CN111564649A - Organic polymer flow battery system - Google Patents
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- CN111564649A CN111564649A CN202010562492.9A CN202010562492A CN111564649A CN 111564649 A CN111564649 A CN 111564649A CN 202010562492 A CN202010562492 A CN 202010562492A CN 111564649 A CN111564649 A CN 111564649A
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 75
- 239000003792 electrolyte Substances 0.000 claims abstract description 102
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000011149 active material Substances 0.000 claims abstract description 26
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003860 storage Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000013543 active substance Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006479 redox reaction Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 229920000642 polymer Polymers 0.000 claims description 33
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- 239000012266 salt solution Substances 0.000 claims description 24
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
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- XIUCEANTZSXBQQ-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl)-trimethylazanium Chemical compound C[N+](C)(C)CC(O)CCl XIUCEANTZSXBQQ-UHFFFAOYSA-N 0.000 claims description 5
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- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
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- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- 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
-
- 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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Abstract
The invention discloses an organic polymer flow battery system, which comprises: the electrolyte storage tanks are distributed at intervals, electrolyte is stored in the dissolving cavity of each electrolyte storage tank, positive active substances are arranged in the electrolyte in one electrolyte storage tank and are TEMPO functionalized organic polymers, negative active substances are arranged in the electrolyte in the other electrolyte storage tank and are viologen functionalized organic polymers, and the positive active substances and the negative active substances are directly dissolved or dispersed in a system taking water as a solvent in a body form and are respectively stored in the corresponding electrolyte storage tanks; and the flow battery stack is communicated with the electrolyte liquid storage, and the electrolyte is input into or output from the electrolyte liquid storage to perform oxidation-reduction reaction. The organic polymer flow battery system is suitable for a battery environment using electrolyte generated in situ, and has the advantages of low cost, stable charge and discharge performance, high solubility of active materials and the like.
Description
Technical Field
The invention belongs to the technical field of flow batteries, and particularly relates to an organic polymer flow battery system.
Background
Energy is an important material basis for human survival and development and is a strategic resource of the national treasury of the affairs. With the continuous development of society, the energy problem and the environmental problem become more serious, and the development of new energy becomes a research hotspot.
The flow battery has become one of the most promising technologies in large-scale energy storage technology due to the characteristics of separate design of energy and power, high safety, long cycle life and the like. The chemical power supply is used for storing electricity, is not limited by geographical conditions, is easy to realize large-scale energy storage and has great social and economic values. Although the conventional flow battery using inorganic substance as active material is developed rapidly, it will face many challenges and uncertainty factors to go to large-scale energy storage due to the problems of expensive battery cost, low electrochemical activity, etc. The organic matter contains C, H, O, N and other rich elements, and has wide material source and low cost. Meanwhile, the organic matter can change the properties such as solubility, oxidation-reduction potential, steric hindrance and the like by accessing functional groups, and the organic active substance replaces the traditional active substances such as metal, halogen and the like, so that the energy density and open-circuit voltage of the flow battery can be remarkably improved, and the stability of the flow battery is greatly enhanced. In addition, the organic active material can realize the cycle of the green battery in a low-carbon emission mode.
The polymer has good stability and diversified designability, and is widely researched as an active substance of the flow battery in recent years in order to solve the problems of poor stability, low energy efficiency, environmental pollution and the like of the traditional flow battery, namely, the polymer with excellent electrochemical activity is required to be designed and introduced as a redox couple, so that the organic polymer redox flow battery with the outstanding advantages of strong stability, good safety, flexible configuration, high response speed, environmental protection and the like is obtained, and the polymer provides a powerful support for the application of a large-scale electrochemical energy storage technology. Meanwhile, a macromolecular polymer is introduced, and a high-price Nafion ion exchange membrane is replaced by a more economic and scale-sensitive dialysis membrane and a microporous membrane, so that cross contamination among ions can be effectively prevented, and the cost of the flow battery is greatly reduced.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art.
Therefore, the organic polymer flow battery system provided by the invention can be suitable for a battery environment using an electrolyte generated in situ, and has the advantages of low cost, easiness in preparation of an active material, high safety performance, high energy density, stable charge and discharge performance, high solubility of the active material and the like.
An organic polymer flow battery system according to an embodiment of the present invention includes: the electrolyte system comprises two electrolyte liquid reservoirs, wherein the two electrolyte liquid reservoirs are distributed at intervals, electrolyte is stored in a dissolving cavity of each electrolyte liquid reservoir, a positive electrode active substance is arranged in the electrolyte in one electrolyte liquid reservoir, the positive electrode active substance is a TEMPO functional organic polymer, a negative electrode active substance is arranged in the electrolyte in the other electrolyte liquid reservoir, the negative electrode active substance is an viologen functional organic polymer, the positive electrode active substance and the negative electrode active substance are directly dissolved or dispersed in a system taking water as a solvent in a body form and are respectively stored in the corresponding electrolyte liquid reservoirs, and the supporting electrolyte is dissolved in the system; the flow battery stack is communicated with the electrolyte liquid storage, and the electrolyte is input into or output from the electrolyte liquid storage to perform oxidation-reduction reaction; wherein the chemical structural formula of the TEMPO functionalized organic polymer is as follows:
wherein TEMPO is used as the most main oxidation-reduction active site, and the solubility is increased by utilizing a sulfonic acid group connected on a polymer;
the chemical structural formula of the viologen functionalized organic polymer is as follows:
wherein, the viologen is used as a main oxidation-reduction active site, and the solubility is increased by utilizing the quaternary ammonium salt connected on the polymer.
