CN109687007A - A kind of organic quinones flow battery and its construction method - Google Patents
A kind of organic quinones flow battery and its construction method Download PDFInfo
- Publication number
- CN109687007A CN109687007A CN201811418593.8A CN201811418593A CN109687007A CN 109687007 A CN109687007 A CN 109687007A CN 201811418593 A CN201811418593 A CN 201811418593A CN 109687007 A CN109687007 A CN 109687007A
- Authority
- CN
- China
- Prior art keywords
- flow battery
- quinones
- organic
- anode
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000004053 quinones Chemical class 0.000 title claims abstract description 47
- 238000010276 construction Methods 0.000 title claims description 6
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 26
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- -1 phenol compound Chemical class 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 12
- 150000004056 anthraquinones Chemical class 0.000 claims description 11
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 150000004054 benzoquinones Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229930192627 Naphthoquinone Natural products 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 150000002791 naphthoquinones Chemical class 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- 239000003115 supporting electrolyte Substances 0.000 claims description 2
- 238000003487 electrochemical reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 229910052720 vanadium Inorganic materials 0.000 description 9
- 230000005611 electricity Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910018828 PO3H2 Inorganic materials 0.000 description 3
- 229910006069 SO3H Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- MMNWSHJJPDXKCH-UHFFFAOYSA-N 9,10-dioxoanthracene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 MMNWSHJJPDXKCH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 229910001456 vanadium ion Inorganic materials 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 150000004055 1,2-benzoquinones Chemical class 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920002465 poly[5-(4-benzoylphenoxy)-2-hydroxybenzenesulfonic acid] polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention belongs to organic flow battery fields, and in particular to a kind of organic quinones flow battery.The present invention has abandoned the intrinsic viewpoint of sulfonated polyether-ether-ketone film, diaphragm of the sulfonated polyether-ether-ketone for selecting proton conductivity high as organic quinones flow battery, volume using organic quinones molecule is big, and the features such as cationic without other in addition to proton in acid quinones electrolyte, using the conductivity of sulfonated polyether-ether-ketone the features such as big and stable structure, sulfonated polyether-ether-ketone film is applied in organic quinones flow battery, effectively raise the voltage efficiency of battery, also the electrochemical energy storage organic active molecular migration in cyclic process is effectively prevented, perfluorosulfonic acid ion film can be substituted completely, significantly reduce the cost of amberplex, reduce the cost of organic quinones flow battery, it is widely used it.
Description
Technical field
The invention belongs to organic flow battery fields, and in particular to a kind of organic quinones flow battery and its construction method.
Background technique
Traditional energy form is mainly fossil fuel, but the reserves of fossil fuel are limited, the combustion of a large amount of fossil fuels
Burning will cause irreversible serious atmospheric pollution, and this facilitate traditional energies to change to new energy.
Currently in order to which to green and the transformation of reproducible new energy, China has been set up many wind energies and solar power generation
It stands, but the power generation of the energy of wind energy and solar energy all has intermittent and unstability, needs intelligent large-scale energy storage system
To realize that stablizing for electric energy exports.Rechargeable battery since it has many advantages, such as response fast, energy-efficient and extensive property,
There is huge application potential in extensive energy storage.Wherein, using the metal vanadium ion of different valence state as electrochemically active molecules
All-vanadium flow battery be proved to the practicality in extensive energy-accumulating power station.But it is a large amount of in all-vanadium flow battery
The vanadium used is reserves metal (crustal abundance 136ppm) not abundant on a kind of earth, and market price fluctuations are big, this
The price of all-vanadium flow battery is set largely to be limited to the price of vanadium.In order to overcome the vanadium resource in flow battery restricted
Problem has risen in recent years and has used organic compound as organic flow battery of electrochemically active molecules to substitute all-vanadium flow electricity
Pond, organic flow battery, which has, meets cost, durability needed for power grid scale electric energy stores, ecological friendly and sustainability etc.
Advantage, undoubtedly very with the flow battery of actual application prospect in energy-storage system.
Organic flow battery restores electricity to respectively as positive and negative half-cell electrolytes using organic oxidation, positive and negative pole material by
Amberplex separates, and when charge and discharge, inside battery is mainly connected by the hydrionic directional migration in electrolyte, organic
Quinones flow battery is as shown in Figure 1.Do not needed in the cell reaction of organic quinones flow battery any heavy metal catalyst or
Person's metal electrode material, this low cost, green flow battery have good development prospect in energy storage utilization.
