CN114085183A - Expanded viologen compound and application thereof in neutral aqueous flow battery - Google Patents
Expanded viologen compound and application thereof in neutral aqueous flow battery Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 85
- 230000007935 neutral effect Effects 0.000 title claims abstract description 45
- 239000003792 electrolyte Substances 0.000 claims abstract description 122
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 24
- 239000010439 graphite Substances 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 238000007600 charging Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract 2
- 238000012360 testing method Methods 0.000 claims description 46
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 40
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 32
- 235000011164 potassium chloride Nutrition 0.000 claims description 20
- 239000001103 potassium chloride Substances 0.000 claims description 20
- 235000002639 sodium chloride Nutrition 0.000 claims description 17
- 239000011780 sodium chloride Substances 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 10
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010277 constant-current charging Methods 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 238000009792 diffusion process Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 84
- 229910052786 argon Inorganic materials 0.000 description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 29
- 239000001301 oxygen Substances 0.000 description 29
- 229910052760 oxygen Inorganic materials 0.000 description 29
- 239000007787 solid Substances 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 27
- 229910021641 deionized water Inorganic materials 0.000 description 27
- 238000005303 weighing Methods 0.000 description 24
- 238000003780 insertion Methods 0.000 description 22
- 230000037431 insertion Effects 0.000 description 22
- 238000007865 diluting Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 16
- 230000002572 peristaltic effect Effects 0.000 description 16
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 15
- 238000005086 pumping Methods 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 9
- 229930192474 thiophene Natural products 0.000 description 7
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical group FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012864 cross contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical group C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses an expanded viologen compound and application thereof in a neutral water system flow battery, and specifically comprises the following components: a water-soluble expanded viologen compound is used as a cathode electrolyte active molecule, a TEMPO derivative or a ferrocene derivative is used as the anode electrolyte active molecule, a neutral salt is used as a supporting electrolyte, a titanium plate or a graphite plate is used as a current collector of a cathode and an anode, a graphite felt or a carbon felt is used as a cathode and an anode, and a commercial anion exchange membrane is used between the cathode electrolyte and the anode. The extended viologen compound disclosed by the invention has the characteristics of low oxidation-reduction potential, rapid diffusion property, high electron transfer rate, excellent reversibility, electrochemical stability and the like; the electrochemical performance of the material is excellent when the material is applied to a neutral water system flow battery: high cycling stability, high energy efficiency, high volume specific capacity, and consistent charging and discharging platforms in the charging and discharging processes of the two electrons, which is beneficial to the management of the voltage of the battery.
Description
Technical Field
The invention belongs to the technical field of large-scale energy storage, and particularly relates to an expanded viologen compound and application thereof in a neutral water system flow battery.
Background
With the growing population and the significant changes in lifestyle, the global energy demand has accelerated. Fossil fuel-based energy structures and consumption patterns have been faced with great dilemma, resulting in depletion of traditional fossil energy sources, and also in deterioration of the environment and climate change. In recent years, new energy systems with solar energy and wind energy as the core are gradually developed and utilized, and the development of energy storage systems is also actively promoted to balance the fluctuation of energy supply and user requirements. Aqueous redox flow batteries are one of the important candidates for large-scale energy storage.
Among them, the all-vanadium redox flow battery is the most developed battery system at present, but it still faces some inherent problems, such as corrosion of pipelines in an acid electrolyte environment, serious self-discharge caused by electrolyte cross-contamination, scarcity of vanadium resources, high cost, etc. Aqueous organic flow batteries exhibit many advantages and great potential compared to inorganic systems: (1) the water-soluble organic molecules are used as electroactive materials, have rich sources, and have rapid oxidation-reduction kinetics and lower cross contamination; (2) more importantly, the physicochemical and electrochemical properties of the organic electroactive molecules, including solubility, redox potential and the like, can be adjusted through reasonable molecular structure engineering and design.
