CN111584915A - Aqueous nano polymer flow battery system - Google Patents

Aqueous nano polymer flow battery system Download PDF

Info

Publication number
CN111584915A
CN111584915A CN202010557305.8A CN202010557305A CN111584915A CN 111584915 A CN111584915 A CN 111584915A CN 202010557305 A CN202010557305 A CN 202010557305A CN 111584915 A CN111584915 A CN 111584915A
Authority
CN
China
Prior art keywords
flow battery
battery system
electrolyte
nano
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010557305.8A
Other languages
Chinese (zh)
Other versions
CN111584915B (en
Inventor
徐俊辉
陈留平
崔耀星
武奕
苏志俊
李丹
马旭强
杜滨阳
朱足妹
聂晶晶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
China Salt Jintan Co Ltd
Original Assignee
Zhejiang University ZJU
China Salt Jintan Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU, China Salt Jintan Co Ltd filed Critical Zhejiang University ZJU
Priority to CN202010557305.8A priority Critical patent/CN111584915B/en
Publication of CN111584915A publication Critical patent/CN111584915A/en
Application granted granted Critical
Publication of CN111584915B publication Critical patent/CN111584915B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • 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
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a water-based nano polymer flow battery system, which comprises a positive active material and a negative active material, wherein TEMPO functional polymer nano particles are used as the positive active material, viologen functional polymer nano particles are used as the negative active material, and the chemical structural formula of the TEMPO functional polymer nano particles is as follows:
Figure DDA0002544747560000011
the chemical structural formula of the viologen functionalized polymer nano-particles is as follows:
Figure DDA0002544747560000012
the aqueous nano polymerThe compound flow battery system is suitable for the battery environment of a salt cavern system (electrolyte generated in situ is utilized), and has the advantages of low cost, easy preparation of active materials, high stability, high response speed, environmental friendliness and the like.

