CN109378510B - Water phase system organic flow battery system based on salt cavern - Google Patents

Water phase system organic flow battery system based on salt cavern Download PDF

Info

Publication number
CN109378510B
CN109378510B CN201811250781.4A CN201811250781A CN109378510B CN 109378510 B CN109378510 B CN 109378510B CN 201811250781 A CN201811250781 A CN 201811250781A CN 109378510 B CN109378510 B CN 109378510B
Authority
CN
China
Prior art keywords
electrolyte
salt
flow battery
based aqueous
organic flow
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.)
Active
Application number
CN201811250781.4A
Other languages
Chinese (zh)
Other versions
CN109378510A (en
Inventor
陈留平
徐俊辉
韩俊甜
崔耀星
苏志俊
李丹
马旭强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Salt Jintan Co Ltd
Original Assignee
China Salt Jintan Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Salt Jintan Co Ltd filed Critical China Salt Jintan Co Ltd
Priority to CN201811250781.4A priority Critical patent/CN109378510B/en
Publication of CN109378510A publication Critical patent/CN109378510A/en
Application granted granted Critical
Publication of CN109378510B publication Critical patent/CN109378510B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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)
  • Secondary Cells (AREA)
  • Fuel Cell (AREA)

Abstract

The invention discloses a salt-cavern-based aqueous phase system organic flow battery system, which comprises two electrolyte liquid storage banks, wherein the electrolyte liquid storage banks are salt caverns which are formed after salt mines and have physical dissolved cavities, electrolyte is stored in the dissolved cavities, the electrolyte comprises a positive active substance, a negative active substance and a supporting electrolyte, and the positive active substance is a 2,2,6, 6-tetramethyl piperidine oxynitride compound; the negative active material is alloxazine compound or riboflavin, the positive active material and the negative active material are directly dissolved or dispersed in a system with water as solvent in a bulk form, and the supporting electrolyte is dissolved in the system; and the flow battery stack is respectively communicated with the two electrolyte liquid storage tanks. The salt-hole-based aqueous phase system organic flow battery system has the advantages of low cost, high safety performance, stable charge and discharge performance, high solubility of active materials and the like, and can also solve the problem of large-scale electrochemical energy storage and fully utilize some waste salt-hole resources.

