CN110444787A - Flow battery system based on amino anthraquinones derivative - Google Patents

Flow battery system based on amino anthraquinones derivative Download PDF

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Publication number
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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China
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electrolyte
active material
derivative
amino anthraquinones
flow battery
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Inventor
陈留平
徐俊辉
韩俊甜
武奕
苏志俊
崔耀星
李丹
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China Salt Jintan Co Ltd
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China Salt Jintan Co Ltd
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Priority to CN201910777098.4A priority Critical patent/CN110444787A/en
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

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

Flow battery system based on amino anthraquinones derivative
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.
CN201910777098.4A 2019-08-22 2019-08-22 Flow battery system based on amino anthraquinones derivative Pending CN110444787A (en)

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Application publication date: 20191112