Description

Aqueous nano polymer flow battery system
Technical Field
The invention belongs to the field of flow batteries, and particularly relates to a water-based nano polymer flow battery system.
Background
With the rapid development of human economy, the problems of environmental pollution, energy shortage and the like are increasingly aggravated, and the world countries are promoted to widely develop and utilize renewable energy sources such as wind energy, solar energy, tidal energy and the like. However, the renewable energy sources have the characteristics of discontinuity, instability, limitation by regional environment and difficult grid connection, so that the utilization rate is low, the wind and light abandoning rate is high, and resources are wasted. There is a need for a robust development of efficient, inexpensive, safe and reliable energy storage technology that can be used in conjunction therewith.
Among various electrochemical energy storage strategies, flow batteries (RFBs) have several particular technical advantages over static batteries such as lithium ion batteries and lead acid batteries, and are most suitable for large-scale (megawatt/megawatt hour) electrochemical energy storage, such as relatively independent energy and power control, high-current and high-power operation (fast response), high safety (mainly, non-flammability and non-explosion), and the like. The redox active material is a carrier for energy conversion of the flow battery and is also the most core part in the flow battery. The current commercialized all-vanadium redox flow battery utilizes inorganic materials as active substances, and the large-scale utilization of the all-vanadium redox flow battery is limited by the defects of high cost, toxicity, limited resources, low electrochemical activity and the like of the inorganic materials.
Polymers have good stability and diversified design properties, and have been widely studied as active materials for flow batteries 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, the polymer functionalized by viologen and TEMPO with excellent electrochemical activity is designed and introduced to be used 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 a powerful support is provided 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 invention provides a waterborne nano-polymer flow battery system, which comprises TEMPO functional polymer nano-particles (Poly (TEMPO-co-APTMACl)) and viologen functional polymer nano-particles (Poly (SVBD-co-APTMACl)), wherein the TEMPO functional polymer nano-particles can be used as positive active substances, the viologen functional polymer nano-particles can be used as negative active substances, and in the charging and discharging process, cheap permeable membranes are selected as ion exchange isolating membranes, so that the cost of the battery is reduced, the ion permeability of the battery is improved, and the effective discharge capacity and the energy efficiency of the waterborne nano-polymer flow battery system are further improved.
The aqueous nano polymer flow battery system comprises a positive electrode active material and a negative electrode active material, wherein TEMPO functionalized polymer nano particles are used as the positive electrode active material, viologen functionalized polymer nano particles are used as the negative electrode active material, and the chemical structural formula of the TEMPO functionalized polymer nano particles is as follows:
Figure BDA0002544747540000021
wherein TEMPO is used as the most main oxidation-reduction active site, and quaternary ammonium salt connected on the polymer is used for increasing the solubility;
the chemical structural formula of the viologen functionalized polymer nano-particles is as follows:
Figure BDA0002544747540000022
wherein, the viologen is used as a main oxidation-reduction active site, and the solubility is increased by utilizing the quaternary ammonium salt and the sulfonic acid group connected on the polymer.
According to the embodiment of the invention, the waterborne nano polymer flow battery system is provided, wherein TEMPO functionalized polymer nano particles are used as positive active materials, and viologen functionalized polymer nano particles are used as negative active materials. The positive active material and the negative active material are both organic polymers, so that cross contamination among ions can be effectively prevented, the problem of efficiency reduction caused by the fact that the discharge capacity is improved by improving the concentration of electrolyte can be solved, the organic polymer redox flow battery with the outstanding advantages of strong stability, good safety, flexible configuration, high response speed, environmental friendliness and the like can be obtained, and TEMPO functional polymer nanoparticles are prepared through free radical polymerization. Namely, the flow battery system has the advantages of easy preparation of active materials, high safety performance, high energy density, stable charge and discharge performance, high solubility of the active materials and the like.
According to one embodiment of the present invention, the preparation of the TEMPO functionalized polymer nanoparticles comprises the following steps: 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-methyl piperidine containing anode active molecules and water-soluble (3-acrylamide propyl) trimethyl ammonium chloride are used as monomers, a water-soluble initiator initiates free radical polymerization reaction to prepare the TEMPO functionalized polymer nanoparticles, and the chemical reaction formula is shown as formula (1):
Figure BDA0002544747540000031
according to one embodiment of the invention, the preparation of the TEMPO functionalized polymer nanoparticles comprises the following specific steps: s11, mixing 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-methyl piperidine and water-soluble (3-acrylamide propyl) trimethyl ammonium chloride, adding deionized water solvent, and adding into N2Heating and stirring to remove oxygen in the atmosphere, and then dropwise adding an aqueous solution of an initiator to react; s12, stopping heating after the reaction is finished, cooling to room temperature, pouring the reaction liquid into a beaker, and adding H2O2And Na2WO4Stirring at room temperature to react, forming a layer of white foam on the upper layer, and adding H2O2Continuously stirring the solution at room temperature for reaction; and S13, dialyzing the reaction solution by using a dialysis bag with the molecular weight cutoff of 3500, and freeze-drying to obtain the TEMPO functionalized polymer nano-particles.