In order to further decrease organic quinones flow battery cost, the critical material-ion that can also change in battery is handed over
Change film.It plays a part of that positive and negative anodes electrolyte is isolated, prevents have electroactive organic molecule infiltration, while can allow matter again
Son passes through so that current lead-through in battery.Diaphragm used in current organic flow battery is mainly that perfluorosulfonic acid ion is handed over
Film is changed, although its stability is good, proton conductivity is high, its is with high costs, remains high flow battery system cost, makes
About being widely used for battery.Therefore not fluorine-containing, inexpensive amberplex is prepared to substitute perfluorosulfonic acid ion exchange
Film is particularly important for organic quinones flow battery.Sulfonated polyether-ether-ketone amberplex be exactly a kind of not fluorine-containing macromolecule from
Proton exchange, still, low nearly half ([1] Kreuer K D.On the of Conductivity Ratio perfluorinated sulfonic acid ion exchange membrane
development of proton conducting polymer membranes for hydrogen and methanol
fuel cells[J].Journal of Membrane Science,2001,185(1):29-39.[2]Jung H Y,Jeong
S,Kwon Y.The effects of different thick sulfonated poly(ether ether ketone)
membranes on performance of vanadium redox flow battery[J].Journal of The
Electrochemical Society, 2016,163 (1): A5090-A5096.), in the flow battery of high current density operation
In would generally reduce the energy efficiency of battery, from without being applied in flow battery.
Summary of the invention
For above-mentioned there are problem or deficiency, to solve, organic quinones flow battery amberplex is with high costs to be asked
Topic, the present invention provides a kind of organic quinones flow battery and its construction methods, using sulfonated polyether-ether-ketone diaphragm.
A kind of organic quinones flow battery, using phenol compound or its oxidation product as positive electrode, Anthraquinones
Compound or its reduzate are as negative electrode material；Using sulfuric acid as supporting electrolyte, using sulfonated polyether-ether-ketone film as ion
Exchange membrane, using two panels copper sheet as anode and cathode current collecting board element, two panels deflector is cathode and anode flow field, two
Piece teflon gasket is cathode and anode gasket, and two panels carbon felt is respectively as cathode and anode.
The working principle of organic quinones flow battery are as follows: it is anti-that reversible electrochemistry occurs in acid condition for naphthoquinone derivatives
It answers.When charging, anode reaction is that phenol compound loses electronics and proton, generates benzoquinones oxidation state product；Negative reaction
Electronics and proton are obtained for quinones, generates reduction-state product.When electric discharge, anode reaction is that benzoquinones oxidation state product obtains
To electronics and proton, phenol compound is generated, negative reaction is that reduction-state product loses electronics and proton, generates Anthraquinones
Close object.
The construction method of above-mentioned organic quinones flow battery, specific as follows:
Step 1 weighs benzoquinone compound and anthraquinone analog compound powder respectively, and dissolution in deionized water, is made into dense
Degree is the quinones solution of 0.5-3.0mol/L, and the quinones chemical combination of corresponding concentration is exchanged for by hydrogen ion exchange resin column
Object acid solution.Sulfuric acid is added again, the mixing for being configured to 0.5-3.0mol/L benzoquinone compound and 2.0mol/L sulfuric acid is molten
The mixed solution of liquid and 1-3mol/L anthraquinone analog compound and 2.0mol/L sulfuric acid.
Step 2, using two panels copper sheet as anode and cathode current collecting board element, two panels deflector is that cathode and anode are led
Flowing plate, two panels teflon gasket are cathode and anode gasket, and two panels carbon felt is respectively as cathode and anode, with sulfonated polyether
Ether ketone film is as amberplex.
Quinone compounds acid solution and anthraquinone analog compound acid solution that step 1 is prepared are respectively charged into electrolyte by step 3
In storage tank, lead to upper nitrogen, inlet tube and outlet tube and circulating pump in connection allow acid solution to circulate, to be made organic
Quinones flow battery.
Sulfonated polyether-ether-ketone film is since its proton conductivity is high and stability is widely noticed in vanadium flow battery fortunately, still
Since its water absorption rate height causes material dilatancy big, aperture size increases, to increase the cross contamination of vanadium ion.Sulfonated polyether
Ether ketone amberplex is due to the low nearly half of Conductivity Ratio perfluorinated sulfonic acid ion exchange membrane, in the liquid stream electricity of high current density operation
The energy efficiency that battery would generally be reduced in pond, from without being applied in flow battery.
The present invention has abandoned the intrinsic viewpoint of sulfonated polyether-ether-ketone film, based on not having in addition to proton in organic electrolyte
Other cations, the volume using organic quinones molecule is big, and in addition to proton is without other cations in acid quinones electrolyte
The features such as, the features such as and stable structure big using the conductivity of sulfonated polyether-ether-ketone, sulfonated polyether-ether-ketone film is applied to organic
In quinones flow battery, the voltage efficiency of battery is effectively raised, also effectively prevents the electrochemical energy storage in cyclic process
Organic active molecular migration can substitute perfluorosulfonic acid ion film completely, significantly reduce the cost of amberplex,
The cost for reducing organic quinones flow battery, is widely used it.
Detailed description of the invention
Fig. 1 is organic quinones flow battery structural schematic diagram；
Fig. 2 is embodiment sulfonated polyether-ether-ketone film in the test data with organic quinones flow battery；
Appended drawing reference: 1- anode electricity loads electrolyte storage tank, 2- negative electricity to electrolyte storage tank, 3-, and 4- is porous
Carbon electrode, 5- amberplex, 6- circulating pump.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
The preparation of concentrated acid sulfonation polyether-ether-ketone, specific as follows:
The 25mL concentrated sulfuric acid is added in the three-necked flask of 250mL step 1, beyond the Great Wall with glass stopper by one of mouth, carries out
Stirring.
Step 2 weighs in the three-necked flask of the dry polyether-ether-ketone PEEK powder addition step 1 of 2g, reacts at 60 DEG C
After 3h, stop stirring；Then gained sulfonated products are added in ice water and are stirred, it is heavy that moment red liquid becomes white
It forms sediment, after stirring, changes water washing and be again stirring for.
Step 3, after step 2 products therefrom be washed with deionized being neutral to pH, at 100 DEG C it is dry for 24 hours, obtain
Sulfonation SPEEK.
Above-mentioned prepared sulfonated polyether-ether-ketone is taken, is dissolved in N, N- dimethyl in the ratio of 1:6 (quality/g: volume/mL)
Formamide, at room temperature stirring and dissolving 20h obtain solution, and solution filters the tape casting coating film forming, prior to 60 DEG C at dry 10h,
Dry 10h, is down to room temperature then to get organic quinones flow battery sulfonated polyether-ether-ketone amberplex, film at 110 DEG C
With a thickness of 60 μm.Prepared sulfonated polyether-ether-ketone film is used for organic quinones flow battery of structure as shown in Figure 1.
The anode electrolyte electrochemically active molecules of organic quinones flow battery be formula C or formula D phenol compound or
Its oxidation product, the anode electrolyte electrochemically active molecules of organic quinones flow battery be formula E anthraquinone analog compound or its
Reduzate, and assisted electrolysis matter compound is dissolved in the electrolytic solution；
In formula,
R1、R2、R3、R4It is each independently selected from the following group: hydrogen (- H), sulfonic group (- SO3H), nitro (- NO2) or phosphate (-
PO3H2)；R5、R6、R7、R8It is each independently selected from the following group: hydrogen (- H), sulfonic group (- SO3H), nitro (- NO2) or phosphate (-
PO3H2)；R9、R10、R11、R12、R13、R14、R15、R16It is each independently selected from the following group: hydrogen (- H), sulfonic group (- SO3H), nitro (-
NO2) or phosphate (- PO3H2)。
The preparation method of organic positive electrolyte of quinones flow battery is specific as follows:
1,2- benzoquinones -3,5- disulfonic acid (BQDS) 3.32g shown in F is taken to heat at 45 DEG C in 30mL deionized water
Being evaporated up to solution is 20mL, and 2mL sulfuric acid is added under stiring, and positive fluid reservoir is added in solution.
The preparation of organic quinones flow battery electrolyte liquid: 9,10- anthraquinone-2-sulfonic acid (AQS) 3.28g shown in G is taken
In 30mL deionized water, 2mL sulfuric acid is added until solution is 20mL in the heating evaporation at 60 DEG C under stiring, by solution plus
Enter cathode fluid reservoir.
Shown in Fig. 2 is sulfonated polyether-ether-ketone film in the test data with organic quinones flow battery, sulfonated polyether ether
Ketone film keeps stablizing under different current densities and recycle, and performance does not decline with the extension of time, shows sulfonated polyether
The chemical stability of ether ketone film is fine.
To sum up, the perfluor sulphur in existing organic quinones flow battery is substituted using sulfonated polyether-ether-ketone film in the present invention
Acid ion exchange membrane greatly reduces cost while guaranteeing its performance parameter.
Claims (3)
1. a kind of organic quinones flow battery, it is characterised in that:
Using phenol compound perhaps its oxidation product as positive electrode anthraquinone analog compound or its reduzate as negative
Pole material；Using sulfuric acid as supporting electrolyte, using sulfonated polyether-ether-ketone film as amberplex；Using two panels copper sheet as sun
Pole and cathode current collector plate, two panels deflector are cathode and anode flow field, and two panels teflon gasket is cathode and sun
Polar cushion piece, two panels carbon felt is respectively as cathode and anode；
Reversible electrochemical reaction occurs in acid condition for naphthoquinone derivatives, and when charging, anode reaction is phenol compound
Electronics and proton are lost, benzoquinones oxidation state product is generated；Negative reaction is that quinones obtains electronics and proton, is generated also
Ortho states product；When electric discharge, anode reaction is that benzoquinones oxidation state product obtains electronics and proton, generates phenol compound, bears
Pole reaction is that reduction-state product loses electronics and proton, generates anthraquinone analog compound.
2. organic quinones flow battery as described in claim 1, it is characterised in that:
The anode electrolyte electrochemically active molecules of organic quinones flow battery be formula C or formula D phenol compound or
Its oxidation product, the anode electrolyte electrochemically active molecules of organic quinones flow battery be formula E anthraquinone analog compound or its
Reduzate, and assisted electrolysis matter compound is dissolved in the electrolytic solution；
R1、R2、R3、R4It is each independently selected from the following group: hydrogen, sulfonic group, nitro or phosphate；
R5、R6、R7、R8It is each independently selected from the following group: hydrogen, sulfonic group, nitro or phosphate；
R9、R10、R11、R12、R13、R14、R15、R16It is each independently selected from the following group: hydrogen, sulfonic group, nitro or phosphate.
3. the construction method of organic quinones flow battery as described in claim 1, specific as follows:
Step 1 weighs benzoquinone compound and anthraquinone analog compound powder respectively, and in deionized water, being made into concentration is for dissolution
The quinones solution of 0.5-3.0mol/L is exchanged for the quinones acid of corresponding concentration by hydrogen ion exchange resin column
Property solution；Sulfuric acid is added again, is configured to the mixed solution of 0.5-3.0mol/L benzoquinone compound and 2.0mol/L sulfuric acid, with
And the mixed solution of 1-3mol/L anthraquinone analog compound and 2.0mol/L sulfuric acid；
Step 2, using two panels copper sheet as anode and cathode current collecting board element, two panels deflector is cathode and anode water conservancy diversion
Plate, two panels teflon gasket are cathode and anode gasket, and two panels carbon felt is respectively as cathode and anode, with sulfonated polyether ether
Ketone film is as amberplex；
Quinone compounds acid solution and anthraquinone analog compound acid solution that step 1 is prepared are respectively charged into electrolyte storage tank by step 3
In, lead to upper nitrogen, inlet tube and outlet tube and circulating pump in connection allow acid solution to circulate, so that organic quinones be made
Flow battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811418593.8A CN109687007A (en) | 2018-11-26 | 2018-11-26 | A kind of organic quinones flow battery and its construction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811418593.8A CN109687007A (en) | 2018-11-26 | 2018-11-26 | A kind of organic quinones flow battery and its construction method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109687007A true CN109687007A (en) | 2019-04-26 |
Family
ID=66184954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811418593.8A Pending CN109687007A (en) | 2018-11-26 | 2018-11-26 | A kind of organic quinones flow battery and its construction method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109687007A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022042735A1 (en) * | 2020-08-28 | 2022-03-03 | 西湖大学 | Phenazine derivative-based electrolyte and application thereof in flow battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102804470A (en) * | 2009-06-09 | 2012-11-28 | 夏普株式会社 | Redox flow battery |
| CN103762375A (en) * | 2014-01-10 | 2014-04-30 | 清华大学深圳研究生院 | Polyfluortetraethylene sandwich layer protective ion exchange membrane, preparation method of membrane and liquid flow battery |
| CN106063017A (en) * | 2013-09-26 | 2016-10-26 | 哈佛大学校长及研究员协会 | Quinone and hydroquinone based flow battery |
| KR20170126727A (en) * | 2016-05-10 | 2017-11-20 | 한국타이어 주식회사 | Fuel Cell Bipolar Plate and Manufacturing Method thereof |
| CN107482243A (en) * | 2017-08-11 | 2017-12-15 | 北京理工大学 | A flow electrode of quinone-based flow battery and its low-cost preparation method |
| US20180097249A1 (en) * | 2016-09-30 | 2018-04-05 | University Of Southern California | Materials for high-performance aqueous organic redox flow batteries |
-
2018
- 2018-11-26 CN CN201811418593.8A patent/CN109687007A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102804470A (en) * | 2009-06-09 | 2012-11-28 | 夏普株式会社 | Redox flow battery |
| CN106063017A (en) * | 2013-09-26 | 2016-10-26 | 哈佛大学校长及研究员协会 | Quinone and hydroquinone based flow battery |
| CN103762375A (en) * | 2014-01-10 | 2014-04-30 | 清华大学深圳研究生院 | Polyfluortetraethylene sandwich layer protective ion exchange membrane, preparation method of membrane and liquid flow battery |
| KR20170126727A (en) * | 2016-05-10 | 2017-11-20 | 한국타이어 주식회사 | Fuel Cell Bipolar Plate and Manufacturing Method thereof |
| US20180097249A1 (en) * | 2016-09-30 | 2018-04-05 | University Of Southern California | Materials for high-performance aqueous organic redox flow batteries |
| CN107482243A (en) * | 2017-08-11 | 2017-12-15 | 北京理工大学 | A flow electrode of quinone-based flow battery and its low-cost preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 尹碧波 等: "全钒液流电池用非氟离子膜的制备与改性", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022042735A1 (en) * | 2020-08-28 | 2022-03-03 | 西湖大学 | Phenazine derivative-based electrolyte and application thereof in flow battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | SiO2-decorated graphite felt electrode by silicic acid etching for iron-chromium redox flow battery | |
| CN111244518B (en) | Water system neutral organic flow battery | |
| CN108193225B (en) | A CO2 Electroreduction Electrolytic Cell with Membrane Electrode Configuration | |
| CN113764714B (en) | Electrolyte of water-based flow battery, all-iron water-based flow battery and application | |
| CN112467179B (en) | An alkaline all-iron flow battery | |
| CN101593841B (en) | Redox flow battery and redox flow battery pack | |
| CN104282923B (en) | Sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane and preparation method thereof | |
| US11605824B2 (en) | Zinc iodine flow battery | |
| WO2011050507A1 (en) | Redox flow battery and method for continually operating the redox flow battery for a long time | |
| CN107482242B (en) | Aqueous single-flow battery based on metal-organic complex liquid flow positive electrode and preparation method thereof | |
| CN103219532A (en) | Sulfonated polyether ether ketone-based blend ion exchange membrane for flow battery, and preparation method thereof | |
| CN112490477B (en) | Aqueous all-organic mixed liquid flow battery based on conjugated microporous polymer negative electrode containing redox active side group unit | |
| CN106549179A (en) | A kind of organic system lithium quinone flow battery | |
| CN119315067A (en) | A covalent organic skeleton cross-linked sulfonated polybenzimidazole proton exchange membrane and its preparation method and application | |
| CN118336061A (en) | Aqueous organic flow battery based on nitrosonaphthol metal complex | |
| CN115275292A (en) | Water-based organic flow battery based on vanadium-based organic cluster molecular aqueous solution | |
| CN105322207B (en) | A kind of phosphorous heteropoly acid positive electrolyte for all-vanadiumredox flow battery and its application | |
| CN109687007A (en) | A kind of organic quinones flow battery and its construction method | |
| CN103601888A (en) | Sulfonated poly (arylene ether sulfone), blend film for all-vanadium flow battery and preparation methods thereof | |
| KR102829049B1 (en) | Process of improving perfomance of vanadium redox flow battery | |
| CN100472873C (en) | Sol-gel mobile phase and preparation method of direct methanol fuel cell | |
| CN107546399A (en) | The amberplex and its preparation and application that main chain separates with ion-exchange group | |
| CN113764713A (en) | A ternary deep eutectic solvent-based flow battery | |
| CN112993355A (en) | Organic flow battery | |
| CN118501018B (en) | Ion permeation testing method for flow battery membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190426 |
|
| RJ01 | Rejection of invention patent application after publication |