CN109585881A - The organic flow battery system of the aqueous phase system with mixed solvent based on salt cave - Google Patents
The organic flow battery system of the aqueous phase system with mixed solvent based on salt cave Download PDFInfo
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- CN109585881A CN109585881A CN201811250801.8A CN201811250801A CN109585881A CN 109585881 A CN109585881 A CN 109585881A CN 201811250801 A CN201811250801 A CN 201811250801A CN 109585881 A CN109585881 A CN 109585881A
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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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- 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
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
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- 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
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Abstract
The invention discloses a kind of organic flow battery system of the aqueous phase system with mixed solvent based on salt cave, it include: 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, molten intracavitary have 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 directly to be dissolved or dispersed in dicyandiamide solution to benzene anthraquinone analog compound, positive active material and negative electrode active material with bulk form；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 with mixed solvent based on salt cave not only has 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 aqueous phase system with mixed solvent based on salt cave has
Machine flow battery system, the 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
It is general to develop and use the renewable energy such as wind energy, solar energy, tide energy.However these renewable energy have discontinuous, shakiness
It is fixed, limit and the characteristic of grid-connected hardly possible by territorial environment, cause its utilization rate low, abandonment abandoning light rate height, waste of resource.Therefore it needs
Greatly developing 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
(Redox Flow Batteries, RFBs) has several special technological merits in pond, 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 107~108m3Between, therefore, salt cave provide one it is huge and pacify
The full underground space is mainly used to natural gas-storing and petroleum for storing electrolyte, salt cave, but domestic many salt at present
Cave is substantially at blank state because its technical indicator is unable to reach the technical requirements of oil storage or gas storage.And using salt cave come
Storage electrolyte requires leakproofness, crushing resistance and the stability aspect in salt cave lower.Therefore, electrolyte is stored using salt cave
It can sufficiently realize the comprehensive utilization in salt cave.But for the battery for being suitable for salt cave system (utilizing generated in-situ electrolyte)
There is still a need for exploitations for system.
The flow battery of simple water phase system still suffers from some challenges at present, for example, active material MOLECULE DESIGN,
Active material (organic matter) solubility is limited, the easy cross contamination of electrolyte, operation electric current density are low, Yi Fasheng water electrolysis side reaction
Deng.Therefore, exploitation overcomes disadvantage mentioned above, and can with potential application in the flow battery of extensive salt cave system be extremely important
's.
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 with mixed solvent based on salt cave,
The organic flow battery system of the aqueous phase system with mixed solvent based on salt cave, should the water with mixed solvent 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 aqueous phase system with mixed solvent organic flow battery system according to an embodiment of the present invention based on salt cave, packet
Include: 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 mine
The salt cave with the molten chamber of physics formed after exploitation, it is described it is molten it is intracavitary store electrolyte, the electrolyte includes positive-active
Substance, negative electrode active material and supporting electrolyte, the positive active material are that 2,2,6,6- tetramethyl piperidine nitrogens are oxide-based
Compound；The negative electrode active material is to benzene anthraquinone analog compound, the positive active material and negative electrode active material with this
Body form is directly dissolved or dispersed in dicyandiamide solution and is stored respectively in two salt caves, the supporting electrolyte dissolution
In the system；Electrolytic cell groove body is filled with the electrolyte in electrolytic cell groove body；Two pole plates, two pole plates are opposite
Setting；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；It follows
Endless tube road, the electrolyte in an electrolyte liquid storage library is inputted or exports the anode region by the circulation line, described to follow
Electrolyte in another electrolyte liquid storage library is inputted or is exported the cathodic region by endless tube road；Circulating pump, the circulating pump
Set on the circulation line, the electrolyte is set to circulate supply by the circulating pump.
The aqueous phase system with mixed solvent organic flow battery system according to an embodiment of the present invention based on salt cave, tool
There are the advantages that at low cost, security performance is high, charge-discharge performance is stable, and active material solubility is high, and the flow battery energy storage
System not only can solve the electrochemical energy storage of extensive (megawatt/megawatt hour), moreover it is possible to make full use of some discarded salt caves
(mine) resource.
According to an embodiment of the present invention, the concentration of the positive active material is 0.05molL-1~3.0molL-1, the concentration of the negative electrode active material is 0.05molL-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 solvent is that water and cosolvent form.
According to an embodiment of the present invention, the cosolvent is methanol, ethyl alcohol, ethylene glycol, 1,2-PD, isopropyl
Alcohol, glycerol, triethylene glycol, methylamine, dimethylamine, formamide, acetamide, hexamethylphosphoric triamide, ethylenediamine, acetone, tetrahydro furan
It mutters, trifluoroacetic acid, acetonitrile, succinonitrile, Isosorbide-5-Nitrae-dioxane, the own sulfoxide of diformazan, at least one of dimethylformamide.
According to an embodiment of the present invention, the cosolvent accounts for the 5%~50% of total solvent volume.
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 range of the pH adjusting agent are as follows: 7.0≤pH≤14.0.
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 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 organic flow battery system of the aqueous phase system with mixed solvent based on salt cave according to an embodiment of the present invention
The structural schematic diagram of system；
Fig. 2 is CV figure of the 1,4-benzoquinone according to an embodiment of the invention under different scanning rates；
Fig. 3 is the fitted figure of 1,4-benzoquinone 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 at 1,4-benzoquinone peak schemes；
Fig. 7 is the circulating battery stability diagram of embodiment according to the present invention 1.
Appended drawing reference:
The organic flow battery system 100 of the aqueous phase system with mixed solvent 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 water phase body with mixed solvent according to an embodiment of the present invention based on salt cave is specifically described
It is organic flow battery system 100.
As shown in Figure 1, the aqueous phase system with mixed solvent organic liquid stream according to an embodiment of the present invention based on salt cave
Battery system 100 includes two electrolyte liquid storage libraries 10 and liquid stream battery stack 20, and liquid stream battery stack 20 includes two pole plates 21, electricity
Solve pond groove body, battery diaphragm 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
To be directly dissolved or dispersed in solvent body with bulk form to benzene anthraquinone analog compound, positive active material and negative electrode active material
In system and be stored respectively in two salt caves, supporting electrolyte is dissolved in system, liquid stream battery stack 20 respectively with two
Electrolyte liquid storage library 10 is connected to, and is filled with electrolyte in electrolytic cell groove body, and two pole plates 21 are oppositely arranged, and battery diaphragm 24 is located at electricity
Solve pond groove body in, battery diaphragm 24 by electrolytic cell groove body be divided into the anode region being connected to an electrolyte liquid storage library 10 and with it is another
The cathodic region that electrolyte liquid storage library 10 is connected to, a pole plate 21 are set to anode region, and another pole plate 21 is set to cathodic region, has in anode region
There is the anode electrolyte 22 including positive active material, there is the electrolyte liquid 23 including negative electrode active material in cathodic region,
Battery diaphragm 24 can be penetrated for supporting electrolyte, prevented the positive active material and the negative electrode active material from penetrating, followed
Endless tube road 25 inputs the electrolyte in an electrolyte liquid storage library 10 or output anode area, circulation line 25 store up another electrolyte
Electrolyte input or output cathode area, circulating pump 26 in liquid library 10 are set to circulation line 25, make electrolyte by circulating pump 26
Circulate supply.
In other words, the aqueous phase system with mixed solvent organic flow battery according to an embodiment of the present invention based on salt cave
System 100 includes two electrolyte liquid storage libraries 10 and liquid stream battery stack 20, and liquid stream battery stack 20 includes two pole plates 21, electrolytic cells
Groove body, battery diaphragm 24, circulation line 25 and circulating pump 26, electrolyte liquid storage library 10 are to leave after water-soluble mode exploits salt mine
Cavern, that is, salt cave is stored with electrolyte, electrolyte includes positive active material, negative electrode active material in salt cave
Matter and supporting electrolyte, the positive active material in anolyte be 2,2,6,6- tetramethyl piperidine nitrogen oxides (2,2,6,
6-tetra-methylpiperidine-1-oxyl, TEMPO) class compound (A), the negative electrode active material in catholyte
For 1,4-benzoquinone class compound (B), positive active material and negative electrode active material are directly dissolved or dispersed in solvent with bulk form
In system, supporting electrolyte is dissolved in system, and liquid stream battery stack 20 passes through circulation line 25 and two electrolyte liquid storages respectively
Library 10 is connected to, and two pole plates 21 are oppositely arranged, and circulating pump 26 is equipped on circulation line 25, follows electrolyte by circulating pump 26
Circulation is moved to pole plate 21, and two pole plates 21 may respectively be positive and negative electrode, and pole plate 21 directly and electrolyte contacts, is provided with rich
The electrochemical reaction place in rich duct, for battery diaphragm 24 between electrolytic cell groove body, battery diaphragm 24 can be for supporting to be electrolysed
Matter penetrates, and prevents positive active material and negative electrode active material from penetrating, battery diaphragm 24 can be cation-exchange membrane.
It should be noted that the structure of above-mentioned TEMPO class compound (A), 1,4-benzoquinone class compound (B) distinguishes following institute
Show:
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 R2To be one of monosubstituted or polysubstituted, described substitution
Base R2For alkyl, H, OH, OMe, OEt, CHO, NH2、N(Me)2、N(Et)2、F、Cl、CN、NO2、COOH、SO3H or other grafting is high
One or more of molecule class compound.
The organic flow battery system of aqueous phase system with mixed solvent according to an embodiment of the present invention based on salt cave as a result,
The device that system 100 is combined using two electrolyte liquid storage libraries 10 and liquid stream battery stack 20, liquid stream battery stack 20 use two poles
The device that plate 21, electrolytic cell groove body, battery diaphragm 24, circulation line 25 and circulating pump 26 combine, can overcome current liquid stream
Battery is at high cost, corrosive electrolyte not environmentally and the limitation of security risk, and active material in aqueous phase system at present
The problems such as (organic matter) solubility is limited, the easy cross contamination of electrolyte, operation electric current density are low, Yi Fasheng water electrolysis side reaction.
The organic flow battery system 100 of aqueous phase system with mixed solvent according to an embodiment of the present invention based on salt cave constructs one
Kind flow battery system, respectively with 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO) class compounds and 1,4-benzoquinone class chemical combination
Object is redox active component, improves Cell current density using cosolvent, which can be suitably used for salt cave system and (utilize
Generated in-situ electrolyte) battery context, the battery system 100 have it is at low cost, security performance is high, charge-discharge performance is steady
It is fixed, the advantages that active material solubility is high, and also the redox flow battery energy storage system not only can solve extensive (megawatt/megawatt hour)
Electrochemical energy storage, moreover 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 0.05molL-1~3.0molL-1,
The concentration of negative electrode active material is 0.05molL-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.
Further, inert gas is nitrogen or argon gas.
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, the solvent is that water and cosolvent form, can using cosolvent
To improve Cell current density.
Optionally, the cosolvent be methanol, ethyl alcohol, ethylene glycol, 1,2-PD, isopropanol, glycerol, triethylene glycol,
Methylamine, dimethylamine, formamide, acetamide, hexamethylphosphoric triamide, ethylenediamine, acetone, tetrahydrofuran, trifluoroacetic acid, second
At least one of nitrile, succinonitrile, Isosorbide-5-Nitrae-dioxane, the own sulfoxide of diformazan (DMSO), dimethylformamide (DMF).
Further, the cosolvent accounts for the 5%~50% of total solvent volume.
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.
According to one embodiment of present invention, the pH range of pH adjusting agent are as follows: 7.0≤pH≤14.0.
Optionally, pH adjusting agent NaOH, KOH, Na2CO3, at least one of CaO.
In certain specific embodiments of the invention, additive is hydroxyethyl cellulose, hydroxypropyl methyl cellulose, gathers
Acrylamide, sodium carboxymethylcellulose, polyethylene oxide, modified starch, polyvinyl alcohol, at least one in polyvinylpyrrolidone
Kind, at a temperature of 25 DEG C, measured using rotational viscometer, add 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.
Have combined with specific embodiments below to the aqueous phase system with mixed solvent based on salt cave of the embodiment of the present invention
Machine flow battery system 100 is specifically described.
In the cyclic voltammetry of electricity pair, using the CS Series Electrochemical work station of Wuhan Gastec company, three electrodes
The chemical property of system test Organic Electricity pair.Working electrode is glass-carbon electrode (Tianjin Ida Heng Sheng company), and reference electrode is
Ag/AgCl electrode is platinum electrode to electrode.Positive and negative anodes 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, oxygen
Change reduction peak current and sweep speed half power carries out linear fit and sees Fig. 3.The CV of positive electricity pair is shown in Fig. 4, and oxidation is also
Parent peak electric 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-discharge mode, current density is
0.5mA cm-2。
Embodiment 1
Negative electrode active material in electrolyte liquid 23 is 0.05molL-11,4-benzoquinone, in anode electrolyte 22 just
Pole active material is 0.05molL-1TEMPO, solvent volume ratio be water: acetonitrile=9:1, anode electrolyte 22 and negative electricity
The supporting electrolyte solved in liquid 23 uses 2.5molL-1Sodium chloride, pH value of solution is adjusted to 7.5 using pH adjusting agent NaOH, group
Fill the coulomb effect of the monocell of the organic flow battery system of the aqueous phase system with mixed solvent (I) based on salt cave formed
Rate, voltage efficiency and energy efficiency are as shown in table 1.
Embodiment 2
Negative electrode active material in electrolyte liquid 23 is 0.05molL-11,4-benzoquinone, in anode electrolyte 22 just
Pole active material is 0.05molL-14-OH-TEMPO, solvent volume ratio be water: dimethyl sulfoxide=9:1, anode electrolyte
22 and electrolyte liquid 23 in supporting electrolyte use 2.5molL-1Sodium sulphate, using pH adjusting agent KOH adjust solution
PH to 8.0 assembles single electricity of the organic flow battery system of the aqueous phase system with mixed solvent (II) based on salt cave of formation
The coulombic efficiency in pond, voltage efficiency and energy efficiency are as shown in table 1.
Embodiment 3
Negative electrode active material in electrolyte liquid 23 is 0.1molL-12,6- di-t-butyl 1,4-benzoquinone, anolyte
Positive active material in liquid 22 is 0.1molL-14-OH-TEMPO, solvent volume ratio be water: methanol=8:2, anode electricity
The supporting electrolyte solved in liquid 22 and electrolyte liquid 23 uses 2.5molL-1Sodium sulphate, using pH adjusting agent NaOH adjust
PH value of solution assembles the organic flow battery system of the aqueous phase system with mixed solvent (III) based on salt cave of formation to 8.0
The coulombic efficiency of monocell, voltage efficiency and energy efficiency are as shown in table 1.
Embodiment 4
Negative electrode active material in electrolyte liquid 23 is 0.1molL-12,6- di-t-butyl 1,4-benzoquinone, anolyte
Positive active material in liquid 22 is 0.1molL-14-OH-TEMPO, solvent volume ratio be water: methanol=8:2, anode electricity
The supporting electrolyte solved in liquid 22 and electrolyte liquid 23 uses 2.5molL-1Sodium sulphate, using pH adjusting agent NaOH adjust
PH value of solution is to 8.0.Polyvinylpyrrolidone is used to adjust the viscosity of electrolyte as 102MPas, assemble formation based on salt cave
Coulombic efficiency, voltage efficiency and the energy dose-effect of the monocell of the organic flow battery system of aqueous phase system (IV) with mixed solvent
Rate is as shown in table 1.
Embodiment 5
Negative electrode active material in electrolyte liquid 23 is 0.05molL-1Parabenzoquinone dioxime, in anode electrolyte 22
Positive active material be 0.05molL-11- oxygroup-TEMPO, solvent volume ratio be water: ethyl alcohol=7:3, anode electrolyte
22 and electrolyte liquid 23 in supporting electrolyte use 2.5molL-1Magnesium chloride, using pH adjusting agent KOH adjust solution
PH to 7.5 assembles single electricity of the organic flow battery system of the aqueous phase system with mixed solvent (V) based on salt cave of formation
The coulombic efficiency in pond, voltage efficiency and energy efficiency are as shown in table 1.
Embodiment 6
Negative electrode active material in electrolyte liquid 23 is 0.05molL-1Parabenzoquinone dioxime, in anode electrolyte 22
Positive active material be 0.05molL-11- oxygroup-TEMPO, solvent volume ratio be water: ethyl alcohol=7:3, anode electrolyte
22 and electrolyte liquid 23 in supporting electrolyte use 2.5molL-1Magnesium chloride, using pH adjusting agent KOH adjust solution
PH to 7.5.Sodium carboxymethylcellulose is used to adjust the viscosity of electrolyte as 102MPas assembles the having based on salt cave of formation
Coulombic efficiency, voltage efficiency and the energy efficiency of the monocell of the organic flow battery system of the aqueous phase system of mixed solvent (VI) are such as
Shown in table 1.
Embodiment 7
Negative electrode active material in electrolyte liquid 23 is 0.1molL-1Isosorbide-5-Nitrae -1,4-benzoquinone, in anode electrolyte 22
Positive active material is 0.1molL-1TEMPO, solvent volume ratio be water: ethyl alcohol=5:5, anode electrolyte 22 and negative electricity
The supporting electrolyte solved in liquid 23 uses 2.5molL-1Potassium sulfate, pH value of solution is adjusted to 8.0 using pH adjusting agent CaO, group
Fill the coulomb effect of the monocell of the organic flow battery system of the aqueous phase system with mixed solvent (VII) based on salt cave formed
Rate, voltage efficiency and energy efficiency are as shown in table 1.
Embodiment 8
Negative electrode active material in electrolyte liquid 23 is 0.2molL-1Chloranil, in anode electrolyte 22
Positive active material is 0.2molL-11- oxygroup-TEMPO, solvent volume ratio be water: dimethylformamide=8:2, anode
Supporting electrolyte in electrolyte 22 and electrolyte liquid 23 uses 2.5molL-1Magnesium sulfate, using pH adjusting agent KOH tune
PH value of solution is saved to 9.0, hydroxypropyl methyl cellulose is used to adjust the viscosity of electrolyte as 102MPas, assemble formation based on salt
Coulombic efficiency, voltage efficiency and the energy of the monocell of the organic flow battery system of aqueous phase system with mixed solvent (VIII) in cave
Amount efficiency is as shown in table 1.
1 monocell performance of table compares
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 1,4-benzoquinone, normal potential is about -0.11V between -0.3V~-0.1V, oxidation spike potential with
The potential difference for restoring spike potential is about 70mV, shows redox electrochemistry that will definitely be inverse.TEMPO 0.4V~0.8V it
Between there are a pair of of redox peaks, normal potential is about 0.61V, 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 anodes electricity to respectively to oxidation process, reduction process
Peak current does linear fit with the half power for sweeping speed and can obtain, and the oxidation-reduction process of positive and negative anodes electricity pair is by electrochemistry
The diffusion of active material controls.
Each embodiment shows good conductivity as a result,.Comparative example 3 and 4 and embodiment 5 and 6 can be sent out
It is existing, it is more efficient that the monocell shown after the viscosity of electrolyte is adjusted by additive.
To sum up, the aqueous phase system organic liquor galvanic electricity with mixed solvent according to an embodiment of the present invention based on salt cave
Cell system 100 has many advantages, such as that at low cost, security performance is high, charge-discharge performance is stable, and active material solubility is high, additionally it is possible to solve
Certainly extensive electrochemical energy storage, makes full use of some discarded salt cave resources.
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 (21)
1. a kind of organic flow battery system of the aqueous phase system with mixed solvent 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 be to benzene anthraquinone analog compound, the positive active material and negative electrode active material with
Bulk form is directly dissolved or dispersed in dicyandiamide solution and is stored respectively in two salt caves, and the supporting electrolyte is molten
In system described in Xie Yu；
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 aqueous phase system with mixed solvent organic flow battery system according to claim 1 based on salt cave,
It is characterized in that, the concentration of the positive active material is 0.05molL-1~3.0molL-1, the negative electrode active material
Concentration is 0.05molL-1~4.0molL-1。
3. the aqueous phase system with mixed solvent organic flow battery system according to claim 1 based on salt cave,
It is characterized in that, electrolyte liquid storage library is sealing container.
4. the aqueous phase system with mixed solvent organic flow battery system according to claim 1 based on salt cave,
It is characterized in that, is passed through inert gas in electrolyte liquid storage library and is protected.
5. the aqueous phase system with mixed solvent organic flow battery system according to claim 4 based on salt cave,
It is characterized in that, the inert gas is nitrogen or argon gas.
6. the aqueous phase system with mixed solvent organic flow battery system according to claim 1 based on salt cave,
It is characterized in that, the battery diaphragm is polymer porous film, and aperture is 10nm~300nm.
7. the aqueous phase system with mixed solvent organic flow battery system according to claim 6 based on salt cave,
It is characterized in that, the polymer porous film includes polypropylene PP film, polytetrafluoroethylene PTFE film, Kynoar pvdf membrane, silicon
One of base polypropylene PP film, polythene PE film, polystyrene PS film, polymetylmethacrylate film.
8. the aqueous phase system with mixed solvent organic flow battery system according to claim 7 based on salt cave,
It is characterized in that, the battery diaphragm is silicon substrate PP, PE or PVDF.
9. the aqueous phase system with mixed solvent organic flow battery system according to claim 8 based on salt cave,
It is characterized in that, the aperture of the battery diaphragm is 150nm~200nm.
10. the organic flow battery of the aqueous phase system according to claim 1 based on salt cave, which is characterized in that described is molten
Agent is that water and cosolvent form.
11. the organic flow battery of the aqueous phase system according to claim 10 based on salt cave, which is characterized in that described is total to
Solvent is methanol, ethyl alcohol, ethylene glycol, 1,2-PD, isopropanol, glycerol, triethylene glycol, methylamine, dimethylamine, formamide, acetyl
Amine, hexamethylphosphoric triamide, ethylenediamine, acetone, tetrahydrofuran, trifluoroacetic acid, acetonitrile, succinonitrile, Isosorbide-5-Nitrae-dioxane,
At least one of the own sulfoxide of diformazan, dimethylformamide.
12. the organic flow battery of aqueous phase system according to claim 11, which is characterized in that the cosolvent accounts for total solvent
The 5%~50% of volume.
13. the aqueous phase system with mixed solvent organic flow battery system according to claim 1 based on salt cave,
It is characterized in that, the supporting electrolyte is NaCl salting liquid, KCl salting liquid, Na2SO4Salting liquid, K2SO4Salting liquid, MgCl2Salt
Solution, MgSO4Salting liquid, CaCl2At least one of salting liquid.
14. the aqueous phase system with mixed solvent organic flow battery system according to claim 13 based on salt cave,
It is characterized in that, the molar concentration of the supporting electrolyte is 0.1molL-1~8.0molL-1。
15. the aqueous phase system with mixed solvent organic flow battery system according to claim 1 based on salt cave,
It is characterized in that, the electrolyte further include:
Additive, the additive are pH adjusting agent or viscosity improver, and the additive is dissolved in the system.
16. the aqueous phase system with mixed solvent organic flow battery system according to claim 15 based on salt cave,
It is characterized in that, the pH range of the pH adjusting agent are as follows: 7.0≤pH≤14.0.
17. the aqueous phase system with mixed solvent organic flow battery system according to claim 15 based on salt cave,
It is characterized in that, the pH adjusting agent is NaOH, KOH, Na2CO3, at least one of CaO.
18. the aqueous phase system with mixed solvent organic flow battery system according to claim 15 based on salt cave,
It is characterized in that, the additive is hydroxyethyl cellulose, hydroxypropyl methyl cellulose, polyacrylamide, carboxymethyl cellulose
At least one of sodium, polyethylene oxide, modified starch, polyvinyl alcohol, polyvinylpyrrolidone, at a temperature of 25 DEG C, addition
The viscosity of the electrolyte after the additive is 1mPas~106mPas。
19. the aqueous phase system with mixed solvent organic flow battery system according to claim 18 based on salt cave,
It is characterized in that, the viscosity of the electrolyte is 10 at a temperature of 25 DEG C2MPas~104mPas。
20. the aqueous phase system with mixed solvent organic flow battery system according to claim 1 based on salt cave,
It is characterized in that, the pole plate is formed as graphite felt.
21. the aqueous phase system with mixed solvent organic flow battery system according to claim 20 based on salt cave,
It is characterized in that, the pole plate with a thickness of 2mm~8mm.
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