According to one embodiment of the invention, the initiator is one or more of azobisisobutylamidine hydrochloride, dimethyl azobisisobutyrate and azobisisobutylimidazoline hydrochloride.
According to one embodiment of the invention, the monomer molar charge ratio of 2,2,6, 6-tetramethyl-4-piperidyl methyl 2-methyl-2-acrylate to water-soluble (3-acrylamidopropyl) trimethylammonium chloride is 1.0-1.5.
According to one embodiment of the present invention, the preparation of the viologen-functionalized polymer nanoparticles comprises the steps of: 4,4' -bipyridine is used as a raw material to gradually synthesize SVBD monomer micromolecules containing negative active molecules, and then a water-soluble (3-acrylamidopropyl) trimethyl ammonium chloride monomer and the SVBD monomer micromolecules are introduced to carry out copolymerization reaction to prepare the viologen functionalized polymer nanoparticles with good water solubility, wherein the chemical reaction formulas are shown as formulas (2) to (4):
Figure BDA0002544747540000041
according to one embodiment of the present invention, the preparation of the viologen-functionalized polymer nanoparticles comprises the steps of: s21, mixing 4,4' -bipyridine and 4-chloromethyl styrene, adding acetonitrile solvent, and adding N2Heating and stirring the mixture to react under the atmosphere, stopping the reaction after the solution is yellow turbid liquid, cooling the solution to room temperature, separating out a large amount of yellow powdery precipitate, carrying out suction filtration on the reaction liquid, respectively washing the reaction liquid by acetonitrile and acetone, and drying the reaction liquid in vacuum to obtain white powdery solid vinylbenzyl-4, 4' -bipyridyl chloride; s22, mixing the vinyl benzyl-4, 4 '-bipyridyl chloride salt prepared in the step S21 and 1, 3-propane sultone, adding an N, N' -dimethylformamide solvent, and adding a N-dimethylformamide solvent2Heating and condensing in the atmosphere, stopping heating after the reaction is completed, cooling to room temperature, pouring the reaction solution into ethyl acetate containing ice for precipitation to separate out pink solid, performing suction filtration, washing with ethyl acetate, and performing vacuum drying to obtain the pink solid SVBD; s23, mixing the prepared SVBD monomer with (3-acrylamidopropyl) trimethyl ammonium chloride, adding deionized water solvent, and continuously filling N under heating condition2Deoxidizing, adding an aqueous solution of an aqueous initiator, keeping a heating condition for reaction, stopping heating after the reaction is finished to obtain yellow turbid liquid, dialyzing with dialysis bag deionized water with molecular weight cutoff of 3500, and freeze-drying to obtain orange yellow solid, wherein the solid is the viologen functionalized polymer nanoparticles.
According to one embodiment of the invention, the initiator is one of potassium persulfate, ammonium persulfate and benzoin dimethyl ether.
According to an embodiment of the present invention, the aqueous nano-polymer flow battery system further includes: the electrolyte comprises two electrolyte liquid reservoirs, wherein the two electrolyte liquid reservoirs are arranged at intervals, each electrolyte liquid reservoir is a liquid storage tank for storing electrolyte or a salt cave which is formed after salt mine mining and is provided with a physical dissolution cavity, the electrolyte in one electrolyte liquid reservoir comprises the positive active substance and supporting electrolyte, the electrolyte in the other electrolyte liquid reservoir comprises the negative active substance and supporting electrolyte, and the positive active substance and the negative active substance are respectively directly dissolved or dispersed in a system taking water as a solvent in a bulk form; the flow battery stack comprises a battery diaphragm, the battery diaphragm divides the flow battery stack into an anode area and a cathode area which are distributed at intervals, the anode area is communicated with one electrolyte liquid storage tank, and the cathode area is communicated with the other electrolyte liquid storage tank.
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 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 one embodiment of the invention, the battery diaphragm is an anion exchange membrane, a cation exchange membrane or a polymer porous membrane with a pore size of 10nm to 300 nm.
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 an embodiment of the present invention, the aqueous nano-polymer flow battery system further includes: 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 aqueous nano-polymer flow battery system according to an embodiment of the present invention;
FIG. 2(a) is a graph of Poly (TEMPO-co-APTMACL) at D of example 1 according to the present invention2Nuclear magnetic hydrogen spectra in O solvent;
FIG. 2(b) is a graph of Poly (TEMPO-co-1.5APTMACL) at D of example 1 according to the invention2Nuclear magnetic hydrogen spectra in O solvent;
FIG. 3 is a GPC curve of Poly (TEMPO-co-APTMACL) according to example 1 of the present invention;
FIG. 4(a) is a view of VBD according to embodiment 2 of the present invention1HNMR spectrogram;
FIG. 4(b) is a view of VBD according to embodiment 2 of the present invention13CNMR spectrogram;
FIG. 5(a) is a diagram of an SVBD according to embodiment 2 of the present invention1HNMR spectrogram;
FIG. 5(b) is a diagram of an SVBD according to embodiment 2 of the present invention13CNMR spectrogram;
FIG. 6 is a 1HNMR spectrum of Poly (SVBD-APTMCl) according to example 2 of the present invention;
FIG. 7 is a graph of CV for Poly (TEMPO-co-APTMACL) (Poly (TEMPO-co-APTMACL) concentration of 5mg/mL in a solution of 1M NaCl as a supporting electrolyte) at different scan rates according to an embodiment of the present invention;
FIG. 8 is a CV diagram of Poly (SVBD-APTMCl) (a mixed solution of Poly (SVBD-co-APTMCl) at a concentration of 0.05mg/mL in 0.1M NaCl as a supporting electrolyte) at a scan rate of 0.1V/s according to an embodiment of the present invention;
FIG. 9 is a graph of the cycling stability of the polymer Poly (TEMPO-co-APTMACl) -Poly (SVBD-APTMCl) according to an embodiment of the present invention.
Reference numerals:
an aqueous nano-polymer flow battery system 100;
an electrolyte reservoir 10;
a flow cell stack 20; a pole 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 aqueous nano-polymer flow battery system 100 according to an embodiment of the present invention is described below with reference to the accompanying drawings.
