CN111463444B - Water system organic oximes/zinc composite flow battery and assembling method thereof - Google Patents

Water system organic oximes/zinc composite flow battery and assembling method thereof Download PDF

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CN111463444B
CN111463444B CN202010275231.9A CN202010275231A CN111463444B CN 111463444 B CN111463444 B CN 111463444B CN 202010275231 A CN202010275231 A CN 202010275231A CN 111463444 B CN111463444 B CN 111463444B
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phenylene
flow battery
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宋江选
范豪
王鸿浩
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Shaanxi Huibo Kaiyuan New Energy Technology Co.,Ltd.
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Abstract

The invention discloses a water system organic oximes/zinc composite flow battery and an assembly method thereof, wherein organic molecules containing a p-phenylene dioxime structural formula are used as a positive electrode; a graphite plate with a flow channel is used as a positive flow field plate; zinc sheets are used as a negative electrode and a negative electrode flow field plate; one or more of an acidic aqueous solution, an alkaline aqueous solution and a neutral aqueous solution are mixed to be used as a supporting electrolyte; an anion exchange membrane is taken as an ion exchange diaphragm; two sheets of graphite felt or carbon paper are used as electrodes. The water system organic oxime/zinc composite flow battery has good electrochemical performance, has the advantages of adjustable active molecular structure, flexible design of battery power and energy, low cost, easiness in large-scale assembly and application and the like, is suitable for large-scale energy storage, and has wide application prospect in power storage of intermittent power generation projects such as photovoltaic power generation and peak clipping and valley filling of a power grid.

Description

Water system organic oximes/zinc composite flow battery and assembling method thereof
Technical Field
The invention belongs to the field of large-scale energy storage, and particularly relates to a water system organic oxime/zinc composite flow battery and an assembling method thereof.
Background
The history of continuous development of human beings shows the continuous demand of human beings on energy, but along with the increasing exploitation and consumption of fossil energy year by year, the aggravation of environmental problems and the limitation of fossil resources continuously remind people to develop the importance of renewable novel energy. Meanwhile, the development of clean and renewable energy sources such as light energy, wind energy and tidal energy provides a new idea for solving crisis. However, at the same time, the energy density of the energy sources is very low, the energy sources have very obvious unsteady-state characteristics and very obvious space-time uncertainty, and the energy sources cannot be directly connected to a power grid for transmission and utilization, so that a large-scale high-power high-efficiency energy storage technology is urgently needed to further promote the development and utilization of the energy technology. In the existing common technologies, such as various energy storage systems in different forms, including super capacitors, compressed air, sodium-sulfur batteries, flow batteries, and the like, the flow batteries are designed with energy and power separated, that is, the capacity of the battery is determined by the concentration and volume of electrolyte, and the power of the battery is determined by the number and size of battery units; the positive and negative electrode activities are respectively stored in the separated storage tanks, the reaction process can be controlled, the battery is not easy to self-discharge, and the safety and the high cycle efficiency are quite high. Therefore, the flow battery has unique advantages in a large-scale high-power high-efficiency energy storage system.
As for the existing flow battery system, the full-vanadium flow battery and the zinc-bromine flow battery are mature. For all-vanadium flow batteries, the battery has the disadvantage of low capacity due to the low solubility of vanadium compounds. For zinc-bromine flow batteries, the bromine aqueous solution has strong corrosivity, is a great hidden danger for long-term operation of the batteries, and is harmful to the environment due to treatment of waste liquid.
In recent years, more organic molecules are reported to be used for developing novel flow batteries, the organic molecules have more varieties than inorganic molecules, the selectivity is greatly improved, and different influences can be caused on the molecular properties due to introduction of different functional groups. The modification and external connection of functional groups on the core structure of the organic molecule can improve the solubility and potential of the active substance, thereby improving the performance of the battery.
In recent years, active materials such as quinones, nitroxide free radicals, viologens and azines have been reported to be used in aqueous organic flow batteries and to exhibit good electrochemical performance. However, the problems of low energy density and short life of the battery due to low solubility of the active material and low chemical stability still remain.
Disclosure of Invention
The invention provides a water system organic oxime/zinc composite flow battery and an assembly method thereof, which promote the solving of the problems of low energy density, short service life and the like in the prior art; meanwhile, an unreported aqueous organic oxime/zinc composite flow battery based on oxime active substances is provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
an aqueous organic oxime/zinc composite flow battery takes an organic molecule containing a p-phenylene dioxime structural formula as a positive electrode; a graphite plate with a flow channel is used as a positive flow field plate; zinc sheets are used as a negative electrode and a negative electrode flow field plate; one or more of an acidic aqueous solution, an alkaline aqueous solution and a neutral aqueous solution are mixed to be used as a supporting electrolyte; an anion exchange membrane is taken as an ion exchange diaphragm; two pieces of graphite felt or carbon paper which are subjected to high-temperature oxidation or dilute acid pretreatment are used as battery electrodes.
Furthermore, the concentration of the organic molecules containing the p-phenylene dioxime structural formula in the supporting electrolyte is 0.001-3 mol/L.
Further, the organic molecules containing the structural formula of p-phenylene dioxime are p-phenylene dioxime and derivatives thereof.
Further, the p-phenylene dioxime derivative is specifically: the benzene ring of the p-phenylene dioxime has a hydrophilic functional group which is-OH, -NH2、-COOH、-SO3H or an alkane substituent containing hydrophilic functional groups, and the number of the functional groups is 1-3.
Furthermore, the acidic aqueous solution is a sulfuric acid solution, and the concentration is 0.1-5 mol/L.
Further, the alkaline aqueous solution is a potassium hydroxide solution, and the concentration is 1-6 mol/L.
Further, the neutral aqueous solution is a potassium chloride solution, and the concentration is 0.1-2 mol/L.
An assembly method of a water system organic oxime/zinc composite flow battery takes an organic molecule containing a p-phenylene dioxime structural formula as a positive electrode; taking a zinc sheet as a negative electrode; one or more of an acidic aqueous solution, an alkaline aqueous solution and a neutral aqueous solution are mixed to be used as a supporting electrolyte; an anion exchange membrane is taken as an ion exchange diaphragm; graphite felt or carbon paper is used as an electrode; the battery is assembled by a zinc sheet, a graphite felt or carbon paper electrode, an anion exchange membrane, a graphite felt or carbon paper electrode and a graphite plate flow channel in sequence.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a water system organic oxime/zinc composite flow battery, which takes an organic molecule containing a p-phenylene dioxime structural formula as a positive electrode, and utilizes that the p-phenylene dioxime active molecule can generate reversible redox reaction, higher redox potential, good electrochemical reversibility and dynamic performance. In particular, under the conditions of acidic, alkaline and neutral aqueous solutions, the aqueous organic oxime/zinc composite flow battery with high voltage can be obtained by matching with a negative electrode zinc sheet. In addition, because the oxime molecules are organic compounds generated by the action of aldehyde and ketone compounds containing carbonyl and hydroxylamine, the organic compounds have the characteristics of good stability, redox reversibility and the like, the invention utilizes that the p-phenylene dioxime active molecules contain dihydroxy, hydrogen bonds are easy to form with water molecules, the solubility is improved, and the organic oxime/zinc composite flow battery with high energy density can be obtained. Meanwhile, the main constituent elements of the molecule are carbon, nitrogen, hydrogen and oxygen, the source is wide and easy to obtain, and the manufacturing cost and the cost are greatly reduced compared with those of the current hot all-vanadium redox flow battery and the like in the production and utilization of the large-scale redox flow battery.
Drawings
FIG. 1 shows the results of cyclic voltammetry tests of a potassium hydroxide solution for p-dioxaxime obtained in example 1 of the present invention, using silver/silver chloride as a reference electrode, at sweep rates of 25mV/s, 50mV/s, 80mV/s and 100 mV/s.
FIG. 2 is a linear fit of the peak current and square root of sweep rate for different sweep rates of the potassium hydroxide solution of p-phenylenedioxime obtained in example 1 of the present invention under cyclic voltammetry.
FIG. 3 shows the results of cyclic voltammetry tests on a p-phenylenedioxime solution prepared in example 2 of the present invention, using silver/silver chloride as a reference electrode, at sweep rates of 25mV/s, 50mV/s, 80mV/s and 100 mV/s.
FIG. 4 is a linear fit of the peak current and square root of sweep rate for the sulfuric acid solution of p-phenylenedioxime obtained in example 2 of the present invention at different sweep rates in the cyclic voltammetry test.
FIG. 5 shows the results of cyclic voltammetry tests on a potassium chloride solution of p-phenylenedioxime obtained in example 3 of the present invention, using silver/silver chloride as a reference electrode, at sweep rates of 25mV/s, 50mV/s, 80mV/s and 100 mV/s.
FIG. 6 is a linear fit of the peak current and square root of sweep rate for different sweep rates of the potassium chloride solution of p-phenylenedioxime obtained in example 3 of the present invention under cyclic voltammetry.
Fig. 7 is a graph of cycle number-capacity-coulombic efficiency-energy efficiency of the assembled battery in example 4 of the present invention, when charged and discharged at a constant current of 25mA for 100 cycles.
Fig. 8 is a time-voltage curve of the first turn of the assembled battery of example 4 of the present invention under the charge and discharge of a current of 25 mA.
Fig. 9 is a graph of cycle number-capacity-coulombic efficiency-energy efficiency under different current discharge conditions of the assembled battery in example 5 of the present invention.
Detailed Description
Embodiments of the invention are described in further detail below:
the invention provides a water system organic oxime/zinc composite flow battery, which is charged and discharged by carrying out redox reaction on active molecules containing a p-phenylene dioxime structural formula; a graphite plate with a flow channel is used as a positive flow field plate; zinc sheets are used as a negative electrode and a negative electrode flow field plate; one or more of an acidic aqueous solution, an alkaline aqueous solution and a neutral aqueous solution are mixed to be used as a supporting electrolyte; an anion exchange membrane is taken as an ion exchange diaphragm; two sheets of graphite felt or carbon paper are used as battery electrodes.
The structural formula of the p-phenylene dioxime is as follows:
Figure BDA0002444539120000041
two symmetrical hydroxyl substituents are easy to generate electron pushing effect, and the oxidation-reduction potential of molecules is improved; meanwhile, hydrogen bonds are easily formed with water molecules, and the molecular solubility is increased.
The structural formula of the p-phenylene dioxime derivative is as follows:
Figure BDA0002444539120000051
wherein R1 and R2 can be hydrophilic functional groups-OH, -NH2、-COOH、-SO3H or an alkane substituent containing a hydrophilic functional group.
The concentration of the active molecules containing the p-phenylene dioxime structural formula in the electrolyte is 0.001-3 mol/L.
Wherein the acidic aqueous solution is a sulfuric acid solution, and the concentration is 0.1-5 mol/L.
The alkaline aqueous solution is a potassium hydroxide solution, and the concentration is 1-6 mol/L.
The neutral aqueous solution is a potassium chloride solution, and the concentration is 0.1-2 mol/L.
The active molecule can be prepared by carrying out limited steps of substitution, addition and oxidation reaction on simple molecules containing benzene rings.
The working principle of the oxime group organic oxime water system zinc secondary composite flow battery is as follows: the active molecule containing the structural formula of p-phenylene dioxime contains active molecules with oxime groups and benzene ring structures, and can perform reversible electrochemical tautomerization reaction under the acidic, alkaline and neutral aqueous solution environments.
The electrode material is graphite felt or carbon paper which is pretreated by high-temperature oxidation or dilute acid.
An assembly method of a water system organic oxime/zinc composite flow battery takes an organic molecule containing a p-phenylene dioxime structural formula as a positive electrode; taking a zinc sheet as a negative electrode; one or more of an acidic aqueous solution, an alkaline aqueous solution and a neutral aqueous solution are mixed to be used as a supporting electrolyte; an anion exchange membrane is taken as an ion exchange diaphragm; graphite felt or carbon paper is used as an electrode; the battery is assembled by a zinc sheet, a graphite felt or carbon paper electrode, an anion exchange membrane, a graphite felt or carbon paper electrode and a graphite plate flow channel in sequence.
The present invention is described in further detail below with reference to examples:
example 1
0.0055g of p-phenylenediamine is weighed and dissolved in 40 ml of 1mol/L potassium hydroxide solution, the solution is shaken evenly, and after a uniform and stable solution is formed, a 0.001mol/L potassium hydroxide solution of p-phenylenediamine is obtained. And (3) performing cyclic voltammetry on the prepared solution by using a three-electrode system, wherein the used reference electrode is a silver/silver chloride electrode, the counter electrode is a graphite electrode, and the working electrode is a glassy carbon electrode. The sweep rates selected were 25mV/s, 50mV/s, 80mV/s and 100 mV/s.
From CV data in fig. 1, it can be seen that p-phenylenedioxime has a pair of significantly reversible redox peaks in the presence of an alkaline supporting electrolyte, and has good electrochemical reversibility, and meanwhile, a silver/silver chloride electrode is used as a reference electrode, the average potential of p-phenylenedioxime is above 0.05V, and the p-phenylenedioxime shows a positive redox potential as a positive electrode material.
In fig. 2, a linear fit of the peak of the oxidation-reduction potential and the square root of the sweep rate indicates that the slopes of the two lines are approximately the same, which demonstrates that the p-phenylene dioxime molecule has reversible electrochemical properties in the presence of an alkaline supporting electrolyte and that the diffusion coefficients of the oxidation reaction and the reduction reaction are approximately the same.
Example 2
0.0055g of p-phenylenediamine is weighed and dissolved in 40 ml of 1mol/L sulfuric acid solution, the solution is shaken uniformly, and after a uniform and stable solution is formed, the 0.001mol/L sulfuric acid solution of p-phenylenediamine is obtained. And (3) performing cyclic voltammetry on the prepared solution by using a three-electrode system, wherein the used reference electrode is a silver/silver chloride electrode, the counter electrode is a graphite electrode, and the working electrode is a glassy carbon electrode. The sweep rates selected were 25mV/s, 50mV/s, 80mV/s and 100 mV/s.
As can be seen from CV data in fig. 3, p-phenylenedioxime has a pair of significantly reversible redox peaks in an acidic supporting electrolyte, has good electrochemical reversibility, and shows a positive redox potential when used as a positive electrode material with a silver/silver chloride electrode as a reference electrode and an average potential of p-phenylenedioxime of 0.6V or more.
In fig. 4, a linear fit of the peak of the oxidation-reduction potential and the square root of the sweep rate indicates that the two-line slopes are approximately the same, which demonstrates that the p-phenylene dioxime molecule has reversible electrochemical properties in an acidic supporting electrolyte, and that the diffusion coefficients of the oxidation reaction and the reduction reaction are approximately the same.
Example 3
0.0055g of p-phenylenediamine is weighed and dissolved in 40 ml of 1mol/L potassium chloride solution, the solution is shaken evenly, and after a uniform and stable solution is formed, the 0.001mol/L potassium chloride solution of p-phenylenediamine is obtained. And (3) performing cyclic voltammetry on the prepared solution by using a three-electrode system, wherein the used reference electrode is a silver/silver chloride electrode, the counter electrode is a graphite electrode, and the working electrode is a glassy carbon electrode. The sweep rates selected were 25mV/s, 50mV/s, 80mV/s and 100 mV/s.
As can be seen from CV data in fig. 5, p-phenylenedioxime has a pair of significantly reversible redox peaks in a neutral supporting electrolyte, and has good electrochemical reversibility, and meanwhile, a silver/silver chloride electrode is used as a reference electrode, and the average potential of p-phenylenedioxime is 0.1V or more, and shows a positive redox potential as a positive electrode material.
In fig. 6, a linear fit of the peak of the redox potential and the square root of the sweep rate indicates that the two-line slopes are approximately the same, which demonstrates that the p-phenylene dioxime molecule has reversible electrochemical properties in a neutral supporting electrolyte and that the diffusion coefficients of the oxidation reaction and the reduction reaction are approximately the same.
Example 4
0.2762g of p-phenylenediamine is weighed and dissolved in 40 mL of 6mol/L potassium hydroxide solution, the solution is shaken and stirred, after a uniform and stable solution is formed, a 0.05mol/L p-phenylenediamine solution is prepared, and 15mL of the solution is taken as a positive electrode. And taking the zinc sheet polished to be bright as a negative electrode. And (3) putting the graphite felt into a 1mol/L dilute sulfuric acid solution, stirring and soaking for 4 hours, taking out, washing with deionized water, and drying for later use. The cell was assembled in the order and position of zinc sheet-graphite felt electrode-anion exchange membrane-graphite felt electrode-graphite plate flow channel and the liquid was driven by peristaltic pump.
The battery is subjected to performance test, constant current charge and discharge test is carried out under the conditions that the charge cut-off voltage is 2.0V, the discharge cut-off voltage is 0.3V and the current is 50mA, and a cycle number-coulombic efficiency, energy efficiency, capacity diagram and first cycle charge and discharge curve can be obtained.
Fig. 7 shows the cycle count-coulombic efficiency, energy efficiency, and capacity curves of 100-cycle charge and discharge of the battery, and it can be seen from the graph that the coulombic efficiency of the battery is maintained at 90% or more from the sixth cycle and gradually increases to approximately 100% with the increase of the cycle count of charge and discharge, and the energy efficiency gradually increases from 30% to 60% or so. This indicates that the battery can normally and stably work and maintain higher energy efficiency and coulombic efficiency.
Fig. 8 shows a first cycle charge/discharge capacity-voltage curve of the battery, which shows that the battery can operate normally and stably and has high coulombic efficiency.
Example 5
0.552g of p-phenylenediamine is weighed and dissolved in 40 mL of 6mol/L potassium hydroxide solution, the solution is stirred in a shaking way, after a uniform and stable solution is formed, 0.1mol/L potassium hydroxide solution of p-phenylenediamine is obtained, and 15mL is taken as a positive electrode. And taking the zinc sheet polished to be bright as a negative electrode. And (3) carrying out heat treatment on the graphite felt, wherein the specific operation is that the graphite felt is placed in a muffle furnace, heated for ten hours at five hundred ℃, cooled to room temperature, taken out and then directly used. The cell was assembled in the order and position of zinc sheet-graphite felt electrode-anion exchange membrane-graphite felt electrode-graphite plate flow channel and the liquid was driven by peristaltic pump.
And (3) testing the charge and discharge performance of the battery, performing charge and discharge tests by adopting different currents, and selecting 20mA, 40mA, 60mA, 80mA, 100mA, 120mA and 140mA currents respectively to obtain coulomb and energy efficiency-cycle number and charge and discharge capacity-cycle number graphs.
As shown in fig. 9, the coulombic efficiency of the battery is stable under different currents, and the battery can still work and output higher energy under a high-current condition, and shows good rate performance.
Example 6
0.552g of p-phenylenediamine is weighed and dissolved in 40 mL of mixed electrolyte formed by mixing 20 mL of 6mol/L potassium hydroxide solution and 20 mL of 2mol/L potassium chloride, the solution is stirred in a shaking way, after a uniform and stable solution is formed, a 0.1mol/L p-phenylenediamine solution is prepared, and 15mL of the solution is taken as an anode. And taking the zinc sheet polished to be bright as a negative electrode. And (3) putting the graphite felt into a 1mol/L dilute sulfuric acid solution, stirring and soaking for 4 hours, taking out, washing with deionized water, and drying for later use. The cell was assembled in the order and position of zinc sheet-graphite felt electrode-anion exchange membrane-graphite felt electrode-graphite plate flow channel and the liquid was driven by peristaltic pump.
Example 7
10.244g of potassium p-phenylenedioxime sulfonate is weighed and dissolved in 40 mL of 6mol/L potassium hydroxide solution, the solution is oscillated and stirred to form a uniform and stable solution, 1mol/L potassium p-phenylenedioxime sulfonate solution is prepared, and 15mL is taken as an anode. And taking the zinc sheet polished to be bright as a negative electrode. And (3) putting the graphite felt into a 1mol/L dilute sulfuric acid solution, stirring and soaking for 4 hours, taking out, washing with deionized water, and drying for later use. The cell was assembled in the order and position of zinc sheet-graphite felt electrode-anion exchange membrane-graphite felt electrode-graphite plate flow channel and the liquid was driven by peristaltic pump.
Example 8
20.172g of 2, 6-diamino-p-phenylenedioxime is weighed and dissolved in 40 mL of 6mol/L potassium hydroxide solution, the solution is shaken and stirred, after a uniform and stable solution is formed, a 3mol/L potassium p-phenylenedioxime sulfonate solution is prepared, and 15mL is taken as a positive electrode. And taking the zinc sheet polished to be bright as a negative electrode. And (3) putting the graphite felt into a 1mol/L dilute sulfuric acid solution, stirring and soaking for 4 hours, taking out, washing with deionized water, and drying for later use. The cell was assembled in the order and position of zinc sheet-graphite felt electrode-anion exchange membrane-graphite felt electrode-graphite plate flow channel and the liquid was driven by peristaltic pump.

Claims (6)

1. The water system organic oximes/zinc composite flow battery is characterized in that organic molecules containing a p-phenylene dioxime structural formula are used as positive electrodes, and the organic molecules containing the p-phenylene dioxime structural formula are p-phenylene dioxime, potassium p-phenylene dioxime sulfonate or 2, 6-diamino-p-phenylene dioxime; a graphite plate with a flow channel is used as a positive flow field plate; zinc sheets are used as a negative electrode and a negative electrode flow field plate; one or more of an acidic aqueous solution, an alkaline aqueous solution and a neutral aqueous solution are mixed to be used as a supporting electrolyte; an anion exchange membrane is taken as an ion exchange diaphragm; two pieces of graphite felt or carbon paper which are subjected to high-temperature oxidation or dilute acid pretreatment are used as battery electrodes.
2. The aqueous organooxime/zinc composite flow battery according to claim 1, wherein the concentration of the organic molecule having a p-phenylenedioxime structural formula in the supporting electrolyte is 0.001 to 3 mol/L.
3. The aqueous organic oxime/zinc composite flow battery according to claim 1, wherein the acidic aqueous solution is a sulfuric acid solution with a concentration of 0.1 to 5 mol/L.
4. The aqueous organic oxime/zinc composite flow battery according to claim 1, wherein the alkaline aqueous solution is a potassium hydroxide solution, and the concentration is 1 to 6 mol/L.
5. The aqueous organic oxime/zinc composite flow battery according to claim 1, wherein the neutral aqueous solution is a potassium chloride solution, and the concentration is 0.1 to 2 mol/L.
6. An assembling method of an aqueous organic oxime/zinc composite flow battery, which is characterized in that the aqueous organic oxime/zinc composite flow battery according to any one of claims 1 to 5 is provided, wherein an organic molecule containing a p-phenylene dioxime structural formula is used as a positive electrode; taking a zinc sheet as a negative electrode; one or more of an acidic aqueous solution, an alkaline aqueous solution and a neutral aqueous solution are mixed to be used as a supporting electrolyte; an anion exchange membrane is taken as an ion exchange diaphragm; graphite felt or carbon paper is used as an electrode; the battery is assembled by a zinc sheet, a graphite felt or carbon paper electrode, an anion exchange membrane, a graphite felt or carbon paper electrode and a graphite plate flow channel in sequence.
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