CN117712439A - Oxidative reduction organic flow battery for energy storage and application thereof - Google Patents
Oxidative reduction organic flow battery for energy storage and application thereof Download PDFInfo
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- CN117712439A CN117712439A CN202311779956.1A CN202311779956A CN117712439A CN 117712439 A CN117712439 A CN 117712439A CN 202311779956 A CN202311779956 A CN 202311779956A CN 117712439 A CN117712439 A CN 117712439A
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- 238000004146 energy storage Methods 0.000 title claims abstract description 23
- 230000009467 reduction Effects 0.000 title description 7
- 230000001590 oxidative effect Effects 0.000 title description 3
- 239000003792 electrolyte Substances 0.000 claims abstract description 33
- 238000003860 storage Methods 0.000 claims abstract description 18
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 10
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- -1 [4,4 '-bipyridine ] -2,2' -dicarboxylic acid dimethyl ester Chemical compound 0.000 claims description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 18
- 229910000071 diazene Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- WSTOEGIEWBZMLU-UHFFFAOYSA-N 2-methyl-4-(2-methylpyridin-4-yl)pyridine Chemical compound C1=NC(C)=CC(C=2C=C(C)N=CC=2)=C1 WSTOEGIEWBZMLU-UHFFFAOYSA-N 0.000 claims description 12
- XHVUFVVPMVIQEY-UHFFFAOYSA-N 4-(2-carboxypyridin-4-yl)pyridine-2-carboxylic acid Chemical compound C1=NC(C(=O)O)=CC(C=2C=C(N=CC=2)C(O)=O)=C1 XHVUFVVPMVIQEY-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 9
- 239000011149 active material Substances 0.000 claims description 8
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- JFBMFWHEXBLFCR-UHFFFAOYSA-N 4-bromo-2-methylpyridine Chemical compound CC1=CC(Br)=CC=N1 JFBMFWHEXBLFCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- 125000003106 haloaryl group Chemical group 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000012432 intermediate storage Methods 0.000 claims description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001449 anionic compounds Chemical class 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002891 organic anions Chemical class 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000000575 pesticide Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 2
- 230000002528 anti-freeze Effects 0.000 claims 1
- 239000012267 brine Substances 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- 238000006479 redox reaction Methods 0.000 abstract description 10
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229940021013 electrolyte solution Drugs 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000010802 Oxidation-Reduction Activity Effects 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 2
- PTKWYSNDTXDBIZ-UHFFFAOYSA-N 9,10-dioxoanthracene-1,2-disulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C3C(=O)C2=C1 PTKWYSNDTXDBIZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007979 citrate buffer Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical class [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- 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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- Fuel Cell (AREA)
Abstract
The invention provides an oxidation-reduction organic flow battery for energy storage and application thereof; the redox organic flow battery for energy storage comprises two electrolyte storage tanks of positive electrode and negative electrode electrolyte, wherein the two electrolyte storage tanks are respectively connected with an inert electrode and are separated by a diaphragm with ion exchange capability; the redox organic flow battery is characterized in that the negative electrode electrolyte of the redox organic flow battery comprises 0.01-99.99% of a component in formula 1; the redox organic flow battery for energy storage not only has excellent performance in the cycle of single electron transfer redox reaction as battery charge and discharge, but also has excellent performance in the redox reaction of double electron transfer.
Description
Technical Field
The invention belongs to the field of flow batteries, and particularly relates to an oxidative reduction organic flow battery for storing electric energy and application thereof.
Background
The high-speed development of society is not separated from the support of traditional fossil energy, and the problems of non-renewable and pollution and the like cause the high demand of sustainable renewable energy, so that the rapid development of green energy technology is promoted. The instability and discontinuity of wind and tidal energy have limited their field of application. Therefore, scientists focus on developing energy storage technologies, and realize stable, safe and controllable output of energy sources by converting green energy sources into physical energy and chemical energy. Batteries are particularly suitable for energy storage device applications, such as redox flow batteries for storing electrical energy, as an emergency back-up power supply, peak load regulated stationary storage, for intermediate storage of discontinuous, unstable electrical energy from renewable energy sources, especially in the photovoltaic and wind industries or biomass, tidal or marine power plants.
Redox flow batteries are electrochemical energy reservoirs. The compounds required for establishing an electrical potential at the electrodes are dissolved redox active species which are converted into their respective other redox state in the electrochemical reactor during charging or spotting. Redox couples of organic and partially organic components are more attractive than redox couples of low molecular inorganic compounds (redox active compounds) previously used in redox flow batteries, such as anthraquinone-disulfonic acid/bromine systems have been disclosed which allow for very high current densities, however, high demands are placed on the safety of the materials and systems of the whole battery components due to the use of elemental bromine (B.Huskinson, M.P.Marshak, C.Suh, S.ErM.R.Gerhardt, C.J.Galvin, X.Chen, A.Aspuru-Guzik, R.G.Gordon, M.J.Aziz: "A metalfree organic-inorganic aqueous flow battery", nature 505,2014,195-198). While other electrolyte systems such as LiPF6 and TEMPO (x.wie, w.xu, M.VijayakumarL.Cosimbescu, T.Liu, v.sprenkle, w.wang: "TEMPO-based Catholyte for high-energydensitiy redox flow batteries" adv. Mater.2014vol.26,45, p 7649-7653) are likewise premised on organic solvents and conductive salts, which in the event of a failure release toxic gases such as hydrogen fluoride, thus imposing high demands on the safety of the system. And the organic redox couple used in the early stage mainly uses single electron transfer redox reaction as the main reaction of the battery in the organic flow battery, and the multi-electron transfer redox reaction propelled energy storage battery has higher energy storage efficiency.
The invention aims to provide a novel redox organic flow battery and application thereof, which can safely and efficiently run with low cost, and has the advantages that the active substances of positive and negative electrolyte are organic substances, the structure is adjustable, the size is generally larger than that of metal ions, so the requirement on a diaphragm is low; the supporting electrolyte of the organic flow battery can be neutral solution such as dilute acid, dilute alkali or water, so that the corrosion resistance requirement of part of components of the battery can be reduced, and meanwhile, the cost is reduced and the service life is prolonged; meanwhile, the double-electron transfer oxidation-reduction reaction can be used as the main reaction of the energy storage battery, so that the energy storage efficiency of the battery is greatly improved.
Disclosure of Invention
In order to solve the problems, the invention discloses an oxidation-reduction organic flow battery for storing electric energy and application thereof, wherein the oxidation-reduction organic flow battery for storing energy not only has excellent performance in the cycle of single electron transfer oxidation-reduction reaction as battery charge and discharge, but also has excellent performance in the oxidation-reduction reaction of double electron transfer.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides an oxidation-reduction organic flow battery for energy storage, which comprises a positive electrolyte storage tank and a negative electrolyte storage tank, wherein an organic compound with oxidation-reduction activity or a compound with oxidation-reduction activity exists in an electrolyte solvent in the two electrolyte storage tanks in a dissolved form or a dispersed form respectively, the positive electrolyte storage tank and the negative electrolyte storage tank are respectively connected with an inert electrode, the two electrolyte storage tanks are separated by a diaphragm with ion exchange capability, and the negative electrolyte contains 0.01-99.99% of an active substance with oxidation-reduction formula 1 or the active substance with oxidation-reduction of the active substance, and the structure of the formula 1 is as follows:
；
wherein,
r1 and R2 independently of one another represent alkyl, alkoxy, haloalkyl, aryl, haloaryl, aralkyl or heterocyclyl; preferably, R1 and R2 are independently methyl;
a and b are each independently an integer from 0 to 4, and a and b may not be 0 at the same time;
m is an inorganic or organic anion in the n-valent state and mixtures of such anions;
n is an integer from 1 to 10.
Further, the negative electrode electrolyte further includes formula 2 or a redox active material thereof;
wherein,
r1 and R2 independently of one another represent alkyl, alkoxy, haloalkyl, aryl, haloaryl, aralkyl or heterocyclyl;
m is an inorganic or organic anion in the n-valent state and mixtures of such anions;
n is an integer from 1 to 10;
R 3 represented by a hydrogen atom, an alkyl group, an alkoxy group, a haloalkyl group, an aryl group, an aralkyl group, a haloaryl group, a halogen, an amino group, a nitro group, or a cyano group.
Further, the positive electrode electrolyte comprises a redox active material of metal ferrocyanide and ammonium salt; preferably, the positive electrode electrolyte uses a metal or ammonium ferrocyanide salt as the redox active material.
Further, the electrolyte also comprises a neutral solvent and an additive; the neutral solvent comprises an organic solvent, a weak acid solvent, a weak base solvent, water or an aqueous solution of inorganic salt, and the additive comprises a surfactant, a viscosity modifier, a pesticide, a buffer, a stabilizer, a catalyst, a phase transfer additive catalyst, an antifreezing agent, a heat stabilizer and a defoaming agent.
Further, the neutral solvent may be a dilute sulfuric acid solution, a dilute sodium hydroxide solution, an alcohol (e.g., ethanol), a nitrile (e.g., acetonitrile), or an aqueous sodium chloride solution, etc., and preferably, the neutral solvent is an aqueous sodium chloride solution.
Further, the additive comprises a surfactant, and the surfactant can be alkyl polyglucoside, alkyl glucoside, saponin or phospholipid.
Further, the additives include buffers, which may be phosphate buffers, acetate buffers, citrate buffers, or the like.
The redox organic flow battery comprises a diaphragm with ion exchange capacity, including an anion exchange membrane, a cation exchange membrane and a porous membrane. For better stability, an attachment support such as a frame, a screen, or the like may be added.
The redox organic flow battery of the present invention comprises additional components in addition to the electroactive components, electrolyte and separator described above. The method comprises the following steps:
delivery mechanisms, such as pumps, and tanks and pipes for transporting and storing the electrolyte and the redox active components therein;
an electrode, which preferably consists of or comprises: carbon rod, carbon nanotube, activated carbon, carbon black or graphene;
an optional current collector, for example, is made of graphite or of metal.
Further, the structure of formula 1 is as follows:
。
further, the preparation method comprises the following steps:
(1) Adding a catalyst Pd-C and hydrazine hydrate into the 4-bromo-2-methylpyridine, and reacting in a nitrogen atmosphere to obtain 2,2 '-dimethyl-4, 4' -bipyridine; the mass ratio of the 4-bromo-2-methylpyridine to the catalyst Pd-C to the hydrazine hydrate is 1:0.001-0.02:0.8-1.5;
；
(2) Adding bromobenzene and tin dioxide into 2,2 '-dimethyl-4, 4' -bipyridine, and reacting to obtain [4,4 '-bipyridine ] -2,2' -dicarboxylic acid; the mass ratio of the 2,2 '-dimethyl-4, 4' -bipyridine, bromobenzene and tin dioxide is 1:6-10:2-4;
；
(3) Adding methanol and concentrated sulfuric acid into the [4,4 '-bipyridine ] -2,2' -dicarboxylic acid obtained in the step (2), and carrying out reflux reaction to obtain [4,4 '-bipyridine ] -2,2' -dicarboxylic acid dimethyl ester; the mass ratio of the [4,4 '-bipyridine ] -2,2' -dicarboxylic acid, methanol and concentrated sulfuric acid is 1:0.25-0.5:3-5;
；
(4) Acetonitrile and methyl iodide are added into the [4,4 '-bipyridine ] -2,2' -dicarboxylic acid dimethyl ester obtained in the step 3, and 2,2 '-bis (methoxycarbonyl) -1,1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine is obtained by reaction; the mass ratio of the [4,4 '-bipyridine ] -2,2' -dicarboxylic acid dimethyl ester, acetonitrile and methyl iodide is 1:1.5-2.5:1-2;
；
(5) Adding dilute sulfuric acid solution into the 2,2 '-bis (methoxycarbonyl) -1,1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine obtained in the step 4, and reacting to obtain 2,2 '-dicarboxyl-1, 1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine; the mass ratio of the 2,2 '-bis (methoxycarbonyl) -1,1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine to the dilute sulfuric acid solution is 1:4-5.5;
。
the invention also provides an application of the redox organic flow battery for energy storage, which comprises the following steps: as an emergency back-up power supply, peak load regulated stationary storage for intermediate storage of discontinuous, unstable electrical energy, including intermediate storage of electrical energy for photovoltaic, wind, biomass, tidal or marine power plants, and for the field of electrical movement, including storage in land, air and water vehicles.
The beneficial effects of the invention are as follows:
the redox organic flow battery for energy storage not only has excellent performance in the cycle of single electron transfer redox reaction as battery charge and discharge, but also has excellent performance in the redox reaction of double electron transfer; when the double-electron transfer redox reaction is used as the main reaction of the energy storage battery, the energy storage efficiency of the battery is greatly improved.
Drawings
FIG. 1 is a cyclic voltammogram of the active material synthesized in example 1, using a carbon rod as the working electrode, a platinum wire as the counter electrode and a silver/silver chloride electrode as the reference; as the electrolyte, an aqueous sodium chloride solution (0.5 mol/L) was used;
fig. 2 is a charge curve of the redox organic flow battery composed in example 3 in charge-discharge cycles.
Detailed Description
The present invention is further illustrated in the following drawings and detailed description, which are to be understood as being merely illustrative of the invention and not limiting the scope of the invention.
Example 1
Electrolyte active material: synthesis of 2,2 '-dicarboxy-1, 1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine (6)
；
Synthesis procedure
Step 1: synthesis of 2,2 '-dimethyl-4, 4' -bipyridine (2)
51.6g of 4-bromo-2-methylpyridine (1) was dissolved in 150mL of DMF, 0.5g of Pd-C catalyst was added, 50g of hydrazine hydrate (80%) was added, the reaction was carried out under nitrogen atmosphere for 12 hours, the reaction was stopped, the solvent and water were removed by a rotary evaporator, and 23.5g of 2,2 '-dimethyl-4, 4' -bipyridine (2) was obtained in 85% yield by column chromatography.
Step 2: synthesis of [4,4 '-bipyridine ] -2,2' -dicarboxylic acid (3)
In a 200mL flask, 18.4g of 2,2 '-dimethyl-4, 4' -bipyridine (2) obtained in step 1, 150g of bromobenzene and 60.0g of tin dioxide were charged, and the reaction was performed at 90℃for 16 hours. After the reaction is completed, the solvent is removed by using a rotary evaporator, the residual solid is dissolved by using 10% KOH solution, insoluble matters are filtered off, the residual liquid is acidified by adding 10% HCl solution, the pH is ensured to be less than 6, ethyl acetate is used for extraction for a plurality of times, an organic phase is collected, the solvent is removed, and the product [4,4 '-bipyridine ] -2,2' -dicarboxylic acid (3) is obtained by 20.4g, and the yield is 83.2%.
Step 3: synthesis of [4,4 '-bipyridine ] -2,2' -dicarboxylic acid dimethyl ester (4)
A150 mL flask was charged with 20.4g of [4,4 '-bipyridine ] -2,2' -dicarboxylic acid (3) obtained in step 2, 5.5g of methanol and 73.6g of concentrated sulfuric acid, and the mixture was refluxed at 115℃for 6 hours. After the reaction was completed, the diluted acid solution was neutralized with 10% potassium carbonate solution, and the diluted acid solution was extracted with ethyl acetate several times, and the organic phase was distilled off to remove the solvent, whereby 21.5g of dimethyl [4,4 '-bipyridine ] -2,2' -dicarboxylate (4) was obtained in a yield of 95%.
Step 4: synthesis of 2,2 '-bis (methoxycarbonyl) -1,1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine (5)
Into a 150mL flask were charged 21.5g of [4,4 '-bipyridine ] -2,2' -dicarboxylic acid dimethyl ester (4) obtained in step 3, 39.3g of acetonitrile and 33.4g of methyl iodide, and reacted at room temperature for 48 hours. After the reaction was completed, the solvent and methyl iodide were removed by a rotary evaporator to obtain 22.8g of 2,2 '-bis (methoxycarbonyl) -1,1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine (5) as a product in a yield of 95.7%.
Step 5: synthesis of 2,2 '-dicarboxy-1, 1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine (6)
22.8g of 2,2 '-bis (methoxycarbonyl) -1,1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine (5) obtained in step 4 and 100g of 10% diluted sulfuric acid solution were put into a 250mL flask and reacted at 80℃for 24 hours. And (3) after the reaction is finished, adding 10% potassium carbonate solution, adjusting the pH to be neutral, removing the solvent by rotary evaporation, adding acetonitrile, filtering to remove insoluble substances, and removing the acetonitrile by rotary evaporation again to obtain 18.2g of the product 2,2 '-dicarboxy-1, 1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine (6) with the yield of 18.2%.
Target product analysis data
2,2 '-dicarboxy-1, 1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine (6)
1 H NMR (400 MHz, D 2 O, TMS) δ(ppm)12.54 (s, 2H), 9.24 (s, 2H), 9.43 (m, 4H), 4.37 (s, 6H).
Example 2
Cyclic voltammetry was performed between-0.8 v and 1.0v on the active material 2,2 '-dicarboxy-1, 1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine (6) obtained in example 1, wherein a carbon rod was used as a working electrode, a platinum wire was used as a counter electrode and a silver/silver chloride electrode was used as a reference; the neutral solvent in the electrolyte is sodium chloride aqueous solution (0.5 mol/L), as shown in the electrolyte circulation curve of figure 1, the sweeping speed is 0.1V/s, two pairs of obvious oxidation/reduction peaks are respectively-0.25V oxidation peak and-0.3V reduction peak, and-0.5V oxidation peak and-0.55V reduction peak, and the two pairs of obvious oxidation/reduction peaks correspond to the double electron transfer oxidation reduction peak, wherein the low potential peak has high symmetry degree, good reversibility and strong reducibility. Almost no loss is caused after 5 times of circulation, and the stability of active substances is good.
Example 3
Redox flow battery composed of formula 3, formula 4 and potassium ferrocyanide
Two electrolyte solutions were prepared: the negative electrolyte solution was prepared from 12.68g of the compound of formula 3, 0.19g of the compound of formula 4 and 731mg of sodium chloride in 25mL of deionized water; the positive electrolyte solution was prepared from 13.8g of potassium ferrocyanide and 731mg of sodium chloride in 25mL of deionized water. The electrolyte solution was tested in a redox flow battery with an active area of 5cm, and the battery was cycled in charge and discharge. Fig. 2 shows the charge curve of the battery.
。
It should be noted that the foregoing merely illustrates the technical idea of the present invention and is not intended to limit the scope of the present invention, and that a person skilled in the art may make several improvements and modifications without departing from the principles of the present invention, which fall within the scope of the claims of the present invention.
Claims (7)
1. An oxidation-reduction organic flow battery for energy storage, comprising a positive electrolyte storage tank and a negative electrolyte storage tank, wherein the positive electrolyte storage tank and the negative electrolyte storage tank are respectively connected with an inert electrode, and the two electrolyte storage tanks are separated by a diaphragm with ion exchange capability, and the oxidation-reduction organic flow battery is characterized in that the negative electrolyte comprises 0.01-99.99% of active substances in formula 1 or oxidation reduction thereof, and the structure of formula 1 is as follows:
；
wherein,
r1 and R2 independently of one another represent alkyl, alkoxy, haloalkyl, aryl, haloaryl, aralkyl and heterocyclyl;
a and b are each independently an integer from 0 to 4, and a and b may not be 0 at the same time;
m is an inorganic or organic anion in the n-valent state and mixtures of such anions;
n is an integer from 1 to 10.
2. The redox organic flow battery for energy storage of claim 1, wherein the negative electrolyte further comprises formula 2 or a redox active material thereof;
；
wherein,
r1 and R2 independently of one another represent alkyl, alkoxy, haloalkyl, aryl, haloaryl, aralkyl or heterocyclyl;
m is an inorganic or organic anion in the n-valent state and mixtures of such anions;
n is an integer from 1 to 10;
R 3 represented by a hydrogen atom, an alkyl group, an alkoxy group, a haloalkyl group, an aryl group, an aralkyl group, a haloaryl group, a halogen, an amino group, a nitro group, or a cyano group.
3. An redox organic flow battery for energy storage as claimed in claim 1 wherein the positive electrode electrolyte comprises a redox active material of a metal ferrocyanide, ammonium salt.
4. The redox organic flow battery for energy storage of claim 1, wherein the electrolyte further comprises a neutral solvent, a surfactant, a viscosity modifier, a pesticide, a buffer, a stabilizer, a catalyst, a phase transfer additive catalyst, an antifreeze, a heat stabilizer, and an antifoaming agent, the neutral solvent comprising an organic solvent, a weak acid solvent, a weak base solvent, water, or an inorganic brine solution.
5. The redox organic flow battery for energy storage of claim 1, wherein formula 1 is structured as follows:
。
6. the redox organic flow battery for energy storage of claim 5, wherein the method of preparation comprises the steps of:
(1) Adding a catalyst Pd-C and hydrazine hydrate into the 4-bromo-2-methylpyridine, and reacting in a nitrogen atmosphere to obtain 2,2 '-dimethyl-4, 4' -bipyridine;
；
(2) Adding bromobenzene and tin dioxide into 2,2 '-dimethyl-4, 4' -bipyridine, and reacting to obtain [4,4 '-bipyridine ] -2,2' -dicarboxylic acid;
；
(3) Adding methanol and concentrated sulfuric acid into the [4,4 '-bipyridine ] -2,2' -dicarboxylic acid obtained in the step (2), and carrying out reflux reaction to obtain [4,4 '-bipyridine ] -2,2' -dicarboxylic acid dimethyl ester;
；
(4) Acetonitrile and methyl iodide are added into the [4,4 '-bipyridine ] -2,2' -dicarboxylic acid dimethyl ester obtained in the step 3, and 2,2 '-bis (methoxycarbonyl) -1,1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine is obtained by reaction;
；
(5) Adding dilute sulfuric acid solution into the 2,2 '-bis (methoxycarbonyl) -1,1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine obtained in the step 4, and reacting to obtain 2,2 '-dicarboxyl-1, 1' -dimethyl- [4,4 '-bipyridine ] -1,1' -diimine;
。
7. use of an redox organic flow battery for energy storage according to any one of claims 1 to 6, wherein the use comprises: as an emergency back-up power supply, peak load regulated stationary storage for intermediate storage of discontinuous, unstable electrical energy, including intermediate storage of electrical energy of photovoltaic, wind, biomass, tidal or marine power plants, and for the field of electrical movement, including storage in land, air and water vehicles.
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