The aqueous nano-polymer flow battery system 100 according to an embodiment of the invention includes a positive active material and a negative active material.
Specifically, the TEMPO functionalized polymer nanoparticles (abbreviated as Poly (TEMPO-co-APTMACl)) are used as the positive active material, the viologen functionalized polymer nanoparticles (abbreviated as Poly (SVBD-co-APTMACl)) are used as the negative active material, and the chemical structural formula of the TEMPO functionalized polymer nanoparticles is as follows:
Figure BDA0002544747540000072
the chemical structural formula of the viologen functionalized polymer nano-particles is as follows:
Figure BDA0002544747540000071
according to one embodiment of the invention, the preparation of Poly (TEMPO-co-APTMACL) polymer comprises the following steps: poly (TEMPO-co-APTMACl) is prepared by taking 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-methyl piperidine (TEMPMA) containing anode active molecules and water-soluble (3-acrylamide propyl) trimethyl ammonium chloride (APTMACl) as monomers and initiating a free radical polymerization reaction by a water-soluble initiator, wherein the chemical reaction formula is shown as the formula (1):
Figure BDA0002544747540000081
in other words, the aqueous nano-polymer flow battery system 100 includes positive active material TEMPO functionalized polymer nanoparticles and negative active material viologen functionalized polymer nanoparticles. The positive active material and the negative active material are both organic polymers, and viologen with excellent electrochemical activity and TEMPO functionalized polymer are introduced as redox couples through design. The positive active material is prepared by initiating a free radical polymerization reaction of 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-methyl piperidine containing positive active molecules and water-soluble (3-acrylamide propyl) trimethyl ammonium chloride under the action of a water-soluble initiator, and introducing a positive active group (TEMPO).
Thus, the aqueous nano-polymer flow battery system 100 according to an embodiment of the present invention, wherein the TEMPO functionalized polymer nanoparticles are positive active materials and the viologen functionalized polymer nanoparticles are negative active materials. The positive active material and the negative active material are both organic polymers, so that cross contamination among ions can be effectively prevented, the problem of efficiency reduction caused by the fact that the discharge capacity is improved by improving the concentration of electrolyte can be solved, the organic polymer redox flow battery with the outstanding advantages of strong stability, good safety, flexible configuration, high response speed, environmental friendliness and the like can be obtained, and TEMPO functional polymer nanoparticles are prepared through free radical polymerization. Namely, the flow battery system has the advantages of easy preparation of active materials, high safety performance, high energy density, stable charge and discharge performance, high solubility of the active materials and the like.
According to one embodiment of the present invention, the preparation of Poly (TEMPO-co-APTMACl) polymer comprises the following specific steps: s11, mixing TEMPMA and APTMACl, adding deionized water solvent, and adding into N2Heating and stirring to remove oxygen in the atmosphere, wherein the heating temperature can be 70 ℃, and then dropwise adding an aqueous solution of an initiator to carry out reaction. S12, stopping heating after the reaction is finished, cooling to room temperature, pouring the reaction liquid into a beaker, and adding H2O2And Na2WO4The reaction mixture solution finally turned yellow and formed a white foam floating on the upper layer. Then adding H2O2Continuously stirring the solution at room temperature for reaction; s13, dialyzing the reaction solution for 6 days by using a dialysis bag with the molecular weight cut-off (MWCO) of 3500, and freeze-drying to obtain the Poly (TEMPO-co-APTMACl) polymer.
Optionally, the initiator is one or more of azobisisobutylamidine hydrochloride (AIBA), dimethyl Azobisisobutyrate (AIBME) and azobisisobutylimidazoline hydrochloride (AIBI).
Further, the monomer molar charge ratio of the TEMPMA to the APTMACl is 1.0-1.5.
According to one embodiment of the present invention, the preparation of Poly (SVBD-co-APTMACl) polymer comprises the following steps: 4,4' -bipyridine (hereinafter referred to as BIPY) is used as a raw material to gradually synthesize SVBD monomer micromolecules containing negative active molecules, and then a water-soluble (3-acrylamidopropyl) trimethyl ammonium chloride monomer (hereinafter referred to as APTMACl) and the SVBD monomer micromolecules are introduced to carry out copolymerization reaction to prepare Poly (SVBD-co-APTMACl) with good water solubility, wherein the chemical reaction formulas are shown as formulas (2) to (4):
Figure BDA0002544747540000091
according to another embodiment of the present invention, the preparation of Poly (SVBD-co-APTMACL) comprises the following steps: s21, mixing 4,4' -Bipyridine (BIPY) and 4-chloromethyl styrene, adding acetonitrile solvent, and adding N2Heating and stirring the mixture to react under the atmosphere, stopping the reaction after the solution is yellow turbid liquid, cooling the solution to room temperature, separating out a large amount of yellow powdery precipitate, carrying out suction filtration on the reaction solution, respectively washing the reaction solution for 2 times by using acetonitrile and acetone, and drying the reaction solution in vacuum to obtain white powdery solid vinylbenzyl-4, 4' -bipyridyl chloride (VBD); s22, mixing the vinyl benzyl-4, 4 '-bipyridyl chloride salt prepared in the step S21 and 1, 3-propane sultone, adding N, N' -dimethylformamide (VBD) solvent, and adding N2Heating and condensing in the atmosphere, wherein the heating temperature can be 70 ℃, stopping heating after the reaction is completed, cooling to room temperature, pouring the reaction solution into ethyl acetate containing ice for precipitation, separating out pink solid, performing suction filtration, washing for 3 times by ethyl acetate, and performing vacuum drying to obtain the pink solid SVBD; s23, mixing the prepared SVBD monomer with (3-acrylamidopropyl) trimethyl ammonium chloride (APTMACL), adding a proper amount of deionized water solvent, and continuously filling N under the heating condition2Deoxidizing, wherein the heating temperature can be 70 ℃, adding an aqueous solution of an aqueous initiator, keeping the heating condition for reaction, the heating temperature can be 70 ℃, stopping heating after the reaction is finished to obtain yellow turbid liquid, dialyzing for 6 days by using deionized water in a dialysis bag with the MWCO of 3500, and freeze-drying to obtain orange-yellow solid, wherein the solid is the Poly (SVBD-co-APTMACl) polymer.