Description

Water phase system organic flow battery system based on salt cavern
Technical Field
The invention belongs to the field of flow batteries, and particularly relates to a salt pit-based aqueous phase system organic flow battery system which can be applied to large-scale chemical energy storage.
Background
With the rapid development of human economy, the problems of environmental pollution, energy shortage and the like are increasingly aggravated, and the world countries are promoted to widely develop and utilize renewable energy sources such as wind energy, solar energy, tidal energy and the like. However, the renewable energy sources have the characteristics of discontinuity, instability, limitation by regional environment and difficult grid connection, so that the utilization rate is low, the wind and light abandoning rate is high, and resources are wasted. There is a need for a robust development of efficient, inexpensive, safe and reliable energy storage technology that can be used in conjunction therewith.
Among the various electrochemical energy storage strategies, flow batteries (RFBs) have several particular technical advantages, most suitable for static batteries such as lithium ion batteries and lead acid batteriesLarge-scale (megawatt/megawatt hour) electrochemical energy storage, such as relatively independent energy and power control, high-current high-power operation (fast response), high safety performance (mainly meaning not easy to burn and explode), and the like. One energy storage project which is popular in China at present is a vanadium redox flow battery. China is a natural storage country of vanadium ores, and in short, vanadium raw materials for vanadium flow batteries are not a problem. But considering the limited vanadium ore resources on a global scale and the high vanadium ore price (V)2O5And 20/kg), the popularization and long-term use of the vanadium flow battery are difficult to realize. Vanadium flow batteries and zinc-bromine flow batteries are both traditional flow battery technologies and have some technical defects: such as self-discharge and low coulombic efficiency due to the shuttling effect of the active material between the electrodes; corrosive electrolytes are not environmentally friendly and have potential safety hazards. The cost of vanadium flow batteries is about $ 450/kilowatt hour, and the popularization price of electrochemical energy storage recommended by the U.S. department of energy is below $ 150/kilowatt hour, which means that a high-performance, economically applicable and brand-new flow battery technology is developed.
The salt cavern is an underground cavern left after salt mine exploitation in a water-soluble mode, the shape and the size of the underground cavern are determined according to different geological conditions, the volume is large, the sealing is good, and the volume is generally 107m3～108m3Therefore, the salt cavern provides a huge and safe underground space for storing electrolyte, the salt cavern is mainly used for storing natural gas and petroleum, but at present, many salt caverns in China are basically in an empty state because the technical indexes of the salt caverns cannot meet the technical requirements of oil storage or gas storage. The electrolyte stored in the water phase system by utilizing the salt cavern has lower requirements on the sealing property, the pressure resistance and the stability of the salt cavern. Therefore, the salt cavern is used for storing the electrolyte, so that the comprehensive utilization of the salt cavern can be fully realized. However, there is still a need for development of battery systems suitable for salt cavern systems (using in situ generated electrolytes).
At present, the aqueous phase flow battery still faces some challenges, such as limited solubility of active materials (organic matters), easy cross contamination of electrolyte, low operating current density, easy occurrence of side reaction of water electrolysis, and the like. Therefore, it is important to develop a flow battery that overcomes the above disadvantages and can be potentially applied to a large-scale salt cavern aqueous system flow battery.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art.
Therefore, the invention provides a salt-cavity-based aqueous phase system organic flow battery system which has the advantages of low cost, high safety performance, stable charge and discharge performance, high solubility of active materials and the like.
According to the embodiment of the invention, the salt cavern-based aqueous phase system organic flow battery system comprises: the electrolyte comprises two electrolyte liquid storage banks, wherein the two electrolyte liquid storage banks are oppositely arranged at intervals, each electrolyte liquid storage bank is a salt cavity which is formed after salt mines are mined and is provided with a physical dissolving cavity, electrolyte is stored in the dissolving cavity, the electrolyte comprises a positive active substance, a negative active substance and supporting electrolyte, and the positive active substance is a 2,2,6, 6-tetramethylpiperidine oxynitride compound; the negative active material is an alloxazine compound or riboflavin, the positive active material and the negative active material are directly dissolved or dispersed in a system with water as a solvent in a bulk form and are respectively stored in the two salt holes, and the supporting electrolyte is dissolved in the system; the flow battery stack is respectively communicated with the two electrolyte liquid storages; the flow cell stack includes: the electrolytic cell body is filled with the electrolyte; the two polar plates are oppositely arranged; the battery diaphragm is positioned in the electrolytic cell body, the battery