According to the organic polymer flow battery system provided by the embodiment of the invention, two electrolyte liquid storage banks are arranged to respectively store the electrolyte containing the positive active material TEMPO functionalized organic polymer and the electrolyte containing the negative active material Viologen functionalized organic polymer, the positive active material and the negative active material are both organic polymers, and the composite macromolecular active material with the positive active group (TEMPO) and the negative active group (Vilogen) is introduced into the organic polymer at the same time, so that the cross contamination among ions can be effectively prevented, and the problem of efficiency reduction caused by the increase of the discharge capacity due to the increase of the concentration of the electrolyte can be solved. Namely, the organic polymer flow battery system can be suitable for a battery environment using electrolyte generated in situ, and has the advantages of low cost, easy preparation of active materials, high safety performance, high energy density, stable charge and discharge performance and high solubility of the active materials.
According to one embodiment of the invention, the TEMPO functionalized organic polymer is obtained by taking 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-methyl piperidide containing anode active molecules and self-synthesized water-soluble VIMS as monomers and initiating a free radical polymerization reaction by using a water-soluble initiator, wherein the chemical reaction formulas are shown as formula (1) and formula (2):
according to one embodiment of the invention, the preparation of the TEMPO functionalized organic polymer comprises the following steps: s11, mixing 1-vinyl imidazole and 1, 3-propane sultone, adding acetonitrile solvent, and adding N2Stirring and reacting under the atmosphere, carrying out suction filtration on the obtained reaction solution after the reaction is finished, washing, and finally carrying out vacuum drying to obtain white powdery solid particles VIMS; s12, mixing 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-methyl piperidine and VIMS, and adding deionized water, N2Heating and stirring to remove oxygen in the atmosphere, adding the aqueous solution of the initiator to react, cooling and cooling after the reaction is completed, and adding H into the reaction solution2O2And Na2WO4Stirring the mixture at normal temperature to react, gradually turning the reaction solution into light yellow and slightly pink, and adding H2O2Continuously stirring the solution at room temperature for reaction; then dialyzing the reaction solution to obtain pure TEMPO functionalized organic polymer.
According to an embodiment of the present invention, the initiator in step S12 is one or more of azobisisobutylamidine hydrochloride, dimethyl azobisisobutyrate and azobisisobutylimidazoline hydrochloride.
According to one embodiment of the invention, the molar ratio of the monomer 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-piperidyl methyl ester to the monomer VIMS is 1: 1-1: 2.
According to one embodiment of the present invention, the viologen-functionalized organic polymer copolymer is obtained by using self-synthesized 3- ((4-vinylbenzyl) - [4,4 '-bipyridyl ] -1,1' -diyl) propane-1-sulfonic acid chloride as a monomer, and initiating the polymerization of the monomer by using a water-soluble initiator, wherein the chemical reaction formulas are shown as formula (3) and formula (4):
according to one embodiment of the present invention, the preparation of the viologen-functionalized organic polymer copolymer comprises the steps of: s21, mixing 4-vinylbenzyl- (4,4' -bipyridine) onium salt and 3-chloro-2-hydroxypropyl trimethyl ammonium oxide, adding ethanol solvent, and adding ethanol solvent in N2Condensing and reacting under the atmosphere, evaporating the solvent after the reaction is finished to obtain an orange red whitish solid, washing with acetonitrile, filtering, and drying in vacuum to finally obtain the orange red solid 3- ((4-vinyl benzyl) - [4,4' -bipyridine)]-1,1' -diimmonium) propane-1-sulfonic acid chloride; s22, mixing the 3- ((4-vinyl benzyl) - [4,4' -dipyridine)]Dissolving the (1, 1' -diimmonium) propane-1-sulfonic acid chloride monomer in deionized water solvent, filling with N2Deoxidizing, then injecting an aqueous solution of an initiator, stopping heating after the reaction is finished to obtain a turbid liquid with reddish white, dialyzing with deionized water to obtain a turbid liquid containing reddish brown precipitates, and freeze-drying the pure reaction liquid to obtain a red solid of the viologen-functionalized organic polymer.
According to an embodiment of the present invention, the initiator in step S22 is one of potassium persulfate, ammonium persulfate, and benzoin dimethyl ether.
According to one embodiment of the present invention, the concentrations of the positive electrode active material and the negative electrode active material are both 0.1mol · L-1～3.0mol·L-1。
According to one embodiment of the invention, each electrolyte reservoir is a salt cavern with a physical cavity formed after the salt mine is mined.
According to one embodiment of the present invention, the electrolyte reservoir is a pressurized and sealed container having a pressure of 0.1 to 0.5 MPa.
According to one embodiment of the invention, an inert gas is introduced into the electrolyte reservoir to purge and maintain pressure.
According to one embodiment of the invention, the inert gas is nitrogen or argon.
According to an embodiment of the present invention, the organic polymer flow battery system further comprises: the battery diaphragm, the battery diaphragm is located the electrolytic cell body and will the electrolytic cell body is separated for with one the positive pole district of electrolyte liquid storage storehouse intercommunication and with another the negative pole district of electrolyte liquid storage storehouse intercommunication, have in the positive pole district including anodal active material's positive pole electrolyte, have in the negative pole district including negative pole active material's negative pole electrolyte, the battery diaphragm can supply support the electrolyte to pierce through, prevents anodal active material with negative pole active material pierces through, the battery diaphragm is anion exchange membrane, cation exchange membrane or is that the aperture is 10nm ~ 300 nm's polymer porous membrane.
According to one embodiment of the invention, the supporting electrolyte is a NaCl salt solution, a KCl salt solution, Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, MgSO4Salt solution, CaCl2Salt solution, NH4At least one of a Cl salt solution.
According to one embodiment of the invention, the supporting electrolyte has a molar concentration of 0.1mol · L-1～8.0mol·L-1。
According to one embodiment of the invention, the anode region and the cathode region are respectively provided with electrodes, and the positive electrode and the negative electrode are carbon material electrodes.
According to one embodiment of the invention, the carbon material electrode is one or a composite of several of carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fiber, activated carbon particles, graphene, graphite felt and glass carbon material.
According to one embodiment of the invention, the electrodes are formed as electrode plates, the thickness of the electrode plates being 2mm to 8 mm.
According to one embodiment of the invention, the polymer flow battery system further comprises: and the current collectors are respectively arranged on two sides of the flow battery stack and can collect and conduct current generated by active substances of the flow battery stack to an external lead.
According to an embodiment of the invention, the current collector is one of a conductive metal plate, a graphite plate or a carbon-plastic composite plate.
According to one embodiment of the present invention, the conductive metal plate includes at least one metal of copper, nickel, and aluminum.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural diagram of an organic polymer flow battery system according to an embodiment of the invention;
FIG. 2(a) is a drawing showing a water-soluble monomer VIMS according to example 1 of the present invention1H NMR spectrum;
FIG. 2(b) is a drawing showing a water-soluble monomer VIMS according to example 1 of the present invention13C NMR spectrum;
FIG. 3(a) is a drawing of example 1 of a Poly (TEMPO-co-VIMS) copolymer according to the present invention1HNMR spectrogram;
FIG. 3(b) is a drawing of example 1 of a Poly (TEMPO-co-0.5VIMS) copolymer according to the present invention1HNMR spectrogram;
FIG. 4(a) shows a CVBD monomer according to example 2 of the present invention1H NMR spectrum;
FIG. 4(b) is a drawing of Poly (CVBD) copolymer according to example 2 of the present invention1HNMR spectrogram;
FIG. 5 is a CV diagram of Poly (TEMPO-co-VIMS) copolymer (0.36 mg/mL in 0.1M aqueous sodium chloride) at a scan rate of 0.1V/s according to an embodiment of the present invention;
FIG. 6 is a CV diagram of Poly (CVBD) copolymer (1.38 mg/mL in 0.1M aqueous sodium chloride) at a scan rate of 0.1V/s, according to an embodiment of the present invention;
FIG. 7 is a graph of the cycling stability of the polymer Poly (TEMPO-co-VIMS) -Poly (CVBD) (-) according to an example of the present invention.
Reference numerals:
an organic polymer flow battery system 100;
an electrolyte reservoir 10;
a flow cell stack 20; an electrode plate 21; the positive electrode electrolyte 22; the negative electrode electrolyte 23; a battery separator 24; a circulation line 25; a circulation pump 26; and a current collector 27.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention. Furthermore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
An organic polymer flow battery system 100 according to an embodiment of the present invention is described below with reference to the accompanying drawings.
As shown in fig. 1 to 7, an organic polymer flow battery system 100 according to an embodiment of the present invention includes: two electrolyte reservoirs 10 and a flow cell stack 20.
Specifically, two electrolyte liquid storage banks 10 are distributed at intervals, an electrolyte is stored in a dissolution cavity of each electrolyte liquid storage bank 10, an electrolyte in one electrolyte liquid storage bank 10 has a positive active material, the positive active material is a TEMPO functionalized organic polymer, an electrolyte in the other electrolyte liquid storage bank 10 has a negative active material, the negative active material is an viologen functionalized organic polymer, the positive active material and the negative active material are directly dissolved or dispersed in a system using water as a solvent in a body form and are respectively stored in the corresponding electrolyte liquid storage banks 10, a support electrolyte is dissolved in the system, a flow battery stack 20 is communicated with the electrolyte liquid storage banks 10, and the electrolyte is input into or output from the electrolyte liquid storage banks 10 for redox reaction; wherein,
the chemical structural formula of the TEMPO functionalized organic polymer is as follows:
the chemical structural formula of the viologen functionalized organic polymer is as follows:
in other words, the organic polymer flow battery system 100 mainly includes two electrolyte reservoirs 10 and a flow battery stack 20, one of the two electrolyte reservoirs 10 stores an electrolyte containing a positive active material, the positive active material is a TEMPO-functionalized organic polymer (hereinafter referred to as Poly (TEMPO-co-VIMS) copolymer) which mainly includes TEMPO and increases the solubility of the TEMPO polymer by introducing Vinylimidazole (VIMS) containing a sulfonic acid group, and the polymer can more effectively reduce the viscosity of the electrolyte than other TEMPO derivatives. Another electrolyte reservoir 10 stores therein an electrolyte containing a negative electrode active material, the negative electrode active material being a viologen-functionalized organic polymer (hereinafter abbreviated as Poly (CVBD) ═ copolymer), 1- (4-vinyl-phenyl) - [4,4' -bipyridine ] -1-chloride (abbreviated as VBD) being a viologen derivative, having a certain electrochemical activity, the solubility of the material being increased by introducing 3-chloro-2-hydroxypropyl trimethylammonium oxide containing a hydrophilic group, and Poly (CVBD) prepared by self-polymerization having a lower viscosity than that of monomer CVBD and having a higher controllability. The TEMPO functionalized organic polymer and the viologen functionalized organic polymer can be directly dissolved or dispersed in a system taking water as a solvent in a bulk form, and the electrolyte can be dissolved in the system. The two electrolyte reservoirs 10 are in communication through a flow cell stack 20.
Therefore, according to the organic polymer flow battery system 100 of the embodiment of the present invention, two electrolyte reservoirs 10 are provided to store an electrolyte containing a cathode active material TEMPO functionalized organic polymer and an electrolyte containing an anode active material Viologen functionalized organic polymer, wherein the cathode active material and the anode active material are both organic polymers, and the introduction of a composite macromolecular active material having a cathode active group (TEMPO) and an anode active group (Viologen) into the organic polymer can not only effectively prevent cross contamination between ions, but also solve the problem of efficiency reduction caused by increasing the electrolyte concentration to increase the discharge capacity. That is, the organic polymer flow battery system 100 can be applied to a battery environment using an in-situ generated electrolyte, and has the advantages of low cost, easy preparation of an active material, high safety performance, high energy density, stable charge and discharge performance, and high solubility of the active material.
According to one embodiment of the invention, the Poly (TEMPO-co-VIMS) copolymer is obtained by taking 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-methyl piperidine (hereinafter abbreviated as TEMPMA) containing anode active molecules and self-synthesized water-soluble VIMS as monomers and initiating a free radical polymerization reaction by using a water-soluble initiator, wherein the chemical reaction formulas are shown as formula (1) and formula (2):
according to one embodiment of the invention, the preparation of a TEMPO functionalized organic polymer comprises the following steps:
s11, mixing 1-Vinyl Imidazole (VIM) and 1, 3-propane sultone, adding acetonitrile solvent, and adding N2The reaction was stirred under an atmosphere, and the reaction temperature was 75 ℃. And after the reaction is finished, carrying out suction filtration on the obtained reaction solution, washing for 3 times, and finally carrying out vacuum drying to obtain white powdery solid particles, which are named as VIMS.
S12, mixing 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-piperidyl methyl ester (TEMPMA) and VIMS prepared in the step S11, and adding deionized water, N2Heating and stirring to remove oxygen in the atmosphere, wherein the heating temperature can be 70 ℃. Then adding an aqueous solution of an initiator for reaction, cooling and cooling after the reaction is completed, pouring the reaction solution into a beaker, and adding H2O2And Na2WO4Stirring at normal temperature to react, and adding a certain amount of H2O2Continuously stirring the solution at room temperature for reaction; then, the reaction solution MWCO 3500 was dialyzed in a dialysis bag to obtain pure Poly (TEMPO-co-VIMS) polymer.
Optionally, in step S12, the initiator is one or more of azobisisobutylamidine hydrochloride (AIBA), dimethyl azobisisobutyrate, and azobisisobutylimidazoline hydrochloride.
Further, the molar ratio of the monomer TEMPMA to the monomer VIMS is 1: 1-1: 2.
According to one embodiment of the present invention, the poly (CVBD) copolymer is obtained by using self-synthesized 3- ((4-vinylbenzyl) - [4,4 '-bipyridyl ] -1,1' -diyl) propane-1-sulfonic acid chloride (hereinafter abbreviated as CVBD) as a monomer, and initiating polymerization of the monomer by using a water-soluble initiator, wherein the chemical reaction formulas are shown as formula (3) and formula (4):
according to one embodiment of the present invention, the preparation of the poly (cvbd) copolymer comprises the steps of:
s21, mixing 4-vinylbenzyl- (4,4' -bipyridine) onium salt (VBD) and 3-chloro-2-hydroxypropyl trimethyl ammonium oxide, adding a proper amount of ethanol solvent, and adding the mixture into N2Condensing and reacting under the atmosphere, wherein the reaction temperature can be 95 ℃, evaporating the solvent after the reaction is finished to obtain an orange red whitish solid, washing the orange red whitish solid with acetonitrile, filtering, and drying in vacuum to finally obtain the orange red solid 3- ((4-vinyl benzyl) - [4,4' -bipyridine)]-1,1' -diimmonium) propane-1-sulfonic acid Chloride (CVBD);
s22, dissolving the CVBD monomer prepared in the step S21 in a deionized water solvent, and filling N at 70 DEG C2Deoxidizing, injecting water solution of initiator, reacting at 70 deg.C, stopping heating after reaction to obtain white reddish turbid liquid, dialyzing with deionized water to obtain suspension containing reddish brown precipitate, and freeze drying pure reaction liquid to obtain red solid Poly (CVBD).
Optionally, the initiator in step S22 is one of potassium persulfate (KPS), Ammonium Persulfate (APS), and benzoin dimethyl ether (DMPA).
According to one embodiment of the present invention, the concentrations of the positive electrode active material and the negative electrode active material are both 0.1mol · L-1～3.0mol·L-1。
According to one embodiment of the invention, each electrolyte reservoir 10 is a salt cavern with a physical cavern formed after mining of the salt mine.
According to one embodiment of the present invention, the electrolyte reservoir 10 is a pressurized and sealed container having a pressure of 0.1MPa to 0.5 MPa.
In some embodiments of the present invention, the electrolyte reservoir 10 is purged with an inert gas and maintained at a pressure, which is always protected by the inert gas during the charging and discharging processes.
Preferably, the inert gas is nitrogen or argon.
According to an embodiment of the present invention, the organic polymer flow battery system 100 further comprises: the battery diaphragm 24 is positioned in the electrolytic cell body and divides the electrolytic cell body into a positive region communicated with one electrolyte liquid storage tank 10 and a negative region communicated with the other electrolyte liquid storage tank 10, the positive region is internally provided with a positive electrolyte 22 comprising a positive active material, the negative region is internally provided with a negative electrolyte 23 comprising a negative active material, the battery diaphragm 24 can be penetrated by a supporting electrolyte to prevent the penetration of the positive active material and the negative active material, and the battery diaphragm 24 is an anion exchange membrane, a cation exchange membrane or a polymer porous membrane with the aperture of 10 nm-300 nm.
Optionally, the supporting electrolyte is NaCl salt solution, KCl salt solution, Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, MgSO4Salt solution, CaCl2Salt solution, NH4At least one of a Cl salt solution.
Further, the molar concentration of the supporting electrolyte was 0.1mol · L-1～8.0mol·L-1。
According to one embodiment of the invention, the anode region and the cathode region are respectively provided with electrodes, and the positive electrode and the negative electrode are carbon material electrodes.
Optionally, the carbon material electrode is one or a composite of several of carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fiber, activated carbon particles, graphene, graphite felt and a glassy carbon material.
Further, the electrode is formed as an electrode plate 21, and the thickness of the electrode plate 21 is 2mm to 8 mm.
According to one embodiment of the present invention, the organic polymer flow battery system 100 further comprises current collectors 27, the current collectors 27 being respectively disposed at both sides of the flow battery stack 20, the current collectors 27 being capable of collecting and conducting the current generated by the active materials of the flow battery stack 20 to an external lead.
Optionally, current collector 27 is one of a conductive metal plate, a graphite plate, or a carbon-plastic composite plate.
Further, the conductive metal plate includes at least one metal of copper, nickel, and aluminum.
Therefore, the organic polymer flow battery system 100 according to the embodiment of the present invention can be applied to a battery environment of a salt cavern system (using an in-situ generated electrolyte), and the battery system 100 has the advantages of low cost, easy preparation of an active material, high safety performance, high energy density, stable charge and discharge performance, high solubility of the active material, and the like.
The organic polymer flow battery system 100 provided by the embodiment of the invention is specifically described below with reference to specific embodiments.
In the cyclic voltammetry test of the galvanic couple, a CS series electrochemical workstation of Wuhan Cornst is adopted, a three-electrode system is adopted to test the electrochemical performance of the organic galvanic couple, a working electrode is a glassy carbon electrode (Tianjin Adamantang Hengcheng company), a reference electrode is an Ag/AgCl electrode, a counter electrode is a platinum electrode, and the scanning ranges of the positive and negative galvanic couples are respectively-1.0V.
Example 1
Preparation of Poly (TEMPO-co-VIMS) copolymer by one-pot method
First, 4.53mL of 1-vinylimidazole (VIM, 0.05mol) as a pale yellow liquid, 5.27mL of 1, 3-propanesultone (0.06mol) as a pale yellow liquid, and 50mL of acetonitrile solvent were added in a three-necked flask in N2Stirring and reacting for 1h at 75 ℃ in the atmosphere, gradually generating white precipitate, and continuing to react for 4h until complete reaction. The resulting reaction solution was filtered with suction, washed 3 times and finally dried in vacuo to give 9.6975g of white powdery solid particles (named VIMS, 89.8% yield). The reaction principle is shown in chemical reaction formula (1).
Then, 0.9014g of white solid 2-methyl-2-propenoic acid-2, 2,6, 6-tetramethyl-4-piperidinemethyl ester (TEMPMA, 8mmol) was added to a three-necked flask, a quantity of white solid VIMS (4 or 8mmol, 0.8560/1.7300g) was added, 50mL of deionized water, N, was added2Heating and stirring at 70 deg.C under atmosphere for 30min to remove oxygen, adding 1mL aqueous solution of initiator AIBA (25mg), and gradually changing reaction solution into milky white after 1 min. And reacting for 7 hours till the reaction is complete, cooling and reducing the temperature, and separating out a small amount of white blocky solid. The milky white reaction solution was poured into a 250mL beaker, and 2mL of 30 wt% H was added2O2And 0.0661g Na2WO4The reaction was stirred at room temperature for 24 hours, and the reaction solution gradually turned pale yellow and slightly pink. 2mL of H were added2O2Continuously stirring the solution at room temperature for reacting for 24 hours; the reaction solution was dialyzed with a dialysis bag containing MWCO 3500 for 6 days to obtain pure Poly (TEMPO-co-VIMS) copolymer. The reaction principle is shown in chemical reaction formula (2).
Example 2
Preparation of Poly (CVBD) copolymer by one-pot Process
First, VBD (5mmol, 1.5380g) was added to a two-necked flask, light yellow liquid 3-chloro-2-hydroxypropyltrimethylammonium oxide (6mmol, 1500uL) was added, 50mL of ethanol solvent was added, and the mixture was stirred under N2Condensing and reacting at 95 ℃ for 48h in the atmosphere, stopping condensing and refluxing to ensure that the methanol solvent is completely volatilized to obtain an orange-red whitish solid, washing the orange-red whitish solid with acetonitrile for 3 times, performing suction filtration and vacuum drying to obtain 1.1378g of the orange-red solid, namely 3- ((4-vinylbenzyl) - [4,4' -bipyridine]1,1' -diimmonium) propane-1-sulfonic acid Chloride (CVBD), weighing a yield of 46%. The reaction principle is shown in chemical reaction formula (3).
Next, CVBD monomer (4mmol, 1.9800g) and 50mL deionized water solvent were added to a two-necked flask, which was maintained N-filled at 70 deg.C2After 30min of atmosphere, 1ml of APS initiator (50mg) aqueous solution was injected, the red solution gradually turned white (3min), the reaction was maintained at 70 ℃ for 6h, heating was stopped to obtain a reddish white turbid solution, deionized water was dialyzed for 6 days to obtain a suspension containing reddish-brown precipitates, and the pure reaction solution was freeze-dried to obtain 0.7845g of a red solid Poly (CVBD) copolymer. The reaction principle is shown in chemical reaction formula (4).
Electrochemical performance test
(1) Poly (TEMPO-co-VIMS) copolymer solutions (0.36 mg/mL in aqueous sodium chloride at pH 7) were studied by Cyclic Voltammetry (CV) with a sweep rate of 0.1V/s. From FIG. 5, the characteristic reduction peak E of the Poly (TEMPO-1.0VIMS) copolymer can be seenpa-0.480V and corresponding oxidation peak Epc-0.373V; and characteristic reduction Peak E of Poly (TEMPO-0.5VIMS) copolymerpa-0.172V and corresponding oxidation peak Epc＝0.491V。
(2) Solutions of poly (cvbd) copolymer (1.38 mg/mL in aqueous sodium chloride at pH 7) were studied by Cyclic Voltammetry (CV). As the scan rate increases in fig. 6, the peak current increases, but the peak value of the peak voltage becomes less and less noticeable. When the scan rate was set at 0.1V/s for the test, the Poly (CVBD) copolymer exhibited a pair of redox peaks, where the voltage E at the reduction peak waspa-0.606V and corresponding oxidation peak voltage EpcHalf-wave voltage E of-0.338V1/2-0.472V. This indicates that the poly (cvbd) copolymer is likely to undergo a one-electron redox reaction at a voltage lower than-0.472V, and the reversibility of electrochemical activity is good.
(3) 37.65mg/mL of mixed solution of V1 polymer nanoparticle suspension and 0.1M NaCl is added into the left negative electrode electrolyte tank, and 50.07mg/mL of mixed solution of T1 polymer nanoparticle suspension and 0.1M NaCl is added into the right positive electrode electrolyte tank, and a regenerated cellulose RC membrane (MWCO ═ 1KD, 3.5 × 3 ═ 0.45cm) of Shanghai biological engineering Co Ltd is adopted as a separation membrane. During the test, the test is set to be static for 5min, then the test is carried out for 100 times in a circulating way by constant current charging (the current is 20mA, the voltage is less than or equal to 1.7V) and constant current discharging (the current is 20mA, the voltage is less than or equal to 0.3V), and finally the test is finished. FIG. 7 is a graph of the cycling stability of the polymer Poly (TEMPO-co-VIMS) -Poly (CVBD).
Through charge and discharge tests, the capacitance and coulombic efficiency stability of the aqueous organic polymer flow battery are improved by using TEMPO functionalized organic polymer nanoparticles and viologen functionalized polymer nanoparticles as active substances.
As shown in fig. 1, according to the organic polymer flow battery system 100 of the embodiment of the present invention, by using a device combining two electrolyte reservoirs 10 and a flow battery stack 20, the flow battery stack 20 uses a device combining two electrode plates 21, an electrolytic cell body, a battery diaphragm 24, a circulation pipeline 25, a circulation pump 26, and a current collector 27, and uses TEMPO functionalized organic polymer nanoparticles and viologen functionalized polymer nanoparticles as active materials as a positive active material and a negative active material, respectively, the organic polymer flow battery system 100 can be applied to a battery environment of a salt cavity system (using an in-situ generated electrolyte), has the advantages of low cost, easy preparation of active materials, high safety, high energy density, stable charging and discharging performance, and high solubility of active materials, and can solve the problem of electrochemical energy storage in a large scale (megawatt/megawatt hour), fully utilizes some waste salt cavern (ore) resources.