Optionally, the initiator is one of potassium persulfate (KPS), Ammonium Persulfate (APS), benzoin dimethyl ether (DMPA).
As shown in fig. 1, the aqueous nano-polymer flow battery system 100 according to an embodiment of the present invention further includes: the electrolyte comprises two electrolyte liquid storage banks 10 and a flow battery stack 20, wherein the two electrolyte liquid storage banks 10 are arranged at intervals, each electrolyte liquid storage bank 10 is a liquid storage tank for storing electrolyte or a salt hole which is formed after salt mine mining and has a physical dissolution cavity, the electrolyte in one electrolyte liquid storage bank 10 comprises a positive electrode active substance and a supporting electrolyte, the electrolyte in the other electrolyte liquid storage bank 10 comprises a negative electrode active substance and the supporting electrolyte, wherein the positive electrode active substance is a TEMPO functional polymer nanoparticle (abbreviated as Poly (TEMPO-co-APTMACl)), and the negative electrode active substance is an ionene functional polymer nanoparticle (abbreviated as Poly (SVBD-co-APTMACl)). The positive active material and the negative active material are respectively directly dissolved or dispersed in a system taking water as a solvent in a body form, the flow battery stack 20 comprises a battery diaphragm 24, the battery diaphragm 24 divides the flow battery stack 20 into an anode region and a cathode region which are distributed at intervals, the anode region is communicated with one electrolyte liquid storage bank 10, and the cathode region is communicated with the other electrolyte liquid storage bank 10. The positive active substance and the negative active substance are both organic polymers, and the composite macromolecular active substance with the positive active group (TEMPO) and the negative active group (Vilogen) is simultaneously introduced into the organic polymers, 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 by increasing the concentration of the electrolyte can be solved.
Alternatively, 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 present invention, the electrolyte reservoir is a pressurized sealed container having a pressure of 0.1MPa to 0.5 MPa.
Further, inert gas is introduced into the electrolyte reservoir 10 to purge and maintain the pressure, and the electrolyte can be protected by the inert gas all the time during the charging and discharging processes.
Preferably, the inert gas is nitrogen or argon.
According to one embodiment of the present invention, the battery separator 24 is an anion exchange membrane, a cation exchange membrane, or a polymer porous membrane having a pore size of 10nm to 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 Cl salt solution, supporting electrolyte can be dissolved in the system, and the battery diaphragm can be penetrated by the supporting electrolyte and prevent the positive electrode active material and the negative electrode active material from penetrating.
Further, the molar concentration of the supporting electrolyte was 0.1mol · L-1～8.0mol·L-1。
In some embodiments of the invention, electrodes are disposed in the anode region and the cathode region, respectively, and the positive and negative electrodes 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 an embodiment of the present invention, the aqueous nano-polymer flow battery system 100 further comprises: the current collectors 27 and 27 are respectively disposed on two sides of the flow cell stack 20, and the current collectors 27 can collect and conduct the current generated by the active materials of the flow cell 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.
Preferably, the conductive metal plate includes at least one metal of copper, nickel, and aluminum.
Therefore, the aqueous nano 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 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 aqueous nano-polymer flow battery system 100 according to an embodiment of the present invention will be specifically described with reference to specific examples.
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
Poly (TEMPO-co-APTMACl) copolymer was prepared using a one-pot method:
first, 2-methyl-2-propenoic acid-2, 2,6, 6-tetramethyl-4-piperidinemethyl ester (TEMPMA, 4mmol, 0.9014g) as a white solid was added to a three-necked flask, a certain amount of a pale yellow liquid (3-acrylamidopropyl) trimethylammonium chloride solution (APTMACl, 4 or 6mmol) was transferred, 45mL of deionized water solvent was added thereto, and the mixture was subjected to N2Heating and stirring at 70 ℃ for 30min under the atmosphere, adding 1mL of AIBA (50mg) aqueous solution as an initiator, gradually changing the reaction liquid into milk white after half a minute, continuing to react for 6h, and cooling to room temperature to obtain a light yellow mixed solution.
Then, the resulting reaction solution was poured into a 250mL beaker, and 2.5mL of 30 wt% H was added2O2And 5mL of Na2WO4(0.0661g) the reaction mixture was stirred at room temperature for one day, and the reaction mixture finally became yellow and formed a white foam floating on the upper layer. 2.5mL of H were added2O2The solution was stirred at room temperature for one day.
Finally, the reaction solution was dialyzed for 6 days in a dialysis bag with MWCO of 3500 to obtain a series of linear chains of Poly (TEMPO-co-APTMACl) copolymers, and the reaction solution was freeze-dried to obtain a yellow fluffy solid.
Example 2
Poly (SVBD-co-APTMCl) copolymer was prepared in one pot:
first, 4' -bipyridine (20mmol, 3.1236g), pale yellow liquid 4-chloromethylstyrene (20mmol, 2.85mL), and 50mL acetonitrile solvent in a two-necked flask were added under N2Magnetically stirring at 70 deg.C under atmosphere for 3 hr to obtain yellow turbid solution, cooling to room temperature, precipitating a large amount of yellow powdery precipitate, vacuum filtering the reaction solution, washing with acetonitrile for 2 times, washing with acetone for 2 times, and vacuum drying to obtain white powdery solidBulk vinyl benzyl-4, 4' -bipyridyl chloride salt (VBD), weighed 2.6148g, and gave a 48.3% yield.
