CN114300723B - Aqueous organic flow battery based on mixed energy storage of insoluble phenazine-based negative electrode and soluble phenazine-based negative electrode electrolyte - Google Patents

Aqueous organic flow battery based on mixed energy storage of insoluble phenazine-based negative electrode and soluble phenazine-based negative electrode electrolyte Download PDF

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CN114300723B
CN114300723B CN202111668605.4A CN202111668605A CN114300723B CN 114300723 B CN114300723 B CN 114300723B CN 202111668605 A CN202111668605 A CN 202111668605A CN 114300723 B CN114300723 B CN 114300723B
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phenazine
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flow battery
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曹剑瑜
夏雪
许娟
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Changzhou University
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Abstract

The invention belongs to the field of new energy, and particularly relates to a water-based organic flow battery based on mixed energy storage of an insoluble phenazine-based negative electrode and a soluble phenazine-based negative electrode electrolyte. The battery anode portion is composed of an insoluble phenazine-based anode active material and a soluble phenazine-based anode electrolyte. The phenazinyl anode and the phenazinyl anode electrolyte store electrical energy through respective reversible redox reactions. The novel aqueous organic flow battery has higher specific capacity and energy density than the traditional organic flow battery, has the advantages of low cost, long cycle life, safety, environmental protection and the like, and has wide application prospect in the fields of large-scale electricity storage of renewable energy and power grid peak regulation.

Description

Aqueous organic flow battery based on mixed energy storage of insoluble phenazine-based negative electrode and soluble phenazine-based negative electrode electrolyte
Technical Field
The invention belongs to the field of new energy, and relates to a water-based organic flow battery based on mixed energy storage of an insoluble phenazine-based negative electrode and a soluble phenazine-based negative electrode electrolyte.
Background
In recent years, electric energy generated from renewable energy sources such as solar energy, wind energy, geothermal energy, and the like is rapidly growing worldwide. Because of the intermittent and regional drawbacks of such clean energy sources, it is desirable to introduce large-scale electrical energy storage systems to stabilize peak-to-valley differences in the electrical grid, regulate the lack of earning and reduce energy waste (Chemical Reviews,2015,115,20).
Flow batteries achieve energy storage and conversion by valence state conversion between different redox active species stored outside the battery, and energy and power output can be decoupled from each other and have an ultra-long life cycle, thus exhibiting superior flexibility and sufficient safety and economy in large-scale electrical energy storage applications (CRC Press, 2017). However, the Energy density of flow batteries is limited by the solubility of electroactive species in solution systems, resulting in their generally lower Energy density, which limits their industrial application (Energy Fuels 2020,34,13384).
In order to increase Energy density, some hybrid flow battery systems incorporating solid state Energy storage electrodes were proposed in succession (Energy Environ.Sci.,2019,12,1834;J.Mater.Chem.A,2020,8,6874;J.Mater.Chem.A,2021,9,27028). However, although the hybrid flow battery can achieve high energy density, high power and long life, there is a certain degree of mutual restriction between different electrode morphologies. For example, the energy density of a hybrid battery is generally lower than a secondary battery using the same solid state electrode, limited by the solubility of the liquid phase electroactive species. Hybrid batteries also suffer from a detent from solid state electrodes, which tend to have lower power densities and cycle lives than conventional flow batteries using the same type of liquid phase active electrolyte, and the energy and power of the system cannot be decoupled.
Semi-solid flow batteries using flowable "slurry" electrode materials as redox active electrolytes can break through the solubility limit of electroactive species (adv. Energy mate. 2011,1,511). However, the higher viscosity of the active electrolyte fluid of such flow batteries will significantly increase the power consumption of the circulation pump. And in operation, a large amount of conductive agent is required to help form a conductive network with a high specific surface area to maintain current density output, which not only results in complex fluid dynamics and reduces energy density and energy efficiency, but also presents serious challenges for system maintenance.
The targeted flow battery is another way which can break through the energy storage limit of liquid phase and solid phase and improve the energy density of the system. In the targeted flow battery, liquid-phase electroactive species are stored in a liquid reservoir, which flows over the surface of the solid electrode material, undergoing a reversible solid-liquid phase chemical reaction, thereby achieving energy storage and release (angel. Chem. Int. Ed.2006,45,8197). However, the utilization of solid phase electrode materials is often subject to relatively slow targeted reaction kinetics at high current densities, resulting in a reversible specific energy dependence of the battery on power output, losing the energy-to-power decoupling advantage of flow batteries (adv. Mater.2018, 1802406).
Disclosure of Invention
The invention aims to provide an aqueous organic flow battery with high energy density.
In order to achieve the above object, the present invention provides a novel structure of a negative electrode of an aqueous organic flow battery based on a combination of an insoluble phenazine derivative and a soluble phenazine derivative. The battery system is composed of a conductive negative electrode, an organic negative electrode active substance, an organic negative electrode active electrolyte solution, a diaphragm, a positive electrode active electrolyte solution, a conductive negative electrode, a storage tank, a circulating pump and other components, wherein the organic negative electrode active substance is an insoluble phenazine derivative, and the organic negative electrode active electrolyte is a water-soluble phenazine derivative.
An insoluble phenazine derivative having the structural formula:
wherein R is 1 -R 12 Can be independently selected from hydrogen, halogen, hydroxy, amino, C 1-6 Alkyl, C 1-6 Alkoxy, amido, cyano or nitro.
The insoluble phenazine derivative is preferably 1,2:3,4-dibenzophenazine (1, 2:3, 4-dibenzophenazine) or 5,6,11,12,17,18-hexaazatrinaphthalene (5,6,11,12,17,18-hexaazatrinaphthalene).
The carrying capacity of the anode insoluble phenazine derivative is 1-20mg/cm 2 。
The water-soluble phenazine derivatives have the following structural formula:
wherein R is 1 -R 10 Can be independently selected from hydrogen, hydroxy, amino, carboxylic acid, sulfonic acid, phosphonic acid, pyrrole, - (OCH) 2 CH 2 ) n＝1-6 -OH、-NH(CH 2 ) n＝1-6 -COOH or- (CH) 2 ) n＝1-6 -COOH
The water-soluble anode active electrolyte is preferably benzo [ a ] hydroxyphenazine-7/8-carboxylic acid (benzo [ a ] hydroxyphenazine-7/8-carboxic acid) or 3,3 '-phenazine-1, 6-dipropionic acid (3, 3' - (phenazine-1, 6-diyl) dipropionic acid).
The concentration of the water-soluble phenazine derivative is 0.01-1mol/L.
The active electrolyte of the positive electrode is potassium ferrocyanide or a mixture of potassium ferrocyanide and sodium ferrocyanide (molar ratio 1:1).
The conductive material of the negative and positive sides includes any carbon electrode, such as carbon felt, carbon paper, carbon cloth, or carbon nanotube array. Titanium nitride electrodes may also be used. Conductive electrodes suitable for use with other redox active electrolyte materials are known in the art.
Ion-conductive membranes allow passage of hydrated cations but block passage of anions or neutral molecules. One example of an ion-conductive membrane is a Nafion membrane (i.e. perfluorosulfonic acid membrane).
The aqueous organic flow battery of the present invention may include additional components known in the art. The redox active material dissolved in the aqueous solution will be contained in a suitable reservoir. The cell also includes a pump to deliver the aqueous solution to the two electrodes. The cell may also typically include a graphite flow field plate and a corrosion resistant metal current collector.
The beneficial effects are that:
the phenazine compound is an important natural product, widely exists in nature, can be obtained by means of plant extraction and the like, can be synthesized in a large scale through a green and environment-friendly chemical reaction way, and has resource reproducibility. The design of the water-based organic flow battery for storing electric energy by utilizing the respective reversible redox reactions of the insoluble phenazine derivative negative electrode and the soluble phenazine derivative negative electrode electrolyte has much higher specific capacity and energy density than that of a conventional organic flow battery, so that the application field of the flow battery is expanded.