The water-soluble viologen-based compound has the advantages of one-electron or two-electron storage capacity, high electron transfer rate and the like. However, based on its intrinsic bipyridylium backbone, the strong electronic communication between the two pyridinium rings results in a positive first electronic redox potential and a large difference (>400mV) between the two electronic redox potentials. These problems necessarily result in low energy density, as well as complex battery voltage management issues. Azizz et al (adv. energy mater.2020,10,2000100) modify the electron donating group (methyl) on the pyridinium ring, but the regulation of the redox potential is very limited (negative shift is only 80mV) and leads to a significant decrease in its stability. Theoretical calculation and experimental results show that mutual electronic communication can be well blocked by inserting an aromatic ring spacer (forming an extended viologen compound) between two pyridinium rings, and finally, an electronic potential is obviously shifted negatively, the difference between two electronic redox potentials is reduced, and the introduced spacer can delocalize electrons, so that the stability of the electronic potential is improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an extended viologen compound, which can better prevent mutual electronic communication by inserting an aromatic ring between two pyridinium rings (forming the extended viologen compound), finally realizes reasonable regulation and control of voltage, and effectively improves the cycling stability of a battery.
The invention aims to provide an application of an expanded viologen compound in a neutral water system flow battery, and the flow battery has the characteristics of high voltage, high cycle stability, high safety, more consistent charge and discharge platforms and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
an extended viologen compound having the structural formula:
further, in the structural general formula of the extended viologen compound, X is an aromatic ring, mainly comprises a five-membered heterocyclic ring, a benzene ring and a six-membered heterocyclic ring, and comprises any one of the following structures:
furthermore, in the structural general formula of the extended viologen compound, R is a hydrophilic quaternary ammonium salt group- (CH)2)nN(CH3)3 +And n is 3 to 5.
Further, the extended viologen compound comprises a counter ion including Cl-And Br-。
An application of an expanded viologen compound in a neutral aqueous flow battery is as follows: the electric pile assembled by the single battery or the plurality of groups of single batteries comprises assemblies such as an end plate, a current collector, an electrode frame, positive and negative electrodes, a diaphragm, supporting electrolyte, positive and negative electrolyte, a flow pipeline, a liquid storage tank, a peristaltic pump and the like. The active molecules of the positive and negative electrolytes all adopt water-soluble organic micromolecules, the active molecules of the positive electrolytes are TEMPO derivatives or ferrocene derivatives, the active molecules of the negative electrolytes are expanded viologen compounds, an expansion group X of the expanded viologen compounds is an aromatic ring, neutral inorganic salt is used as supporting electrolyte, pure water is used as a solvent, the single battery and the electric pile both adopt graphite felts or carbon felts as positive and negative electrodes, metal titanium plates or graphite plates are used as current collectors, and commercial anion exchange membranes are adopted as diaphragms; the structural formulas of the TEMPO derivative and the ferrocene derivative are respectively as follows:
further, the thickness of the metal titanium plate is 0.5-5 mm.
Further, the thickness of the metal titanium plate is 2 mm.
Further, the thickness of the graphite felt is 1-10 mm, and the side length is 1-30 cm.
Further, the thickness of the graphite felt is 5mm, and the side length is 3 multiplied by 3 cm.
Further, the anion exchange membrane is a DSV membrane, an AMV membrane or an ASV membrane, and the thickness is 80-130 μm.
Further, the anion exchange membrane adopts a DSV membrane with the thickness of 100 μm.
Further, the supporting electrolyte is one of potassium chloride, sodium chloride, potassium nitrate and sodium nitrate, and the concentration of the supporting electrolyte in the electrolyte is 0.5-2 mol/L.
Further, the supporting electrolyte is neutral potassium chloride or sodium chloride, and the concentration of the supporting electrolyte in the electrolyte is 0.5-2.0 mol/L.
Further, the positive electrode electrolyte active molecules and the negative electrode electrolyte active molecules are both water-soluble organic compounds.
Further, the concentration of the expanded viologen compound in the negative electrode electrolyte is 0.1-1.0 mol/L; the neutral water system flow battery can be charged and discharged by one electron or two electrons, and the two electron charging and discharging platforms are relatively consistent (the oxidation-reduction potential difference of the two single electron processes is less than 120 mV); the test process of the neutral water system flow battery adopts constant current charging and discharging, and the current density is 20-120 mA/cm2。
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides a reasonable molecular regulation and control means, and realizes the synergistic improvement of voltage and stability by introducing the physicochemical and electrochemical properties of the aromatic ring-modulated viologen-based electroactive molecule. Specifically, the inserted aromatic ring (forming the extended viologen compound) can better block the electronic communication between two pyridinium rings, so that an electronic potential is shifted negatively (namely, the cell voltage is increased), and the difference between two single-electron oxidation-reduction potentials is reduced, thereby being beneficial to the cell voltage management; meanwhile, the middle aromatic ring and the pyridinium ring can form an expanded conjugated system in a two-electron reduction state, electrons are effectively delocalized, and the stability of molecules is improved, so that high battery cycle stability is ensured. The method provides a new strategy for constructing the neutral aqueous organic flow battery with high performance and high stability, and can be suitable for large-scale energy storage.
Drawings
FIG. 1 shows the NMR spectrum of an extended viologen compound EV-S.
FIG. 2 is a cyclic voltammogram of the extended viologen compound EV-S and a comparative viologen (1,1 '-bis [3- (trimethylammonium) propyl ] -4, 4' -bipyridyl tetrabromide, labeled V).
Fig. 3 is a graph showing charge/discharge cycle performance of the neutral aqueous flow battery in example 1.
Fig. 4 is a charge/discharge curve diagram of the neutral aqueous flow battery in example 2 with different numbers of turns.
Fig. 5 is a graph showing charge/discharge cycle performance of the neutral aqueous flow battery in example 4.
Fig. 6 is a graph showing charge/discharge cycle performance of the neutral aqueous flow battery in example 5.
Detailed Description
The following is a further description of the examples of the present invention and is not intended to limit the scope of the invention.
1. The positive and negative electrodes are made of graphite felt with the side length of 3 multiplied by 3cm and the thickness of 5 mm;
2. the diaphragm adopts a DSV anion exchange membrane with the thickness of 100 mu m; the current collector adopts a metal titanium plate with the thickness of 2 mm;
3. preparing electrolyte: the active substance of the positive electrode electrolyte is TEMPO derivative TMAP-TEMPO or ferrocene derivative FcNCl, and the preparation concentration is 0.1-1.0 mol/L; the active molecules of the cathode electrolyte adopt the prepared expanded viologen compound: in particular, the amount of the solvent to be used,
(1) the insertion group X is a thiophene ring, and the hydrophilic group R is a quaternary ammonium salt chain- (CH)2)3N(CH3)3 +The counter ion is Br-The expanded viologen is named as EV-S, and the preparation concentration range is 0.1-1.0 mol/L;
(2) the insertion group X is furan ring, the hydrophilic group R is quaternary ammonium salt chain- (CH)2)3N(CH3)3 +The counter ion is Br-The expanded viologen is named as EV-O, and the preparation concentration is 0.1 mol/L;
(3) the insertion group X is a selenophene ring, and the hydrophilic group R is a quaternary ammonium salt chain- (CH)2)3N(CH3)3 +The counter ion is Br-The expanded viologen is named as EV-Se, and the preparation concentration is 0.1 mol/L;
(4) the insertion group X is a pyrrole ring, hydrophilicThe group R is a quaternary ammonium salt chain- (CH)2)3N(CH3)3 +The counter ion is Br-The expanded viologen is named as EV-N, and the preparation concentration is 0.1 mol/L;
(5) the insertion group X is benzene ring, and the hydrophilic group R adopts quaternary ammonium salt chain- (CH)2)4N(CH3)3 +The counter ion is Cl-The expanded viologen is named as EV-BH, and the preparation concentration is 0.1 mol/L;
(6) the insertion group X is a pyridine ring, and the hydrophilic group R is a quaternary ammonium salt chain- (CH)2)3N(CH3)3 +The counter ion is Br-The expanded viologen is named as EV-BD, and the preparation concentration is 0.1 mol/L;
(7) the insertion group X is a pyrazine ring, and the hydrophilic group R is a quaternary ammonium salt chain- (CH)2)4N(CH3)3 +The counter ion is Cl-The expanded viologen is named as EV-BQ, and the preparation concentration is 0.1 mol/L;
(8) the insertion group X is 1, 2-difluorobenzene, the hydrophilic group R is a quaternary ammonium salt chain- (CH)2)5N(CH3)3 +The counter ion is Cl-The expanded viologen is named as EV-FB, and the preparation concentration is 0.1 mol/L;
the supporting electrolyte is 0.5-2 mol/L potassium chloride or sodium chloride aqueous solution, and the used distilled water is subjected to oxygen removal treatment;
4. assembling the battery: assembling components such as an end plate, a current collector, an electrode frame, positive and negative electrodes, a diaphragm, supporting electrolyte, positive and negative electrolyte, a flow pipeline, a liquid storage tank, a peristaltic pump and the like according to a specific flow in a glove box filled with Ar atmosphere;
5. testing and electrochemical characterization of the cells: the battery test system is adopted to carry out charge-discharge cycle and multiplying power test on the battery, and the current density range is 20-120 mA/cm2(ii) a The electrochemical properties were characterized using Cyclic Voltammetry (CV) measurements.
Example 1
An application of an extended viologen compound in a neutral water system flow battery is characterized in that a novel extended viologen molecule EV-S constructed by a thiophene insertion group is used as a negative electrolyte active molecule, a ferrocene derivative FcNCl is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquids.
Weighing 0.380 g of EV-S compound and 0.745 g of KCl solid, dissolving in deionized water, diluting to 5 ml to obtain a cathode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; weighing 0.235 g of FcNCl compound and 1.192 g of KCl solid, dissolving in deionized water, diluting to 8 ml to obtain positive electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the current density of the battery with the current density of 60mA/cm2And carrying out constant current charge and discharge test on the battery.
FIG. 1 shows the NMR spectrum of an extended viologen compound EV-S. As can be seen from FIG. 1, the synthesized extended viologen compound EV-S has high purity. FIG. 2 is a cyclic voltammogram of the extended viologen compound EV-S and a comparative viologen (1,1 '-bis [3- (trimethylammonium) propyl ] -4, 4' -bipyridyl tetrabromide, labeled V) employed in the examples. As shown in FIG. 2, the one-electron oxidation-reduction potential of the extended viologen compound EV-S is negatively shifted by 200mV, which significantly increases the voltage of the cell. Fig. 3 is a graph showing charge/discharge cycle performance of the neutral aqueous flow battery in example 1. As shown in fig. 3, the flow battery assembled with the extended viologen compound EV-S as the negative electrolyte exhibited excellent long-term cycling stability.
Example 2
An application of an extended viologen compound in a neutral water system flow battery is characterized in that novel extended viologen molecule EV-S constructed by a thiophene insertion group is used as a negative electrolyte active molecule, TMAP-TEMPO is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquids.
1.520 g of EV-S compound and 0.373 g of KCl solid are weighed and dissolved in deionized water, and the volume is fixed to 5 ml to prepare cathode electrolysisContinuously introducing high-purity argon, and removing dissolved oxygen for later use; weighing 0.865 g of TMAP-TEMPO compound and 0.522 g of KCl solid, dissolving in deionized water, diluting to 7 ml to obtain positive electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the battery with a current density of 80mA/cm2And carrying out constant current charge and discharge test on the battery.
Fig. 4 is a charge/discharge curve diagram of the neutral aqueous flow battery in example 2 with different numbers of turns. As shown in fig. 4, it exhibits a higher discharge voltage plateau, and the 500-turn charge and discharge curves almost coincide, indicating that the stability is higher even at high concentration.
Example 3
An application of an extended viologen compound in a neutral water system flow battery is characterized in that novel extended viologen molecule EV-S constructed by a thiophene insertion group is used as a negative electrolyte active molecule, TMAP-TEMPO is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquids.
3.800 g of EV-S compound and 0.186 g of KCl solid are weighed and dissolved in deionized water, the volume is constant to 5 ml to prepare cathode electrolyte, then high-purity argon is continuously introduced, and dissolved oxygen is removed for standby; weighing 2.163 g of TMAP-TEMPO compound and 0.261 g of KCl solid, dissolving in deionized water, diluting to 7 ml to obtain positive electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the current density of the battery with the current density of 60mA/cm2And carrying out constant current charge and discharge test on the battery.
Example 4
An application of an extended viologen compound in a neutral water system flow battery is characterized in that novel extended viologen molecule EV-S constructed by a thiophene insertion group is used as a negative electrolyte active molecule, TMAP-TEMPO is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquids.
Weighing 0.380 g of EV-S compound and 0.745 g of KCl solid, dissolving in deionized water, diluting to 5 ml to obtain a cathode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; weighing 0.371 g of TMAP-TEMPO compound and 1.788 g of KCl solid, dissolving in deionized water, diluting to 12 ml to obtain positive electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the current density of the battery with the current density of 60mA/cm2And carrying out constant current charge and discharge test on the battery.
Fig. 5 is a graph showing charge/discharge cycle performance of the neutral aqueous flow battery in example 4. As shown in fig. 5, the negative electrode electrolyte of EV-S molecular composition also exhibited good stability (100 cycles capacity retention rate close to 99%) when two-electron charge and discharge cycles were performed.
Example 5
An application of an extended viologen compound in a neutral water system flow battery is characterized in that a novel extended viologen molecule EV-S constructed by a thiophene insertion group is used as a negative electrolyte active molecule, a ferrocene derivative FcNCl is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquids.
Weighing 0.380 g of EV-S compound and 0.745 g of KCl solid, dissolving in deionized water, diluting to 5 ml to obtain a cathode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; weighing 0.352 g of FcNCl compound and 1.788 g of KCl solid, dissolving in deionized water, diluting to a constant volume of 12 ml to obtain an anode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, and connecting the positive electrode and the negative electrode of the battery into a battery test systemSystem, at a current density of 60mA/cm2And carrying out constant current charge and discharge test on the battery.
Fig. 6 is a graph showing charge/discharge cycle performance of the neutral aqueous flow battery in example 5. As shown in fig. 6, after 500 cycles of the two-electron charge and discharge cycles, the capacity retention rate of the battery was as high as 88.4%.
Example 6
An application of an extended viologen compound in a neutral water system flow battery is characterized in that a novel extended viologen molecule EV-S constructed by a thiophene insertion group is used as a negative electrolyte active molecule, a ferrocene derivative FcNCl is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquids.
Weighing 1.140 g of EV-S compound and 0.373 g of KCl solid, dissolving in deionized water, diluting to 5 ml to obtain a cathode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; weighing 1.057 g of FcNCl compound and 5.364 g of KCl solid, dissolving in deionized water, diluting to 36 ml to obtain anode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the current density of the battery with the current density of 60mA/cm2And carrying out constant current charge and discharge test on the battery.
Example 7
An application of an extended viologen compound in a neutral water system flow battery is characterized in that a novel extended viologen molecule EV-S constructed by a thiophene insertion group is used as a negative electrolyte active molecule, a ferrocene derivative FcNCl is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquids.
Weighing 1.140 g of EV-S compound and 0.745 g of KCl solid, dissolving in deionized water, diluting to 5 ml to obtain a cathode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; weighing 1.057 g of FcNCl compound and 1.788 g of KCl solid, dissolving in deionized water, and diluting to constant volume of 12 ml to obtain the anode electrolyteThen continuously introducing high-purity argon gas, and removing dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the current density of 120mA/cm2And carrying out constant current charge and discharge test on the battery.
Example 8
An application of an extended viologen compound in a neutral water system flow battery is characterized in that a novel extended viologen molecule EV-BD constructed by a pyridine insertion group is used as a negative electrolyte active molecule, a ferrocene derivative FcNCl is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquid.
Weighing 0.378 g of EV-BD compound and 0.745 g of KCl solid, dissolving in deionized water, diluting to 5 ml to obtain a cathode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; weighing 0.352 g of FcNCl compound and 1.788 g of KCl solid, dissolving in deionized water, diluting to a constant volume of 12 ml to obtain an anode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the current density of the battery with the current density of 60mA/cm2And carrying out constant current charge and discharge test on the battery.
Example 9
An application of an extended viologen compound in a neutral water system flow battery is characterized in that a novel extended viologen molecule EV-O constructed by a furan insertion group is used as a negative electrolyte active molecule, a ferrocene derivative FcNCl is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquids.
Weighing 0.372 g of EV-O compound and 0.584 g of NaCl solid, dissolving in deionized water, diluting to 5 ml to obtain a cathode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; 0.235 g of FcNCl compound and 0.934 g of NaCl solid were weighed out and dissolvedIn ionized water, preparing anode electrolyte by fixing the volume to 8 milliliters, and then continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the current density of the battery with the current density of 60mA/cm2And carrying out constant current charge and discharge test on the battery.
Example 10
An application of an extended viologen compound in a neutral water system flow battery is characterized in that a novel extended viologen molecule EV-Se constructed by a selenophen insertion group is used as a negative electrolyte active molecule, a ferrocene derivative FcNCl is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquids.
Weighing 0.404 g of EV-Se compound and 0.584 g of NaCl solid, dissolving in deionized water, diluting to 5 ml to obtain a cathode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; weighing 0.235 g of FcNCl compound and 0.934 g of NaCl solid, dissolving in deionized water, diluting to 8 ml to obtain positive electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the current density of the battery with the current density of 60mA/cm2And carrying out constant current charge and discharge test on the battery.
Example 11
An application of an extended viologen compound in a neutral water system flow battery is characterized in that a novel extended viologen molecule EV-N constructed by a pyrrole insertion group is used as a negative electrolyte active molecule, a ferrocene derivative FcNCl is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquids.
Weighing 0.372 g of EV-N compound and 0.584 g of NaCl solid, dissolving in deionized water, diluting to 5 ml to obtain a cathode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; weighing 0Dissolving 235 g of FcNCl compound and 0.934 g of NaCl solid in deionized water, fixing the volume to 8 ml to prepare positive electrolyte, and then continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the battery with a current density of 20mA/cm2And carrying out constant current charge and discharge test on the battery.
Example 12
An application of an extended viologen compound in a neutral water system flow battery is characterized in that a novel extended viologen molecule EV-BH constructed by a benzene ring insertion group is used as a negative electrolyte active molecule, a ferrocene derivative FcNCl is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquid.
Weighing 0.302 g of EV-BH compound and 0.584 g of NaCl solid, dissolving in deionized water, diluting to 5 ml to obtain a cathode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; weighing 0.352 g of FcNCl compound and 1.402 g of NaCl solid, dissolving in deionized water, fixing the volume to 12 ml to prepare anode electrolyte, and then continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the current density of the battery with the current density of 60mA/cm2And carrying out constant current charge and discharge test on the battery.
Example 13
An application of an extended viologen compound in a neutral water system flow battery is characterized in that a novel extended viologen molecule EV-BQ constructed by a pyrazine insertion group is used as a negative electrolyte active molecule, a ferrocene derivative FcNCl is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquid.
0.303 g of EV-BQ compound and 0.584 g of NaCl solid are weighed and dissolved in deionized water, the volume is determined to be 5 ml to prepare cathode electrolyte, and then the cathode electrolyte is heldContinuously introducing high-purity argon, and removing dissolved oxygen for later use; weighing 0.352 g of FcNCl compound and 1.402 g of NaCl solid, dissolving in deionized water, fixing the volume to 12 ml to prepare anode electrolyte, and then continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the current density of the battery with the current density of 60mA/cm2And carrying out constant current charge and discharge test on the battery.
Example 14
An application of an extended viologen compound in a neutral water system flow battery is characterized in that a novel extended viologen molecule EV-FB constructed by a 1, 2-difluorobenzene insertion group is used as a negative electrolyte active molecule, a ferrocene derivative FcNCl is used as a positive electrolyte active molecule, a titanium plate is used as a current collector, a graphite felt is used as an electrode, and a DSV anion exchange membrane is used for separating positive and negative electrode liquid.
Weighing 0.334 g of EV-FB compound and 0.584 g of NaCl solid, dissolving in deionized water, diluting to 5 ml to obtain a cathode electrolyte, and continuously introducing high-purity argon to remove dissolved oxygen for later use; weighing 0.352 g of FcNCl compound and 1.402 g of NaCl solid, dissolving in deionized water, fixing the volume to 12 ml to prepare anode electrolyte, and then continuously introducing high-purity argon to remove dissolved oxygen for later use; then assembling the battery in an argon glove box, specifically, respectively injecting the prepared electrolyte into an electrolyte tank, pumping the electrolyte into a battery device through a peristaltic pump, connecting the positive electrode and the negative electrode of the battery into a battery test system, and testing the current density of the battery with the current density of 60mA/cm2And carrying out constant current charge and discharge test on the battery.
The flow battery performance data corresponding to the above embodiment is tabulated as follows:
the results show that: as can be seen from the electrical property data in the above table, the neutral aqueous flow battery composed of the extended viologen compound EV-S as the negative electrode electrolyte active molecule exhibited excellent electrochemical properties: after 2000 times of charging and discharging, the capacity retention rate of the battery is as high as 95.9% (figure 3), and the average coulombic efficiency is as high as 99.98%; at the same time, high stability was also exhibited under high concentration operating conditions (500 cycles @ 96.3%, FIG. 4).
Claims (10)
3. the extended viologen compound of claim 1, wherein R is a hydrophilic quaternary ammonium salt group- (CH)2)nN(CH3)3 +And n is 3 to 5.
4. The extended viologen compound of claim 1, comprisingCounter ions, including Cl-And Br-。
5. The application of the expanded viologen compound in the neutral aqueous flow battery is characterized in that the expanded viologen compound is applied to a single battery or a galvanic pile assembled by a plurality of groups of single batteries, the single battery and the galvanic pile both adopt graphite felts or carbon felts as positive and negative electrodes, metal titanium plates or graphite plates as current collectors, and commercial anion exchange membranes are adopted as diaphragms; the neutral salt is used as a supporting electrolyte, the water-soluble expanded viologen compound is used as a negative electrolyte active molecule, and the positive electrolyte active molecule adopts TEMPO derivative or ferrocene derivative.
6. The use of the extended viologen compound in a neutral aqueous flow battery according to claim 5, wherein the thickness of the titanium plate is 0.5 to 5 mm.
7. The use of the extended viologen compound in a neutral aqueous flow battery as in claim 5, wherein the graphite felt has a thickness of 1-10 mm and a side length of 1-30 cm.
8. The use of the extended viologen compound in a neutral aqueous flow battery according to claim 5, wherein the anion exchange membrane is a DSV membrane, an AMV membrane or an ASV membrane and has a thickness of 80-130 μm.
9. The use of the extended viologen compound in a neutral aqueous flow battery according to claim 5, wherein the supporting electrolyte is one of potassium chloride, sodium chloride, potassium nitrate and sodium nitrate, and the concentration of the supporting electrolyte in the electrolyte is 0.5-2 mol/L.
10. The use of the extended viologen compound in a neutral aqueous flow battery according to claim 5, wherein the concentration of the extended viologen compound in the negative electrolyte is 0.1-1.0 mol/L; the neutral water system flow battery can be charged and discharged by one electron or two electrons, and the two electron charging and discharging platforms are relatively consistent; the test process of the neutral water system flow battery adopts constant current charging and discharging, and the current density is 20-120 mA/cm2。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111244518A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Water system neutral organic flow battery |
CN111293340A (en) * | 2020-02-26 | 2020-06-16 | 西北大学 | Neutral organic redox flow battery |
CN111628185A (en) * | 2020-05-27 | 2020-09-04 | 西安交通大学 | Pyrroline/alkyl nitrogen oxygen free radical compound water system organic flow battery |
CN112103546A (en) * | 2020-09-16 | 2020-12-18 | 中盐金坛盐化有限责任公司 | Double-electronic compound flow battery system based on salt caverns |
CN113214235A (en) * | 2021-03-22 | 2021-08-06 | 西安交通大学 | Thienyl and selenophenyl viologen derivatives, and synthetic method and application thereof |
-
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111244518A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Water system neutral organic flow battery |
CN111293340A (en) * | 2020-02-26 | 2020-06-16 | 西北大学 | Neutral organic redox flow battery |
CN111628185A (en) * | 2020-05-27 | 2020-09-04 | 西安交通大学 | Pyrroline/alkyl nitrogen oxygen free radical compound water system organic flow battery |
CN112103546A (en) * | 2020-09-16 | 2020-12-18 | 中盐金坛盐化有限责任公司 | Double-electronic compound flow battery system based on salt caverns |
CN113214235A (en) * | 2021-03-22 | 2021-08-06 | 西安交通大学 | Thienyl and selenophenyl viologen derivatives, and synthetic method and application thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024149891A1 (en) * | 2023-01-13 | 2024-07-18 | Cambridge Enterprise Limited | Redox flow battery |
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