Then, VBD (5mmol, 1.5380g), a pale yellow liquid of 1, 3-propane sultone (6mmol, 527uL), and 50Ml of DMF solvent were added to a three-necked flask in N2And (3) condensing and reacting at 70 ℃ for 2h under the atmosphere, observing that the yellow reaction liquid gradually becomes a reddish brown mixed liquid, continuously reacting for 24h completely, cooling to room temperature, slowly pouring the reaction liquid into a large amount of ice ethyl acetate for precipitation, separating out a pink solid, performing suction filtration, washing with ethyl acetate for 3 times, and performing vacuum drying to obtain 1.9101g of the pink Solid (SVBD).
Finally, SVBD monomer (4mmol, 1.7202g), yellow liquid APTMACL (4mmol, 0.9014g) and 50mL deionized water solvent were added to a three-necked flask, and N was continuously charged at 70 deg.C2Injecting 1ml of APS initiator (50mg) aqueous solution under the atmosphere for 30min, gradually changing the red solution into yellow turbid solution, keeping the temperature at 70 ℃ for reacting for 8h, stopping heating to obtain yellow turbid solution, dialyzing with dialysis bag deionized water with MWCO of 3500 for 6 days, and standing for 1 day to precipitate yellow solid. The purified reaction solution was further freeze-dried to obtain 0.9063g of an orange-yellow solid (Poly (SVBD-APTMCl)).
Electrochemical property test
(1) In fig. 7, characteristic reduction peaks of TEMPO groups in Poly (TEMPO-1.0APTMACl) copolymer were slightly increased and peak currents were significantly increased with increasing scan rate by Cyclic Voltammetry (CV) to study Poly (TEMPO-co-APTMACl) copolymer solutions (Poly (TEMPO-co-APTMACl) concentration was 5mg/mL in 1 mnacal supporting electrolyte solution). Characteristic reduction peak voltage E of Poly (TEMPO-1.0APTMACl) copolymer at a scan rate of 0.3V/spa-0.305V and corresponding oxidation peak voltage Epc1.035V, half-wave potential E1/20.365V; characteristic reduction Peak E of Poly (TEMPO-1.5APTMACl) copolymerpa-0.187V and corresponding oxidation peak Epc0.993V, half-wave potential E1/20.403V. Furthermore, the peak areas of the oxidation peak and the reduction peak of the Poly (TEMPO-1.5APTMACl) copolymer are closer to 1:1, so that the Poly (TEMPO-1.5APTMACl) copolymer is more suitable for being used as the positive electrode active material.
(2) Poly (SVBD-co-APTMCl) copolymer solution (a mixed solution of Poly (SVBD-co-APTMCl) at a concentration of 0.05mg/mL in 0.1M NaCl as supporting electrolyte) was studied by Cyclic Voltammetry (CV) at a scan rate of 0.5V/s. The CV curve of this compound in FIG. 8 shows its reduction peak at around-0.500V and oxidation peak at around-0.420V.
(3) As shown in fig. 1, 43.17mg/mL of a mixed solution of Poly (SVBD-co-aptml) suspension and 0.1 mnaacl was added to the left negative electrode electrolyte tank, and 47.80mg/mL of a mixed solution of Poly (TEMPO-co-APTMACl) suspension and 0.1 mnaacl was added to the right positive electrode electrolyte tank, and a regenerated cellulose RC membrane (MWCO 1KD, 3.5 x 3 0.45cm) from shanghai bio-engineering gmbh was used as a separator. During the test, the test is set to be static for 5 min, 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. 9 is a graph of the cycling stability of the polymer Poly (TEMPO-co-APTMACl) -Poly (SVBD-APTMCl).
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.
According to the flow battery system 100 of the embodiment of the invention, by adopting a device combining two electrolyte liquid storage reservoirs 10 and a flow battery stack 20, the flow battery stack 20 adopts a device combining two polar plates 21, an electrolytic cell body, a battery diaphragm 24, a circulating pipeline 25, a circulating pump 26 and a current collector 27, and TEMPO functionalized organic polymer nanoparticles and viologen functionalized polymer nanoparticles are adopted as active materials to be respectively used as a positive active material and a negative active material, the flow battery system 100 can be suitable for the battery environment of a salt cavern system (by using electrolyte generated in situ), 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, meanwhile, the problem of electrochemical energy storage in a large scale (megawatt/megawatt hour) can be solved, and some waste salt cavern (ore) resources are fully utilized.
In summary, the aqueous nano polymer flow battery system 100 according to the embodiment of the present invention has the advantages of low cost, high safety performance, stable charging and discharging performance, high solubility of active materials, and the like, and the positive and negative active materials are easy to prepare, and can also solve the problem of large-scale electrochemical energy storage and fully utilize 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 aqueous nano polymer flow battery system, which is characterized by comprising a positive electrode active material and a negative electrode active material, wherein TEMPO functionalized polymer nano particles are used as the positive electrode active material, viologen functionalized polymer nano particles are used as the negative electrode active material, and the chemical structural formula of the TEMPO functionalized polymer nano particles is as follows:
Figure FDA0002544747530000011
the chemical structural formula of the viologen functionalized polymer nano-particles is as follows:
Figure FDA0002544747530000012
2. the aqueous nano-polymer flow battery system of claim 1, wherein the preparation of the TEMPO functionalized polymer nanoparticles comprises the steps of:
2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-methyl piperidine containing anode active molecules and water-soluble (3-acrylamide propyl) trimethyl ammonium chloride are used as monomers, a water-soluble initiator initiates free radical polymerization reaction to prepare the TEMPO functionalized polymer nanoparticles, and the chemical reaction formula is shown as formula (1):
Figure FDA0002544747530000021
3. the aqueous nano-polymer flow battery system of claim 2, wherein the preparation of the TEMPO functionalized polymer nanoparticles comprises the following specific steps:
s11, mixing 2-methyl-2-acrylic acid-2, 2,6, 6-tetramethyl-4-methyl piperidine and water-soluble (3-acrylamide propyl) trimethyl ammonium chloride, adding deionized water solvent, and adding into N2Heating and stirring to remove oxygen in the atmosphere, and then dropwise adding an aqueous solution of an initiator to react;