In summary, the organic polymer flow battery system 100 according to the embodiment of the present invention has the advantages of low cost, high safety, stable charge and discharge performance, high solubility of active materials, easy preparation, good electrochemical activity, and the like, and is suitable for a battery environment using an in-situ generated electrolyte, thereby solving the problem of large-scale electrochemical energy storage and fully utilizing some waste salt cavern resources.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (22)
1. An organic polymer flow battery system, comprising:
the electrolyte system comprises two electrolyte liquid reservoirs, wherein the two electrolyte liquid reservoirs are distributed at intervals, electrolyte is stored in a dissolving cavity of each electrolyte liquid reservoir, a positive electrode active substance is arranged in the electrolyte in one electrolyte liquid reservoir, the positive electrode active substance is a TEMPO functional organic polymer, a negative electrode active substance is arranged in the electrolyte in the other electrolyte liquid reservoir, the negative electrode active substance is an viologen functional organic polymer, the positive electrode active substance and the negative electrode active substance are directly dissolved or dispersed in a system taking water as a solvent in a body form and are respectively stored in the corresponding electrolyte liquid reservoirs, and the supporting electrolyte is dissolved in the system;
the flow battery stack is communicated with the electrolyte liquid storage, and the electrolyte is input into or output from the electrolyte liquid storage to perform oxidation-reduction reaction; wherein,
the chemical structural formula of the TEMPO functionalized organic polymer is as follows:
the chemical structural formula of the viologen functionalized organic polymer is as follows:
2. the organic polymer flow battery system of claim 1, wherein the TEMPO functionalized organic polymer is obtained by taking 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-methyl piperidine containing anode active molecules, self-synthesized water-soluble VIMS as a monomer, and initiating a free radical polymerization reaction by using a water-soluble initiator, wherein the chemical reaction formulas of the monomers are shown as formula (1) and formula (2):
3. the organic polymer flow battery system of claim 2, wherein the preparation of the TEMPO functionalized organic polymer comprises the steps of:
s11 preparation of 1-vinylimidazoleMixing with 1, 3-propane sultone, adding acetonitrile solvent, and adding N2Stirring and reacting under the atmosphere, carrying out suction filtration on the obtained reaction solution after the reaction is finished, washing, and finally carrying out vacuum drying to obtain white powdery solid particles VIMS;
s12, mixing 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-methyl piperidine and VIMS, and adding deionized water, N2Heating and stirring to remove oxygen in the atmosphere, adding the aqueous solution of the initiator to react, cooling and cooling after the reaction is completed, and adding H into the reaction solution2O2And Na2WO4Stirring the mixture at normal temperature to react, gradually turning the reaction solution into light yellow and slightly pink, and adding H2O2Continuously stirring the solution at room temperature for reaction; then dialyzing the reaction solution to obtain pure TEMPO functionalized organic polymer.
4. The organic polymer flow battery system of claim 3, wherein the initiator in step S12 is one or more of azobisisobutylamidine hydrochloride, dimethyl azobisisobutyrate, and azobisisobutylimidazoline hydrochloride.
5. The organic polymer flow battery system of claim 2, wherein the molar ratio of monomeric 2-methyl-2-propenoic acid-2, 2,6, 6-tetramethyl-4-piperidinemethyl ester to monomeric VIMS is 1:1 to 1: 2.
6. The organic polymer flow battery system of claim 1, wherein the viologen-functionalized organic polymer copolymer is obtained by using a water-soluble initiator to initiate the polymerization of a monomer, which is a self-synthesized 3- ((4-vinylbenzyl) - [4,4 '-bipyridyl ] -1,1' -diimmonium group) propane-1-sulfonic acid chloride monomer, and the chemical reaction formulas of the monomer are shown as formula (3) and formula (4):
7. the organic polymer flow battery system of claim 6, wherein the preparation of the viologen-functionalized organic polymer copolymer comprises the steps of:
s21, mixing 4-vinylbenzyl- (4,4' -bipyridine) onium salt and 3-chloro-2-hydroxypropyl trimethyl ammonium oxide, adding ethanol solvent, and adding ethanol solvent in N2Condensing and reacting under the atmosphere, evaporating the solvent after the reaction is finished to obtain an orange red whitish solid, washing with acetonitrile, filtering, and drying in vacuum to finally obtain the orange red solid 3- ((4-vinyl benzyl) - [4,4' -bipyridine)]-1,1' -diimmonium) propane-1-sulfonic acid chloride;
s22, mixing the 3- ((4-vinyl benzyl) - [4,4' -dipyridine)]Dissolving the (1, 1' -diimmonium) propane-1-sulfonic acid chloride monomer in deionized water solvent, filling with N2Deoxidizing, then injecting an aqueous solution of an initiator, stopping heating after the reaction is finished to obtain a turbid liquid with reddish white, dialyzing with deionized water to obtain a turbid liquid containing reddish brown precipitates, and freeze-drying the pure reaction liquid to obtain a red solid of the viologen-functionalized organic polymer.
8. The organic polymer flow battery system of claim 7, wherein the initiator in the step S22 is one of potassium persulfate, ammonium persulfate and benzoin dimethyl ether.
9. The polymer flow battery system of claim 1, wherein the concentration of the positive electrode active material and the negative electrode active material are both 0.1 mol-L-1～3.0mol·L-1。
10. The polymer flow battery system of claim 1, wherein each electrolyte reservoir is a salt cavern with a physical cavern formed after mining of a salt mine.
11. The polymer flow battery system of claim 1, wherein the electrolyte reservoir is a pressurized sealed container with a pressure of 0.1MPa to 0.5 MPa.
12. The polymer flow battery system of claim 1, wherein an inert gas is introduced into the electrolyte reservoir to purge and maintain pressure.
13. The polymer flow battery system of claim 12, wherein the inert gas is nitrogen or argon.
14. The polymer flow battery system of claim 1, further comprising:
the battery diaphragm, the battery diaphragm is located the electrolytic cell body and will the electrolytic cell body is separated for with one the positive pole district of electrolyte liquid storage storehouse intercommunication and with another the negative pole district of electrolyte liquid storage storehouse intercommunication, have in the positive pole district including anodal active material's positive pole electrolyte, have in the negative pole district including negative pole active material's negative pole electrolyte, the battery diaphragm can supply support the electrolyte to pierce through, prevents anodal active material with negative pole active material pierces through, the battery diaphragm is anion exchange membrane, cation exchange membrane or is that the aperture is 10nm ~ 300 nm's polymer porous membrane.
15. The polymer flow battery system of claim 1, wherein the supporting electrolyte is a NaCl salt solution, a KCl salt solution, Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, MgSO4Salt solution, CaCl2Salt solution, NH4At least one of a Cl salt solution.
16. The polymer flow battery system of claim 15, wherein the supporting electrolyte has a molar concentration of 0.1 mol-L-1～8.0mol·L-1。
17. The polymer flow battery system of claim 14, wherein electrodes are disposed in the anode region and the cathode region, respectively, and the positive and negative electrodes are carbon material electrodes.
18. The polymer flow battery system of claim 17, wherein the carbon material electrode is one or more of carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fiber, activated carbon particles, graphene, graphite felt, and a glass carbon material.
19. The polymer flow battery system of claim 17, wherein the electrodes are formed as electrode plates having a thickness of 2mm to 8 mm.
20. The polymer flow battery system of claim 1, further comprising:
and the current collectors are respectively arranged on two sides of the flow battery stack and can collect and conduct current generated by active substances of the flow battery stack to an external lead.
21. The polymer flow battery system of claim 20, wherein the current collector is one of a conductive metal plate, a graphite plate, or a carbon-plastic composite plate.
22. The polymer flow battery system of claim 21, wherein the conductive metal plate comprises at least one metal of copper, nickel, and aluminum.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478902A (en) * | 2022-01-07 | 2022-05-13 | 中盐金坛盐化有限责任公司 | Water-based positive electrode polymer, preparation method thereof and small-molecule flow battery system |
| WO2022236241A1 (en) * | 2021-05-03 | 2022-11-10 | Wisconsin Alumni Research Foundation | Pyridinium derivatives made by hydrothermal synthesis for use as anolytes in electrochemical cells |
| CN118373841A (en) * | 2024-06-21 | 2024-07-23 | 天合光能股份有限公司 | Ionic liquid and preparation method thereof, perovskite solar cell and preparation method thereof, and photovoltaic module |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180072669A1 (en) * | 2016-07-25 | 2018-03-15 | Utah State University | Materials for use in an aqueous organic redox flow battery |
| CN108140864A (en) * | 2015-08-07 | 2018-06-08 | 耶拿电池有限公司 | Redox flow batteries for storing electric energy and application thereof |
| CN109378510A (en) * | 2018-10-25 | 2019-02-22 | 中盐金坛盐化有限责任公司 | The organic flow battery system of aqueous phase system based on salt cave |
| CN110444787A (en) * | 2019-08-22 | 2019-11-12 | 中盐金坛盐化有限责任公司 | Flow battery system based on amino anthraquinones derivative |
-
2020
- 2020-06-18 CN CN202010562492.9A patent/CN111564649B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108140864A (en) * | 2015-08-07 | 2018-06-08 | 耶拿电池有限公司 | Redox flow batteries for storing electric energy and application thereof |
| US20180072669A1 (en) * | 2016-07-25 | 2018-03-15 | Utah State University | Materials for use in an aqueous organic redox flow battery |
| CN109378510A (en) * | 2018-10-25 | 2019-02-22 | 中盐金坛盐化有限责任公司 | The organic flow battery system of aqueous phase system based on salt cave |
| CN110444787A (en) * | 2019-08-22 | 2019-11-12 | 中盐金坛盐化有限责任公司 | Flow battery system based on amino anthraquinones derivative |
Non-Patent Citations (2)
| Title |
|---|
| 韩俊甜等: "应用于水相有机液流电池的双电子紫精化合物", 《高等学校化学学报》 * |
| 韩红静等: "盐穴电池储能技术及发展前景", 《全球能源互联网》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022236241A1 (en) * | 2021-05-03 | 2022-11-10 | Wisconsin Alumni Research Foundation | Pyridinium derivatives made by hydrothermal synthesis for use as anolytes in electrochemical cells |
| CN114478902A (en) * | 2022-01-07 | 2022-05-13 | 中盐金坛盐化有限责任公司 | Water-based positive electrode polymer, preparation method thereof and small-molecule flow battery system |
| CN118373841A (en) * | 2024-06-21 | 2024-07-23 | 天合光能股份有限公司 | Ionic liquid and preparation method thereof, perovskite solar cell and preparation method thereof, and photovoltaic module |
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