CN116454341A - Iron-chromium flow battery pile system - Google Patents
Iron-chromium flow battery pile system Download PDFInfo
- Publication number
- CN116454341A CN116454341A CN202310529531.9A CN202310529531A CN116454341A CN 116454341 A CN116454341 A CN 116454341A CN 202310529531 A CN202310529531 A CN 202310529531A CN 116454341 A CN116454341 A CN 116454341A
- Authority
- CN
- China
- Prior art keywords
- valve
- negative electrode
- liquid path
- pile
- pump
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 147
- 239000003792 electrolyte Substances 0.000 claims abstract description 65
- 238000004140 cleaning Methods 0.000 claims abstract description 56
- 239000011259 mixed solution Substances 0.000 claims description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- 239000001257 hydrogen Substances 0.000 claims description 43
- 238000003860 storage Methods 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 19
- 238000011045 prefiltration Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 11
- -1 iron ions Chemical class 0.000 claims description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 10
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 10
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- 229910001430 chromium ion Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 229910001447 ferric ion Inorganic materials 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002500 ions Chemical group 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004880 explosion Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
-
- 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
- H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
-
- 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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- 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)
- Hybrid Cells (AREA)
Abstract
The invention discloses an iron-chromium flow battery pile system, which comprises: the positive electrolyte flows out of the positive liquid tank and then flows back to the positive liquid tank through a third valve, a positive pump, a fourth valve, a positive liquid path of the galvanic pile and a sixth valve in sequence; the negative electrode electrolyte flows out of the negative electrode liquid tank, sequentially passes through the first valve, the negative electrode pump, the second valve, the negative electrode liquid path of the galvanic pile and the fifth valve, and then flows back to the negative electrode liquid tank; the seventh valve and the eighth valve are bridged between the positive and negative circulating liquid paths, and the electric pile is closed when being charged and discharged; the first cleaning mode for cleaning the galvanic pile comprises the following steps: the positive electrode pump and the negative electrode pump are closed firstly, then the second valve, the third valve, the fourth valve, the sixth valve, the seventh valve, the eighth valve, the positive electrode pump and the negative electrode pump are opened under the condition that the galvanic pile is not charged, and meanwhile the first valve and the fifth valve are closed, so that the galvanic pile is cleaned by utilizing positive electrolyte. The invention improves the performance and service life of the iron-chromium flow battery pile.
Description
Technical Field
The invention belongs to the technical field of liquid flow energy storage, and particularly relates to an iron-chromium liquid flow battery pile system.
Background
With the continuous increase of world economy, people have increasingly demanded energy, the shortage of energy is more serious, the consumption of traditional fossil energy is large, and the environmental problems are increasing. Renewable energy sources such as wind energy and solar energy have important significance for improving energy structure, protecting ecological environment, coping with climate change and realizing sustainable development of economy and society.
Renewable energy sources such as wind energy and solar energy have the characteristics of instability and discontinuity, and a large-scale energy storage technology, particularly a long-time energy storage technology is required to be used for improving the power quality and reliability of renewable energy source power generation. The liquid flow energy storage battery technology in chemical energy storage has great advantages in energy density, efficiency, scale, cycle life, cost and the like. The energy storage density of the liquid flow energy storage battery technology reaches 10 Wh/kg-30 Wh/kg, and the efficiency is 60% -85%; moreover, the power and the capacity of the device can be separately and independently designed, the charging and discharging reaction is rapid, the application range is wide, the device can be applied to peak clipping and valley filling, can also be used for standby power supply or emergency power supply, and can also be applied to improving the quality of power, regulating voltage and frequency and the like.
As a typical device of an electrochemical energy storage technology, the iron-chromium flow battery has the outstanding advantages of high efficiency, long cycle life, independent design of capacity and power, quick response, high safety, high cost performance in life cycle and the like, and is particularly suitable for large-scale energy storage. A plurality of iron-chromium flow batteries are connected in series, and an energy storage system unit structure, namely a galvanic pile, of a higher level can be formed through assembly and combination.
However, in the electrochemical process of the electrolyte of the iron-chromium flow battery, elements such as copper, nickel and the like are gradually attached/deposited inside the galvanic pile, and when the deposition amount gradually increases along with the time, the hydrogen evolution amount of the iron-chromium flow battery is gradually increased; the hydrogen evolution of the iron-chromium flow battery can cause the attenuation of the battery, so that insufficient hydrogen ions are not reduced to trivalent iron in the charging and discharging process, the content of the trivalent iron is too high, the capacity of the battery is attenuated, the performance of the battery is influenced, and the service life of a galvanic pile is shortened.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an iron-chromium flow battery pile system.
