CN109378510A - The organic flow battery system of aqueous phase system based on salt cave - Google Patents
The organic flow battery system of aqueous phase system based on salt cave Download PDFInfo
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- CN109378510A CN109378510A CN201811250781.4A CN201811250781A CN109378510A CN 109378510 A CN109378510 A CN 109378510A CN 201811250781 A CN201811250781 A CN 201811250781A CN 109378510 A CN109378510 A CN 109378510A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of organic flow battery systems of the aqueous phase system based on salt cave, including two electrolyte liquid storage libraries, electrolyte liquid storage library is the salt cave with the molten chamber of physics that is formed after salt well accident, it is molten intracavitary to store electrolyte, electrolyte includes positive active material, negative electrode active material and supporting electrolyte, positive active material 2,2, the oxide-based compound of 6,6- tetramethyl piperidine nitrogens；Negative electrode active material is alloxazine class compound or riboflavin, and positive active material and negative electrode active material are directly dissolved or dispersed in the system taken water as a solvent with bulk form, and supporting electrolyte is dissolved in system；Liquid stream battery stack, liquid stream battery stack are connected to two electrolyte liquid storage libraries respectively.The organic flow battery system of aqueous phase system based on salt cave not only has many advantages, such as that at low cost, security performance is high, charge-discharge performance is stable, active material solubility is high, extensive electrochemical energy storage can also be solved, some discarded salt cave resources are made full use of.
Description
Technical field
The invention belongs to flow battery fields, and in particular to a kind of organic flow battery system of aqueous phase system based on salt cave
System, the battery system can be applied to extensive chemical energy storage.
Background technique
With human economy fast development, the problems such as environmental pollution and energy shortage, increasingly sharpens, and promotes countries in the world wide
The renewable energy such as general development and utilization wind energy, solar energy, tide energy.However these renewable energy have it is discontinuous, unstable,
It is limited and the characteristic of grid-connected hardly possible by territorial environment, causes its utilization rate low, light rate height, waste of resource are abandoned in abandonment.Therefore it needs big
Power development can efficient, cheap, safe and reliable energy storage technology used in conjunction with.
In various electrochemical energy storage strategies, relative to static battery such as lithium ion battery and lead-acid battery, liquid stream electricity
There are several special technological merits in pond (RedoxFlowBatteries, RFBs), is most suitable for extensive (megawatt/megawatt hour)
Electrochemical energy storage, such as relatively independent energy and the high-power operation of power control, high current (response is fast), security performance
High (being primarily referred to as nonflammable and explosion) etc..A domestic popular energy storage project is exactly vanadium flow battery at present.China
It is the natural storage big country of navajoite, in the short term, the vanadium raw materials for vanadium flow battery are not problems.But consider global range
Interior limited navajoite resource and high navajoite price (V2O5, $ 20/kg), the universal and long-time service of vanadium flow battery is all difficult
It realizes.Vanadium flow battery and zinc-bromine flow battery are all traditional flow battery technologies, and there are some technological deficiencies: such as living
Property substance self discharge caused by interelectrode shuttle effect and coulombic efficiency are low；Corrosive electrolyte is not environmentally and safe
Hidden danger.The cost of vanadium flow battery is probably 450/ kilowatt hour of $, and the universal price for the electrochemical energy storage that U.S. Department of Energy is recommended is wanted
In 150/ kilowatt hour of $ hereinafter, this means that high-performance to be developed, economic and practical completely new flow battery technology.
Salt cave is that the cavern left after salt mine is exploited in the way of water-soluble, and shape is from size according to different geology items
Depending on part, bulky and good seal, volume is generally 107m3~108m3Between, therefore, salt cave provide one it is huge and
The underground space of safety is mainly used to natural gas-storing and petroleum for storing electrolyte, salt cave, but domestic at present very much
Salt cave is substantially at blank state because its technical indicator is unable to reach the technical requirements of oil storage or gas storage.And utilize salt cave
It is lower to being required in terms of the leakproofness, crushing resistance and stability in salt cave to store the electrolyte of aqueous phase system.Therefore, salt cave is utilized
The comprehensive utilization in salt cave can be sufficiently realized to store electrolyte.But (generated in-situ electricity is utilized for salt cave system is suitable for
Solve liquid) battery system there is still a need for exploitations.
Water phase flow battery still suffers from some challenges at present, as active material (organic matter) solubility is limited, electrolysis
The easy cross contamination of liquid, operation electric current density is low, easy generation water electrolysis side reaction etc..Therefore, exploitation overcomes disadvantage mentioned above, and can
It is very important with potential application in extensive salt cave aqueous phase system flow battery.
Summary of the invention
The present invention is directed at least solve one of the technical problems existing in the prior art.
For this purpose, the present invention proposes a kind of organic flow battery system of the aqueous phase system based on salt cave, it should the water based on salt cave
The organic flow battery system of phase system is at low cost, security performance is high, charge-discharge performance is stable, active material solubility height etc.
Advantage.
The organic flow battery system of aqueous phase system according to an embodiment of the present invention based on salt cave, comprising: two electrolyte
Liquid storage library, two electrolyte liquid storage libraries are spaced apart and are oppositely arranged, and electrolyte liquid storage library is to be formed after salt well accident
Salt cave with the molten chamber of physics, it is described it is molten it is intracavitary store electrolyte, the electrolyte includes positive active material, negative electrode active
Substance and supporting electrolyte, the positive active material are 2,2,6, the 6- oxide-based compounds of tetramethyl piperidine nitrogen；It is described negative
Pole active material is alloxazine class compound or riboflavin, and the positive active material and negative electrode active material are direct with bulk form
It is dissolved or dispersed in the system taken water as a solvent and is stored respectively in two salt caves, the supporting electrolyte is dissolved in
In the system；Liquid stream battery stack, the liquid stream battery stack are connected to two electrolyte liquid storage libraries respectively；The liquid stream electricity
Chi Dui includes: electrolytic cell groove body, and the electrolyte is filled in electrolytic cell groove body；Two pole plates, two pole plates are oppositely arranged；
Battery diaphragm, the battery diaphragm are located in the electrolytic cell groove body, and the electrolytic cell groove body is divided by the battery diaphragm
The anode region being connected to an electrolyte liquid storage library and the cathodic region being connected to another electrolyte liquid storage library, the pole
Plate is set to the anode region, and another pole plate is set to the cathodic region, and having in the anode region includes the positive-active
The anode electrolyte of substance, has the electrolyte liquid including the negative electrode active material in the cathodic region, the battery every
Film can be penetrated for the supporting electrolyte, and the positive active material and the negative electrode active material is prevented to penetrate；Circulation pipe
Electrolyte in one electrolyte liquid storage library is inputted or is exported the anode region, the circulation pipe by road, the circulation line
Electrolyte in another electrolyte liquid storage library is inputted or is exported the cathodic region by road；Circulating pump, the circulating pump are set to
The circulation line makes the electrolyte circulate supply by the circulating pump.
The organic flow battery system of aqueous phase system according to an embodiment of the present invention based on salt cave has at low cost, safety
The advantages that performance is high, charge-discharge performance is stablized, and active material solubility is high, and the redox flow battery energy storage system not only can solve
The electrochemical energy storage of (megawatt/megawatt hour) on a large scale, moreover it is possible to make full use of some discarded salt cave (mine) resources.
According to an embodiment of the present invention, the concentration of the positive active material is 0.1molL-1~3.0molL-1,
The concentration of the negative electrode active material is 0.1molL-1~4.0molL-1。
According to an embodiment of the present invention, electrolyte liquid storage library is sealing container.
According to an embodiment of the present invention, inert gas is passed through in electrolyte liquid storage library to be protected.
According to an embodiment of the present invention, the inert gas is nitrogen or argon gas.
According to an embodiment of the present invention, the battery diaphragm is polymer porous film, and aperture is 10nm~300nm.
According to an embodiment of the present invention, the polymer porous film include polypropylene PP film, polytetrafluoroethylene PTFE film,
Kynoar pvdf membrane, silicon substrate polypropylene PP film, polythene PE film, polystyrene PS film, polymetylmethacrylate
One of film.
According to an embodiment of the present invention, the battery diaphragm is silicon substrate PP, PE or PVDF.
According to an embodiment of the present invention, the aperture of the battery diaphragm is 150nm~200nm.
According to an embodiment of the present invention, the supporting electrolyte is NaCl salting liquid, KCl salting liquid, Na2SO4Salt is molten
Liquid, K2SO4Salting liquid, MgCl2Salting liquid, MgSO4Salting liquid, CaCl2At least one of salting liquid.
According to an embodiment of the present invention, the molar concentration of the supporting electrolyte is 0.1molL-1~8.0molL-1。
According to an embodiment of the present invention, the electrolyte further include: additive, the additive be pH adjusting agent or
Viscosity improver, the additive are dissolved in the system.
According to an embodiment of the present invention, the pH adjusting agent is NaOH, KOH, Na2CO3, at least one of CaO.
According to an embodiment of the present invention, the pH range of the pH adjusting agent are as follows: 8.5≤pH≤14.0.
According to an embodiment of the present invention, the additive is hydroxyethyl cellulose, hydroxypropyl methyl cellulose, polypropylene
At least one of amide, sodium carboxymethylcellulose, polyethylene oxide, modified starch, polyvinyl alcohol, polyvinylpyrrolidone,
At a temperature of 25 DEG C, the viscosity of the electrolyte after adding the additive is 1mPas~106mPas。
According to an embodiment of the present invention, at a temperature of 25 DEG C, the viscosity of the electrolyte is 102MPas~104mPas。
According to an embodiment of the present invention, the pole plate is formed as graphite felt.
According to an embodiment of the present invention, the pole plate with a thickness of 2mm~8mm.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the structural representation of the organic flow battery system of the aqueous phase system based on salt cave according to an embodiment of the present invention
Figure；
Fig. 2 is CV figure of the riboflavin according to an embodiment of the invention under different scanning rates；
Fig. 3 is the fitted figure of riboflavin peak current according to an embodiment of the invention Yu sweep speed half power；
Fig. 4 is CV figure of the TEMPO according to an embodiment of the invention under different scanning rates；
Fig. 5 is the fitted figure of TEMPO peak current according to an embodiment of the invention Yu sweep speed half power；
Fig. 6 is just extremely TEMPO according to an embodiment of the invention, and cathode is that the CV of riboflavin schemes；
Fig. 7 is the relational graph of embodiment according to the present invention 1 OH-TEMPO normal potential and pH into embodiment 5；
Fig. 8 is the relational graph of embodiment according to the present invention 1 riboflavin normal potential and pH into embodiment 5；
Fig. 9 is the circulating battery stability diagram of embodiment according to the present invention 1.
Appended drawing reference:
The organic flow battery system 100 of aqueous phase system based on salt cave；
Electrolyte liquid storage library 10；
Liquid stream battery stack 20；Pole plate 21；Anode electrolyte 22；Electrolyte liquid 23；Battery diaphragm 24；Circulation line 25；
Circulating pump 26.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, and for explaining only the invention, and is not considered as limiting the invention.
In the description of the present invention, it is to be understood that, term " center ", " longitudinal direction ", " transverse direction ", " length ", " width ",
" thickness ", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom" "inner", "outside", " up time
The orientation or positional relationship of the instructions such as needle ", " counterclockwise ", " axial direction ", " radial direction ", " circumferential direction " be orientation based on the figure or
Positional relationship is merely for convenience of description of the present invention and simplification of the description, rather than the device or element of indication or suggestion meaning must
There must be specific orientation, be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.In addition, limit
There is the feature of " first ", " second " to can explicitly or implicitly include one or more of the features surely.Of the invention
In description, unless otherwise indicated, the meaning of " plurality " is two or more.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected；It can
To be mechanical connection, it is also possible to be electrically connected；It can be directly connected, can also can be indirectly connected through an intermediary
Connection inside two elements.For the ordinary skill in the art, above-mentioned term can be understood at this with concrete condition
Concrete meaning in invention.
Below with reference to the accompanying drawings the organic flow battery of the aqueous phase system based on salt cave according to an embodiment of the present invention is specifically described
System 100.
As shown in Figure 1, the organic flow battery system 100 of the aqueous phase system according to an embodiment of the present invention based on salt cave includes
Two electrolyte liquid storage libraries 10 and liquid stream battery stack 20, liquid stream battery stack 20 include two pole plates 21, electrolytic cell groove body, battery every
Film 24, circulation line 25 and circulating pump 26.
Specifically, two electrolyte liquid storage libraries 10 are spaced apart and are oppositely arranged, electrolyte liquid storage library 10 is after salt well accident
Formed the salt cave with the molten chamber of physics, it is molten it is intracavitary store electrolyte, electrolyte includes positive active material, negative electrode active material
Matter and supporting electrolyte, 2,2,6, the 6- oxide-based compound of tetramethyl piperidine nitrogen of positive active material；Negative electrode active material
For alloxazine class compound or riboflavin, positive active material and negative electrode active material be directly dissolved or dispersed in bulk form with
Water is in the system of solvent and to be stored respectively in two salt caves, and supporting electrolyte is dissolved in system, liquid stream battery stack
20 are connected to two electrolyte liquid storage libraries 10 respectively, and electrolyte is filled in electrolytic cell groove body, and two pole plates 21 are oppositely arranged, electricity
Pond diaphragm 24 is located in electrolytic cell groove body, and electrolytic cell groove body is divided by battery diaphragm 24 to be connected to an electrolyte liquid storage library 10
Anode region and the cathodic region being connected to another electrolyte liquid storage library 10, a pole plate 21 are set to anode region, and another pole plate 21 is set to yin
Polar region has the anode electrolyte 22 including positive active material in anode region, has in cathodic region including negative electrode active material
Electrolyte liquid 23, battery diaphragm 24 can penetrate for supporting electrolyte, prevent the positive active material and the cathode
Active material penetrates, circulation line 25 by an electrolyte liquid storage library 10 electrolyte input or output anode area, circulation line
25 by another electrolyte liquid storage library 10 electrolyte input or output cathode area, circulating pump 26 be set to circulation line 25, pass through
Circulating pump 26 makes electrolyte circulate supply.
In other words, the organic flow battery system 100 of the aqueous phase system according to an embodiment of the present invention based on salt cave includes two
A electrolyte liquid storage library 10 and liquid stream battery stack 20, liquid stream battery stack 20 include two pole plates 21, electrolytic cell groove body, battery diaphragm
24, circulation line 25 and circulating pump 26, electrolyte liquid storage library 10 are the cavern left after water-soluble mode exploits salt mine,
It is exactly salt cave, electrolyte is stored in salt cave, electrolyte includes positive active material, negative electrode active material and supports to be electrolysed
Matter, 2,2,6,6- tetramethyl piperidine nitrogen oxides (2,2,6,6- tetramethyl-piperidine- of positive active material
1-oxyl, TEMPO) class compound (A)；Negative electrode active material is alloxazine class compound (B) or riboflavin (C), positive electrode active material
Matter and negative electrode active material are dissolved or dispersed in the system taken water as a solvent with bulk form, and supporting electrolyte is dissolved in
In system, liquid stream battery stack 20 is connected to by circulation line 25 with two electrolyte liquid storage libraries 10 respectively, and two pole plates 21 are opposite
Setting is equipped with circulating pump 26 on circulation line 25, circulates electrolyte to pole plate 21, two pole plates by circulating pump 26
21 can distinguish positive and negative electrode, and pole plate 21 directly and electrolyte contacts, provides the electrochemical reaction place with abundant duct, electricity
Pond diaphragm 24 is located in electrolytic cell groove body, and battery diaphragm 24 can be penetrated for supporting electrolyte, prevents positive active material and bears
Pole active material penetrates, and battery diaphragm 24 can be cation-exchange membrane.
It should be noted that the structure of above-mentioned TEMPO class compound (A), alloxazine class (B) and riboflavin (C) compound
It is as follows respectively:
Wherein, substituent R1For OH, OMe, OEt, CHO, NH2、N(Me)2、N(Et)2、F、Cl、CN、NO2、 COOH、SO3H
Or one of other grafting polymer class compounds；Substituent R2It is that 1,2,3,4 positions are one of monosubstituted or polysubstituted,
Also, described substituent R2For OH, OMe, OEt, CHO, NH2、N(Me)2、N(Et)2、 F、Cl、CN、NO2、COOH、SO3H
Or one or more of other grafting polymer class compounds.
The organic flow battery system 100 of the aqueous phase system according to an embodiment of the present invention based on salt cave uses two as a result,
The device that electrolyte liquid storage library 10 and liquid stream battery stack 20 combine, liquid stream battery stack 20 use two pole plates 21, electrolytic cell slot
The device that body, battery diaphragm 24, circulation line 25 and circulating pump 26 combine can be suitably used for salt cave system and (utilize in-situ preparation
Electrolyte) battery context, the battery system 100 have it is at low cost, security performance is high, charge-discharge performance is stable, active material
Expect the advantages that solubility is high, and the redox flow battery energy storage system not only can solve the electrochemistry of extensive (megawatt/megawatt hour)
Energy storage, additionally it is possible to make full use of some discarded salt cave (mine) resources.
According to one embodiment of present invention, the concentration of positive active material is 0.1molL-1~3.0molL-1, bear
The concentration of pole active material is 0.1molL-1~4.0molL-1。
In certain specific embodiments of the invention, electrolyte liquid storage library 10 is sealing container.
According to one embodiment of present invention, inert gas is passed through in electrolyte liquid storage library 10 to be protected, charging, putting
It can be all the time by inert gas shielding in electric process.
Further, inert gas can be nitrogen, and inert gas may be argon gas etc..
According to one embodiment of present invention, battery diaphragm 24 is according to the film of screening principle preparation, and battery diaphragm 24 can
For polymer porous film, aperture is 10nm~300nm.
Optionally, polymer porous film include polypropylene PP film, polytetrafluoroethylene PTFE film, Kynoar pvdf membrane,
One of silicon substrate polypropylene PP film, polythene PE film, polystyrene PS film, polymetylmethacrylate film.
Further, battery diaphragm 24 is silicon substrate PP, PE or PVDF.
According to one embodiment of present invention, the aperture of battery diaphragm 24 is 150nm~200nm.
In certain specific embodiments of the invention, supporting electrolyte is NaCl salting liquid, KCl salting liquid, Na2SO4Salt
Solution, K2SO4Salting liquid, MgCl2Salting liquid, MgSO4Salting liquid, CaCl2At least one of salting liquid.
Further, the molar concentration of supporting electrolyte is 0.1molL-1~8.0molL-1。
According to one embodiment of present invention, electrolyte further includes additive, and additive is that pH adjusting agent or viscosity change
Into agent, additive is dissolved in system, and wherein viscosity improver can improve viscosity.
Optionally, pH adjusting agent NaOH, KOH, Na2CO3, at least one of CaO.
According to one embodiment of present invention, the pH range of pH adjusting agent are as follows: 8.5≤pH≤14.0.
In certain specific embodiments of the invention, additive can for hydroxyethyl cellulose, hydroxypropyl methyl cellulose,
Polyacrylamide, sodium carboxymethylcellulose, polyethylene oxide, modified starch, polyvinyl alcohol, in polyvinylpyrrolidone at least
One kind, at a temperature of 25 DEG C, using rotational viscometer measure addition additive after electrolyte viscosity be 1mPas~
106mPas。
Further, at a temperature of 25 DEG C, the viscosity of electrolyte is 102MPas~104mPas。
According to one embodiment of present invention, pole plate 21 is formed as graphite felt.
Optionally, pole plate 21 with a thickness of 2mm~8mm.
Combined with specific embodiments below to the organic flow battery system of the aqueous phase system based on salt cave of the embodiment of the present invention
100 are specifically described.
In the cyclic voltammetry of electricity pair, using the CS Series Electrochemical work station of Wuhan Gastec company, three electrodes
System tests the chemical property of Organic Electricity pair, and working electrode is glass-carbon electrode (Tianjin Ida Heng Sheng company), and reference electrode is
Ag/AgCl electrode is platinum electrode to electrode, and positive and negative electrode electricity is -1.0V~1.0V respectively to scanning range, and sweep speed is
10mV·s-1, 20mVs-1, 40mVs-1, 60mVs-1, 80mVs-1, 100mVs-1.The CV of negative electricity pair is shown in Fig. 2,
Redox peak current and sweep speed half power carry out linear fit and see Fig. 3；The CV of positive electricity pair is shown in Fig. 4, aoxidizes
Reduction peak current and sweep speed half power carry out linear fit and see Fig. 5.
In battery testing, the flow velocity of electrolyte about 5.0mLmin-1, under constant current charge and discharge mode, current density is
0.5mA·cm-2。
Embodiment 1
Negative electrode active material in electrolyte liquid 23 is 0.1molL-1Riboflavin, the anode in anode electrolyte 22
Active material is 0.2molL-1TEMPO, the supporting electrolyte in anode electrolyte 22 and electrolyte liquid 23 is all made of
2.5mol·L-1Sodium chloride solution, pH value of solution adjusted to 10.0 using pH adjusting agent NaOH, assemble formation based on salt cave
Coulombic efficiency, voltage efficiency and the energy efficiency of the monocell of the organic flow battery system of aqueous phase system (I) are as shown in table 1.
Embodiment 2
Negative electrode active material in electrolyte liquid 23 is 0.1molL-1Riboflavin, the anode in anode electrolyte 22
Active material is 0.2molL-1TEMPO, the supporting electrolyte in anode electrolyte 22 and electrolyte liquid 23 is all made of
2.5mol·L-1Sodium chloride solution, pH value of solution adjusted to 10.5 using pH adjusting agent NaOH, assemble formation based on salt cave
Coulombic efficiency, voltage efficiency and the energy efficiency of the monocell of the organic flow battery system of aqueous phase system (II) are as shown in table 1.
Embodiment 3
Negative electrode active material in electrolyte liquid 23 is 0.1molL-1Riboflavin, the anode in anode electrolyte 22
Active material is 0.2molL-1TEMPO, the supporting electrolyte in anode electrolyte 22 and electrolyte liquid 23 is all made of
2.5mol·L-1Sodium chloride solution, using pH adjusting agent NaOH adjust pH value of solution to 9.5, assemble the water based on salt cave of formation
Coulombic efficiency, voltage efficiency and the energy efficiency of the monocell of the organic flow battery system of phase system (III) are as shown in table 1.
Embodiment 4
Negative electrode active material in electrolyte liquid 23 is 0.1molL-1Riboflavin, the anode in anode electrolyte 22
Active material is 0.2molL-1TEMPO, the supporting electrolyte in anode electrolyte 22 and electrolyte liquid 23 is all made of
2.5mol·L-1Sodium chloride solution, using pH adjusting agent NaOH adjust pH value of solution to 8.5, assemble the water based on salt cave of formation
Coulombic efficiency, voltage efficiency and the energy efficiency of the monocell of the organic flow battery system of phase system (IV) are as shown in table 1.
Embodiment 5
Negative electrode active material in electrolyte liquid 23 is 0.1molL-1Riboflavin, the anode in anode electrolyte 22
Active material is 0.2molL-1TEMPO, the supporting electrolyte in anode electrolyte 22 and electrolyte liquid 23 is all made of
2.5mol·L-1Sodium chloride solution, using pH adjusting agent NaOH adjust pH value of solution to 7.5, assemble the water based on salt cave of formation
Coulombic efficiency, voltage efficiency and the energy efficiency of the monocell of the organic flow battery system of phase system (V) are as shown in table 1.
Embodiment 6
Negative electrode active material in electrolyte liquid 23 is 0.1molL-1Riboflavin, the anode in anode electrolyte 22
Active material is 0.2molL-14- amino-TEMPO, the supporting electrolyte in anode electrolyte 22 and electrolyte liquid 23 is equal
Using 2.5molL-1Metabisulfite solution, pH value of solution is adjusted to 8.0 using pH adjusting agent KOH, assemble formation based on salt cave
The coulombic efficiency of monocell of the organic flow battery system of aqueous phase system (VI), voltage efficiency and energy efficiency it is as shown in table 1.
Embodiment 7
Negative electrode active material in electrolyte liquid 23 is 0.2molL-17,8- lumichrome, anode electrolyte 22
In positive active material be 0.4molL-14- oxygroup-TEMPO, the support in anode electrolyte 22 and electrolyte liquid 23
Electrolyte solution is all made of 3.0molL-1Klorvess Liquid, pH value of solution is adjusted to 8.0 using pH adjusting agent KOH, assembles shape
At the coulombic efficiency of monocell of the organic flow battery system of the aqueous phase system based on salt cave (VII), voltage efficiency and can dose-effect
Rate is as shown in table 1.
Embodiment 8
Negative electrode active material in electrolyte liquid 23 is 0.2molL-17,8- lumichrome, anode electrolyte 22
In positive active material be 0.4molL-14- oxygroup-TEMPO, the support in anode electrolyte 22 and electrolyte liquid 23
Electrolyte solution is all made of 3.0molL-1Klorvess Liquid, using pH adjusting agent KOH adjust pH value of solution to 8.0, using hydroxyl
The viscosity that propyl methocel adjusts electrolyte is 102MPas assembles the organic liquid stream of the aqueous phase system based on salt cave of formation
The coulombic efficiency of the monocell of battery system (VIII), voltage efficiency and energy efficiency are as shown in table 1.
1 monocell performance of table compares
| 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 shown in Table 1, the organic electrochemistry activity and invertibity of positive and negative electrode electricity pair show well, it will be appreciated from fig. 6 that
There are a pair of of redox peaks in riboflavin, normal potential is about -0.56V between -0.7V~-0.3V, oxidation spike potential with
The potential difference for restoring spike potential is about 50mV, shows redox electrochemistry that will definitely be inverse.TEMPO is in 0.3V~1.0V
Between there are a pair of of redox peaks, normal potential is about 0.63V, and oxidation spike potential and the potential difference of reduction spike potential are about
60mV shows redox electrochemistry that will definitely be inverse.By to positive and negative electrode electricity to respectively to oxidation process, reduction process
Peak current do linear fit with the half power for sweeping speed and can obtain, the oxidation-reduction process of positive and negative anodes electricity pair is by electrification
Learn the diffusion control of active material.Also, it can be obtained by Fig. 7 and Fig. 8, in the range of pH is 7.50~10.50, positive and negative anodes are organic
Linear relationship is presented in the normal potential and pH of electricity pair.
As a result, as shown in Table 1, each embodiment shows good conductivity, and as shown in Figure 9, single electricity after assembling
Pond stabilised efficiency, cycle performance are good.
To sum up, the organic flow battery system 100 of the aqueous phase system according to an embodiment of the present invention based on salt cave has
At low cost, the advantages that security performance is high, charge-discharge performance is stable, and active material solubility is high, additionally it is possible to solve extensive electrification
Energy storage is learned, some discarded salt cave resources are made full use of.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " illustrative examples ",
The description of " example ", " specific example " or " some examples " etc. means specific features described in conjunction with this embodiment or example, knot
Structure, material or feature are included at least one embodiment or example of the invention.In the present specification, to above-mentioned term
Schematic representation may not refer to the same embodiment or example.Moreover, specific features, structure, material or the spy of description
Point can be combined in any suitable manner in any one or more of the embodiments or examples.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: not
A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where being detached from the principle of the present invention and objective, this
The range of invention is defined by the claims and their equivalents.
Claims (18)
1. a kind of organic flow battery system of aqueous phase system based on salt cave characterized by comprising
Two electrolyte liquid storage libraries, two electrolyte liquid storage libraries, which are spaced apart, to be oppositely arranged, and electrolyte liquid storage library is salt
The salt cave with the molten chamber of physics that is formed after mine exploitation, it is described it is molten it is intracavitary store electrolyte, the electrolyte includes anode work
Property substance, negative electrode active material and supporting electrolyte, the positive active material be 2,2,6,6- tetramethyl piperidine nitrogen oxides
Class compound；The negative electrode active material is alloxazine class compound or riboflavin, the positive active material and negative electrode active material
Matter is directly dissolved or dispersed in the system taken water as a solvent with bulk form and is stored respectively in two salt caves, described
Supporting electrolyte is dissolved in the system；
Liquid stream battery stack, the liquid stream battery stack are connected to two electrolyte liquid storage libraries respectively；
The liquid stream battery stack includes:
Electrolytic cell groove body is filled with the electrolyte in electrolytic cell groove body；
Two pole plates, two pole plates are oppositely arranged；
Battery diaphragm, the battery diaphragm are located in the electrolytic cell groove body, and the battery diaphragm divides the electrolytic cell groove body
The cathodic region for being divided into the anode region being connected to an electrolyte liquid storage library and being connected to another electrolyte liquid storage library, an institute
Pole plate is stated set on the anode region, another pole plate is set to the cathodic region, and having in the anode region includes the anode
The anode electrolyte of active material has the electrolyte liquid including the negative electrode active material, the electricity in the cathodic region
Pond diaphragm can be penetrated for the supporting electrolyte, and the positive active material and the negative electrode active material is prevented to penetrate；
Electrolyte in one electrolyte liquid storage library is inputted or is exported the anode region by circulation line, the circulation line,
Electrolyte in another electrolyte liquid storage library is inputted or is exported the cathodic region by the circulation line；
Circulating pump, the circulating pump are set to the circulation line, so that the electrolyte is circulated supply by the circulating pump.
2. the organic flow battery system of the aqueous phase system according to claim 1 based on salt cave, which is characterized in that it is described just
The concentration of pole active material is 0.1molL-1~3.0molL-1, the concentration of the negative electrode active material is 0.1molL-1
~4.0molL-1。
3. the organic flow battery system of the aqueous phase system according to claim 1 based on salt cave, which is characterized in that the electricity
Solution liquid liquid storage library is sealing container.
4. the organic flow battery system of the aqueous phase system according to claim 1 based on salt cave, which is characterized in that the electricity
Inert gas is passed through in solution liquid liquid storage library to be protected.
5. the organic flow battery system of the aqueous phase system according to claim 4 based on salt cave, which is characterized in that described lazy
Property gas be nitrogen or argon gas.
6. the organic flow battery system of the aqueous phase system according to claim 1 based on salt cave, which is characterized in that the electricity
Pond diaphragm is polymer porous film, and aperture is 10nm~300nm.
7. the organic flow battery system of the aqueous phase system according to claim 6 based on salt cave, which is characterized in that described poly-
Object perforated membrane is closed to include polypropylene PP film, polytetrafluoroethylene PTFE film, Kynoar pvdf membrane, silicon substrate polypropylene PP film, gather
One of ethylene PE film, polystyrene PS film, polymetylmethacrylate film.
8. the organic flow battery system of the aqueous phase system according to claim 7 based on salt cave, which is characterized in that the electricity
Pond diaphragm is silicon substrate PP, PE or PVDF.
9. the organic flow battery system of the aqueous phase system according to claim 8 based on salt cave, which is characterized in that the electricity
The aperture of pond diaphragm is 150nm~200nm.
10. the organic flow battery system of the aqueous phase system according to claim 1 based on salt cave, which is characterized in that described
Supporting electrolyte is NaCl salting liquid, KCl salting liquid, Na2SO4Salting liquid, K2SO4Salting liquid, MgCl2Salting liquid, MgSO4Salt is molten
Liquid, CaCl2At least one of salting liquid.
11. the organic flow battery system of the aqueous phase system according to claim 10 based on salt cave, which is characterized in that described
The molar concentration of supporting electrolyte is 0.1molL-1~8.0molL-1。
12. the organic flow battery system of the aqueous phase system according to claim 1 based on salt cave, which is characterized in that described
Electrolyte further include:
Additive, the additive are pH adjusting agent or viscosity improver, and the additive is dissolved in the system.
13. the organic flow battery system of the aqueous phase system according to claim 12 based on salt cave, which is characterized in that described
PH adjusting agent is NaOH, KOH, Na2CO3, at least one of CaO.
14. the organic flow battery system of the aqueous phase system according to claim 13 based on salt cave, which is characterized in that described
The pH range of pH adjusting agent are as follows: 8.5≤pH≤14.0.
15. the organic flow battery system of the aqueous phase system according to claim 12 based on salt cave, which is characterized in that described
Additive is hydroxyethyl cellulose, hydroxypropyl methyl cellulose, polyacrylamide, sodium carboxymethylcellulose, polyethylene oxide, changes
At least one of property starch, polyvinyl alcohol, polyvinylpyrrolidone, institute at a temperature of 25 DEG C, after adding the additive
The viscosity for stating electrolyte is 1mPas~106mPas。
16. the organic flow battery system of the aqueous phase system according to claim 15 based on salt cave, which is characterized in that 25
At a temperature of DEG C, the viscosity of the electrolyte is 102MPas~104mPas。
17. the organic flow battery system of the aqueous phase system according to claim 1 based on salt cave, which is characterized in that described
Pole plate is formed as graphite felt.
18. the organic flow battery system of the aqueous phase system according to claim 17 based on salt cave, which is characterized in that described
Pole plate with a thickness of 2mm~8mm.
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