s12, stopping heating after the reaction is finished, cooling to room temperature, pouring the reaction liquid into a beaker, and adding H2O2And Na2WO4Stirring at room temperature to react, forming a layer of white foam on the upper layer, and adding H2O2Continuously stirring the solution at room temperature for reaction;
and S13, dialyzing the reaction solution by using a dialysis bag with the molecular weight cutoff of 3500, and freeze-drying to obtain the TEMPO functionalized polymer nano-particles.
4. The aqueous nano-polymer flow battery system of claim 2, wherein the initiator is one or more of azobisisobutylamidine hydrochloride, dimethyl azobisisobutyrate, and azobisisobutylimidazoline hydrochloride.
5. The synthesis method according to claim 1, wherein the monomer molar charge ratio of 2-methyl-2-propenoic acid-2, 2,6, 6-tetramethyl-4-piperidylmethyl ester to water-soluble (3-acrylamidopropyl) trimethylammonium chloride is 1.0-1.5.
6. The aqueous nano-polymer flow battery system of claim 1, wherein the preparation of the viologen-functionalized polymer nanoparticles comprises the steps of:
4,4' -bipyridine is used as a raw material to gradually synthesize SVBD monomer micromolecules containing negative active molecules, and then a water-soluble (3-acrylamidopropyl) trimethyl ammonium chloride monomer and the SVBD monomer micromolecules are introduced to carry out copolymerization reaction to prepare the viologen functionalized polymer nanoparticles with good water solubility, wherein the chemical reaction formulas are shown as formulas (2) to (4):
Figure FDA0002544747530000031
7. the synthesis method according to claim 6, characterized in that the preparation of the viologen-functionalized polymer nanoparticles comprises the following steps:
s21, mixing 4,4' -bipyridine and 4-chloromethyl styrene, adding acetonitrile solvent, and adding N2Heating and stirring the mixture to react under the atmosphere, stopping the reaction when the solution is yellow turbid liquid, cooling the solution to room temperature, separating out yellow powdery precipitate, carrying out suction filtration on the reaction solution, respectively washing the reaction solution by acetonitrile and acetone, and drying the reaction solution in vacuum to obtain white powdery solid vinylbenzyl-4, 4' -bipyridyl chloride;
s22, mixing the vinyl benzyl-4, 4 '-bipyridyl chloride salt prepared in the step S21 and 1, 3-propane sultone, adding an N, N' -dimethylformamide solvent, and adding a N-dimethylformamide solvent2Heating and condensing in the atmosphere, stopping heating after the reaction is completed, cooling to room temperature, pouring the reaction solution into ethyl acetate containing ice for precipitation to separate out pink solid, performing suction filtration, washing with ethyl acetate, and performing vacuum drying to obtain the pink solid SVBD;
s23, mixing the prepared SVBD monomer with (3-acrylamidopropyl) trimethyl ammonium chloride, adding deionized water solvent, and continuously filling N under heating condition2Deoxidizing, adding an aqueous solution of an aqueous initiator, keeping a heating condition for reaction, stopping heating after the reaction is finished to obtain yellow turbid liquid, dialyzing with dialysis bag deionized water with molecular weight cutoff of 3500, and freeze-drying to obtain orange yellow solid, wherein the solid is the viologen functionalized polymer nanoparticles.
8. The synthesis method according to claim 6, wherein the initiator is one of potassium persulfate, ammonium persulfate and benzoin dimethyl ether.
9. The aqueous nano-polymer flow battery system of claim 1, further comprising:
the electrolyte comprises two electrolyte liquid reservoirs, wherein the two electrolyte liquid reservoirs are arranged at intervals, each electrolyte liquid reservoir is a liquid storage tank for storing electrolyte or a salt cave which is formed after salt mine mining and is provided with a physical dissolution cavity, the electrolyte in one electrolyte liquid reservoir comprises the positive active substance and supporting electrolyte, the electrolyte in the other electrolyte liquid reservoir comprises the negative active substance and supporting electrolyte, and the positive active substance and the negative active substance are respectively directly dissolved or dispersed in a system taking water as a solvent in a bulk form;
the flow battery stack comprises a battery diaphragm, the battery diaphragm divides the flow battery stack into an anode area and a cathode area which are distributed at intervals, the anode area is communicated with one electrolyte liquid storage tank, and the cathode area is communicated with the other electrolyte liquid storage tank.
10. The aqueous nano-polymer flow battery system of claim 9, 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。
11. The aqueous nano-polymer flow battery system of claim 9, wherein the electrolyte reservoir is a pressurized sealed container with a pressure of 0.1MPa to 0.5 MPa.
12. The aqueous nano-polymer flow battery system of claim 9, wherein an inert gas is introduced into the electrolyte reservoir to purge and maintain pressure.
13. The aqueous nano-polymer flow battery system of claim 12, wherein the inert gas is nitrogen or argon.
14. The aqueous nano polymer flow battery system of claim 9, wherein the battery diaphragm is an anion exchange membrane, a cation exchange membrane or a polymer porous membrane with a pore size of 10nm to 300 nm.
15. The aqueous nano-polymer flow battery system of claim 9, 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 aqueous nano-polymer flow battery system of claim 15, wherein the molar concentration of the supporting electrolyte is 0.1 mol-L-1～8.0mol·L-1。
17. The aqueous nano-polymer flow battery system of claim 9, 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 aqueous nano-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 glassy carbon material.
19. The aqueous nano-polymer flow battery system of claim 18, wherein the electrodes are formed as electrode plates having a thickness of 2mm to 8 mm.
20. The aqueous nano-polymer flow battery system of claim 9, 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 aqueous nano-polymer flow battery system of claim 18, wherein the current collector is one of a conductive metal plate, a graphite plate, or a carbon-plastic composite plate.
22. The aqueous nano-polymer flow battery system of claim 19, wherein the conductive metal plate comprises at least one metal of copper, nickel, aluminum.
CN202010557305.8A 2020-06-18 2020-06-18 Aqueous nano polymer flow battery system Active CN111584915B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010557305.8A CN111584915B (en) 2020-06-18 2020-06-18 Aqueous nano polymer flow battery system

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010557305.8A CN111584915B (en) 2020-06-18 2020-06-18 Aqueous nano polymer flow battery system

Publications (2)

Publication Number Publication Date
CN111584915A true CN111584915A (en) 2020-08-25
CN111584915B CN111584915B (en) 2023-03-21

Family

ID=72125826

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010557305.8A Active CN111584915B (en) 2020-06-18 2020-06-18 Aqueous nano polymer flow battery system

Country Status (1)

Country Link
CN (1) CN111584915B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN114497667A (en) * 2022-02-09 2022-05-13 中盐金坛盐化有限责任公司 Method for improving performance of aqueous polymer flow battery
CN115084612A (en) * 2022-07-28 2022-09-20 江苏大学 Method for improving transmission performance of flow battery by using nano particles and flow battery
CN115732731A (en) * 2022-11-02 2023-03-03 宿迁时代储能科技有限公司 Water-phase-organic redox flow battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN110444799A (en) * 2019-08-22 2019-11-12 中盐金坛盐化有限责任公司 Neutral aqueous phase system flow battery system

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN110444799A (en) * 2019-08-22 2019-11-12 中盐金坛盐化有限责任公司 Neutral aqueous phase system flow battery system

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN112103546B (en) * 2020-09-16 2021-09-03 中盐金坛盐化有限责任公司 Preparation method of asymmetric type double-electron viologen compound
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
CN114497667A (en) * 2022-02-09 2022-05-13 中盐金坛盐化有限责任公司 Method for improving performance of aqueous polymer flow battery
CN114497667B (en) * 2022-02-09 2024-02-02 中盐金坛盐化有限责任公司 Method for improving performance of aqueous polymer flow battery
CN115084612A (en) * 2022-07-28 2022-09-20 江苏大学 Method for improving transmission performance of flow battery by using nano particles and flow battery
CN115084612B (en) * 2022-07-28 2023-10-10 江苏大学 Method for improving transmission performance of flow battery by using nano particles and flow battery
CN115732731A (en) * 2022-11-02 2023-03-03 宿迁时代储能科技有限公司 Water-phase-organic redox flow battery

Also Published As

Publication number Publication date
CN111584915B (en) 2023-03-21

Similar Documents

Publication Publication Date Title
CN111584915B (en) Aqueous nano polymer flow battery system
KR102661988B1 (en) Redox flow cell for electrical energy storage and uses thereof
AU2016356485B2 (en) Hybrid flow battery for storing electrical energy and use thereof
CN110668996B (en) Bipyridine compound, synthetic method and symmetrical flow battery system thereof
US9905876B2 (en) Redox flow cell comprising high molecular weight compounds as redox pair and semipermeable membrane for storage of electrical energy
CN113809325B (en) Alkaline aqueous secondary battery based on electroactive covalent organic framework polymer and application thereof
US20220073448A1 (en) Method for synthesizing carboxy-containing anthraquinone derivative, carboxy-containing anthraquinone derivative prepared thereby, and battery system comprising same
CN110444787A (en) Flow battery system based on amino anthraquinones derivative
WO2021139162A1 (en) Application of quaternary ammonium salt type anthraquinone active substance, and organic aqueous phase salt cavern battery
CN112490477B (en) Aqueous all-organic mixed liquid flow battery based on conjugated microporous polymer negative electrode containing redox active side group unit
CN112103546B (en) Preparation method of asymmetric type double-electron viologen compound
CN110734515B (en) Imidazole iron polymer, synthetic method, battery and battery system
CN111564649B (en) Organic polymer flow battery system
CN111613823B (en) Polymer flow battery system
CN110444799B (en) Neutral aqueous phase system flow battery system
CN110452161A (en) Bipyridyliums compound, synthetic method and the flow battery system with it
CN109638329A (en) A kind of water system flow battery
CN113261135A (en) Aqueous electrolyte, redox flow battery and use thereof
CN115548400A (en) Mixed electrolyte of flow battery and preparation method and application thereof
CN114824398B (en) Polyacrylic acid grafted polymer flow battery system
CN114478902B (en) Water-based positive electrode polymer, preparation method thereof and small-molecule flow battery system
CN115332546A (en) Water-soluble organic polymer flow battery negative electrode polymer material and preparation method thereof
CN114300723B (en) Aqueous organic flow battery based on mixed energy storage of insoluble phenazine-based negative electrode and soluble phenazine-based negative electrode electrolyte
CN114122414A (en) Piperidine nitroxide free radical/zinc composite redox flow battery and preparation method thereof
CN116693818A (en) Viologen polymer and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant