH required for the redox reactions of ferrous and ferric ions is less than 1 to promote the redox kinetics and minimize hydroxide formation.
The concentration gradient of the membrane barrier separating the electrolytes causes crossover of the electrolytes. Fe from the redox side (more acidic) to the plating side (less acidic)3+Contamination can result in Fe (OH)3Formation of a precipitate of (a). Such precipitates may destroy the organic functional groups of the ion-exchange membrane or clog the micropores of the microporous membrane. In both cases, the sheet ohmic resistance increases over time and the cell performance decreases.
In view of the above, there is a need to design a new battery system to overcome the above-mentioned disadvantages of the existing battery systems.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides an iron-based redox flow battery system, which can reduce the formation of Fe (OH)3 precipitates and improve the performance and stability of the battery system.
In order to solve the technical problems, the invention adopts the following technical scheme:
an iron-based redox flow battery system, the battery system comprising: the device comprises a control system, an electroplating electrolyte storage tank, a redox electrolyte storage tank, a first sensor, a second sensor, a first external storage tank, a second external storage tank, a cathode additive pump, an anode additive pump, a cathode, an anode, a cathode iron-plated layer, a diaphragm, a cathode reactor, an anode reactor, a first probe, a second probe, a first pump body and a second pump body;
the control system is respectively connected with the first sensor, the second sensor, the first probe, the second probe, the cathode additive pump, the anode additive pump, the first pump body and the second pump body, receives data sensed by the first sensor, the second sensor, the first probe and the second probe, and controls the actions of the cathode additive pump, the anode additive pump, the first pump body and the second pump body; the electrolyte can be pumped out of the reactor through the first pump body and the second pump body;
the first sensor and the second sensor are used for determining the chemical properties of the electrolyte, including pH value, and are used as optical sensors; the first probe and the second probe are used for measuring the chemical property of the electrolyte;
the electroplating electrolyte storage tank and the redox electrolyte storage tank are used for storing electrolyte; the electrolyte has the functions of generating chemical reaction in the charging process, storing electric quantity and releasing charges in the electrolyte in the discharging process;
the first external storage tank and the second external storage tank are used for respectively storing an electroplating electrolyte additive and a redox electrolyte additive and pumping the additives to adjust the pH value when the pH values of the electrolytes in the electroplating electrolyte storage tank and the redox electrolyte storage tank are changed;
the first external storage tank and the second external storage tank are used for storing cathode additives and anode additives respectively; the first external storage tank is connected with the cathode reactor through a cathode additive pump, and the second external storage tank is connected with the anode reactor through an anode additive pump; the first and second external reservoirs are capable of coupling fluid to a cathode reactor and an anode reactor, respectively, of the battery system; electrolyte additives can be pumped into corresponding electroplating electrolyte storage tanks and redox electrolyte storage tanks from the first external storage tank and the second external storage tank respectively;
the electroplating electrolyte storage tank is connected with the cathode reactor through two pipelines, one pipeline is provided with a first pump body, and the other pipeline is provided with a first sensor;
the redox electrolyte storage tank is connected with the anode reactor through two pipelines, one pipeline is provided with a second pump body, and the other pipeline is provided with a second sensor;
the cathode, the cathode iron-plated layer, the cathode reactor, the diaphragm, the anode reactor and the anode are sequentially arranged;
the diaphragm is used for isolating the negative reactor, the positive reactor and respective electrolytes thereof; the membrane is a membrane barrier, being an ion exchange membrane or microporous membrane, disposed between the redox electrolyte and the electroplating electrolyte to prevent crossover of the electrolytes and provide ionic conductivity;
the electroplating electrolyte storage tank is used for storing electroplating electrolyte, and the redox electrolyte storage tank is used for storing redox electrolyte; the electroplating electrolyte and the redox electrolyte both adopt the same metal salt, but the concentrations of the metal salt and the redox electrolyte are different;
the anode is a redox electrode coupling the fluid to a redox electrolyte reservoir; the cathode is an electroplating electrode coupling fluid to an electroplating electrolyte reservoir;
these may contain different additives and be controlled by different programs; an all-iron flow battery IFB (all Ironflow Battery) has an anode additive or a cathode additive;
during the operation of the battery, the concentration gradient at two sides of the diaphragm drives a large amount of Fe3+From the redox electrolyte to the electroplating electrolyte; the sharp change in pH from electroplating electrolyte to redox electrolyte results in Fe (OH)3Formation and precipitation of species; these precipitates degrade the ion-exchange membrane by poisoning the organic functional groups of the membrane or blocking the pores of the microporous membrane, thereby causing the ohmic resistance of the cell to increase; cleaning the cell with acid to remove the precipitate, but frequent maintenance limits the commercial use of the cell, which also relies on the periodic preparation of the electrolyte; the reaction is inhibited by adding a specific organic acid to the electrolyte in response to the pH of the electrolyte;
electrolyte is pumped through respective electrodes in the IFB system; measuring the pH of the electrolyte of the cell using an iron probe and determining the electrolyte potential from a reference electrode, including Ag/AgCl or H plating the electrode2An electrode; in addition, the pH value is monitored by measuring the reflection spectrum of the electrolyte using an optical sensor; other designated pH sensing devices are also used for pH determination;
the sensors and/or probes communicate the pH of the electrolyte to the control system; if the pH of the bath is found to be above a set first threshold, the control system activates the release of the pre-treated acid, which may be added to the plating electrolyte; if the pH of the redox electrolyte is found to be above a set second threshold, the control system actuates the release of the pre-prepared acid to the redox electrolyte; the acidic additives added to the cathode and anode are the same or different and include boric acid, ascorbic acid, glycolic acid, or any combination thereof; this process may be repeated until the pH is below the threshold; if the pH value is lower than the IFB of the threshold value, the charging or discharging is continued;
the use of a combination of organic acid additives to achieve an optimal iron plating layer to improve its performance, efficiency and stability; in FeCl2And NaCl electrolyte solution, boric acid is added to inhibit H2Side reaction and increase of coulomb efficiency; in addition, ascorbic acid is added to improve the stability of iron ions, and glycolic acid is added to reduce the generation of carbon;
on the negative side of the IFB system, Fe is charged during charging2+Accepting two electrons to form Fe0(ii) a Competitive reaction at the negative side of the cell, H+Accepting an electron to form H2The pH value of the electrolyte on the negative electrode side of the all-iron flow battery IFB is gradually increased from 2 to 6, and the change of the pH value is monitored through the probe and the sensor;
the pH change may result in a cell with an apparent performance loss of up to 100 millivolts due to a high equilibrium potential drift. To mitigate performance loss, Fe potential probes or optical sensors are used to monitor the state of charge of the battery and the pH level of the electrolyte;
the pH value of the operation window of the battery electroplating electrolyte is between 3 and 4; when the Fe potential probe or optical sensor indicates a pH above 4, a small amount of pre-calculated acid is added to the plating electrolyte solution to return the plating electrode to the optimal pH range.
An iron-based redox flow battery system, comprising: the device comprises a plating electrode, a redox electrode, a plating electrolyte storage tank, a redox electrolyte storage tank, a first reactor, a second reactor, a control system, a monitoring device, a first external storage tank and a second external storage tank;
the electroplating electrolyte storage tank is used for storing electroplating electrolyte, and the redox electrolyte storage tank is used for storing redox electrolyte;
the redox electrode fluidly coupled to a redox electrolyte reservoir and the plating electrode fluidly coupled to a plating electrolyte reservoir;
the electroplating electrolyte storage tank is connected with the first reactor through a first conveying pipeline, and the redox electrolyte storage tank is connected with the second reactor through a second conveying pipeline; the first reactor is connected with the electroplating electrode, and the second reactor is connected with the oxidation-reduction electrode;
the monitoring device is used for detecting the chemical property of the electrolyte in the electroplating electrolyte storage tank or/and the redox electrolyte storage tank or/and the first conveying pipeline or/and the second conveying pipeline;
the control system is connected with the monitoring device and controls the additives of the first external storage tank and the second external storage tank to be pumped into the electrolyte storage tank according to the data monitored by the monitoring device.
As a preferable scheme of the invention, the electroplating electrolyte storage tank and the redox electrolyte storage tank are used for storing electrolyte; the electrolyte has the functions of generating chemical reaction in the charging process, storing electric quantity and releasing charges in the electrolyte in the discharging process;
the first external storage tank and the second external storage tank are used for storing an electroplating electrolyte additive and a redox electrolyte additive respectively and pumping the additives to adjust the pH value when the pH values of the electrolytes in the electroplating electrolyte storage tank and the redox electrolyte storage tank are changed.
As a preferable scheme of the present invention, the battery system further includes a cathode additive pump, an anode additive pump, a first pump body, and a second pump body; the control system is respectively connected with the first additive pump, the second additive pump, the first pump body and the second pump body; the first reactor is a cathode reactor, and the second reactor is an anode reactor;
the first external storage tank and the second external storage tank are used for storing cathode additives and anode additives respectively; the first external storage tank is connected with the cathode reactor through a cathode additive pump, and the second external storage tank is connected with the anode reactor through an anode additive pump; the first and second external reservoirs are capable of coupling fluid to a cathode reactor and an anode reactor, respectively, of the battery system;
the electroplating electrolyte storage tank is connected with the electroplating electrode through a third conveying pipeline, and the third conveying pipeline is provided with a first pump body;
the redox electrolyte storage tank is connected with the redox electrode through a fourth conveying pipeline, and the fourth conveying pipeline is provided with a second pump body.
In a preferred embodiment of the present invention, the plating electrolyte or redox electrolyte comprises FeCl2、FeCl3Or any combination thereof;
the monitoring device comprises a Fe potential probe passing through a clean iron wire and a reference electrode, such as Ag/AgCl electrode or H2The electrodes are connected;
the plating electrolyte additive, redox electrolyte additive, includes boric acid, ascorbic acid, acetic acid, malic acid, lactic acid, citric acid, tartaric acid, erythorbic acid, malonic acid, glycolic acid, or any combination thereof.
As a preferred aspect of the present invention, the monitoring device includes a first sensor and a second sensor, the first sensor is disposed on the first conveying pipeline, and the second sensor is disposed on the second conveying pipeline; the first sensor and the second sensor are used for determining the chemical properties of the electrolyte, including pH value; or,
the monitoring device comprises a first probe and a second probe which are respectively arranged in the electroplating electrolyte storage tank and the redox electrolyte storage tank and are used for measuring the chemical properties of the electrolyte.
In a preferred embodiment of the present invention, a cathode iron plating layer is disposed between the plating electrode and the first reactor.
In a preferred embodiment of the present invention, a membrane is disposed between the first reactor and the second reactor.
As a preferable aspect of the present invention, the plating electrode is a cathode, and the redox electrode is an anode; a cathode iron plating layer is arranged between the electroplating electrode and the first reactor; a diaphragm is arranged between the cathode reactor and the anode reactor; the cathode, the cathode iron-plated layer, the cathode reactor, the diaphragm, the anode reactor and the anode are sequentially arranged;
the diaphragm is used for isolating the negative reactor, the positive reactor and respective electrolytes thereof; the membrane is a membrane barrier, being an ion exchange membrane or microporous membrane, disposed between the redox electrolyte and the electroplating electrolyte to prevent crossover of the electrolytes and provide ionic conductivity;
the electroplating electrolyte storage tank is used for storing electroplating electrolyte, and the redox electrolyte storage tank is used for storing redox electrolyte; the electroplating electrolyte and the redox electrolyte both adopt the same metal salt, but the concentrations of the metal salt and the redox electrolyte are different;
the anode is a redox electrode coupling the fluid to a redox electrolyte reservoir; the cathode is an electroplating electrode coupling fluid to an electroplating electrolyte reservoir;
as a preferred variant of the invention, these may contain different additives and be controlled by different programs; the IFB of the all-iron flow battery is provided with an anode additive or a cathode additive;
concentration on both sides of the separator during battery operationGradient drives a large amount of Fe3+From the redox electrolyte to the electroplating electrolyte; the sharp change in pH from electroplating electrolyte to redox electrolyte (from 1 to 3-6) results in Fe (OH)3Formation and precipitation of species; these precipitates degrade the ion-exchange membrane by poisoning its organic functional groups or plugging the pores of the microporous membrane, resulting in an increase in the ohmic resistance of the cell. Cleaning the cell with acid can remove the precipitate, but frequent maintenance limits the commercial use of the cell, which also relies on the periodic preparation of the electrolyte; the reaction is inhibited by adding a specific organic acid to the electrolyte in response to the pH of the electrolyte;
the electrolyte is pumped through respective electrodes within the IFB system; measuring the pH of the electrolyte of the cell using an iron probe and determining the electrolyte potential from a reference electrode, including Ag/AgCl or H plating the electrode2An electrode; in addition, the pH value is monitored by measuring the reflection spectrum of the electrolyte using an optical sensor; other designated pH sensing devices are also used for pH determination;
the sensors and/or probes communicate the pH of the electrolyte to the control system; if the pH of the bath is found to be above a set first threshold, the control system activates the release of the pre-treated acid, which may be added to the plating electrolyte; if the pH of the redox electrolyte is found to be above a set second threshold, the control system actuates the release of the pre-prepared acid to the redox electrolyte; the acidic additives added to the cathode and anode are the same or different and include boric acid, ascorbic acid, glycolic acid, or any combination thereof; this process may be repeated until the pH is below the threshold; if the pH value is lower than the IFB of the threshold value, the charging or discharging is continued;
the use of a combination of organic acid additives to achieve an optimal iron plating layer to improve its performance, efficiency and stability; in FeCl2And NaCl electrolyte solution, boric acid is added to inhibit H2Side reaction and increase of coulomb efficiency; in addition, ascorbic acid is added to improve the stability of iron ions, and glycolic acid is added to reduce the generation of carbon;
on the negative side of the IFB system, Fe during charging2+Accepting two electrons to form Fe0(ii) a Competitive reaction at the negative side of the cell, H+Accepting an electron to form H2The pH value of the electrolyte on the negative electrode side of the IFB is gradually increased from 2 to 6, and the change of the pH value is monitored by the probe and the sensor;
the pH change may result in a cell with an apparent performance loss of up to 100 millivolts due to a high equilibrium potential drift. To mitigate performance loss, Fe potential probes or optical sensors are used to monitor the state of charge of the battery and the pH level of the electrolyte;
the pH value of the operation window of the battery electroplating electrolyte is between 3 and 4; when the Fe potential probe or optical sensor indicates a pH above 4, a small amount of pre-calculated acid is added to the plating electrolyte solution to return the plating electrode to the optimal pH range.
The invention has the beneficial effects that: the iron-based redox flow battery system provided by the invention can improve the performance of the battery system and the efficiency of the battery system.
The invention solves the problems that the cycle performance and the efficiency of the battery are low due to different pH value ranges of the cathode and the redox electrolyte in the total iron redox flow battery which tend to be stable, and the crossing of the electrolyte causes Fe (OH)3The formation of precipitates (2) eventually leads to an increase in the ohmic resistance of the thin film with the lapse of time, thereby leading to a decrease in the performance of the battery.
The invention can reduce Fe (OH) by adding chemical chelating agent in the form of organic compound3A precipitate formed. These organic compounds may form complexes in which Fe3+Transitioning from the redox side to the plating side. These complexes are relatively soluble in acidic environments, thereby stabilizing the iron ions.
In addition, the color and potential of these complex compounds are related to the pH of the solution. Thus, the present invention monitors the pH of the electrolyte via optical sensors and/or electrochemical probes to enable the metering of added chemical additives to achieve and maintain the desired pH of the electrolyte to prevent precipitation and preserve coulombic efficiency.
Drawings
Fig. 1 is a schematic structural diagram of an all-iron redox flow battery system disclosed in the present invention.
Figure 2 is a graph of coulombic plating efficiency for pH values for two different acid additives.
FIG. 3 is a graph of the color of the electrolyte as a function of pH.
The drawings are labeled as follows:
01- -electroplating electrolyte tank; 02-redox electrolyte tank; 03-a sensor; 04-a sensor;
05-a first external reservoir; 06-a second external tank; 07-cathode additive pump; 08-anode additive pump;
09-cathode; 10-an anode; 11-plating iron layer on the cathode; 12-a diaphragm;
13-a cathode reactor; 14-anode reactor; 15-probe; 16-a probe;
17 — a first pump body; 18 — a second pump body.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example one
Referring to fig. 1, the present invention discloses an iron-based redox flow battery system, including: the device comprises a control system, a plating electrolyte storage tank 01, a redox electrolyte storage tank 02, a first sensor 03, a second sensor 04, a first external storage tank 05, a second external storage tank 06, a cathode additive pump 07, an anode additive pump 08, a cathode 9, an anode 10, a cathode iron coating 11, a diaphragm 12, a cathode reactor 13, an anode reactor 14, a first probe 15, a second probe 16, a first pump body 17 and a second pump body 18;
the control system is respectively connected with the first sensor 03, the second sensor 04, the first probe 15, the second probe 16, the cathode additive pump 07, the anode additive pump 08, the first pump body 17 and the second pump body 18, receives data sensed by the first sensor 03, the second sensor 04, the first probe 15 and the second probe 16, and controls the actions of the cathode additive pump 07, the anode additive pump 08, the first pump body 17 and the second pump body 18; the electrolyte can be pumped out of the reactors (cathode 13, anode 14) through a first pump 17, a second pump 18.
The first sensor 03, the second sensor 04 are used for determining the chemical properties of the electrolyte, including the pH value, and are used as optical sensors; the first probe and the second probe are used for measuring the chemical property of the electrolyte.
The electroplating electrolyte storage tank and the redox electrolyte storage tank are used for storing electrolyte; the electrolyte has the functions of generating chemical reaction in the charging process, storing electric quantity and releasing electric charge in the electrolyte in the discharging process.
The first external storage tank and the second external storage tank are used for storing an electroplating electrolyte additive and a redox electrolyte additive respectively and pumping the additives to adjust the pH value when the pH values of the electrolytes in the electroplating electrolyte storage tank and the redox electrolyte storage tank are changed.
The first external storage tank 05 and the second external storage tank 06 store a cathode additive and an anode additive respectively; the first external storage tank 05 is connected with the cathode reactor 13 through a cathode additive pump, and the second external storage tank 06 is connected with the anode reactor 14 through an anode additive pump; the first and second external reservoirs 05, 06 can be fluidly coupled to the cathode reactor 13, the anode reactor 14, respectively, of the battery system; the electrolyte additive can be pumped into the corresponding electroplating electrolyte storage tank 01 and the redox electrolyte storage tank 02 from the first external storage tank 05 and the second external storage tank 06 respectively.
The electroplating electrolyte storage tank 01 is connected with the cathode reactor 13 through two pipelines, one pipeline is provided with a first pump body 17, and the other pipeline is provided with a first sensor 03; the redox electrolyte storage tank 02 is connected to the anode reactor 14 through two pipelines, one of which is provided with a second pump 18, and the other of which is provided with a second sensor 04.
The cathode 09, the cathode iron-plated layer 11, the cathode reactor 13, the diaphragm 12, the anode reactor 14 and the anode 10 are sequentially arranged.
The membrane 12 is used to isolate the negative reactor 13, the positive reactor 14 and their respective electrolytes; the separator 12 is a membrane barrier, which is an ion exchange membrane or microporous membrane, interposed between the redox electrolyte and the electroplating electrolyte to prevent crossover of the electrolytes and provide ionic conductivity.
The electroplating electrolyte storage tank 01 is used for storing electroplating electrolyte, and the redox electrolyte storage tank 02 is used for storing redox electrolyte; the electroplating electrolyte and the redox electrolyte may both employ the same metal salt, but at different concentrations.
The anode 10 is a redox electrode that couples fluid to a redox electrolyte reservoir 02; the cathode 09 is a plating electrode that couples fluid to the plating electrolyte reservoir 01.
The Battery system can be applied to an IFB (All Iron Flow Battery) system; the method can also be used for the iron-zinc flow battery, and a flow battery system containing Fe ions can be applied. In IFB, these may contain different additives and are controlled by different programs; IFB (All Iron Flow Battery) has an anode additive or a cathode additive.
During the operation of the battery, the concentration gradient at two sides of the diaphragm drives a large amount of Fe3+From the redox electrolyte to the electroplating electrolyte; the sharp change in pH from electroplating electrolyte to redox electrolyte results in Fe (OH)3Formation and precipitation of species; these precipitates degrade the ion-exchange membrane by poisoning the organic functional groups of the membrane or blocking the pores of the microporous membrane, thereby causing the ohmic resistance of the cell to increase; cleaning the cell with acid to remove the precipitate, but frequent maintenance limits the commercial use of the cell, which also relies on the periodic preparation of the electrolyte; the above reaction is suppressed by adding a specific organic acid to the electrolyte in response to the pH of the electrolyte.
The electrolyte is pumped through respective electrodes within the IFB system; measuring the pH of the electrolyte of the cell using an iron probe and determining the electrolyte potential from a reference electrode, including Ag/AgCl or H plating the electrode2An electrode; in addition, the pH value is monitored by measuring the reflection spectrum of the electrolyte using an optical sensor; other designated pH sensing devices are also used for pH determination.
The sensors and/or probes communicate the pH of the electrolyte to the control system; if the pH of the bath is found to be above a set first threshold, the control system activates the release of the pre-treated acid, which may be added to the plating electrolyte; if the pH of the redox electrolyte is found to be above a set second threshold, the control system actuates the release of the pre-prepared acid to the redox electrolyte; the acidic additives added to the cathode and anode are the same or different and include boric acid, ascorbic acid, glycolic acid, or any combination thereof; this process may be repeated until the pH is below the threshold; if the pH is below the IFB threshold, the charging or discharging will continue.
The use of a combination of organic acid additives to achieve an optimal iron plating layer to improve its performance, efficiency and stability; in FeCl2And NaCl electrolyte solution, boric acid is added to inhibit H2Side reaction and increase of coulomb efficiency; in addition, ascorbic acid is added to improve the stability of iron ions, and glycolic acid is added to reduce carbon generation.
On the negative side of the IFB system, Fe during charging2+Accepting two electrons to form Fe0(ii) a Competitive reaction at the negative side of the cell, H+Accepting an electron to form H2This results in a gradual increase in the pH of the electrolyte on the negative side of the IFB from 2 to 6, with the pH change being monitored by the probe and sensor described above.
The pH change may result in a cell with an apparent performance loss of up to 100 millivolts due to a high equilibrium potential drift. To mitigate performance loss, Fe potential probes or optical sensors are used to monitor the state of charge of the battery and the pH level of the electrolyte.
The pH value of the operation window of the battery electroplating electrolyte is between 3 and 4; when the Fe potential probe or optical sensor indicates a pH above 4, a small amount of pre-calculated acid is added to the plating electrolyte solution to return the plating electrode to the optimal pH range.
Example two
An example of an all-iron redox flow battery (IFB) system is shown in FIG. 1. The electroplating electrolyte may be stored in an electroplating electrolyte tank and the redox electrolyte may be stored in a redox electrolyte tank. The electroplating electrolyte and the electrolyte may be a suitable salt dissolved in water, e.g. FeCl2And FeCl3. The same metal salt is used for both the plating solution and the electrolyte, but at different concentrations. Two external reservoirs may be fluidly coupled to the anode reactor 14 and the cathode reactor 13 of the cell. The separator 12 separates the cathode and anode reactors and their respective electrolytes. The separator may be a membrane barrier, such as an ion exchange membrane or microporous membrane, interposed between the redox electrolyte and the electroplating electrolyte to prevent crossover of the electrolytes and provide ionic conductivity. Sensors 03 and 04 can be used to determine the chemistry of the electrolyte, including pH, and can be used as optical sensors. Probes 15 and 16 may additionally or alternatively be used to determine the chemistry of the electrolyte. OthersEmbodiments may have a plating electrolyte probe, a plating electrolyte sensor, a redox electrolyte probe, a redox electrolyte sensor, or some combination thereof. The acid additive may be placed in the external reservoirs 05 and 06. These may contain different additives and be controlled by different programs. In other embodiments, the IFB may also have an anodic additive or a cathodic additive. The anode additive may be pumped into the anode reactor 13 by an anode additive pump 08 and the cathode additive may be pumped into the cathode reactor 14 by a cathode additive pump 07. The electrolyte additive may be pumped into reservoirs 01 and 02. The pumps 13 and 14 may be driven by a control system communicatively connected to the pumps. The control system may be responsive to probe 15, probe 16, sensor 03, sensor 04, or any combination thereof. The electrolyte may be pumped from the reactor by means of a pump 17.
During the operation of the battery, the concentration gradient at two sides of the diaphragm drives a large amount of Fe3+From the redox electrolyte to the electroplating electrolyte. The sharp change in pH from electroplating electrolyte to redox electrolyte (from 1 to 3-6) results in Fe (OH)3Formation and precipitation of species. These precipitates degrade the ion-exchange membrane by poisoning its organic functional groups or plugging the pores of the microporous membrane, resulting in an increase in the ohmic resistance of the cell. Cleaning the cell with acid can remove the precipitate, but frequent maintenance limits the commercial use of the cell, which also relies on the periodic preparation of the electrolyte. However, the method disclosed herein suppresses the above reaction by adding a specific organic acid to the electrolyte in response to the pH of the electrolyte.
The electrolyte may be pumped through respective electrodes within the IFB system. The pH of the electrolyte of the cell can be determined using an iron probe to measure the electrolyte potential and a reference electrode, such as Ag/AgCl or H for a plated electrode2And an electrode. In addition, the pH value can be monitored by measuring the reflection spectrum of the electrolyte using an optical sensor. Other designated pH sensing devices may also be used for pH determination.
In the present invention, the sensors and/or probes may communicate the pH of the electrolyte to the control system. If the pH of the bath is found to be above a threshold value, such as pH > 4, the control system may actuate the release of pre-treated acid which may be added to the plating electrolyte. If the pH of the redox electrolyte is found to be above a threshold value, such as pH > 1, the control system may actuate the release of the pre-prepared acid to the redox electrolyte. The acidic additives added to the cathode and anode may be the same or different and may include, but are not limited to, boric acid, ascorbic acid, glycolic acid, or any combination thereof. This process may be repeated until the pH is below the threshold. If the pH is below the threshold IFB, charging or discharging may continue.
The disclosed embodiments achieve suppression of the above problematic reactions by adding specific chemicals (acid additives) to the electrolyte. The acidic additive in the electrolyte stabilizes the Fe from the redox electrolyte to the electroplating electrolyte3+The acid additive used in this example therefore has a specific chemical nature. The acids studied and some of their attributes are listed in table 1.
Table 1 organic acid test for stabilization of IFB electrolyte
TABLE 2 organic acids-Fe2+/Fe3+Stability at different pH values
The invention is used for preparing Fe with different proportions: organic acids the same H-cell test was performed to investigate the stability of the cross iron ions of the electroplated layers at different pH values, as shown in figure 2. In an embodiment of the present system, the results of fig. 2 are utilized by the control system to determine the pH required to achieve the desired coulombic efficiency versus the electrolytic solution. FIG. 2 graphically depicts the iron plating coulombic efficiency for baths of different pH values. As shown in table 2 and figure 2, acetic acid and glycolic acid alone are not able to stabilize the cross-ferric ions under high pH conditions. However, the use of ascorbic acid or erythorbic acid alone as the organic acid is undesirable because the formation of C results in a decrease in coulombic efficiency. The formation of carbon was detected by scanning the iron plating layer formed by adding ascorbic acid alone with a scanning electron microscope.
Thus, in embodiments of the present invention, a combination of organic acid additives may be used to achieve an optimal iron plating layer to improve its performance, efficiency and stability. In the examples, in FeCl2And NaCl electrolyte solution, a first acid (such as boric acid) is added to inhibit H2Side reactions and increase coulomb efficiency. In addition, a second acid (e.g., ascorbic acid) may be added to improve iron ion stability, and a third acid (e.g., glycolic acid) may be added to reduce carbon formation.
In other embodiments of the system of the present invention, the pH of the electrolyte may also be monitored by a sensor that may be used alone or in combination with the probe. In an embodiment, the optical sensor may measure the absorption spectrum of the ambient light through the liquid to determine the corresponding pH value. Optical sensors can also be used to monitor the charge state of the cell if chelating organic acids are added to the electrolyte to improve iron stability. This is because the chelated iron complexes exhibit different colors at different pH values. For example, if ascorbic acid is used as a chelating agent, the color of the iron solution changes from green to purple and finally to black during the change of the pH of the solution from 2 to 6.
A control system communicatively coupled to the sensor may determine the pH using the pH versus color relationship depicted in fig. 3. In the pH-color relationship diagram, the vertical axis represents the H bound to each carbon atom+Mean of (d), Logh on the horizontal axis. As shown in fig. 3, at low pH, the solution appears green or white, gradually turning purple and finally black as the pH increases. By measuring the wavelength of ambient light orThe pH of the electrolyte may be determined from light from a known source and/or reflected by the electrolyte.
In an embodiment, the white light may be incident on a surface of the electrolyte. A beam splitter can be used within the sensor to determine the wavelength of light reflected by the electrolyte. If a reflected or transmitted wavelength is found, for example, an acid solution less than 450nm (corresponding to violet) may be added with additives to lower the pH of the electrolyte. In addition, the spectroscope may continue to monitor the absorption spectrum of the electrolyte and the addition of the acidic additive may be terminated if the reflection and/or emission wavelength is found to exceed a threshold, such as 510nm (corresponding to green).
On the negative side of the IFB system, Fe during charging2+Accepting two electrons to form Fe0. Competitive reaction at the negative side of the cell (H)+Accepting an electron to form H2) This results in a gradual increase in the pH of the electrolyte on the negative side of the IFB from 2 to 6, so that in an embodiment of the system of the present invention the pH change can be monitored with the above probes and sensors.
The pH change may result in a cell with an apparent performance loss of up to 100 millivolts due to a high equilibrium potential drift. To mitigate performance loss, such as the sensor embodiments described above, the Fe potential probe or optical sensor disclosed herein, can be used to monitor the state of charge of the battery and the pH level of the electrolyte.
The battery plating electrolyte has an operating window pH between 3 and 4. Thus, in embodiments, when an Fe potential probe or optical sensor indicates a pH above 4, a small amount of pre-calculated acid may be added to the plating electrolyte solution to return the plating electrode to the optimal pH range. As a result, the battery performance can be stabilized.
EXAMPLE III
An iron-based redox flow battery system, the battery system comprising: the device comprises a plating electrode, a redox electrode, a plating electrolyte storage tank, a redox electrolyte storage tank, a first reactor, a second reactor, a first external storage tank, a second external storage tank, a control system and a monitoring device;
the electroplating electrolyte storage tank is used for storing electroplating electrolyte, and the redox electrolyte storage tank is used for storing redox electrolyte;
the redox electrode fluidly coupled to a redox electrolyte reservoir and the plating electrode fluidly coupled to a plating electrolyte reservoir;
the electroplating electrolyte storage tank is connected with the first reactor through a first conveying pipeline, and the redox electrolyte storage tank is connected with the second reactor through a second conveying pipeline; the first reactor is connected with the electroplating electrode, and the second reactor is connected with the oxidation-reduction electrode;
the monitoring device is used for detecting the chemical property of the electrolyte in the electroplating electrolyte storage tank or/and the redox electrolyte storage tank or/and the first conveying pipeline or/and the second conveying pipeline;
the control system is connected with the monitoring device and controls the additives of the first external storage tank and the second external storage tank to be pumped into the electrolyte storage tank according to the data monitored by the monitoring device.
In summary, the iron-based redox flow battery system provided by the invention can improve the performance and efficiency of the battery system.
The invention solves the problems that the cycle performance and the efficiency of the battery are low due to different pH value ranges of the cathode and the redox electrolyte in the total iron redox flow battery which tend to be stable, and the crossing of the electrolyte causes Fe (OH)3The formation of precipitates (2) eventually leads to an increase in the ohmic resistance of the thin film with the lapse of time, thereby leading to a decrease in the performance of the battery.
The invention can reduce Fe (OH) by adding chemical chelating agent in the form of organic compound3A precipitate formed. These organic compounds may form complexes, whichMiddle Fe3+Transitioning from the redox side to the plating side. These complexes are relatively soluble in acidic environments, thereby stabilizing the iron ions.
In addition, the color and potential of these complex compounds are related to the pH of the solution. Thus, the present invention monitors the pH of the electrolyte via optical sensors and/or electrochemical probes to enable the metering of added chemical additives to achieve and maintain the desired pH of the electrolyte to prevent precipitation and preserve coulombic efficiency.
The description and applications of the invention herein are illustrative and are not intended to limit the scope of the invention to the embodiments described above. Variations and modifications of the embodiments disclosed herein are possible, and alternative and equivalent various components of the embodiments will be apparent to those skilled in the art. It will be clear to those skilled in the art that the present invention may be embodied in other forms, structures, arrangements, proportions, and with other components, materials, and parts, without departing from the spirit or essential characteristics thereof. Other variations and modifications of the embodiments disclosed herein may be made without departing from the scope and spirit of the invention.
Claims (10)
1. An iron-based redox flow battery system, comprising: the device comprises a control system, an electroplating electrolyte storage tank, a redox electrolyte storage tank, a first sensor, a second sensor, a first external storage tank, a second external storage tank, a cathode additive pump, an anode additive pump, a cathode, an anode, a cathode iron-plated layer, a diaphragm, a cathode reactor, an anode reactor, a first probe, a second probe, a first pump body and a second pump body;
the control system is respectively connected with the first sensor, the second sensor, the first probe, the second probe, the cathode additive pump, the anode additive pump, the first pump body and the second pump body, receives data sensed by the first sensor, the second sensor, the first probe and the second probe, and controls the actions of the cathode additive pump, the anode additive pump, the first pump body and the second pump body; the electrolyte can be pumped out of the reactor through the first pump body and the second pump body;
the first sensor and the second sensor are used for determining the chemical properties of the electrolyte, including pH value, and are used as optical sensors; the first probe and the second probe are used for measuring the chemical property of the electrolyte;
the electroplating electrolyte storage tank and the redox electrolyte storage tank are used for storing electrolyte; the electrolyte has the functions of generating chemical reaction in the charging process, storing electric quantity and releasing charges in the electrolyte in the discharging process;
the first external storage tank and the second external storage tank are used for respectively storing an electroplating electrolyte additive and a redox electrolyte additive and pumping the additives to adjust the pH value when the pH values of the electrolytes in the electroplating electrolyte storage tank and the redox electrolyte storage tank are changed;
the first external storage tank and the second external storage tank are used for storing cathode additives and anode additives respectively; the first external storage tank is connected with the cathode reactor through a cathode additive pump, and the second external storage tank is connected with the anode reactor through an anode additive pump; the first and second external reservoirs are capable of coupling fluid to a cathode reactor and an anode reactor, respectively, of the battery system; electrolyte additives can be pumped into corresponding electroplating electrolyte storage tanks and redox electrolyte storage tanks from the first external storage tank and the second external storage tank respectively;
the electroplating electrolyte storage tank is connected with the cathode reactor through two pipelines, one pipeline is provided with a first pump body, and the other pipeline is provided with a first sensor;
the redox electrolyte storage tank is connected with the anode reactor through two pipelines, one pipeline is provided with a second pump body, and the other pipeline is provided with a second sensor;
the cathode, the cathode iron-plated layer, the cathode reactor, the diaphragm, the anode reactor and the anode are sequentially arranged;
the diaphragm is used for isolating the negative reactor, the positive reactor and respective electrolytes thereof; the membrane is a membrane barrier, being an ion exchange membrane or microporous membrane, disposed between the redox electrolyte and the electroplating electrolyte to prevent crossover of the electrolytes and provide ionic conductivity;
the electroplating electrolyte storage tank is used for storing electroplating electrolyte, and the redox electrolyte storage tank is used for storing redox electrolyte; the electroplating electrolyte and the redox electrolyte both adopt the same metal salt, but the concentrations of the metal salt and the redox electrolyte are different;
the anode is a redox electrode coupling the fluid to a redox electrolyte reservoir; the cathode is an electroplating electrode coupling fluid to an electroplating electrolyte reservoir;
the battery system is an all-iron flow battery IFB system; these may contain different additives and be controlled by different programs; the IFB of the all-iron flow battery is provided with an anode additive or a cathode additive;
during the operation of the battery, the concentration gradient at two sides of the diaphragm drives a large amount of Fe3+From the redox electrolyte to the electroplating electrolyte; the sharp change in pH from electroplating electrolyte to redox electrolyte results in Fe (OH)3Formation and precipitation of species; these precipitates degrade the ion-exchange membrane by poisoning the organic functional groups of the membrane or blocking the pores of the microporous membrane, thereby causing the ohmic resistance of the cell to increase; cleaning the cell with acid to remove the precipitate, but frequent maintenance limits the commercial use of the cell, which also relies on the periodic preparation of the electrolyte; the reaction is inhibited by adding a specific organic acid to the electrolyte in response to the pH of the electrolyte;
electrolyte is pumped through respective electrodes in the IFB system; measuring the pH of the electrolyte of the cell using an iron probe and determining the electrolyte potential from a reference electrode, including Ag/AgCl or H plating the electrode2An electrode; in addition, the pH value is monitored by measuring the reflection spectrum of the electrolyte using an optical sensor; other pH sensing devices specifiedFor pH determination;
the sensors and/or probes communicate the pH of the electrolyte to the control system; if the pH of the bath is found to be above a set first threshold, the control system activates the release of the pre-treated acid, which may be added to the plating electrolyte; if the pH of the redox electrolyte is found to be above a set second threshold, the control system actuates the release of the pre-prepared acid to the redox electrolyte; the acidic additives added to the cathode and anode are the same or different and include boric acid, ascorbic acid, glycolic acid, or any combination thereof; this process may be repeated until the pH is below the threshold; if the pH value is lower than the IFB of the threshold value, the charging or discharging is continued;
the use of a combination of organic acid additives to achieve an optimal iron plating layer to improve its performance, efficiency and stability; in FeCl2And NaCl electrolyte solution, boric acid is added to inhibit H2Side reaction and increase of coulomb efficiency; in addition, ascorbic acid is added to improve the stability of iron ions, and glycolic acid is added to reduce the generation of carbon;
on the negative side of the IFB system, Fe is charged during charging2+Accepting two electrons to form Fe0(ii) a Competitive reaction at the negative side of the cell, H+Accepting an electron to form H2The pH value of the electrolyte on the negative electrode side of the all-iron flow battery IFB is gradually increased from 2 to 6, and the change of the pH value is monitored through the probe and the sensor;
the pH change may result in a cell with an apparent performance loss of up to 100 millivolts due to a high equilibrium potential drift. To mitigate performance loss, Fe potential probes or optical sensors are used to monitor the state of charge of the battery and the pH level of the electrolyte;
the pH value of the operation window of the battery electroplating electrolyte is between 3 and 4; when the Fe potential probe or optical sensor indicates a pH above 4, a small amount of pre-calculated acid is added to the plating electrolyte solution to return the plating electrode to the optimal pH range.
2. An iron-based redox flow battery system, comprising: the device comprises a plating electrode, a redox electrode, a plating electrolyte storage tank, a redox electrolyte storage tank, a first reactor, a second reactor, a first external storage tank, a second external storage tank, a control system and a monitoring device;
the electroplating electrolyte storage tank is used for storing electroplating electrolyte, and the redox electrolyte storage tank is used for storing redox electrolyte;
the redox electrode fluidly coupled to a redox electrolyte reservoir and the plating electrode fluidly coupled to a plating electrolyte reservoir;
the electroplating electrolyte storage tank is connected with the first reactor through a first conveying pipeline, and the redox electrolyte storage tank is connected with the second reactor through a second conveying pipeline; the first reactor is connected with the electroplating electrode, and the second reactor is connected with the oxidation-reduction electrode;
the monitoring device is used for detecting the chemical property of the electrolyte in the electroplating electrolyte storage tank or/and the redox electrolyte storage tank or/and the first conveying pipeline or/and the second conveying pipeline;
the control system is connected with the monitoring device and controls the additives of the first external storage tank and the second external storage tank to be pumped into the electrolyte storage tank according to the data monitored by the monitoring device.
3. The iron-based redox flow battery system of claim 2, wherein:
the electroplating electrolyte storage tank and the redox electrolyte storage tank are used for storing electrolyte; the electrolyte has the functions of generating chemical reaction in the charging process, storing electric quantity and releasing charges in the electrolyte in the discharging process;
the first external storage tank and the second external storage tank are used for storing an electroplating electrolyte additive and a redox electrolyte additive respectively and pumping the additives to adjust the pH value when the pH values of the electrolytes in the electroplating electrolyte storage tank and the redox electrolyte storage tank are changed.
4. The iron-based redox flow battery system of claim 2, wherein:
the battery system also comprises a cathode additive pump, an anode additive pump, a first pump body and a second pump body; the control system is respectively connected with the first additive pump, the second additive pump, the first pump body and the second pump body; the first reactor is a cathode reactor, and the second reactor is an anode reactor;
the first external storage tank and the second external storage tank are used for storing cathode additives and anode additives respectively; the first external storage tank is connected with the cathode reactor through a cathode additive pump, and the second external storage tank is connected with the anode reactor through an anode additive pump; the first and second external reservoirs are capable of coupling fluid to a cathode reactor and an anode reactor, respectively, of the battery system;
the electroplating electrolyte storage tank is connected with the electroplating electrode through a third conveying pipeline, and the third conveying pipeline is provided with a first pump body;
the redox electrolyte storage tank is connected with the redox electrode through a fourth conveying pipeline, and the fourth conveying pipeline is provided with a second pump body.
5. The iron-based redox flow battery system of claim 2, wherein:
the plating electrolyte or redox electrolyte comprises FeCl2、FeCl3Or any combination thereof;
the monitoring device comprises a Fe potential probe passing through a clean iron wire and a reference electrode, such as Ag/AgCl electrode or H2The electrodes are connected;
the plating electrolyte additive, redox electrolyte additive, includes boric acid, ascorbic acid, acetic acid, malic acid, lactic acid, citric acid, tartaric acid, erythorbic acid, malonic acid, glycolic acid, or any combination thereof.
6. The iron-based redox flow battery system of claim 2, wherein:
the monitoring device comprises a first sensor and a second sensor, wherein the first sensor is arranged on the first conveying pipeline, and the second sensor is arranged on the second conveying pipeline; the first sensor and the second sensor are used for determining the chemical properties of the electrolyte, including pH value; or,
the monitoring device comprises a first probe and a second probe which are respectively arranged in the electroplating electrolyte storage tank and the redox electrolyte storage tank and are used for measuring the chemical properties of the electrolyte.
7. The iron-based redox flow battery system of claim 2, wherein:
and a cathode iron plating layer is arranged between the electroplating electrode and the first reactor.
8. The iron-based redox flow battery system of claim 6, wherein:
and a diaphragm is arranged between the first reactor and the second reactor.
9. The iron-based redox flow battery system of claim 4, wherein:
the electroplating electrode is a cathode, and the redox electrode is an anode; a cathode iron plating layer is arranged between the electroplating electrode and the first reactor; a diaphragm is arranged between the cathode reactor and the anode reactor; the cathode, the cathode iron-plated layer, the cathode reactor, the diaphragm, the anode reactor and the anode are sequentially arranged;
the diaphragm is used for isolating the negative reactor, the positive reactor and respective electrolytes thereof; the membrane is a membrane barrier, being an ion exchange membrane or microporous membrane, disposed between the redox electrolyte and the electroplating electrolyte to prevent crossover of the electrolytes and provide ionic conductivity;
the electroplating electrolyte storage tank is used for storing electroplating electrolyte, and the redox electrolyte storage tank is used for storing redox electrolyte; the electroplating electrolyte and the redox electrolyte both adopt the same metal salt, but the concentrations of the metal salt and the redox electrolyte are different;
the anode is a redox electrode coupling the fluid to a redox electrolyte reservoir; the cathode is an electroplating electrode that couples the fluid to an electroplating electrolyte reservoir.
10. The iron-based redox flow battery system of claim 4, wherein:
the battery system is an all-iron flow battery IFB; these may contain different additives and be controlled by different programs; the IFB of the all-iron flow battery is provided with an anode additive or a cathode additive;
during the operation of the battery, the concentration gradient at two sides of the diaphragm drives a large amount of Fe3+From the redox electrolyte to the electroplating electrolyte; the sharp change in pH from electroplating electrolyte to redox electrolyte (from 1 to 3-6) results in Fe (OH)3Formation and precipitation of species; these precipitates degrade the ion-exchange membrane by poisoning its organic functional groups or plugging the pores of the microporous membrane, resulting in an increase in the ohmic resistance of the cell. Cleaning the cell with acid can remove the precipitate, but frequent maintenance limits the commercial use of the cell, which also relies on the periodic preparation of the electrolyte; the reaction is inhibited by adding a specific organic acid to the electrolyte in response to the pH of the electrolyte;
the electrolyte is pumped through respective electrodes within the IFB system; measuring the pH of the electrolyte of the cell using an iron probe and determining the electrolyte potential from a reference electrode, including Ag/AgCl or H plating the electrode2An electrode; in addition, the pH value is monitored by measuring the reflection spectrum of the electrolyte using an optical sensor; other designated pH sensing devices are also used for pH determination;
the sensors and/or probes communicate the pH of the electrolyte to the control system; if the pH of the bath is found to be above a set first threshold, the control system activates the release of the pre-treated acid, which may be added to the plating electrolyte; if the pH of the redox electrolyte is found to be above a set second threshold, the control system actuates the release of the pre-prepared acid to the redox electrolyte; the acidic additives added to the cathode and anode are the same or different and include boric acid, ascorbic acid, glycolic acid, or any combination thereof; this process may be repeated until the pH is below the threshold; if the pH value is lower than the IFB of the threshold value, the charging or discharging is continued;
the use of a combination of organic acid additives to achieve an optimal iron plating layer to improve its performance, efficiency and stability; in FeCl2And NaCl electrolyte solution, boric acid is added to inhibit H2Side reaction and increase of coulomb efficiency; in addition, ascorbic acid is added to improve the stability of iron ions, and glycolic acid is added to reduce the generation of carbon;
on the negative side of the IFB system, Fe during charging2+Accepting two electrons to form Fe0(ii) a Competitive reaction at the negative side of the cell, H+Accepting an electron to form H2The pH value of the electrolyte on the negative electrode side of the IFB is gradually increased from 2 to 6, and the change of the pH value is monitored by the probe and the sensor;
the pH change may result in a cell with an apparent performance loss of up to 100 millivolts due to a high equilibrium potential drift. To mitigate performance loss, Fe potential probes or optical sensors are used to monitor the state of charge of the battery and the pH level of the electrolyte;
the pH value of the operation window of the battery electroplating electrolyte is between 3 and 4; when the Fe potential probe or optical sensor indicates a pH above 4, a small amount of pre-calculated acid is added to the plating electrolyte solution to return the plating electrode to the optimal pH range.
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