diaphragm divides the electrolytic cell body into an anode area communicated with one electrolyte liquid storage and a cathode area communicated with the other electrolyte liquid storage, one polar plate is arranged in the anode area, the other polar plate is arranged in the cathode area, a positive electrolyte containing the positive active substance is arranged in the anode area, a negative electrolyte containing the negative active substance is arranged in the cathode area, and the battery diaphragm can be penetrated by the supporting electrolyte to prevent the positive active substance and the negative active substance from penetrating; the circulating pipeline inputs or outputs the electrolyte in one electrolyte storage reservoir to or from the anode region, and the circulating pipeline inputs or outputs the electrolyte in the other electrolyte storage reservoir to or from the cathode region; and the circulating pump is arranged on the circulating pipeline and enables the electrolyte to circularly flow and be supplied through the circulating pump.
The salt-cavern-based aqueous phase system organic flow battery system disclosed by the embodiment of the invention has the advantages of low cost, high safety performance, stable charge and discharge performance, high solubility of active materials and the like, and the flow battery energy storage system not only can solve the problem of large-scale (megawatt/megawatt hour) electrochemical energy storage, but also can fully utilize some waste salt-cavern (ore) resources.
According to one embodiment of the present invention, the concentration of the positive electrode active material is 0.1mol · L-1～3.0mol·L-1The concentration of the negative electrode active material is 0.1 mol.L-1～4.0mol·L-1。
According to one embodiment of the invention, the electrolyte reservoir is a sealed container.
According to one embodiment of the invention, inert gas is introduced into the electrolyte reservoir for protection.
According to one embodiment of the invention, the inert gas is nitrogen or argon.
According to one embodiment of the invention, the battery separator is a polymer porous membrane with a pore size of 10nm to 300 nm.
According to an embodiment of the present invention, the polymer porous membrane includes one of a polypropylene PP membrane, a polytetrafluoroethylene PTFE membrane, a polyvinylidene fluoride PVDF membrane, a silicon-based polypropylene PP membrane, a polyethylene PE membrane, a polystyrene PS membrane, and a polymethyl methacrylate PMMA membrane.
According to one embodiment of the invention, the battery separator is silicon-based PP, PE or PVDF.
According to one embodiment of the invention, the pore size of the battery separator is 150nm to 200 nm.
According to one embodiment of the invention, the supporting electrolyte is a NaCl salt solution, a KCl salt solution,Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, MgSO4Salt solution, CaCl2At least one salt solution.
According to one embodiment of the invention, the supporting electrolyte has a molar concentration of 0.1mol · L-1～8.0mol·L-1。
According to one embodiment of the invention, the electrolyte further comprises: an additive which is a pH adjuster or a viscosity modifier, the additive being dissolved in the system.
According to one embodiment of the invention, the pH regulator is NaOH, KOH, Na2CO3And at least one of CaO.
According to one embodiment of the invention, the pH range of the pH adjusting agent is: the pH value is more than or equal to 8.5 and less than or equal to 14.0.
According to one embodiment of the invention, the additive is at least one of hydroxyethyl cellulose, hydroxypropyl methyl cellulose, polyacrylamide, sodium carboxymethyl cellulose, polyethylene oxide, modified starch, polyvinyl alcohol and polyvinylpyrrolidone, and the viscosity of the electrolyte after the additive is added is 1 mPas-10 at a temperature of 25 DEG C6mPas。
According to one embodiment of the invention, the viscosity of the electrolyte is 10 at a temperature of 25 deg.C2mPas～104mPas。
According to one embodiment of the invention, the plates are formed as graphite felt.
According to one embodiment of the invention, the thickness of the plate is 2mm to 8 mm.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural diagram of a salt cavern based aqueous system organic flow battery system according to an embodiment of the invention;
FIG. 2 is a graph of CV for riboflavin at different scan rates, in accordance with an embodiment of the present invention;
FIG. 3 is a plot of peak riboflavin current fitted to the power of one-half of the scan rate, in accordance with an embodiment of the present invention;
FIG. 4 is a graph of CV at different scan rates for TEMPO according to an embodiment of the present invention;
FIG. 5 is a plot of TEMPO peak current versus scan rate to the power of one-half according to an embodiment of the present invention;
FIG. 6 is a CV diagram of TEMPO for positive electrode and riboflavin for negative electrode according to an embodiment of the present invention;
FIG. 7 is a graph of OH-TEMPO standard potential versus pH for examples 1 to 5 according to the present invention;
FIG. 8 is a graph of the standard potential of riboflavin versus pH in examples 1 to 5 according to the present invention;
fig. 9 is a battery cycle stability diagram according to example 1 of the present invention.
Reference numerals:
a salt cavern based aqueous system organic flow battery system 100;
an electrolyte reservoir 10;
a flow cell stack 20; a pole plate 21; the positive electrode electrolyte 22; the negative electrode electrolyte 23; a battery separator 24; a circulation line 25; a circulation pump 26.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention. Furthermore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The following describes in detail an aqueous system organic flow battery system 100 based on salt caverns according to an embodiment of the invention with reference to the drawings.
As shown in fig. 1, the salt cavern-based aqueous system organic flow battery system 100 according to the embodiment of the invention includes two electrolyte reservoirs 10 and a flow battery stack 20, and the flow battery stack 20 includes two electrode plates 21, an electrolyte tank body, a battery diaphragm 24, a circulation pipeline 25 and a circulation pump 26.
Specifically, the two electrolyte liquid reservoirs 10 are arranged oppositely at intervals, the electrolyte liquid reservoirs 10 are salt cavities with physical dissolving cavities formed after salt mines are mined, electrolyte is stored in the dissolving cavities, the electrolyte comprises a positive active substance, a negative active substance and supporting electrolyte, and the positive active substance is a 2,2,6, 6-tetramethyl piperidine oxynitride compound; the negative active substance is alloxazine compound or riboflavin, the positive active substance and the negative active substance are directly dissolved or dispersed in a system using water as solvent in a body form and are respectively stored in two salt holes, the supporting electrolyte is dissolved in the system, the flow battery stack 20 is respectively communicated with two electrolyte liquid storage banks 10, the electrolyte is filled in the electrolytic cell body, two polar plates 21 are oppositely arranged, a battery diaphragm 24 is positioned in the electrolytic cell body, the electrolytic cell body is divided into an anode region communicated with one electrolyte liquid storage bank 10 and a cathode region communicated with the other electrolyte liquid storage bank 10 by the battery diaphragm 24, one polar plate 21 is arranged in the anode region, the other polar plate 21 is arranged in the cathode region, the anode region is provided with positive electrolyte 22 containing the positive active substance, the cathode region is provided with negative electrolyte 23 containing the negative active substance, the battery diaphragm 24 can be penetrated by the supporting electrolyte, the penetration of the positive electrode active material and the negative electrode active material is prevented, the electrolyte in one electrolyte reservoir 10 is input or output to the anode region through the circulation pipeline 25, the electrolyte in the other electrolyte reservoir 10 is input or output to the cathode region through the circulation pipeline 25, and the circulation pump 26 is provided in the circulation pipeline 25 and circulates and supplies the electrolyte through the circulation pump 26.
In other words, the salt-pit-based aqueous-phase-system organic flow battery system 100 according to the embodiment of the present invention includes two electrolyte solution reservoirs 10 and a flow battery stack 20, the flow battery stack 20 includes two electrode plates 21, an electrolytic cell body, a battery diaphragm 24, a circulation pipeline 25 and a circulation pump 26, the electrolyte solution reservoir 10 is an underground pit, i.e., a salt pit, left after salt mine is mined in a water-soluble manner, an electrolyte solution is stored in the salt pit, the electrolyte solution includes a positive active material, a negative active material and a supporting electrolyte, the positive active material is a compound (a) such as 2,2,6, 6-tetramethylpiperidine oxynitride (2,2,6, 6-tetramethylpiperidine-1-oxyl, TEMPO); the negative active substance is alloxazine compound (B) or riboflavin (C), the positive active substance and the negative active substance are dissolved or dispersed in a system using water as solvent in a form of a body, supporting electrolyte is dissolved in the system, the flow battery stack 20 is respectively communicated with the two electrolyte liquid storage reservoirs 10 through a circulating pipeline 25, the two polar plates 21 are oppositely arranged, a circulating pump 26 is arranged on the circulating pipeline 25, the electrolyte circularly flows to the polar plates 21 through the circulating pump 26, the two polar plates 21 can be respectively a positive electrode and a negative electrode, the polar plates 21 are directly contacted with the electrolyte to provide an electrochemical reaction site with rich pore channels, a battery diaphragm 24 is positioned in the electrolytic cell body, the battery diaphragm 24 can be penetrated by the supporting electrolyte to prevent the positive active substance and the negative active substance from penetrating, and the battery diaphragm 24 can be a cation exchange membrane.
The structures of the TEMPO-based compound (a), the alloxazine-based compound (B), and the riboflavin-based compound (C) are as follows:
Figure RE-GDA0001922034970000061
wherein, the substituent R1Is OH, OMe, OEt, CHO, NH2、N(Me)2、N(Et)2、F、Cl、CN、NO2、 COOH、SO3H or one of other grafted macromolecular compounds; substituent R2Is one of mono-or polysubstituted in the 1,2,3, 4-position, and the substituents R described2Is OH, OMe, OEt, CHO, NH2、N(Me)2、N(Et)2、 F、Cl、CN、NO2、COOH、SO3H or one or more of other grafted macromolecular compounds.
Therefore, the salt-sink-based aqueous phase system organic flow battery system 100 according to the embodiment of the present invention employs a device combining two electrolyte reservoirs 10 and a flow battery stack 20, and the flow battery stack 20 employs a device combining two electrode plates 21, an electrolytic cell tank body, a battery diaphragm 24, a circulation pipeline 25 and a circulation pump 26, which can be suitable for a battery environment of a salt-sink system (using an in-situ generated electrolyte), and the battery system 100 has the advantages of low cost, high safety performance, stable charging and discharging performance, high solubility of active materials, and the like, and the flow battery energy storage system can not only solve the electrochemical energy storage of a large scale (megawatt/megawatt hour), but also fully utilize some waste salt-sink (mine) resources.
According to one embodiment of the present invention, the concentration of the positive electrode active material is 0.1mol·L-1～3.0mol·L-1The concentration of the negative electrode active material was 0.1 mol. L-1～4.0mol·L-1。
In some embodiments of the invention, the electrolyte reservoir 10 is a sealed container.
According to an embodiment of the present invention, the electrolyte reservoir 10 is protected by an inert gas, which is always protected by the inert gas during the charging and discharging processes.
Further, the inert gas may be nitrogen, or the inert gas may be argon, or the like.
According to one embodiment of the present invention, the battery separator 24 is a membrane prepared according to the sieving principle, and the battery separator 24 may be a polymer porous membrane having a pore size of 10nm to 300 nm.
Optionally, the polymer porous membrane comprises one of a polypropylene PP membrane, a polytetrafluoroethylene PTFE membrane, a polyvinylidene fluoride PVDF membrane, a silicon-based polypropylene PP membrane, a polyethylene PE membrane, a polystyrene PS membrane, and a polymethyl methacrylate PMMA membrane.
Further, the battery separator 24 is silicon-based PP, PE or PVDF.
According to one embodiment of the invention, the pore size of the battery separator 24 is between 150nm and 200 nm.
In some embodiments of the invention, the supporting electrolyte is a NaCl salt solution, a KCl salt solution, Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, MgSO4Salt solution, CaCl2At least one salt solution.
Further, the molar concentration of the supporting electrolyte was 0.1mol · L-1～8.0mol·L-1。
According to one embodiment of the invention, the electrolyte further comprises an additive, the additive being a pH adjuster or a viscosity modifier, the additive being dissolved in the system, wherein the viscosity modifier is capable of modifying the viscosity.
Optionally, the pH regulator is NaOH, KOH, Na2CO3And at least one of CaO.
According to one embodiment of the invention, the pH range of the pH adjusting agent is: the pH value is more than or equal to 8.5 and less than or equal to 14.0.
In some embodiments of the present invention, the additive may be at least one of hydroxyethyl cellulose, hydroxypropyl methylcellulose, polyacrylamide, sodium carboxymethylcellulose, polyethylene oxide, modified starch, polyvinyl alcohol, and polyvinylpyrrolidone, and the viscosity of the electrolyte solution after the additive is added is 1mPas to 10 mPas measured by a rotational viscometer at a temperature of 25 ℃6mPas。
Further, the viscosity of the electrolyte was 10 at a temperature of 25 deg.C2mPas～104mPas。
According to one embodiment of the invention, the plates 21 are formed as graphite felt.
Optionally, the plate 21 has a thickness of 2mm to 8 mm.
The salt cavern-based aqueous system organic flow battery system 100 according to the embodiment of the invention is specifically described below with reference to specific examples.
In the cyclic voltammetry test of the galvanic couple, a CS series electrochemical workstation of Wuhan Cornst is adopted, a three-electrode system is adopted to test the electrochemical performance of the organic galvanic couple, a working electrode is a glassy carbon electrode (Tianjin Adamantang Hengcheng), a reference electrode is an Ag/AgCl electrode, a counter electrode is a platinum electrode, the scanning ranges of the positive and negative galvanic couples are-1.0V respectively, and the scanning speed is 10mV s-1，20mV·s-1，40mV·s-1，60mV·s-1，80mV·s-1，100mV·s-1. The CV of the negative electrode couple is shown in fig. 2, and the linear fitting of the oxidation-reduction peak current and the half power of the scanning rate is shown in fig. 3; the CV of the positive electrode couple is shown in fig. 4, and a linear fit of the redox peak current to the half power of the scan rate is shown in fig. 5.
In the cell test, the flow rate of the electrolyte was about 5.0 mL-min-1In constant current charge/discharge mode, the current density is 0.5 mA/cm-2。
Example 1
The negative electrode active material in the negative electrode electrolyte 23 was 0.1 mol. L-1The amount of the positive electrode active material in the positive electrode electrolyte 22 is 0.2 mol. L-1TEMPO, 2.5 mol. L for the supporting electrolyte in the positive electrolyte 22 and the negative electrolyte 23-1The pH of the sodium chloride solution is adjusted to 10.0 by using a pH regulator NaOH, and the coulombic efficiency, the voltage efficiency and the energy efficiency of a single cell of the salt-cavity-based aqueous phase system organic flow battery system (I) are shown in Table 1.
Example 2
The negative electrode active material in the negative electrode electrolyte 23 was 0.1 mol. L-1The amount of the positive electrode active material in the positive electrode electrolyte 22 is 0.2 mol. L-1TEMPO, 2.5 mol. L for the supporting electrolyte in the positive electrolyte 22 and the negative electrolyte 23-1The pH of the sodium chloride solution is adjusted to 10.5 by using a pH regulator NaOH, and the coulombic efficiency, the voltage efficiency and the energy efficiency of a single cell of the salt-cavern-based aqueous phase system organic flow battery system (ii) are shown in table 1.
Example 3
The negative electrode active material in the negative electrode electrolyte 23 was 0.1 mol. L-1The amount of the positive electrode active material in the positive electrode electrolyte 22 is 0.2 mol. L-1TEMPO, 2.5 mol. L for the supporting electrolyte in the positive electrolyte 22 and the negative electrolyte 23-1The pH of the sodium chloride solution is adjusted to 9.5 by using a pH regulator NaOH, and the coulombic efficiency, the voltage efficiency and the energy efficiency of the single cell of the salt-cavern-based aqueous system organic flow battery system (iii) are shown in table 1.
Example 4
The negative electrode active material in the negative electrode electrolyte 23 was 0.1 mol. L-1The amount of the positive electrode active material in the positive electrode electrolyte 22 is 0.2 mol. L-1TEMPO, 2.5 mol. L for the supporting electrolyte in the positive electrolyte 22 and the negative electrolyte 23-1The pH of the sodium chloride solution is adjusted to 8.5 by using a pH regulator NaOH, and the coulombic efficiency, the voltage efficiency and the energy efficiency of a single cell of the salt-cavern-based aqueous phase system organic flow battery system (IV) are shown in Table 1.
Example 5
Negative electrode in negative electrode electrolyte solution 23The active substance is 0.1 mol.L-1The amount of the positive electrode active material in the positive electrode electrolyte 22 is 0.2 mol. L-1TEMPO, 2.5 mol. L for the supporting electrolyte in the positive electrolyte 22 and the negative electrolyte 23-1The pH of the sodium chloride solution is adjusted to 7.5 by using a pH adjuster NaOH, and the coulombic efficiency, the voltage efficiency and the energy efficiency of a single cell of the salt-cavity-based aqueous system organic flow battery system (v) are shown in table 1.
Example 6
The negative electrode active material in the negative electrode electrolyte 23 was 0.1 mol. L-1The amount of the positive electrode active material in the positive electrode electrolyte 22 is 0.2 mol. L-12.5 mol. L of the supporting electrolyte in the 4-amino-TEMPO, the positive electrolyte 22 and the negative electrolyte 23 are used-1The pH of the sodium sulfate solution is adjusted to 8.0 by using a pH regulator KOH, and the coulombic efficiency, the voltage efficiency and the energy efficiency of a single cell of the salt-cavity-based aqueous phase system organic flow battery system (VI) are shown in Table 1.
Example 7
The negative electrode active material in the negative electrode electrolyte 23 was 0.2 mol. L -17, 8-dimethylalloxazine, 0.4mol · L of the positive electrode active material in the positive electrode electrolyte 22-1The supporting electrolyte solution in the 4-oxyl-TEMPO, the positive electrolyte 22 and the negative electrolyte 23 is 3.0 mol.L-1The pH of the potassium chloride solution is adjusted to 8.0 by using a pH adjusting agent KOH, and the coulombic efficiency, the voltage efficiency and the energy efficiency of the single cell of the salt-cavern-based aqueous system organic flow battery system (vii) are shown in table 1.
Example 8
The negative electrode active material in the negative electrode electrolyte 23 was 0.2 mol. L -17, 8-dimethylalloxazine, 0.4mol · L of the positive electrode active material in the positive electrode electrolyte 22-1The supporting electrolyte solution in the 4-oxyl-TEMPO, the positive electrolyte 22 and the negative electrolyte 23 is 3.0 mol.L-1The pH of the potassium chloride solution is adjusted to 8.0 by adopting a pH regulator KOH, and the viscosity of the electrolyte is adjusted to 10 by adopting hydroxypropyl methyl cellulose2mPas, assembled to formThe coulombic efficiency, the voltage efficiency and the energy efficiency of the single cell of the salt cavern-based aqueous system organic flow battery system (VIII) are shown in Table 1.
TABLE 1 comparison of cell Performance
Coulombic efficiency (%) Voltage efficiency (%) Energy efficiency (%)
(Ⅰ) 90.9 81.5 73.6
(Ⅱ) 90.8 81.3 73.4
(Ⅲ) 90.8 81.4 73.5
(Ⅳ) 90.6 81.3 73.1
(Ⅴ) 90.2 81.0 73.6
(Ⅵ) 91.5 81.6 74.1
(Ⅶ) 92.4 81.5 74.9
(Ⅷ) 92.1 81.3 75.2
As can be seen from Table 1, the organic electrochemical activity and reversibility of the positive and negative electrode pairs are good, and as can be seen from FIG. 6, a pair of redox peaks exists between-0.7V and-0.3V in riboflavin, the standard potential is about-0.56V, and the potential difference between the oxidation peak potential and the reduction peak potential is about 50mV, which shows quasi-reversible redox electrochemistry. TEMPO has a pair of oxidation-reduction peaks between 0.3V and 1.0V, the standard potential is about 0.63V, and the potential difference between the oxidation peak potential and the reduction peak potential is about 60mV, thus showing quasi-reversible redox electrochemistry. The linear fitting is carried out on the peak current and the half power of the sweep rate of the oxidation process and the reduction process respectively by the positive electrode couple and the negative electrode couple, and the oxidation reduction process of the positive electrode couple and the negative electrode couple is controlled by the diffusion of electrochemical active substances. Further, as can be seen from fig. 7 and 8, the standard potential of the positive and negative electrode organic pair is linearly related to pH in the range of pH 7.50 to 10.50.
From table 1, it is seen that each example exhibited good electrical conductivity, and from fig. 9, the cell efficiency was stable after assembly, and the cycle performance was good.
In summary, the salt-sink-based aqueous-phase organic flow battery system 100 according to the embodiment of the present invention has the advantages of low cost, high safety performance, stable charging and discharging performance, high solubility of active materials, and the like, and can also solve the problem of large-scale electrochemical energy storage and fully utilize some waste salt-sink resources.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.

Claims (18)

1. An aqueous phase system organic flow battery system based on salt cavern, which is characterized by comprising:
the electrolyte comprises two electrolyte liquid storage banks, wherein the two electrolyte liquid storage banks are oppositely arranged at intervals, each electrolyte liquid storage bank is a salt cavity which is formed after salt mines are mined and is provided with a physical dissolving cavity, electrolyte is stored in the dissolving cavity, the electrolyte comprises a positive active substance, a negative active substance and supporting electrolyte, and the positive active substance is a 2,2,6, 6-tetramethylpiperidine oxynitride compound; the negative active material is an alloxazine compound or riboflavin, the positive active material and the negative active material are directly dissolved or dispersed in a system with water as a solvent in a bulk form and are respectively stored in the two salt holes, and the supporting electrolyte is dissolved in the system;
the flow battery stack is respectively communicated with the two electrolyte liquid storages;
the flow cell stack includes:
the electrolytic cell body is filled with the electrolyte;
the two polar plates are oppositely arranged;
the battery diaphragm is positioned in the electrolytic cell body, the battery diaphragm divides the electrolytic cell body into an anode area communicated with one electrolyte liquid storage and a cathode area communicated with the other electrolyte liquid storage, one polar plate is arranged in the anode area, the other polar plate is arranged in the cathode area, a positive electrolyte containing the positive active substance is arranged in the anode area, a negative electrolyte containing the negative active substance is arranged in the cathode area, and the battery diaphragm can be penetrated by the supporting electrolyte to prevent the positive active substance and the negative active substance from penetrating;
the circulating pipeline inputs or outputs the electrolyte in one electrolyte storage reservoir to or from the anode region, and the circulating pipeline inputs or outputs the electrolyte in the other electrolyte storage reservoir to or from the cathode region;
and the circulating pump is arranged on the circulating pipeline and enables the electrolyte to circularly flow and be supplied through the circulating pump.
2. The salt cavern-based aqueous-phase-system organic flow battery system as claimed in claim 1, wherein the concentration of the positive active material is 0.1 mol-L-1～3.0mol·L-1The concentration of the negative electrode active material is 0.1 mol.L-1～4.0mol·L-1。
3. The salt cavern-based aqueous organic flow battery system of claim 1, wherein the electrolyte reservoir is a sealed container.
4. The salt cavern-based aqueous system organic flow battery system as claimed in claim 1, wherein inert gas is introduced into the electrolyte reservoir for protection.
5. The salt cavern-based aqueous organic flow battery system of claim 4, wherein the inert gas is nitrogen or argon.
6. The salt cavern-based aqueous system organic flow battery system as claimed in claim 1, wherein the battery separator is a polymer porous membrane with a pore size of 10nm to 300 nm.
7. The salt cavern-based aqueous system organic flow battery system of claim 6, wherein the polymer porous membrane comprises one of a polypropylene (PP) membrane, a Polytetrafluoroethylene (PTFE) membrane, a polyvinylidene fluoride (PVDF) membrane, a silicon-based polypropylene (PP) membrane, a Polyethylene (PE) membrane, a Polystyrene (PS) membrane, and a polymethyl methacrylate (PMMA) membrane.
8. The salt cavern-based aqueous system organic flow battery system of claim 7, wherein the battery separator is silicon-based PP, PE, or PVDF.
9. The salt cavern-based aqueous system organic flow battery system of claim 8, wherein the battery separator has a pore size of 150nm to 200 nm.
10. The salt cavern-based aqueous system organic flow battery system of claim 1, wherein the supporting electrolyte is a NaCl salt solution, a KCl salt solution, Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, MgSO4Salt solution, CaCl2In salt solutionsAt least one of them.
11. The salt cavern-based aqueous system organic flow battery system of claim 10, wherein the molar concentration of the supporting electrolyte is 0.1 mol-L-1～8.0mol·L-1。
12. The salt cavern-based aqueous organic flow battery system of claim 1, wherein the electrolyte further comprises:
an additive which is a pH adjuster or a viscosity modifier, the additive being dissolved in the system.
13. The salt cavern-based aqueous system organic flow battery system of claim 12, wherein the pH regulator is NaOH, KOH, Na2CO3And at least one of CaO.
14. The salt cavern-based aqueous system organic flow battery system of claim 13, wherein the pH of the pH adjuster is in the range of: the pH value is more than or equal to 8.5 and less than or equal to 14.0.
15. The salt cavern-based aqueous phase system organic flow battery system as claimed in claim 12, wherein the additive is at least one of hydroxyethyl cellulose, hydroxypropyl methylcellulose, polyacrylamide, sodium carboxymethyl cellulose, polyethylene oxide, modified starch, polyvinyl alcohol and polyvinylpyrrolidone, and the viscosity of the electrolyte after the additive is added is 1 mPas-10 mPas at 25 ℃6mPas。
16. The salt cavern-based aqueous system organic flow battery system of claim 15, wherein the electrolyte has a viscosity of 10 at a temperature of 25 ℃2mPas～104mPas。
17. The salt cavern based aqueous system organic flow battery system of claim 1, wherein the plate is formed as a graphite felt.
18. The salt cavern-based aqueous organic flow battery system of claim 17, wherein the plate has a thickness of 2mm to 8 mm.
CN201811250781.4A 2018-10-25 2018-10-25 Water phase system organic flow battery system based on salt cavern Active CN109378510B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811250781.4A CN109378510B (en) 2018-10-25 2018-10-25 Water phase system organic flow battery system based on salt cavern

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811250781.4A CN109378510B (en) 2018-10-25 2018-10-25 Water phase system organic flow battery system based on salt cavern

Publications (2)

Publication Number Publication Date
CN109378510A CN109378510A (en) 2019-02-22
CN109378510B true CN109378510B (en) 2021-03-02

Family

ID=65401982

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811250781.4A Active CN109378510B (en) 2018-10-25 2018-10-25 Water phase system organic flow battery system based on salt cavern

Country Status (1)

Country Link
CN (1) CN109378510B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110444799B (en) * 2019-08-22 2021-10-12 中盐金坛盐化有限责任公司 Neutral aqueous phase system flow battery system
CN110444787A (en) * 2019-08-22 2019-11-12 中盐金坛盐化有限责任公司 Flow battery system based on amino anthraquinones derivative
CN110734515B (en) * 2019-09-25 2021-09-03 中盐金坛盐化有限责任公司 Imidazole iron polymer, synthetic method, battery and battery system
CN111628185B (en) * 2020-05-27 2021-11-16 西安交通大学 Pyrroline/alkyl nitrogen oxygen free radical compound water system organic flow battery
CN111564649B (en) * 2020-06-18 2021-06-29 中盐金坛盐化有限责任公司 Organic polymer flow battery system
CN111584915B (en) * 2020-06-18 2023-03-21 中盐金坛盐化有限责任公司 Aqueous nano polymer flow battery system
CN114665135B (en) * 2022-01-30 2023-05-26 电子科技大学 High-voltage-efficiency flow battery system

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9130218B2 (en) * 2012-04-04 2015-09-08 Battelle Memorial Institute Hybrid energy storage systems utilizing redox active organic compounds
CN105742727B (en) * 2014-12-09 2018-05-22 中国科学院物理研究所 A kind of preparation method of secondary cell, purposes and its cathode
DE102015010083A1 (en) * 2015-08-07 2017-02-09 Friedrich-Schiller-Universität Jena Redox flow cell for storing electrical energy and its use
CN108483573B (en) * 2018-03-28 2020-10-27 华南师范大学 Method for desalting by utilizing fluid battery and application thereof

Also Published As

Publication number Publication date
CN109378510A (en) 2019-02-22

Similar Documents

Publication Publication Date Title
CN109599577B (en) Water phase system organic flow battery system based on salt cavern
CN109378510B (en) Water phase system organic flow battery system based on salt cavern
CN109546182B (en) Water phase system organic flow battery system based on salt cavern
CN103000924B (en) Organic phase dual flow battery
CN109585881B (en) Salt cavern-based water-phase system organic flow battery system with mixed solvent
CN110668996B (en) Bipyridine compound, synthetic method and symmetrical flow battery system thereof
US20220073448A1 (en) Method for synthesizing carboxy-containing anthraquinone derivative, carboxy-containing anthraquinone derivative prepared thereby, and battery system comprising same
CN109509901B (en) Alkaline zinc-iron flow battery
US11677091B2 (en) Use of quaternary ammonium salt-type anthraquinone-based active material and salt cavern organic aqueous redox flow battery
CN202153549U (en) Zinc-bromine flow battery and battery pack
CN106981371A (en) A kind of water system electrolyte super capacitance cell
CN105680082A (en) Long-lifetime zinc-bromine flow battery structure and electrolyte
CN110444787A (en) Flow battery system based on amino anthraquinones derivative
CN106549179B (en) A kind of organic system lithium quinone flow battery
CN110444799B (en) Neutral aqueous phase system flow battery system
CN102237541A (en) Electrolytic solution for total Fe flow cells and single electrolyte total Fe flow cell
CN107946624A (en) A kind of water system full stress-strain flow battery and its construction method and application based on indigo derivative
US10522863B2 (en) Electrolyte solution for redox flow battery containing organic active material and redox flow battery using the same
CN110452161A (en) Bipyridyliums compound, synthetic method and the flow battery system with it
Xie et al. An aqueous ZnCl 2/Fe (bpy) 3 Cl 2 flow battery with mild electrolyte
CN111564649B (en) Organic polymer flow battery system
CN111564650A (en) Iron-based aqueous flow battery based on salt cavern
CN1893162B (en) Liquid accumulator cell with double functions of accumulating and electrochemical synthesizing
CA3201816A1 (en) Rechargeable flow battery
CN112310453A (en) Organic aqueous phase flow battery containing additive based on salt cavern

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
GR01 Patent grant
GR01 Patent grant