Description of the drawings:
FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum of 1,2:3,4-Dibenzophenazine (DPHZ) of example 1 1 H NMR) map.
FIG. 2 is a Cyclic Voltammogram (CV) plot of 1,2:3,4-Dibenzophenazine (DPHZ) of example 1 at different sweep rates in 1mol/L KOH.
FIG. 3 is a 1,2:3,4-dibenzophenazine graph of example 1DPHZ) standard potential (E 0 ) -pH profile.
FIG. 4 is benzo [ a ] of example 2]Hydroxy phenazine-7/8-carboxylic acid (BHPC) nuclear magnetic resonance hydrogen spectrum 1 H NMR) map.
FIG. 5 is a Cyclic Voltammogram (CV) plot of benzo [ a ] hydroxyphenozine-7/8-carboxylic acid (BHPC) of example 2 at various sweep rates.
FIG. 6 is benzo [ a ] of example 2]Standard potential of hydroxyphenozine-7/8-carboxylic acid (BHPC) (E 0 ) -pH profile.
FIG. 7 (A) is a 1,2:3,4-Dibenzophenazine (DPHZ) anode and benzo [ a ]]Hydroxyphenozine-7/8-carboxylic acid (BHPC) was subjected to Cyclic Voltammetry (CV) diagram in a 1mol/L KOH system. The sweeping speed is 25mV s -1 . FIG. 7 (B) is a schematic illustration of the presence or absence of benzo [ a ] in an electrolyte solution]Cyclic voltammograms of glassy carbon electrodes supporting a porous layer of magnesium oxide (MgO) or a layer of magnesium oxide-1, 2:3,4-dibenzophenazine (MgO-DPHZ) in the presence of hydroxyphenozine-7/8-carboxylic acid (BHPC). The sweeping speed is 50mV s -1 。
FIG. 8 is a voltage-capacity graph (A) and cycle life graph (B) for an aqueous organic flow battery of example 3 based on a 1,2:3,4-dibenzophenazine negative electrode and a benzo [ a ] hydroxyphenozine-7/8-carboxylic acid negative electrode electrolyte hybrid energy storage.
FIG. 9 is a schematic structural diagram of an electroactive phenazine-based negative electrode and a phenazine-based negative electrode electrolyte hybrid energy storage aqueous organic flow battery.
Detailed Description
Example 1 Synthesis of insoluble negative electrode Material 1,2:3,4-dibenzophenazine and electrochemical Properties thereof
1,2:3,4-dibenzophenazine is synthesized by a coupling reaction, and the experimental steps are as follows: o-phenylenediamine (1.0 mmol) and 9, 10-phenanthrenequinone (1.0 mmol) and phthalic acid (0.05 mmol) were added together to a mixed solution composed of 7mL of ethanol and 3mL of water. The mixture was stirred at 60 ℃ with reflux for 2 hours. After cooling to room temperature, 30mL of deionized water was added. Standing for 12 hours, and completely separating out the precipitate. The precipitate was collected by suction filtration, washed with deionized water and dried under vacuum at 60 ℃ to give a yellow solid (99% yield). FIG. 1 is a 1,2:3,4-dibenzophenazine 1 H NMR chart.
Mix 2 mg 1,2:3,4Dibenzophenazine and 2 milligrams of Ketjen Black carbon powder, 0.5mL of isopropyl alcohol and 0.5mL of deionized water were added, sonicated for 1 hour, then 75 μl of perfluorosulfonic acid ionomer solution (5%) was added, and sonication was continued for 1 hour to form a uniform slurry. And transferring 3 mu L of the slurry to the surface of the glassy carbon electrode through a microsyringe, and airing to serve as a working electrode. Electrochemical properties of 1,2:3,4-dibenzophenazine were tested by cyclic voltammetry in a standard three electrode system with a platinum sheet electrode as the counter electrode, a mercury/mercury oxide electrode (0.098V versus standard hydrogen electrode) as the reference electrode, and 1mol/L KOH as the supporting electrolyte solution. Before testing, nitrogen is introduced into KOH solution to remove dissolved oxygen, and the whole testing process is carried out in nitrogen atmosphere. FIG. 2 is a cyclic voltammogram (standard potential E) of 1,2:3,4-dibenzophenazine at different sweep rates in 1mol/L KOH 0 -0.777V). FIG. 3E of 1,2:3,4-dibenzophenazine 0 pH profile (reversible 2 electron/2 proton redox).
EXAMPLE 2 Synthesis of soluble negative electrode active electrolyte benzo [ a ] hydroxyphenozine-7/8-carboxylic acid and electrochemical Properties thereof
3, 4-diaminobenzoic acid (1.0 mmol) was added to 100mL of glacial acetic acid, and then 2-hydroxy 1, 4-naphthoquinone (1.0 mmol) was slowly added thereto, and the reaction was refluxed at 50℃for 12 hours with stirring. After the reaction was completed, the solution was poured into a large amount of water, left to stand, suction-filtered, and the cake was vacuum-dried at 60℃for 12 hours to give the product (yield 94.7%) (see ACS Energy Lett.2020,5, 411-417). FIG. 4 is benzo [ a ]]Hydroxy phenazine-7/8-carboxylic acid 1 H NMR chart.
0.05 mmole of benzo [ a ]]The hydroxyphenozine-7/8-carboxylic acid was dissolved in 50mL of 1mol/L KOH solution to give 1mmol/L benzo [ a ]]A mixed solution of hydroxyphenazine-7/8-carboxylic acid and 1mol/L KOH is used as a supporting electrolyte solution. The electrochemical properties of 1,2:3,4-dibenzophenazine were tested using a standard three electrode system and cyclic voltammetry, clean glassy carbon electrode as working electrode, platinum sheet as counter electrode, mercury/mercury oxide electrode (0.098V versus standard hydrogen electrode) as reference electrode. Before testing, nitrogen is introduced into the supporting electrolyte solution to remove dissolved oxygen, and the whole testing process is carried out in a nitrogen atmosphere. The cyclic voltammetry test procedure was as in example 1. FIG. 5 is benzo [ a ]]Hydroxy phenazine-7/8-carboxylic acid inCyclic voltammograms at different sweep rates. Benzo [ a ]]The cyclic voltammogram of hydroxyphenoxazine-7/8-carboxylic acid shows a pair of reversible redox peaks, E 0 is-0.774V. FIG. 6 is benzo [ a ]]Standard potential of hydroxyphenozine-7/8-carboxylic acid (E 0 ) -pH profile. E (E) 0 The pH function corresponds to the Nernst equation revealing benzo [ a ]]Electrochemical reaction of hydroxyphenozine-7/8-carboxylic acid in strongly alkaline media is also a reversible 2 electron/2 proton process.
The standard potential of the 1,2:3,4-dibenzophenazine of example 1 was very close to that of the benzo [ a ] hydroxyphenozine-7/8-carboxylic acid of example 2 in 1mol/L KOH solution, differing by only 0.003V (FIG. 7A). FIG. 7 (B) is a cyclic voltammogram of a glassy carbon electrode carrying a porous layer of magnesium oxide or a layer of magnesium oxide-1, 2:3,4-dibenzophenazine (MgO-DPHZ) in the presence or absence of benzo [ a ] hydroxyphenozine-7/8-carboxylic acid (BHPC) in an electrolyte solution, revealing the presence of a reversible solid-liquid phase targeted chemical reaction between benzo [ a ] hydroxyphenozine-7/8-carboxylic acid and 1,2:3, 4-dibenzophenazine.
Example 3 construction of an aqueous organic flow Battery for hybrid storage of negative-negative electrolyte and Battery Performance thereof
1,2:3,4-dibenzophenazine from example 1 (15 mg/cm loading) 2 ) Benzo [ a ] of example 2 as a negative electrode of a battery filled in a carbon felt electrode of high porosity]The hydroxyphenoxazine-7/8-carboxylic acid (0.05 mol/L) was dissolved in 5mL of 1mol/L KOH as a negative electrode redox active electrolyte material, potassium ferrocyanide (0.2 mol/L) was dissolved in 10mL of 1mol/L KOH as a positive electrode active electrolyte solution, and a blank carbon felt was used as a conductive positive electrode. The Nafion112 membrane is used as a diaphragm to separate positive and negative active electrolyte, and a water-based organic flow battery system is constructed. In charge and discharge, to prevent oxidation of the negative electrode product by oxygen in the air, the battery was placed in a glove box filled with nitrogen.
FIG. 8 is a voltage-capacity graph (A) and cycle life graph (B) of an aqueous organic flow battery based on a 1,2:3,4-dibenzophenazine negative electrode and a benzo [ a ] hydroxyphenozine-7/8-carboxylic acid negative electrode electrolyte hybrid energy storage. The novel structure of the battery exhibits a significant capacity enhancement over hybrid flow batteries employing only 1,2:3,4-dibenzophenazine cathodes and aqueous organic flow batteries employing only benzo [ a ] hydroxyphenozine-7/8-carboxylic acid cathodes electrolytes. After 200 constant current charge and discharge cycles, the current efficiency was about 97.1%, the energy efficiency was 84.4%, and the discharge capacity retention rate reached 96.6%.
The current density was 20mA/cm 2 When the material utilization of the 1,2:3,4-dibenzophenazine negative electrode was about 42%, the negative electrolyte benzo [ a ]]The material utilization rate of the hydroxyphenoxazine-7/8-carboxylic acid is close to 90%. Negative electrolyte benzo [ a ]]When the concentration of the hydroxyphenoxazine-7/8-carboxylic acid is increased from 0.05mol/L to 0.1mol/L, the material utilization ratio of the 1,2:3,4-dibenzophenazine remains basically unchanged, and the benzo [ a ]]The material utilization of hydroxyphenoxazine-7/8-carboxylic acid increased slightly to 92%.
Example 4 construction of an aqueous organic flow Battery with Single energy storage by negative electrolyte and Battery Performance thereof
Benzo [ a ] of example 2]Hydroxy phenazine-7/8-carboxylic acid (0.05 mol/L) was dissolved in 5mL of 1mol/L KOH as a negative electrode active electrolyte solution. Potassium ferrocyanide (0.2 mol/L) is dissolved in 5mL 1mol/L KOH to serve as an anode active electrolyte solution, 2 blank carbon felts serve as a conductive anode and a conductive cathode respectively, and a Nafion112 membrane serves as a diaphragm to form a conventional aqueous organic flow battery. The cells were placed in a glove box filled with nitrogen for testing. The battery was at 10mA/cm 2 The reversible specific capacity is 2.52Ah/L, which is close to the theoretical value of 2.68Ah/L.
EXAMPLE 5 Synthesis of negative active electrolyte 3,3' -phenazine-1, 6-dipropionic acid and battery performance thereof
Palladium chloride (106 mg,0.596 mmol), tris (2-tolyl) phosphine (726 mg, 2.284 mmol), tetrabutylammonium bromide (1.92 g,5.96 mmol), 1, 6-dibromophenazine (10 g,29.8 mmol), ethyl acrylate (17.9 g,178.8 mmol), sodium carbonate (12.6 g,119.2 mmol), N-dimethylformamide and water were added sequentially to the Schlenk tube. Sealing, charging nitrogen, stirring at 100 deg.C for 8-16 hr. After the reaction is finished, cooling to room temperature, carrying out suction filtration, and washing a filter cake by water and petroleum ether in sequence. It was then dissolved in dichloroethane and washed with brine. The organic layer was separated and the aqueous layer was extracted with dichloroethane. The combined organic layers were dried over anhydrous sodium sulfateDrying, suction filtering, and concentrating under reduced pressure. Then, the product A was purified by silica gel column chromatography (see Joule 2021,5,1-13). Pd powder (414 mg) was added to the dried flask along with 4.6g (12.23 mmol) of product A. 150mL of ethyl acetate was then added. The reaction was then stirred at 85℃under a hydrogen atmosphere for 12h. The resulting reaction mixture was filtered through celite and concentrated under reduced pressure. Purifying by silica gel column chromatography to obtain the product B. To a solution of product B (4.4 g,11.6 mmol) in methanol was added NaOH solution (9.28 g NaOH in 25mL water). Then, the reaction was stirred at 65℃for 12 hours. Cooled to room temperature and acidified with concentrated HCl. Suction filtration and washing of the product with water. Drying to obtain the final product 3,3' -phenazine-1, 6-dipropionic acid. Standard potential E of 3,3' -phenazine-1, 6-dipropionic acid in 1mol/L KOH solution 0 is-0.556V.