The technical problems to be solved by the invention are realized by the following technical scheme:
an iron-chromium flow battery pile system, wherein positive electrolyte and negative electrolyte of an iron-chromium flow battery in the system are mixed solutions of ferrous ions, trivalent chromium ions and hydrochloric acid, and part of ferrous ions are oxidized into trivalent iron ions after pile operation;
the system comprises: the system comprises a galvanic pile, an anode liquid tank, a cathode liquid tank, a first valve, a second valve, a third valve, a fourth valve, a fifth valve, a sixth valve, a seventh valve, an eighth valve, an anode pump and a cathode pump; wherein,,
after flowing out of the positive electrolyte tank, the positive electrolyte sequentially passes through a third valve, a positive pump, a fourth valve, a positive liquid path of the galvanic pile and a sixth valve and then flows back to the positive electrolyte tank to form a positive circulating liquid path;
the negative electrode electrolyte flows out of the negative electrode liquid tank, sequentially passes through the first valve, the negative electrode pump, the second valve, the negative electrode liquid path of the galvanic pile and the fifth valve and then flows back to the negative electrode liquid tank to form a negative electrode circulating liquid path;
the seventh valve and the eighth valve are bridged between the positive circulation liquid path and the negative circulation liquid path; one end of the seventh valve is communicated with a pipeline between the negative electrode pump and the second valve, and the other end of the seventh valve is communicated with a pipeline between the positive electrode pump and the fourth valve; one end of the eighth valve is communicated with a pipeline between the sixth valve and an outlet of a positive electrode liquid path of the electric pile, and the other end of the eighth valve is communicated with a pipeline between the fifth valve and an outlet of a negative electrode liquid path of the electric pile;
when the electric pile is charged and discharged, the first valve, the second valve, the third valve, the fourth valve, the fifth valve, the sixth valve, the positive electrode pump and the negative electrode pump are opened, and the seventh valve and the eighth valve are closed;
the first cleaning mode for cleaning the galvanic pile comprises the following steps:
closing the positive electrode pump and the negative electrode pump;
under the condition that the galvanic pile is not charged, the second valve, the third valve, the fourth valve, the sixth valve, the seventh valve, the eighth valve, the positive electrode pump and the negative electrode pump are opened, and the first valve and the fifth valve are closed at the same time, so that the whole galvanic pile is cleaned by utilizing positive electrolyte.
Optionally, the system further comprises: a first pre-filter and a second pre-filter;
the first pre-filter is positioned at an anode liquid path inlet of the electric pile, and the second pre-filter is positioned at a cathode liquid path inlet of the electric pile.
Optionally, the system further comprises: a first post-filter and a second post-filter;
the first post filter is positioned at an outlet of a positive electrode liquid path of the electric pile, and the second post filter is positioned at an outlet of a negative electrode liquid path of the electric pile;
the second cleaning mode for cleaning the galvanic pile comprises the following steps:
and injecting ferric iron solution into the galvanic pile from an anode liquid path inlet and a cathode liquid path inlet of the galvanic pile, so as to collect nickel chloride and copper chloride at an anode liquid path outlet and a cathode liquid path outlet of the galvanic pile by utilizing the first post filter and the second post filter.
Optionally, the system further comprises: a first storage tank, a second storage tank, a ninth valve, a tenth valve, an eleventh valve, and a twelfth valve; wherein,,
injecting a first mixed solution of ferric iron and hydrochloric acid into a first storage tank, and injecting a second mixed solution of water and hydrochloric acid into a second storage tank;
the ninth valve, the first storage tank and the tenth valve are sequentially connected through pipelines to form a first branch; the eleventh valve, the second storage tank and the twelfth valve are sequentially connected through pipelines to form a second branch; one end of the first branch and one end of the second branch are communicated with a pipeline between the fifth valve and the negative electrode liquid path outlet of the electric pile, and the other end of the first branch and the other end of the second branch are communicated with a pipeline between the first valve and the negative electrode pump;
the third cleaning mode for cleaning the galvanic pile comprises the following steps:
closing the positive electrode pump and the negative electrode pump, and closing the first valve, the fifth valve and the sixth valve; simultaneously, the second valve, the fourth valve, the seventh valve and the eighth valve are all in an open state; the ninth valve, the tenth valve, the eleventh valve and the twelfth valve are all in a closed state;
opening a ninth valve and a tenth valve and starting a negative electrode pump to enable the first mixed solution to circulate along the first liquid path and the second liquid path respectively; in the first liquid path, after flowing out of the first storage tank, the first mixed solution sequentially passes through a tenth valve, a negative electrode pump, a second valve, a negative electrode liquid path of the electric pile and a ninth valve and flows back to the first storage tank; in the second liquid path, after flowing out of the first storage tank, the first mixed solution sequentially flows back to the first storage tank through a tenth valve, a negative electrode pump, a seventh valve, a fourth valve, an anode liquid path of the electric pile, an eighth valve and a ninth valve;
closing the negative electrode pump, the ninth valve and the tenth valve;
opening an eleventh valve and a twelfth valve and starting a negative electrode pump to enable the second mixed solution to circulate along the third liquid path and the fourth liquid path respectively; in the third liquid path, the second mixed solution flows out of the second storage tank and then flows back to the second storage tank after sequentially passing through a twelfth valve, a negative electrode pump, a second valve, a negative electrode liquid path of the electric pile and an eleventh valve; in the fourth liquid path, after flowing out of the second storage tank, the second mixed solution sequentially passes through a twelfth valve, a negative electrode pump, a seventh valve, a fourth valve, an anode liquid path of the electric pile, an eighth valve and an eleventh valve and then flows back to the second storage tank.
Optionally, the electric pile is cleaned for a plurality of times in the process of charging the electric pile, the cleaning time is determined according to the open-circuit voltage OCV of the electric pile, and the open-circuit voltage OCV of the electric pile is at least ensured to be above the potential difference of the ferrochromium redox reaction during the primary cleaning.
Optionally, the system further comprises: a hydrogen sensor;
the hydrogen sensor is used for monitoring the hydrogen evolution quantity of the galvanic pile; and when the hydrogen evolution quantity of the galvanic pile exceeds the early warning value, cleaning the galvanic pile.
Optionally, the filter pore diameters of the first pre-filter, the second pre-filter, the first post-filter and the second post-filter are all 0.1 μm to 1 μm.
Optionally, the system further comprises: a remote control end; any valve is an electric remote control valve;
the remote control end is used for controlling the opening and closing of the positive electrode pump, the negative electrode pump and the electric remote control valve.
Optionally, the volume of the first tank fills at least the first liquid path and the second liquid path with liquid;
the volume of the second tank fills at least the third and fourth liquid paths with liquid.
Optionally, in the first mixed solution, the concentration of ferric iron is 0.2-3 mol/L, and the concentration of hydrochloric acid is 0.5-3 mol/L;
in the second mixed solution, the concentration of hydrochloric acid is 0.5 mol/L-3 mol/L.
Optionally, the case of not charging the galvanic pile includes: the stack discharges or, with the charging device turned off, the stack is left to stand.
In the iron-chromium flow battery pile system provided by the invention, when the pile is charged and discharged, the first valve, the second valve, the third valve, the fourth valve, the fifth valve, the sixth valve, the positive electrode pump and the negative electrode pump are opened, and the seventh valve and the eighth valve are closed; after flowing out of the positive electrolyte tank, the positive electrolyte sequentially passes through a third valve, a positive pump, a fourth valve, a positive liquid path of the galvanic pile and a sixth valve and then flows back to the positive electrolyte tank to form a positive circulating liquid path; the negative electrode electrolyte flows out of the negative electrode liquid tank, sequentially passes through the first valve, the negative electrode pump, the second valve, the negative electrode liquid path of the galvanic pile and the fifth valve and then flows back to the negative electrode liquid tank to form a negative electrode circulating liquid path; based on the structure, the first cleaning mode can be adopted to clean the electric pile, the positive electrode pump and the negative electrode pump are firstly closed during cleaning, then the second valve, the third valve, the fourth valve, the sixth valve, the seventh valve, the eighth valve, the positive electrode pump and the negative electrode pump are opened under the condition that the electric pile is not charged, and meanwhile the first valve and the fifth valve are closed; in this way, after flowing out of the positive electrode electrolyte tank, the positive electrode electrolyte is divided into two liquid paths through a third valve and a positive electrode pump, and one liquid path sequentially passes through a fourth valve, the positive electrode liquid path of the electric pile and a sixth valve and flows back to the positive electrode tank; the other liquid path sequentially passes through the seventh valve, the second valve, the negative electrode liquid path of the electric pile, the eighth valve and the sixth valve and then flows back to the positive electrode tank. Because the positive electrolyte and the negative electrolyte of the chromium flow battery in the system are mixed solutions of ferrous ions, trivalent chromium ions and hydrochloric acid, part of ferrous ions are oxidized into ferric ions after the operation of the galvanic pile. Therefore, after ferric ions and hydrochloric acid in the positive electrolyte flow into the galvanic pile, enough hydrogen ions exist, the ferric ions can dissolve copper and nickel in the metal form in the galvanic pile into nickel chloride, copper chloride and other compounds in the ion form, and particularly, after the positive electrolyte enters the negative electrode, the hydrogen ions can be supplemented for the negative electrode with serious hydrogen evolution, so that the positive electrolyte is utilized to clean the whole galvanic pile.
The present invention will be described in further detail with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic structural diagram of an iron-chromium flow battery pile system according to an embodiment of the present invention;
FIG. 2 is a schematic illustration of a positive and negative circulation fluid circuit when charging and discharging a stack based on the system of FIG. 1;
FIG. 3 is a schematic view of the circulation of positive electrolyte when the stack is cleaned in a first cleaning mode based on the system of FIG. 1;
FIG. 4 is a schematic diagram of another iron-chromium flow battery pile system according to an embodiment of the present invention;
FIG. 5 is a schematic diagram of a further exemplary iron-chromium flow battery cell stack system according to an embodiment of the present invention;
FIG. 6 is a schematic illustration of a circulation circuit of the first mixed solution when the stack is cleaned in a third cleaning mode based on the system of FIG. 5;
FIG. 7 is a schematic illustration of another circulation path for the first mixed solution when the stack is being cleaned in a third cleaning mode based on the system of FIG. 5;
FIG. 8 is a schematic illustration of a circulation circuit of the second mixed solution when the stack is cleaned in a third cleaning mode based on the system of FIG. 5;
FIG. 9 is a schematic illustration of another circulation path for the second mixed solution when the stack is being cleaned in a third cleaning mode based on the system of FIG. 5;
fig. 10 is a schematic structural diagram of still another iron-chromium flow battery pile system according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
In order to improve performance and service life of an iron-chromium flow battery pile, the embodiment of the invention provides an iron-chromium flow battery pile system, wherein positive electrolyte and negative electrolyte of an iron-chromium flow battery in the system are mixed solutions of ferrous ions, trivalent chromium ions and hydrochloric acid, the content of the hydrochloric acid is not high, and for example, the content of the hydrochloric acid is less than 0.1mol/L. It will be appreciated that some of the ferrous ions in the mixed solution are oxidized to ferric ions after operation of the stack.
The components of the positive electrode electrolyte and the negative electrode electrolyte in the conventional iron-chromium flow battery are mainly iron ions, and are different from the electrolyte in the embodiment of the invention. The main reasons for the difference between the prior iron-chromium flow battery and the electrolyte of the embodiment of the invention are that: ion exchange membranes are usually adopted in the existing iron-chromium flow batteries, the holes of the membranes are small, and iron and chromium ions cannot penetrate through the membranes; the iron-chromium flow battery in the embodiment of the invention is a porous membrane which allows iron and chromium ions to penetrate through each other, and the energy density is half less than that of a galvanic pile adopting an ion conduction membrane, but the cost can be reduced by hundreds of times than that of a traditional ion exchange membrane. The iron-chromium flow battery pile system provided by the embodiment of the invention is constructed based on the iron-chromium flow battery adopting the porous membrane.
As shown in fig. 1, an iron-chromium flow battery pile system provided by an embodiment of the present invention includes: the electric pile, the positive electrode liquid tank, the negative electrode liquid tank, the first valve 1, the second valve 2, the third valve 3, the fourth valve 4, the fifth valve 5, the sixth valve 6, the seventh valve 7, the eighth valve 8, the positive electrode pump 14 and the negative electrode pump 13 and also comprise pipelines between the first valve and the second valve. In fig. 1 and the subsequent figures, the positive electrode tank is marked with a positive sign "+" and the negative electrode tank is marked with a negative sign "-".
As shown by dotted lines in fig. 2, when the electric pile is charged and discharged, the first valve 1, the second valve 2, the third valve 3, the fourth valve 4, the fifth valve 5, the sixth valve 6, the positive electrode pump 14 and the negative electrode pump 13 are opened, and the seventh valve 7 and the eighth valve 8 are closed; the positive electrolyte flows out of the positive liquid tank, sequentially passes through the third valve 3, the positive pump 14, the fourth valve 4, the positive liquid path of the galvanic pile and the sixth valve 6, and flows back to the positive liquid tank to form a positive circulating liquid path. The negative electrode electrolyte flows out of the negative electrode liquid tank, sequentially passes through the first valve 1, the negative electrode pump 13, the second valve 2, the negative electrode liquid path of the galvanic pile and the fifth valve 5 and then flows back to the negative electrode liquid tank to form a negative electrode circulating liquid path.
The seventh valve 7 and the eighth valve 8 are bridged between the positive circulation liquid path and the negative circulation liquid path; wherein one end of the seventh valve 7 is communicated with a pipeline between the negative electrode pump 13 and the second valve 2, and the other end is communicated with a pipeline between the positive electrode pump 14 and the fourth valve 4; one end of the eighth valve 8 is communicated with a pipeline between the sixth valve 6 and the outlet of the positive electrode liquid path of the electric pile, and the other end is communicated with a pipeline between the fifth valve 5 and the outlet of the negative electrode liquid path of the electric pile.
Based on the structure of the system shown in fig. 1, in the process of normal charging and discharging of the galvanic pile, the galvanic pile can be cleaned by adopting a first cleaning mode, which includes:
(1) The positive electrode pump 14 and the negative electrode pump 13 are turned off;
(2) Under the condition that the galvanic pile is not charged, the second valve 2, the third valve 3, the fourth valve 4, the sixth valve 6, the seventh valve 7, the eighth valve 8, the positive electrode pump 14 and the negative electrode pump 13 are opened, and the first valve 1 and the fifth valve 5 are closed at the same time, so that the whole galvanic pile is cleaned by utilizing positive electrode electrolyte.
The case where the pile is not charged includes: the stack discharges, for example at maximum current, or stands still with the charging device shut down. The actual charging device includes: the power supply, the power supply converter and the energy storage converter (Power Conversion System, PCS) are closed.
As shown by the broken line in fig. 3, when the first cleaning mode is adopted to clean the galvanic pile, the positive electrolyte flows out from the positive electrode liquid tank and is divided into two liquid paths through the third valve 3 and the positive electrode pump 14, one liquid path flows back to the positive electrode tank after passing through the fourth valve 4, the positive electrode liquid path of the galvanic pile and the sixth valve 6, and the other liquid path flows back to the positive electrode tank after passing through the seventh valve 7, the second valve 2, the negative electrode liquid path of the galvanic pile, the eighth valve 8 and the sixth valve 6 in sequence.
Since both the positive electrode electrolyte and the negative electrode electrolyte are mixed solutions of ferrous ions, trivalent chromium ions and hydrochloric acid, part of the ferrous ions are oxidized into ferric ions. Therefore, after ferric ions and hydrochloric acid in the positive electrolyte flow into the galvanic pile, enough hydrogen ions exist, the ferric ions can dissolve copper and nickel in the metal form in the galvanic pile into nickel chloride, copper chloride and other compounds in the ion form, and particularly, after the positive electrolyte enters the negative electrode, the hydrogen ions can be supplemented for the negative electrode with serious hydrogen evolution, so that the positive electrolyte is utilized to clean the whole galvanic pile.
It should be noted that, the above-mentioned first cleaning method is not suitable for the existing common galvanic pile with different components of the positive electrode electrolyte and the negative electrode electrolyte, and the positive electrode electrolyte and the negative electrode electrolyte are mutually rotated in the cleaning process, so that the galvanic pile is scrapped.
In addition, in the prior art, the hydrogen evolution reaction of the anode side of the iron-chromium flow battery is serious, the concentration of hydrogen evolution substances copper and nickel reaches 5 mg/L-20 mg/L, and a catalyst is often required to be matched, so that the overall efficiency and the power density of the electric pile are difficult to be improved to reasonable levels. The electrolyte is used as a key component of the iron-chromium flow battery, is a core material for storing energy of the flow battery, and the reaction characteristic of an electrode and an electrolyte interface directly influences and determines the performance of the battery, so that the electrolyte determines the efficiency and the stability of the battery to a great extent. According to the embodiment of the invention, after the positive electrode electrolyte enters the negative electrode, hydrogen ions can be supplemented for the negative electrode with serious hydrogen evolution, the reaction characteristic of an interface between the electrode and the electrolyte is improved, and the hydrogen evolution quantity is reduced in the charging and discharging process of the battery by dissolving the hydrogen evolution substances, so that the content of the hydrogen ions repeatedly used by the electrolyte is improved, the attenuation of the battery is reduced, the capacity of the battery is kept, the service life of the battery is prolonged, and the overall efficiency and the power density of the electric pile are improved. And, as the stack is operated for a long time, the positive electrolyte and the negative electrolyte of the stack are balanced, and the life of the stack is longer.
Wherein, the reaction formula of the ferric ion for dissolving nickel in a metal form into nickel chloride in an ion form is as follows:
；
the reaction formula of ferric ion to dissolve copper in metallic form into cupric chloride in ionic form is:
。
in practical application, after each valve and pump are configured in the manner shown in fig. 3, the negative electrode pump 13 is continuously turned on for a period of time to complete cleaning. For example, assuming that the frequency of the negative electrode pump 13 is 20hz to 40hz, the cleaning can be completed by continuously opening for about 10 minutes. At the moment, the electrolyte is sent to be checked or the hydrogen evolution speed of the galvanic pile is detected to be smaller than 5L/min, so that the galvanic pile can be known to be in a healthy state.
After the electric pile is cleaned by the first cleaning mode, the system is restored to the state shown in fig. 2, and the electric pile can be continuously charged and discharged.
In one embodiment, referring to fig. 4, the iron-chromium flow battery pile system provided by the embodiment of the present invention may further include: a first pre-filter 18 and a second pre-filter 16.
Wherein the first pre-filter 18 is located at the positive fluid path inlet of the stack and the second pre-filter 16 is located at the negative fluid path inlet of the stack.
It can be understood that, because harmful impurities with larger volumes such as fossil, organic matters, metal and the like are inevitably mixed in the electrolyte in the production process of the iron-chromium flow battery, the impurities can enter the galvanic pile along with the electrolyte, so that the interior of the galvanic pile is blocked, the fluency of a liquid path is influenced, the running stability of the galvanic pile is seriously influenced, and the service life of the galvanic pile is shortened. Therefore, the pre-filter is arranged at the inlet of the positive electrode liquid path and the inlet of the negative electrode liquid path of the electric pile, so that the problem that impurities enter the electric pile to cause the blockage of liquid flow in the electric pile and influence the fluency of the liquid path of the whole system can be effectively avoided.
In one embodiment, referring to fig. 4, the iron-chromium flow battery pile system provided by the embodiment of the present invention may further include: a first post-filter 17 and a second post-filter 15.
Wherein the first post-filter 17 is located at the outlet of the positive electrode liquid path of the galvanic pile, and the second post-filter 15 is located at the outlet of the negative electrode liquid path of the galvanic pile.
Based on the system shown in fig. 4, the second cleaning manner may be further used to clean the galvanic pile, including: ferric solution is injected into the galvanic pile from the positive and negative electrode liquid path inlets of the galvanic pile to collect nickel chloride and copper chloride at the positive and negative electrode liquid path outlets of the galvanic pile using the first and second post-filters 17 and 15.
As is known to those skilled in the art, in order to maintain the chemical stability of the ferric solution, a small amount of hydrochloric acid is contained in the ferric solution in practice, so that after the ferric solution is injected into the galvanic pile from the positive electrode liquid path inlet and the negative electrode liquid path inlet of the galvanic pile, the chemical reaction generated inside the galvanic pile is the same as the first cleaning mode, that is, ferric ions dissolve copper and nickel in the metallic form inside the galvanic pile into nickel chloride, copper chloride and other compounds in the ionic form.
In practical applications, after the galvanic pile is charged, the galvanic pile can be cleaned by the second cleaning mode.
Preferably, the filter pore sizes of the first pre-filter 18, the second pre-filter 16, the first post-filter 17 and the second post-filter 15 may be 0.1 μm to 1 μm. This can more effectively filter out impurities such as fossil, organic matter, metal, etc. which may be contained in the electrolyte.
In one embodiment, on the basis of the system shown in fig. 1, as shown in fig. 5, the iron-chromium flow battery pile system provided by the embodiment of the invention may further include: a first tank, a second tank, a ninth valve 9, a tenth valve 10, an eleventh valve 11, and a twelfth valve 12.
Wherein, a first mixed solution of ferric iron and hydrochloric acid is injected into a first storage tank, and a second mixed solution of water and hydrochloric acid is injected into a second storage tank; the ninth valve 9, the first storage tank and the tenth valve 10 are sequentially connected through pipelines to form a first branch; the eleventh valve 11, the second storage tank and the twelfth valve 12 are sequentially connected through pipelines to form a second branch; wherein, the pipeline between the negative pole liquid way export of fifth valve 5 and pile is all linked together to the one end of first branch road and second branch road, and the pipeline between first valve 1 and negative pole pump 13 is all linked together to the other end of first branch road and second branch road.
Based on the structure of the system shown in fig. 5, a third mode may be further adopted to clean the galvanic pile, including:
(1) The positive electrode pump 14 and the negative electrode pump 13 are closed, and the first valve 1, the fifth valve 5 and the sixth valve 6 are closed; simultaneously, the second valve 2, the fourth valve 4, the seventh valve 7 and the eighth valve 8 are all in an open state; the ninth valve 9, the tenth valve 10, the eleventh valve 11 and the twelfth valve 12 are all in a closed state;
(2) Opening a ninth valve 9 and a tenth valve 10 and starting a cathode pump 13 to circulate the first mixed solution along the first liquid path and the second liquid path respectively;
referring to fig. 6, in the first liquid path, after the first mixed solution flows out from the first storage tank, the first mixed solution flows back to the first storage tank through the tenth valve 10, the negative electrode pump 13, the second valve 2, the negative electrode liquid path of the galvanic pile and the ninth valve 9 in sequence; referring to fig. 7, in the second liquid path, after the first mixed solution flows out from the first storage tank, the first mixed solution flows back to the first storage tank through the tenth valve 10, the negative electrode pump 13, the seventh valve 7, the fourth valve 4, the positive electrode liquid path of the galvanic pile, the eighth valve 8 and the ninth valve 9 in sequence. Thus, the first mixed solution, namely the mixed solution of ferric iron and hydrochloric acid is utilized to dissolve copper and nickel in the metal form in the galvanic pile into nickel chloride, copper chloride and other compounds in the ion form;
in practical application, after the first mixed solution enters the galvanic pile, cleaning the galvanic pile, and refluxing the cleaned liquid into a first storage tank, so that the liquid is circularly cleaned for 1-5 times, and copper and nickel in a metal form in the galvanic pile can be dissolved into compounds such as nickel chloride and copper chloride in an ion form;
(3) Closing the negative electrode pump 13, the ninth valve 9 and the tenth valve 10;
(4) The eleventh valve 11, the twelfth valve 12 and the negative electrode pump 13 are opened to circulate the second mixed solution along the third liquid path and the fourth liquid path, respectively.
Referring to fig. 8, in the third liquid path, the second mixed solution flows out from the second storage tank, sequentially passes through the twelfth valve 12, the negative electrode pump 13, the second valve 2, the negative electrode liquid path of the galvanic pile, and the eleventh valve 11, and then flows back to the second storage tank; referring to fig. 9, in the fourth liquid path, the second mixed solution flows out of the second storage tank, sequentially passes through the twelfth valve 12, the negative electrode pump 13, the seventh valve 7, the fourth valve 4, the positive electrode liquid path of the galvanic pile, the eighth valve 8, and the eleventh valve 11, and then flows back to the second storage tank. Thereby, the excess ferric ions introduced into the interior of the pile by the first mixed solution are washed away by the second mixed solution, i.e., the mixed solution of water and hydrochloric acid.
In practical application, after the second mixed solution enters the galvanic pile, the galvanic pile is cleaned, the cleaned liquid flows back to the first storage tank, and the trivalent iron introduced by the first mixed solution can be washed out after being circularly cleaned for 1-5 times.
After the cleaning of the galvanic pile is completed by the third cleaning mode, the negative electrode pump 13, the eleventh valve 11 and the twelfth valve 12 are closed, and the cleaning is interrupted; then, the first valve 1, the fifth valve 5, the sixth valve 6, the positive electrode pump 14 and the negative electrode pump 13 are opened, and the charge and discharge of the electric pile are continued according to the positive electrode circulation liquid path and the positive electrode circulation liquid path shown in fig. 2.
It should be noted that the third cleaning method is not applicable to the conventional common galvanic pile with different components of the positive electrode electrolyte and the negative electrode electrolyte, and the residual positive electrode electrolyte and the negative electrode electrolyte in the pipeline are mixed after the seventh valve 7 and the eighth valve 8 are opened in the cleaning process, so that the performance of the galvanic pile is affected.
In one embodiment, the systems shown in fig. 4 and 5 may be combined into a system as shown in fig. 10. In this way, when the stack is cleaned by the first cleaning method or the third cleaning method, the dissolved nickel chloride, copper chloride, or other compounds can be filtered by the first post-filter 17 and the second post-filter 15.
In practical application, in the process of charging the electric pile, the electric pile can be cleaned for multiple times by adopting a first cleaning mode or a third cleaning mode, the cleaning time can be determined according to the open-circuit voltage OCV (Open Circuit Voltage, open-circuit voltage) of the electric pile, and the OCV of the electric pile is at least ensured to be above the potential difference of the iron-chromium oxidation reduction reaction during the primary cleaning.
For example, the first cleaning mode or the third cleaning mode may be used to clean the galvanic pile when the OCV reaches 0.8V, 0.9V, 1V, 1.1V, 1.15V.
In practical applications, it is preferable to start the cleaning of the stack by the first cleaning method or the third cleaning method when the State of Charge (SOC) of the stack is greater than 30%. This is because when the SOC is lower than 30%, nickel and copper in the stack remain in an ionic state, and metallic nickel and copper deposited in the stack are small.
In one embodiment, the iron-chromium flow battery pile system provided by the embodiment of the invention further comprises: a hydrogen sensor; the hydrogen sensor is used for monitoring the hydrogen evolution quantity of the galvanic pile; and when the hydrogen evolution quantity of the galvanic pile exceeds the early warning value, cleaning the galvanic pile.
In practical application, when the hydrogen evolution quantity of the galvanic pile exceeds the early warning value, the hydrogen sensor can trigger the alarm to give an alarm, so that an operator is informed to clean the galvanic pile. Here, the magnitude of the early warning value may be set according to the pile power, for example, when the pile power is around 100kW, the early warning value may be set to 5L/min, or not more than 5L/min. Therefore, the explosion risk caused by overlarge amount of hydrogen precipitated by the iron-chromium flow battery can be effectively avoided.
In one implementation manner, the iron-chromium flow battery pile system provided by the embodiment of the invention can further comprise: a remote control end; any valve is an electric remote control valve; thus, the remote control end can control the opening and closing of the positive electrode pump 14, the negative electrode pump 13 and the electric remote control valves.
And the hydrogen sensor can be in communication connection with the remote control end, so that when the hydrogen sensor monitors that the hydrogen evolution quantity of the galvanic pile exceeds an early warning value, the remote control end can be informed of the fact that the remote control end can automatically clean the galvanic pile by controlling the positive electrode pump 14, the negative electrode pump 13 and the electric remote control valve.
It should be noted that, in the prior art, since the hydrogen evolution amount of the cathode of the electric pile is large, in order to prevent the explosion caused by the concentrated discharge of a large amount of hydrogen, a hydrogen collecting/processing device is additionally arranged on the electric pile. In the embodiment of the invention, only the hydrogen sensor is used for monitoring the hydrogen, and the galvanic pile is cleaned once the hydrogen evolution quantity is detected to exceed the early warning value, so that the further occurrence of the hydrogen evolution phenomenon is interfered/relieved, and a small part of the hydrogen which is already separated out in the process of cleaning the galvanic pile can be dispersed and not be intensively discharged in a large quantity, and the explosion risk is avoided.
It should be noted that the terms "first," "second," and the like are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the disclosed embodiments described herein may be implemented in other sequences than those illustrated or otherwise described herein. The implementations described in the following exemplary examples are not representative of all implementations consistent with the present disclosure. Rather, they are merely examples of apparatus and methods consistent with aspects of the present disclosure.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Further, one skilled in the art can engage and combine the different embodiments or examples described in this specification.
Although the present application has been described herein with respect to various embodiments, other variations of the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed application, from a review of the figures and the disclosure. In the description of the present invention, the word "comprising" does not exclude other elements or steps, the "a" or "an" does not exclude a plurality, and the "a" or "an" means two or more, unless specifically defined otherwise. Moreover, some measures are described in mutually different embodiments, but this does not mean that these measures cannot be combined to produce a good effect.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly under and obliquely below the second feature, or simply means that the first feature is less level than the second feature.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (11)
1. The iron-chromium flow battery pile system is characterized in that positive electrolyte and negative electrolyte of an iron-chromium flow battery in the system are mixed solutions of ferrous ions, trivalent chromium ions and hydrochloric acid, and part of ferrous ions are oxidized into trivalent iron ions after pile operation;
the system comprises: the system comprises a galvanic pile, an anode liquid tank, a cathode liquid tank, a first valve, a second valve, a third valve, a fourth valve, a fifth valve, a sixth valve, a seventh valve, an eighth valve, an anode pump and a cathode pump; wherein,,
after flowing out of the positive electrolyte tank, the positive electrolyte sequentially passes through a third valve, a positive pump, a fourth valve, a positive liquid path of the galvanic pile and a sixth valve and then flows back to the positive electrolyte tank to form a positive circulating liquid path;
the negative electrode electrolyte flows out of the negative electrode liquid tank, sequentially passes through the first valve, the negative electrode pump, the second valve, the negative electrode liquid path of the galvanic pile and the fifth valve and then flows back to the negative electrode liquid tank to form a negative electrode circulating liquid path;
the seventh valve and the eighth valve are bridged between the positive circulation liquid path and the negative circulation liquid path; one end of the seventh valve is communicated with a pipeline between the negative electrode pump and the second valve, and the other end of the seventh valve is communicated with a pipeline between the positive electrode pump and the fourth valve; one end of the eighth valve is communicated with a pipeline between the sixth valve and an outlet of a positive electrode liquid path of the electric pile, and the other end of the eighth valve is communicated with a pipeline between the fifth valve and an outlet of a negative electrode liquid path of the electric pile;
when the electric pile is charged and discharged, the first valve, the second valve, the third valve, the fourth valve, the fifth valve, the sixth valve, the positive electrode pump and the negative electrode pump are opened, and the seventh valve and the eighth valve are closed;
the first cleaning mode for cleaning the galvanic pile comprises the following steps:
closing the positive electrode pump and the negative electrode pump;
under the condition that the galvanic pile is not charged, the second valve, the third valve, the fourth valve, the sixth valve, the seventh valve, the eighth valve, the positive electrode pump and the negative electrode pump are opened, and the first valve and the fifth valve are closed at the same time, so that the whole galvanic pile is cleaned by utilizing positive electrolyte.
2. The iron chromium flow battery cell stack system of claim 1, further comprising: a first pre-filter and a second pre-filter;
the first pre-filter is positioned at an anode liquid path inlet of the electric pile, and the second pre-filter is positioned at a cathode liquid path inlet of the electric pile.
3. The iron chromium flow battery cell stack system of claim 2, further comprising: a first post-filter and a second post-filter;
the first post filter is positioned at an outlet of a positive electrode liquid path of the electric pile, and the second post filter is positioned at an outlet of a negative electrode liquid path of the electric pile;
the second cleaning mode for cleaning the galvanic pile comprises the following steps:
and injecting ferric iron solution into the galvanic pile from an anode liquid path inlet and a cathode liquid path inlet of the galvanic pile, so as to collect nickel chloride and copper chloride at an anode liquid path outlet and a cathode liquid path outlet of the galvanic pile by utilizing the first post filter and the second post filter.
4. The iron chromium flow battery cell stack system of claim 1, further comprising: a first storage tank, a second storage tank, a ninth valve, a tenth valve, an eleventh valve, and a twelfth valve; wherein,,
injecting a first mixed solution of ferric iron and hydrochloric acid into a first storage tank, and injecting a second mixed solution of water and hydrochloric acid into a second storage tank;
the ninth valve, the first storage tank and the tenth valve are sequentially connected through pipelines to form a first branch; the eleventh valve, the second storage tank and the twelfth valve are sequentially connected through pipelines to form a second branch; one end of the first branch and one end of the second branch are communicated with a pipeline between the fifth valve and the negative electrode liquid path outlet of the electric pile, and the other end of the first branch and the other end of the second branch are communicated with a pipeline between the first valve and the negative electrode pump;
the third cleaning mode for cleaning the galvanic pile comprises the following steps:
closing the positive electrode pump and the negative electrode pump, and closing the first valve, the fifth valve and the sixth valve; simultaneously, the second valve, the fourth valve, the seventh valve and the eighth valve are all in an open state; the ninth valve, the tenth valve, the eleventh valve and the twelfth valve are all in a closed state;
opening a ninth valve and a tenth valve and starting a negative electrode pump to enable the first mixed solution to circulate along the first liquid path and the second liquid path respectively; in the first liquid path, after flowing out of the first storage tank, the first mixed solution sequentially passes through a tenth valve, a negative electrode pump, a second valve, a negative electrode liquid path of the electric pile and a ninth valve and flows back to the first storage tank; in the second liquid path, after flowing out of the first storage tank, the first mixed solution sequentially flows back to the first storage tank through a tenth valve, a negative electrode pump, a seventh valve, a fourth valve, an anode liquid path of the electric pile, an eighth valve and a ninth valve;
closing the negative electrode pump, the ninth valve and the tenth valve;
opening an eleventh valve and a twelfth valve and starting a negative electrode pump to enable the second mixed solution to circulate along the third liquid path and the fourth liquid path respectively; in the third liquid path, the second mixed solution flows out of the second storage tank and then flows back to the second storage tank after sequentially passing through a twelfth valve, a negative electrode pump, a second valve, a negative electrode liquid path of the electric pile and an eleventh valve; in the fourth liquid path, after flowing out of the second storage tank, the second mixed solution sequentially passes through a twelfth valve, a negative electrode pump, a seventh valve, a fourth valve, an anode liquid path of the electric pile, an eighth valve and an eleventh valve and then flows back to the second storage tank.
5. The iron chromium flow battery stack system according to claim 1 or 4, wherein the stack is cleaned a plurality of times during the process of charging the stack, the cleaning timing is determined according to the open circuit voltage OCV of the stack, and the open circuit voltage OCV of the stack is at least ensured to be above the potential difference of the iron chromium redox reaction during the initial cleaning.
6. The iron chromium flow battery cell stack system of claim 1 or 4, further comprising: a hydrogen sensor;
the hydrogen sensor is used for monitoring the hydrogen evolution quantity of the galvanic pile; and when the hydrogen evolution quantity of the galvanic pile exceeds the early warning value, cleaning the galvanic pile.
7. The iron chromium flow battery stack system of claim 3 wherein the first pre-filter, the second pre-filter, the first post-filter, and the second post-filter each have a filter pore size of 0.1 μm to 1 μm.
8. The iron chromium flow battery cell stack system of claim 1 or 4, further comprising: a remote control end; any valve is an electric remote control valve;
the remote control end is used for controlling the opening and closing of the positive electrode pump, the negative electrode pump and the electric remote control valve.
9. The iron chromium flow battery cell stack system of claim 4 wherein the iron chromium flow battery cell stack system comprises a plurality of cells,
the volume of the first storage tank at least fills the first liquid path and the second liquid path with liquid;
the volume of the second tank fills at least the third and fourth liquid paths with liquid.
10. The iron chromium flow battery cell stack system of claim 4 wherein the iron chromium flow battery cell stack system comprises a plurality of cells,
in the first mixed solution, the concentration of ferric iron is 0.2-3 mol/L, and the concentration of hydrochloric acid is 0.5-3 mol/L;
in the second mixed solution, the concentration of hydrochloric acid is 0.5-3 mol/L.
11. The iron chromium flow battery cell stack system of claim 1, wherein the case of not charging the cell stack comprises: the stack discharges or, with the charging device turned off, the stack is left to stand.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310529531.9A CN116454341A (en) | 2023-05-11 | 2023-05-11 | Iron-chromium flow battery pile system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310529531.9A CN116454341A (en) | 2023-05-11 | 2023-05-11 | Iron-chromium flow battery pile system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116454341A true CN116454341A (en) | 2023-07-18 |
Family
ID=87122075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310529531.9A Pending CN116454341A (en) | 2023-05-11 | 2023-05-11 | Iron-chromium flow battery pile system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116454341A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116666717A (en) * | 2023-08-02 | 2023-08-29 | 北京普能世纪科技有限公司 | Flow battery cleaning device, cleaning method and system |
| CN118398856A (en) * | 2024-06-27 | 2024-07-26 | 青岛儒海船舶工程有限公司 | Iron-chromium liquid flow energy storage system for ship and control system thereof |
-
2023
- 2023-05-11 CN CN202310529531.9A patent/CN116454341A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116666717A (en) * | 2023-08-02 | 2023-08-29 | 北京普能世纪科技有限公司 | Flow battery cleaning device, cleaning method and system |
| CN116666717B (en) * | 2023-08-02 | 2024-03-22 | 北京普能世纪科技有限公司 | Flow battery cleaning device, cleaning method and system |
| CN118398856A (en) * | 2024-06-27 | 2024-07-26 | 青岛儒海船舶工程有限公司 | Iron-chromium liquid flow energy storage system for ship and control system thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN116454341A (en) | Iron-chromium flow battery pile system | |
| CN101997129B (en) | Liquid flow battery | |
| CN107112570A (en) | The operation method and redox flow battery system of redox flow batteries | |
| WO2018123962A1 (en) | Redox flow battery system and redox flow battery operation method | |
| WO2016184393A1 (en) | Repairable electrochemical energy storage device | |
| CN103137986A (en) | Zinc bromine single flow cell | |
| CN109638317B (en) | Comprehensive management system and method for electrolyte of metal-air fuel cell | |
| CN113270624B (en) | Flow battery subsystem with catalyst management and electrolyte capacity rebalancing | |
| CN109962264B (en) | Built-in deionization system of water tank of fuel cell | |
| CN112234238B (en) | Method for preparing iron-chromium redox battery electrolyte | |
| CN101567459A (en) | Acid single flow cell | |
| CN103928716A (en) | Lead-acid battery with coexisting acid, alkali and salt electrolyte solutions | |
| Jossen et al. | Advances in redox-flow batteries | |
| TW202011634A (en) | Method for operating redox flow cell and redox flow cell | |
| CN107565151B (en) | Regeneration method of electrode activity of all-vanadium redox flow battery | |
| CN109638309B (en) | Gas-phase countercurrent diaphragm-free metal-oxygen-containing gas flow battery | |
| CN110224157B (en) | Non-circulating flow battery | |
| CN109841931B (en) | Magnesium chloride fuel cell | |
| WO2020077653A1 (en) | Zinc-air flow battery air electrode and battery system comprising same | |
| JPH03192662A (en) | Cell capacity recovery method for redox-flow cell | |
| CN212366010U (en) | All-vanadium redox flow battery device capable of online balancing valence state of electrolyte | |
| CN209929451U (en) | Chlorine-magnesium fuel cell | |
| JP6629911B2 (en) | Redox flow battery | |
| CN114171766A (en) | High-efficiency zinc-iodine adsorption auxiliary flow battery with low-cost film | |
| CN109830712B (en) | Magnesium chloride fuel cell electrolyte regeneration system and regeneration method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |