CN110444787A - Flow battery system based on amino anthraquinones derivative - Google Patents
Flow battery system based on amino anthraquinones derivative Download PDFInfo
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- CN110444787A CN110444787A CN201910777098.4A CN201910777098A CN110444787A CN 110444787 A CN110444787 A CN 110444787A CN 201910777098 A CN201910777098 A CN 201910777098A CN 110444787 A CN110444787 A CN 110444787A
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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
- H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
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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
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
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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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2455—Grouping of fuel cells, e.g. stacking of fuel cells with liquid, solid or electrolyte-charged reactants
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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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- 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
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Abstract
The present invention provides a kind of flow battery system based on amino anthraquinones derivative, it include: two electrolyte liquid storage libraries, two electrolyte liquid storage libraries are spaced apart setting, storage tank or molten intracavitary storage electrolyte, electrolyte includes positive active material, negative electrode active material and supporting electrolyte, positive active material 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO) class compounds；Negative electrode active material is that the anthraquinone derivative containing carboxyl, 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 are stored respectively in two salt caves, and supporting electrolyte is dissolved in system；Liquid stream battery stack, liquid stream battery stack are connected to two electrolyte liquid storage libraries respectively.Flow battery system according to an embodiment of the present invention based on amino anthraquinones derivative has many advantages, such as that at low cost, security performance is high, charge-discharge performance is stable, active material solubility is high.
Description
Technical field
The present invention relates to flow battery field more particularly to a kind of flow battery systems based on amino anthraquinones derivative.
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
(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..Redox active substance is the carrier and liquid of flow battery energy conversion
Most crucial part in galvanic battery.Traditional flow battery using inorganic material as active material (such as vanadium system flow battery),
However, inorganic material is at high cost, toxicity, resource is limited, form dendrite and the disadvantages such as electro-chemical activity is low limit flow battery
Large-scale application.Organic active substance due to can easily be accommodated at low cost, " green ", resourceful, molecular entergy level and electricity
The advantages that fast is chemically reacted, extensive concern both domestic and external is caused.
The electrolyte of the organic flow battery of water system has the advantages that non-flammable, behaves safer.In addition, in water system
In organic flow battery, electrolyte conductivity is high, and electrochemical reaction speed is fast, and output power is high.Therefore, water system organic liquor galvanic electricity
Pond is a kind of ideal extensive energy storage technology.The organic flow battery of water phase still suffers from some challenges at present, such as active material
Expect limited (organic matter) solubility, the easy cross contamination of electrolyte, low, the Yi Fasheng water electrolysis side reaction of operation electric current density etc..Cause
This, exploitation overcomes disadvantage mentioned above, develops new organic active substance and (such as opens a way for extending organic flow battery chemical space
Voltage, energy density and stability etc.) it is of great significance.
Anthraquinone is a kind of generally existing natural products, can be extracted from specified plant, can also be artificial synthesized, therefore, can
To realize large-scale production.The inorganic ions that traditional flow battery is replaced with anthraquinone type organic, not only greatly reduces battery
Cost, and increase the environmentally friendly of battery.Moreover, quinones substance has designability in structure, in liquid stream
Possess huge potentiality in battery development.
Summary of the invention
In view of this, the present invention provides a kind of flow battery system based on amino anthraquinones derivative, battery system peace
Full performance is high, energy density is high, charge-discharge performance is stable, low in cost.
Flow battery system according to an embodiment of the present invention based on amino anthraquinones derivative includes: two electrolyte liquid storages
Library, two electrolyte liquid storage libraries are spaced apart setting, and electrolyte liquid storage library is to be formed after small-sized storage tank or salt well accident
The salt cave with the molten chamber of physics, the storage tank or molten intracavitary storage electrolyte, the electrolyte includes positive active material, negative
Pole active material and supporting electrolyte, the positive active material are 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO) classes
Compound；The negative electrode active material is the anthraquinone derivative containing carboxyl, the positive active material and negative electrode active material
It is directly dissolved or dispersed in the system taken water as a solvent and is stored respectively in two salt caves with bulk form, the branch
Electrolyte dissolution is held in the system；Liquid stream battery stack, the liquid stream battery stack respectively with two electrolyte liquid storage libraries
Connection；The liquid stream battery stack includes: electrolytic cell groove body, and the electrolyte is filled in electrolytic cell groove body；Two electrodes, two institutes
Electrode is stated to be oppositely arranged；Battery diaphragm, the battery diaphragm are located in the electrolytic cell groove body, and the battery diaphragm is by the electricity
Solution pond groove body is divided into the positive polar region being connected to an electrolyte liquid storage library and is connected to another electrolyte liquid storage library
Cathode area, an electrode are set to the positive polar region, and another electrode is set to the cathode area, has packet in the positive polar region
The anode electrolyte of the positive active material is included, there is the electrolyte including the negative electrode active material in the cathode area
Liquid, the battery diaphragm can be penetrated for the supporting electrolyte, prevent the positive active material and the negative electrode active material
Matter penetrates；The electric current that the liquid stream battery stack active material generates is collected and is conducted by collector, the collector；Circulation pipe
Electrolyte in one electrolyte liquid storage library is inputted or is exported the positive polar region, the circulation pipe by road, the circulation line
Electrolyte in another electrolyte liquid storage library is inputted or is exported the cathode area by road；Circulating pump, the circulating pump are set to
The circulation line makes the electrolyte circulate supply by the circulating pump.
Two electrolyte liquid storage libraries are used according to the flow battery system based on amino anthraquinones derivative of the embodiment of the present invention
The device combined with liquid stream battery stack, liquid stream battery stack using two electrodes, electrolytic cell groove body, battery diaphragm, circulation line,
The device that circulating pump and collector combine can be suitably used for the battery context of salt cave system (utilizing generated in-situ electrolyte),
There is the battery system at low cost, active material easily to prepare, security performance is high, energy density is high, charge-discharge performance is stable, activity
The high feature of material solubility, and the redox flow battery energy storage system not only can solve the electrification of extensive (megawatt/megawatt hour)
Learn energy storage problem, additionally it is possible to make full use of some discarded salt cave (mine) resources.
Flow battery system according to an embodiment of the present invention based on amino anthraquinones derivative can also have following technology
Feature.
According to one embodiment of present invention, the chemical formula of the anthraquinone derivative are as follows:
Wherein, R1~R7The amino position of substituent group and quantity in anthraquinone are represented, amino anthraquinones can be 1- amino anthracene
Quinone, 2- amino anthraquinones, 1,2- diamino-anthraquinone, 1,4- diamino-anthraquinone, 1,5- diamino-anthraquinone, 1,8- diamino-anthraquinone, 2,
One of 6- diamino-anthraquinone.N represents the length of carbochain in dicarboxylic acids, the binary acid containing carboxyl end group can for malonic acid,
One of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid.
According to one embodiment of present invention, the chemical formula of the positive active material are as follows:
Wherein, substituent R OH, OMe, OEt, CHO, NH2、N(Me)2、N(Et)2、N(Me)3 +、F、Cl、CN、NO2、
COOH、SO3One of H or other grafting polymer class compounds.
According to one embodiment of 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 one embodiment of present invention, electrolyte liquid storage library is the pressurization of pressure 0.1MPa~0.5MPa
Container.
According to one embodiment of present invention, inert gas is passed through in electrolyte liquid storage library to be purged and maintained to press
Power.
According to one embodiment of present invention, the inert gas is nitrogen or argon gas.
According to one embodiment of present invention, the battery diaphragm be anion-exchange membrane, cation-exchange membrane either
Aperture is the polymer porous film of 10nm~300nm.
According to one embodiment of present invention, the supporting electrolyte is NaCl salting liquid, KCl salting liquid, Na2SO4Salt is molten
Liquid, K2SO4Salting liquid, MgCl2Salting liquid, MgSO4Salting liquid, CaCl2Salting liquid, NH4At least one of Cl salting liquid.
According to one embodiment of present invention, the molar concentration of the supporting electrolyte is 0.1molL-1~8.0mol
L-1。
According to one embodiment of present invention, the electrolyte further include: additive, additive are potassium hydroxide or hydrogen
Sodium oxide molybdena, additive are dissolved in system for improving the solubility property of negative electrode active material.
According to one embodiment of present invention, the electrode is carbon material electrode.
According to one embodiment of present invention, the carbon material electrode includes carbon felt, carbon paper, carbon cloth, carbon black, active carbon fibre
Dimension, active carbon particle, graphene, graphite felt, glass carbon material.
According to one embodiment of present invention, the electrode with a thickness of 2mm~8mm.
According to one embodiment of present invention, the collector is in conductive metal sheet, graphite plate or carbon plastic clad plate
One kind.
According to one embodiment of present invention, the conductive metal sheet includes at least one of copper, nickel, aluminium metal.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the flow battery system according to an embodiment of the present invention based on amino anthraquinones derivative；
Fig. 2 is that (concentration is 1- according to an embodiment of the invention [N- (5- carboxybutyl acyl group)] amino anthraquinones solution
2mM, in the potassium hydroxide aqueous solution of pH=14) scanning speed be 20mV/s when CV figure；
Fig. 3 is that (concentration is 1- according to an embodiment of the invention [N- (6- carboxy pentyl acyl group)] amino anthraquinones solution
2mM, in the potassium hydroxide aqueous solution of pH=14) scanning speed be 20mV/s when CV figure；
Fig. 4 is that (concentration is 1- according to an embodiment of the invention [N- (7- carboxyhexyl acyl group)] amino anthraquinones solution
2mM, in the potassium hydroxide aqueous solution of pH=14) scanning speed be 20mV/s when CV figure；
Fig. 5 is that (concentration is 1- according to an embodiment of the invention [N- (8- carboxyheptyl acyl group)] amino anthraquinones solution
2mM, in the potassium hydroxide aqueous solution of pH=14) scanning speed be 20mV/s when CV figure；
Fig. 6 is the nucleus magnetic hydrogen spectrum figure of 1- according to an embodiment of the invention [N- (6- carboxy pentyl acyl group)] amino anthraquinones；
Fig. 7 is the nucleus magnetic hydrogen spectrum figure of 1- according to an embodiment of the invention [N- (8- carboxyheptyl acyl group)] amino anthraquinones；
Fig. 8 is the mass spectrogram of 1- according to an embodiment of the invention [N- (6- carboxy pentyl acyl group)] amino anthraquinones；
Fig. 9 is the mass spectrogram of 1- according to an embodiment of the invention [N- (8- carboxyheptyl acyl group)] amino anthraquinones；
Figure 10 is that 2,2,6,6- tetramethyl piperidine -1- oxygen radical (TEMPO) according to an embodiment of the invention is being scanned
CV figure when speed is 20mV/s；
Figure 11 is that 2,2,6,6- tetramethylpiperidinol (OH-TEMPO) according to an embodiment of the invention is in scanning speed
CV figure when 20mV/s；
Figure 12 is 1- according to an embodiment of the invention [N- (6- carboxy pentyl acyl group)] amino anthraquinones as cathode, OH-
TEMPO is as the positive neutral aqueous phase system flow battery formed in 80mA/cm2Coulombic efficiency, voltage under charging and discharging currents
Efficiency and energy efficiency；
Figure 13 is bis- (3- (dimethylamino) propyl)-[4,4'- bipyridyl] tetrabromos of 1,1'- according to an embodiment of the invention
Salt is as cathode, and OH-TEMPO is as the positive neutral aqueous phase system flow battery formed in 80mA/cm2It is electric under charging and discharging currents
Pond recycles the 2nd, 25,50 capacity and the relationship change figure of voltage.
Appended drawing reference:
Flow battery system 100 based on amino anthraquinones derivative；
Electrolyte liquid storage library 10；
Liquid stream battery stack 20；Electrode 21；Anode electrolyte 22；Electrolyte liquid 23；Battery diaphragm 24；Circulation line 25；
Circulating pump 26；Collector 27.
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.
The liquid stream electricity according to an embodiment of the present invention based on amino anthraquinones derivative is specifically described in conjunction with attached drawing first below
Cell system 100.
Flow battery system 100 according to an embodiment of the present invention based on amino anthraquinones derivative includes two electrolyte storages
Liquid library 10 and liquid stream battery stack 20.
Specifically, two electrolyte liquid storage libraries 10 are spaced apart setting, electrolyte liquid storage library 10 is small-sized storage tank or salt mine
The salt cave with the molten chamber of physics formed after exploitation, storage tank or molten intracavitary storage electrolyte, electrolyte include positive active material,
Negative electrode active material and supporting electrolyte, positive active material 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO) class
Close object；Negative electrode active material is the anthraquinone derivative containing carboxyl, and positive active material and negative electrode active material are with bulk form
It is directly dissolved or dispersed in the system taken water as a solvent and is stored respectively in two salt caves, supporting electrolyte is dissolved in system
In, liquid stream battery stack 20 is connected to two electrolyte liquid storage libraries 10 respectively.
Wherein, liquid stream battery stack 20 includes electrolytic cell groove body, two electrodes 21, battery diaphragm 24, collector 27, circulation pipe
Road 25 and circulating pump 26.Specifically, electrolyte is filled in electrolytic cell groove body, two electrodes 21 are oppositely arranged, and battery diaphragm 24
In in electrolytic cell groove body, battery diaphragm 24 by electrolytic cell groove body be divided into the positive polar region being connected to an electrolyte liquid storage library 10 and with
The cathode area that another electrolyte liquid storage library 10 is connected to, an electrode 21 are set to positive polar region, and another electrode 21 is set to cathode area, positive polar region
It is interior that there is the anode electrolyte including positive active material, there is the electrolyte liquid including negative electrode active material in cathode area,
Battery diaphragm 24 can be penetrated for supporting electrolyte, and positive active material and negative electrode active material is prevented to penetrate, and collector 27 will
The electric current that 20 active material of liquid stream battery stack generates collects and conducts, and circulation line 25 is by the electrolysis in an electrolyte liquid storage library 10
Liquid input or output cathode area, circulation line 25 by another electrolyte liquid storage library 10 electrolyte input or output negative pole area,
Circulating pump 26 is set to circulation line 25, so that electrolyte is circulated supply by circulating pump 26.
That is, as shown in Figure 1, a kind of flow battery based on amino anthraquinones derivative according to an embodiment of the present invention
System 100 includes two electrolyte liquid storage libraries 10 and liquid stream battery stack 20, and liquid stream battery stack 20 includes two electrodes 21, electrolytic cells
Groove body, battery diaphragm 24, circulation line 25, circulating pump 26 and collector 27.
Be oppositely arranged specifically, two electrolyte liquid storage libraries 10 are spaced apart, electrolyte liquid storage library 10 be small-sized storage tank or
The salt cave with physics cavity formed after salt well accident, it is molten it is intracavitary store electrolyte, electrolyte include positive active material,
Negative electrode active material and supporting electrolyte, positive active material 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO) class
Close object；Negative electrode active material is carboxylic novel amino anthraquinone derivative, positive active material and negative electrode active material with this
Body form is directly dissolved or dispersed in the system taken water as a solvent and is stored respectively in two salt caves, supporting electrolyte
It being dissolved in system, liquid stream battery stack 20 is connected to two electrolyte liquid storage libraries 10 respectively, it is filled with electrolyte in electrolytic cell groove body,
Two electrodes 21 are oppositely arranged, and battery diaphragm 24 is located in electrolytic cell groove body, battery diaphragm 24 by electrolytic cell groove body be divided into
The positive polar region of one electrolyte liquid storage library 10 connection and the cathode area being connected to another electrolyte liquid storage library 10, an electrode 21 are set to just
Polar region, another electrode 21 are set to cathode area, have in positive polar region include positive active material anode electrolyte 22, in cathode area
With the electrolyte liquid 23 including negative electrode active material, battery diaphragm 24 can be penetrated for supporting electrolyte, and prevention is described just
Pole active material and the negative electrode active material penetrate, circulation line 25 by an electrolyte liquid storage library 10 electrolyte input or
Output cathode area, circulation line 25 by another electrolyte liquid storage library 10 electrolyte input or output negative pole area, circulating pump 26
Set on circulation line 25, electrolyte is set to circulate supply by circulating pump 26, two collectors 27 are active by liquid stream battery stack
The electric current that substance generates collects and conducts to outer lead.
In other words, the flow battery system 100 according to an embodiment of the present invention based on amino anthraquinones derivative includes two
Electrolyte liquid storage library 10 and liquid stream battery stack 20, liquid stream battery stack 20 include two electrodes 21, two collectors 27, electrolytic cell slots
Body, battery diaphragm 24, circulation line 25 and circulating pump 26, electrolyte liquid storage library 10 leave after water-soluble mode exploits salt mine
Cavern, that is, salt cave, are stored with electrolyte in salt cave, and electrolyte includes positive active material, negative electrode active material
And supporting electrolyte, positive active material 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO) class compound；Negative electrode active
Substance is that carboxylic novel amino anthraquinone derivative, positive active material and negative electrode active material are dissolved or divided with bulk form
It is dispersed in the system taken water as a solvent, supporting electrolyte is dissolved in system, and liquid stream battery stack 20 passes through circulation line 25 respectively
It is connected to two electrolyte liquid storage libraries 10, two electrodes 21 are oppositely arranged, and circulating pump 26 are equipped on circulation line 25, by following
Ring pump 26 circulates electrolyte to electrode 21, and two electrodes 21 can be divided into positive and negative electrode, and electrode 21 directly connects with electrolyte
Touching provides the electrochemical reaction place with abundant duct, and battery diaphragm 24 is located in electrolytic cell groove body, and battery diaphragm 24 can
It is penetrated for supporting electrolyte, positive active material and negative electrode active material is prevented to penetrate, battery diaphragm 24 can be handed over for cation
Change film.
As a result, according to the flow battery system 100 based on amino anthraquinones derivative of the embodiment of the present invention using two electrolysis
The device that liquid liquid storage library 10 and liquid stream battery stack 20 combine, liquid stream battery stack 20 use two electrodes 21, electrolytic cell groove body, electricity
The device that pond diaphragm 24, circulation line 25, circulating pump 26 and collector 27 combine can be suitably used for salt cave system and (utilize original position
The electrolyte of generation) battery context, which there is at low cost, active material easily to prepare, security performance is high, energy
The feature that metric density is high, charge-discharge performance is stable, active material solubility is high, and the redox flow battery energy storage system can not only solve
The electrochemical energy storage problem of certainly extensive (megawatt/megawatt hour), additionally it is possible to some discarded salt caves (mine) be made full use of to provide
Source.
Some specific embodiments according to the present invention, the chemical formula of anthraquinone derivative are as follows:
Wherein, R1~R7The amino position of substituent group and quantity in anthraquinone are represented, amino anthraquinones can be 1- amino anthracene
Quinone, 2- amino anthraquinones, 1,2- diamino-anthraquinone, 1,4- diamino-anthraquinone, 1,5- diamino-anthraquinone, 1,8- diamino-anthraquinone, 2,
One of 6- diamino-anthraquinone.N represents the length of carbochain in dicarboxylic acids, the binary acid containing carboxyl end group can for malonic acid,
One of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid.
It should be noted that it mainly includes following step that the novel anthraquinone derivatives containing carboxyl, which include following synthetic method,
It is rapid:
Step 1: the chloride of the binary acid containing carboxyl end group
Binary acid containing carboxyl end group is mixed in investment reactor with thionyl chloride, it is molten as reaction that toluene is then added
Agent, then plus proper catalyst be catalyzed, be warming up to 60 DEG C of reactions, vacuum distillation removes solvent and thionyl chloride after reaction,
It adds toluene distillation (20mL × 2), residue is for further reacting.Reaction process is as follows:
Step 2: the synthesis of the amino anthraquinones containing carboxyl
The product that the first step obtains is mixed in investment reactor with amino anthraquinones, it is molten as reaction that toluene is then added
Agent is warming up to back flow reaction, and vacuum distillation removes solvent after reaction, and then into residue, the potassium carbonate of addition 20% is molten
Liquid is filtered to remove solid, and acetic acid adjusts filtrate pH (pH is adjusted to 6), there is yellow solid precipitation, the product of precipitation is filtered, heat
Water (or alcohol) washing, dry target product.Under reaction process:
Wherein, the binary acid in the first step containing carboxyl end group be malonic acid, it is succinic acid, glutaric acid, adipic acid, pimelic acid, pungent
One of diacid；Amino anthraquinones in second step is 1- amino anthraquinones, 2- amino anthraquinones, 1,2- diamino-anthraquinone, 1,4- bis-
One of amino anthraquinones, 1,5- diamino-anthraquinone, 1,8- diamino-anthraquinone, 2,6- diamino-anthraquinone.Catalyst in the first step
For N,N-dimethylformamide, pyridine, N, one of accelerine, caprolactam.
The molar ratio of binary acid and thionyl chloride in the first step containing carboxyl end group be 1:10, the reaction time be 12~for 24 hours；The
The molar ratio of amino anthraquinones and binary acid acylate is 1:5 in two steps, the reaction time is 15~for 24 hours.
According to still another embodiment of the invention, the chemical formula of positive active material are as follows:
Wherein, substituent R OH, OMe, OEt, CHO, NH2、N(Me)2、N(Et)2、N(Me)3 +、F、Cl、CN、NO2、
COOH、SO3One of H or other grafting polymer class compounds.
Optionally, the concentration of positive active material is 0.1molL-1~3.0molL-1, the concentration of negative electrode active material
For 0.1molL-1~4.0molL-1。
According to one embodiment of present invention, the pressurization that electrolyte liquid storage library 10 is pressure 0.1MPa~0.5MPa is held
Device.
According to still another embodiment of the invention, inert gas is passed through in electrolyte liquid storage library 10 to be purged and maintained to press
Power.
Further, inert gas is nitrogen or argon gas.
Optionally, battery diaphragm 24 is anion-exchange membrane, cation-exchange membrane either aperture is 10nm~300nm's
Polymer porous film.
In one embodiment of the invention, supporting electrolyte is NaCl salting liquid, KCl salting liquid, Na2SO4Salting liquid,
K2SO4Salting liquid, MgCl2Salting liquid, MgSO4Salting liquid, CaCl2Salting liquid, NH4At least one of Cl salting liquid.
Preferably, the molar concentration of supporting electrolyte is 0.1molL-1~8.0molL-1。
According to one embodiment of present invention, electrolyte further include: additive, additive are potassium hydroxide or hydroxide
Sodium, additive are dissolved in system for improving the solubility property of negative electrode active material.
According to still another embodiment of the invention, electrode is carbon material electrode.
Further, carbon material electrode includes carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fibre, active carbon particle, graphite
Alkene, graphite felt, glass carbon material.
Preferably, electrode with a thickness of 2mm~8mm.
In implementing at of the invention one, collector 27 is one in conductive metal sheet, graphite plate or carbon plastic clad plate
Kind.
According to one embodiment of present invention, conductive metal sheet includes at least one of copper, nickel, aluminium metal.
Combined with specific embodiments below with attached drawing 1 to Figure 13 to the liquid based on amino anthraquinones derivative of the embodiment of the present invention
Galvanic electricity cell 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
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
20mV·s-1。
In battery testing, the flow velocity of electrolyte about 5.0mLmin-1, under constant current charge-discharge mode, current density is
80mA·cm-2。
Embodiment 1
The synthesis of 1- [N- (6- carboxy pentyl acyl group)] amino anthraquinones
By 2.92g adipic acid (0.02mol) and 15mL thionyl chloride mixed dissolution in 35mL toluene, 0.01g is added
DMF is as catalyst.60 DEG C of back flow reactions are warming up to, (12h-24h) stops reaction when solvent is in light yellow.Vacuum distillation removes
Thionyl chloride and toluene are removed, is added toluene distillation (20mL × 2), residue is used for following reaction.
40mL toluene, 0.89g 1- amino anthraquinones are sequentially added in above-mentioned residue, slowly increase temperature to reflux.With
Reaction progress, reaction solution is gradually become orange-yellow by red.By TLC monitor reaction process, when reaction almost
(15h-20h) stops reaction.Vacuum distillation removes solvent toluene (steaming completely as far as possible), and gained mixture is dissolved in 200mL carbon
In acid sodium solution (concentration 12%), it is filtered to remove unreacted 1- amino anthraquinones；Acetic acid is added dropwise in filtrate, has yellowish
Color precipitating generates, it is to be precipitated completely after, filter, hot water washing precipitating, to remove excessive 1,6- adipic acid, product is dry in vacuum
It is dry in dry case, yield 80%.
Embodiment 2
The synthesis of 1- [N- (8- carboxyheptyl acyl group)] amino anthraquinones
By 3.48g suberic acid (0.02mol) and 15mL thionyl chloride mixed dissolution in 35mL toluene, 0.01g pyrrole is added
Pyridine is as catalyst.60 DEG C of back flow reactions are warming up to, (12h-24h) stops reaction when solvent is in light yellow.Vacuum distillation removes
Thionyl chloride and toluene are removed, is added toluene distillation (20mL × 2), residue is used for following reaction.
40mL toluene, 0.89g 1- amino anthraquinones are sequentially added in above-mentioned residue, slowly increase temperature to reflux.With
Reaction progress, reaction solution is gradually become orange-yellow by red.By TLC monitor reaction process, when reaction almost
(15h-20h) stops reaction.Vacuum distillation removes solvent toluene (steaming completely as far as possible), and gained mixture is dissolved in 200mL carbon
In sour potassium solution (concentration 12%), it is filtered to remove unreacted 1- amino anthraquinones；Acetic acid is added dropwise in filtrate, has yellowish
Color precipitating generates, it is to be precipitated completely after, filter, ethanol wash precipitating, to remove excessive 1,8- suberic acid, product is dry in vacuum
It is dry in dry case, yield 85%.
Embodiment 3
By cyclic voltammetry (CV) study 1- [N- (5- carboxybutyl acyl group)] amino anthraquinones solution (concentration 2mM, in
In the potassium hydroxide aqueous solution of pH=14).In Fig. 2 the CV curve of the compound show its be located at the reduction peak of -0.65V and -
The oxidation peak of 0.60V.
Embodiment 4
By cyclic voltammetry (CV) study 1- [N- (6- carboxy pentyl acyl group)] amino anthraquinones solution (concentration 2mM, in
In the potassium hydroxide aqueous solution of pH=14).In Fig. 3 the CV curve of the compound show its be located at the reduction peak of -0.66V and -
The oxidation peak of 0.60V.
Embodiment 5
By cyclic voltammetry (CV) study 1- [N- (7- carboxyhexyl acyl group)] amino anthraquinones solution (concentration 2mM, in
In the potassium hydroxide aqueous solution of pH=14).In Fig. 4 the CV curve of the compound show its be located at the reduction peak of -0.67V and -
The oxidation peak of 0.60V.
Embodiment 6
By cyclic voltammetry (CV) study 1- [N- (8- carboxyheptyl acyl group)] amino anthraquinones solution (concentration 2mM, in
In the potassium hydroxide aqueous solution of pH=14).In Fig. 5 the CV curve of the compound show its be located at the reduction peak of -0.68V and -
The oxidation peak of 0.60V.
Embodiment 7
TEMPO (concentration 4mM, in the sodium chloride brine of 1.5M) is studied by cyclic voltammetry (CV).In Figure 10
The CV curve of the compound shows that it is located at the reduction peak of 0.48V and the oxidation peak of 0.54V.
Embodiment 8
OH-TEMPO (concentration 4mM, in the sodium chloride brine of 1.5M) is studied by cyclic voltammetry (CV).Figure 11
In the CV curve of the compound show that it is located at the reduction peak of 0.57V and the oxidation peak of 0.63V.
Embodiment 9
Negative electrode active material in electrolyte liquid 23 is 0.1molL-11- [N- (6- carboxy pentyl acyl group)] amino
Anthraquinone, the positive active material in anode electrolyte 22 are 0.2molL-1OH-TEMPO, anode electrolyte 22 and negative electricity
Supporting electrolyte in solution liquid 23 is all made of 2.5molL-1Sodium chloride solution, using additive KOH adjust electrolyte liquid
PH value of solution assembles the monocell of the organic flow battery system of the aqueous phase system based on salt cave of formation, monocell circulation 50 to 14
Secondary volumetric efficiency, voltage efficiency and energy efficiency are as shown in figure 12.Using cation-exchange membrane, 80mA/cm2Charge and discharge electricity
It flows down, the volumetric efficiency of monocell is 98%, and voltage efficiency and energy efficiency are between 75%~80%.
To sum up, the flow battery system 100 according to an embodiment of the present invention based on amino anthraquinones derivative have at
The advantages that this is low, security performance is high, charge-discharge performance is stable, active material solubility is high, additionally it is possible to solve extensive electrochemistry
Energy storage problem makes full use of some discarded salt cave resources.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (16)
1. a kind of flow battery system based on amino anthraquinones derivative characterized by comprising
Two electrolyte liquid storage libraries, two electrolyte liquid storage libraries are spaced apart setting, and electrolyte liquid storage library is small-sized storage
The salt cave with the molten chamber of physics formed after tank or salt well accident, the storage tank or molten intracavitary storage electrolyte, the electrolyte
Including positive active material, negative electrode active material and supporting electrolyte, the positive active material is 2,2,6,6- tetramethyl piperazines
Pyridine nitrogen oxides (TEMPO) class compound；The negative electrode active material is the anthraquinone derivative containing carboxyl, the positive-active
Substance and negative electrode active material are directly dissolved or dispersed in the system taken water as a solvent with bulk form and are stored respectively in two
In a salt cave, the 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 electrodes, two electrodes 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 cathode area for being divided into the positive polar region being connected to an electrolyte liquid storage library and being connected to another electrolyte liquid storage library, an institute
Electrode is stated set on the positive polar region, another electrode is set to the cathode area, and having in the positive polar region includes the anode
The anode electrolyte of active material has the electrolyte liquid including the negative electrode active material, the electricity in the cathode area
Pond diaphragm can be penetrated for the supporting electrolyte, and the positive active material and the negative electrode active material is prevented to penetrate；
The electric current that the liquid stream battery stack active material generates is collected and is conducted by collector, the collector；
Electrolyte in one electrolyte liquid storage library is inputted or is exported the positive polar region by circulation line, the circulation line,
Electrolyte in another electrolyte liquid storage library is inputted or is exported the cathode area 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 flow battery system according to claim 1 based on amino anthraquinones derivative, which is characterized in that the anthraquinone
The chemical formula of derivative are as follows:
Wherein, R1~R7The amino position of substituent group and quantity in anthraquinone are represented, amino anthraquinones can be 1- amino anthraquinones, 2-
Amino anthraquinones, 1,2- diamino-anthraquinone, 1,4- diamino-anthraquinone, 1,5- diamino-anthraquinone, 1,8- diamino-anthraquinone, 2,6- diamino
One of base anthraquinone.N represents the length of carbochain in dicarboxylic acids, the binary acid containing carboxyl end group can for malonic acid, succinic acid,
One of glutaric acid, adipic acid, pimelic acid, suberic acid.
3. the flow battery system according to claim 1 based on amino anthraquinones derivative, which is characterized in that the anode
The chemical formula of active material are as follows:
Wherein, substituent R OH, OMe, OEt, CHO, NH2、N(Me)2、N(Et)2、N(Me)3 +、F、Cl、CN、NO2、COOH、SO3H
Or one of other grafting polymer class compounds.
4. the flow battery system according to claim 1 based on amino anthraquinones derivative, which is characterized in that the anode
The concentration of active material is 0.1molL-1~3.0molL-1, the concentration of the negative electrode active material is 0.1molL-1~
4.0mol·L-1。
5. the flow battery system according to claim 1 based on amino anthraquinones derivative, which is characterized in that the electrolysis
Liquid liquid storage library is the pressurized sealed container of pressure 0.1MPa~0.5MPa.
6. the flow battery system according to claim 1 based on amino anthraquinones derivative, which is characterized in that the electrolysis
Inert gas, which is passed through, in liquid liquid storage library is purged and maintained pressure.
7. the flow battery system according to claim 6 based on amino anthraquinones derivative, which is characterized in that the inertia
Gas is nitrogen or argon gas.
8. the flow battery system according to claim 1 based on amino anthraquinones derivative, which is characterized in that the battery
Diaphragm is the polymer porous film that anion-exchange membrane, cation-exchange membrane either aperture are 10nm~300nm.
9. the flow battery system according to claim 1 based on amino anthraquinones derivative, which is characterized in that the support
Electrolyte is NaCl salting liquid, KCl salting liquid, Na2SO4Salting liquid, K2SO4Salting liquid, MgCl2Salting liquid, MgSO4Salting liquid,
CaCl2Salting liquid, NH4At least one of Cl salting liquid.
10. the flow battery system according to claim 1 based on amino anthraquinones derivative, which is characterized in that the branch
The molar concentration for holding electrolyte is 0.1molL-1~8.0molL-1。
11. the flow battery system according to claim 1 based on amino anthraquinones derivative, which is characterized in that described
Electrolyte further include: additive, additive are potassium hydroxide or sodium hydroxide, and additive is dissolved in system for improving cathode
The solubility property of active material.
12. the flow battery system according to claim 1 based on amino anthraquinones derivative, which is characterized in that the electricity
Extremely carbon material electrode.
13. the flow battery system according to claim 12 based on amino anthraquinones derivative, which is characterized in that the carbon
Material electrodes include carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fibre, active carbon particle, graphene, graphite felt, glass carbon materials
Material.
14. the flow battery system according to claim 12 based on amino anthraquinones derivative, which is characterized in that the electricity
Pole with a thickness of 2mm~8mm.
15. the flow battery system according to claim 1 based on amino anthraquinones derivative, which is characterized in that the collection
Fluid is one of conductive metal sheet, graphite plate or carbon plastic clad plate.
16. the flow battery system according to claim 15 based on amino anthraquinones derivative, which is characterized in that described to lead
Electric metal plate includes at least one of copper, nickel, aluminium metal.
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| CN113066992A (en) * | 2021-03-08 | 2021-07-02 | 常州大学 | Alkaline aqueous single flow battery based on double-metal MOF positive electrode and organic matter negative electrode |
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