Similar to example 4, a conventional aqueous organic flow battery was constructed using 0.05 mol/L3, 3' -phenazine-1, 6-dipropionic acid (5 mL) as the negative active electrolyte and excess potassium ferrocyanide as the positive active electrolyte. The battery was at 10mA/cm 2 The reversible specific capacity is about 2.36Ah/L, and the material utilization rate of the 3,3' -phenazine-1, 6-dipropionic acid is 88%.
Similar to example 3, 5,6,11,12,17,18-hexaazatrinaphthalene (5 mg/cm loading) packed in carbon felt 2 ) Is a negative electrode, benzo [ a ]]A mixed solution (4 mL, dissolved in 1mol/L KOH) of hydroxyphenazine-7/8-carboxylic acid (0.05 mol/L) and 3,3' -phenazine-1, 6-dipropionic acid (0.05 mol/L) is taken as a negative electrolyte, and is combined with a cathode potassium ferrocyanide solution to form the aqueous organic flow battery. The current density was 5mA/cm 2 When the material utilization rate of the 5,6,11,12,17,18-hexaazatrinaphthalene negative electrode is about 67%, the material utilization rate of the negative electrode active electrolyte is about 80%. After 40 constant current charge-discharge cycles, the current efficiency is about 96.2%, the energy efficiency is about 86.3%, and the discharge capacity retention rate reaches 91.3%.

Claims (6)

1. An aqueous organic flow battery based on insoluble phenazine-based negative electrode and soluble phenazine-based negative electrode electrolyte hybrid energy storage, characterized in that: the water-based organic flow battery consists of a conductive negative electrode, an organic negative electrode active substance, an organic negative electrode active electrolyte solution, a diaphragm, a positive electrode active electrolyte solution, a conductive positive electrode, a storage tank and a circulating pump, wherein the organic negative electrode active substance is an insoluble phenazine derivative, and the organic negative electrode active electrolyte is a water-soluble phenazine derivative;
the insoluble phenazine derivatives are as follows: 1,2:3,4-dibenzophenazine having the structural formula:
，
the water-soluble phenazine derivatives are: benzo [ a ] hydroxyphenoxazine-7/8-carboxylic acid having the structural formula:
；
or the insoluble phenazine derivatives are: 5,6,11,12,17,18-hexaazatrinaphthalene of the formula:
，
the water-soluble phenazine derivatives are: a mixture of benzo [ a ] hydroxyphenazine-7/8-carboxylic acid and 3,3 '-phenazine-1, 6-dipropionic acid, wherein the 3,3' -phenazine-1, 6-dipropionic acid has the structural formula:
。
2. the aqueous organic flow battery of claim 1, wherein: the insoluble phenazine derivative has a loading of 0.5-30 mg/cm 2 。
3. The aqueous organic flow battery of claim 1, wherein: the concentration of the water-soluble phenazine derivative is 0.01-1mol/L.
4. The aqueous organic flow battery of claim 1, wherein: the separator is a cation conductive film.
5. The aqueous organic flow battery of claim 1, wherein: the positive electrode active electrolyte is potassium ferrocyanide, sodium ferrocyanide, ammonium ferrocyanide or a mixture thereof.
6. The aqueous organic flow battery of claim 1, wherein: the conductive negative electrode and the conductive positive electrode are both carbon-based conductive materials.
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