CN113527543B - Aqueous neutral piperidine nitrogen-oxygen free radical organic flow battery electrolyte, battery and preparation method - Google Patents

Aqueous neutral piperidine nitrogen-oxygen free radical organic flow battery electrolyte, battery and preparation method Download PDF

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CN113527543B
CN113527543B CN202110701152.4A CN202110701152A CN113527543B CN 113527543 B CN113527543 B CN 113527543B CN 202110701152 A CN202110701152 A CN 202110701152A CN 113527543 B CN113527543 B CN 113527543B
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宋江选
范豪
付发望
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Suqian Unitechem Co ltd
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Abstract

The invention discloses an electrolyte of a water system neutral piperidine nitrogen oxygen free radical type organic flow battery, a battery and a preparation method, wherein the electrolyte consists of an inclusion compound and a supporting electrolyte solution, the inclusion compound consists of an organic electrolyte object and an inclusion compound host for including the organic electrolyte object, the inclusion compound host is an external hydrophilic and internal hydrophobic annular polymer which is formed by connecting a plurality of glucose units and is provided with a cavity, and the organic electrolyte object is an organic electrolyte which is low in solubility in water or almost insoluble and is provided with a negative charge group; the battery comprises a single battery and a galvanic pile consisting of more than two single batteries, wherein the electrolyte of the positive electrode of the single battery adopts water system neutral piperidine nitrogen oxygen free radical organic flow battery electrolyte. The invention can improve the solubility of the organic electrolyte without chemical modification, and finally improve the stability and energy density of the flow battery.

Description

Aqueous neutral piperidine nitrogen-oxygen free radical organic flow battery electrolyte, battery and preparation method
Technical Field
The invention belongs to the field of large-scale energy storage, and particularly relates to a water system neutral piperidine nitroxide free radical (2,2,6,6-tetramethy-1-piperidine carbonyl radial) organic flow battery electrolyte, a battery and a preparation method.
Background
The energy storage technology is an important link of the smart grid and is one of key support technologies of the smart grid. The rapid development of renewable energy power generation brings new development opportunities for the energy storage industry. But the method has the characteristics of randomness, intermittence and fluctuation, and brings huge challenges to power grid peak regulation, operation control, power supply quality and the like when the method is accessed in a large scale. Therefore, a large-scale energy storage technology with low cost and high performance is developed, the capability of a power grid for accepting clean energy is hopefully improved, and the problem of safety and stability of the power grid caused by access of large-scale renewable energy sources is solved.
The water system flow battery has the characteristics of high safety, quick response, long service life and the like, and has a good development prospect in the field of large-scale energy storage. The emerging aqueous organic flow battery draws wide attention due to the characteristics that the organic redox active substance of the battery is easy to prepare, can be produced in large scale, has strong cutting property and the like. However, the development of the method is mostly limited by the problems of few types of organic redox active substances with high potential, low solubility in water, unstable chemical properties and the like. The piperidine nitroxide free radical (2,2,6,6-tetramethyloxy-1-piperidinyloxy radial, TEMPO) and ferrocene derivatives are two common choices of the anode active substance of the water-based organic flow battery, and the former (> 0.8V vs. RHE) has the advantages of higher oxidation-reduction potential, easily adjustable structure and the like compared with the latter. The existing research shows that the oxidation-reduction potential, the water solubility and the compatibility with an ion exchange membrane of two active substances can be modulated through molecular design synthetic engineering, and the performance of the power-assisted battery is improved. Nevertheless, the improvement in chemical stability is still limited, and the actual operating life of the battery is far from scale-up.
Disclosure of Invention
The invention aims to provide a water system neutral piperidine nitrogen oxygen free radical type organic flow battery electrolyte, a battery and a preparation method, and aims to solve the problems that the existing flow battery is too high in cost, poor in electrolyte solubility or hardly soluble in the electrolyte, low in energy density, poor in cycling stability and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the aqueous neutral piperidine nitrogen-oxygen free radical type organic flow battery electrolyte consists of an inclusion compound and a first supporting electrolyte solution, wherein the inclusion compound consists of an organic electrolyte object and an inclusion compound host for including the organic electrolyte object, the inclusion compound host is an external hydrophilic annular polymer which is formed by connecting a plurality of glucose units, the interior of the annular polymer is hydrophobic, the annular polymer is provided with a cavity, and the organic electrolyte object is an organic electrolyte which is low in solubility in water or almost insoluble and has a negative charge group.
Further, the main body of the inclusion compound is cyclodextrin and derivatives thereof.
Further, the cyclodextrin and the derivative thereof are gamma-cyclodextrin or gamma-cyclodextrin derivatives.
Further, the organic electrolyte guest is a piperidine nitroxide radical or a derivative thereof.
Further, the piperidine nitrogen-oxygen free radical derivative is 4-OPO 3 Na-TEMPO、4-NHCOCH 2 SO 3 Na-TEMPO、4-OSO 3 Na-TEMPO、4-NHSO 2 CF 3 Na-TEMPO、4-OSO 2 CF 3 Na-TEMPO、4-OPO 3 K-TEMPO、4-NHCOCH 2 SO 3 K-TEMPO、4-OSO 3 K-TEMPO、4-NHSO 2 CF 3 K-TEMPO and 4-OSO 2 CF 3 One of K-TEMPO.
Further, the first supporting electrolyte solution is an aqueous solution of sodium chloride or an aqueous solution of potassium chloride, and the concentration of the first supporting electrolyte solution is 1mol/L.
Further, the molar ratio of the organic electrolyte guest to the clathrate host is 1: (0.3-3), and the concentration of the inclusion compound in the first supporting electrolyte solution is 0.05-0.5 mol/L.
A preparation method of a water system neutral piperidine nitrogen oxygen free radical type organic flow battery electrolyte is characterized in that an organic electrolyte object and an inclusion compound main body including the organic electrolyte object are added into a supporting electrolyte solution, and the water system neutral piperidine nitrogen oxygen free radical type organic flow battery electrolyte is obtained after ultrasonic and stirring.
The utility model provides a water system neutral piperidine nitroxide free radical type organic liquid flow battery, includes the electric pile that monomer battery and two or more monomer batteries are constituteed, monomer battery is including the anodal electrolyte, anodal flow field board, anodal electrode, ionic membrane, negative electrode, negative pole flow field board and the negative pole electrolyte of assembling in proper order, anodal electrolyte adopts water system neutral piperidine nitroxide free radical type organic liquid flow battery electrolyte.
Further, the negative electrode electrolyte consists of a viologen or anthraquinone organic electrolyte with high water solubility and a second supporting electrolyte solution; the second supporting electrolyte solution is an aqueous solution of sodium chloride or potassium chloride; the anode flow field plate and the cathode flow field plate are both graphite plates engraved with flow channels; the positive electrode and the negative electrode are both graphite felt or carbon electrodes, and the ion diaphragm is a cation exchange membrane.
Compared with the prior art, the invention has the following beneficial technical effects:
the clathrate compound main body is a cyclic polymer which is formed by connecting a plurality of glucose units, is hydrophilic outside, is hydrophobic inside and has a cavity, and the organic electrolyte object is an organic electrolyte which is poor in water solubility or is hardly dissolved in electrolyte and has a negative charge group. The two are combined through the attraction of positive and negative charges, no chemical reaction occurs, and finally the inclusion compound with good solubility is formed. The inclusion compound based on ion recognition not only has the characteristic of high water solubility of ionic groups, but also has the stabilizing effect of positive and negative charge electrostatic attraction driving force, avoids chemical modification of organic electrolyte, and based on the stabilizing effect, the water solubility of the TEMPO derivatives is expected to be greatly improved by utilizing a subject-object electrostatic interaction strategy, and side reactions such as disproportionation reaction, ring opening reaction and the like existing in the reaction process are effectively inhibited.
In addition, under the environment of a neutral supporting electrolyte solution, the battery can be matched with a proper cathode to form a water system neutral organic flow battery with high potential and high performance, the battery simultaneously promotes the water solubility and the oxidation reduction potential of the piperidine nitrogen oxygen free radical organic electrolyte, the stability and the energy density of the flow battery are improved, the performance of the battery is further greatly improved, reference is provided for development of the high-performance water system all-organic flow battery, the cost of the flow battery is reduced, and the battery can be used for a large-scale energy storage technology.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is
Figure GDA0003838664340000041
(the molar ratio is 1:1) and the formed electrolyte is subjected to cyclic voltammetry curves at different sweep rates, wherein the sweep rates are 25mV/s,100mV/s,225mV/s,625mV/s and 900mV/s;
FIG. 2 is
Figure GDA0003838664340000042
(the molar ratio is 1:1) performing inclusion, and performing linear fitting on peak current and square root of sweep rate of the formed electrolyte at different sweep rates in cyclic voltammetry tests, wherein the sweep rates are 25mV/s,100mV/s,225mV/s,625mV/s and 900mV/s;
FIG. 3 is
Figure GDA0003838664340000043
(molar ratio 1:1)/first-turn time-voltage curve of charging and discharging of the sulfonic acid group viologen system neutral organic flow battery under the current of 30 mA;
FIG. 4 is
Figure GDA0003838664340000044
(the molar ratio is 3:1) and the formed electrolyte is subjected to cyclic voltammetry curves at different sweep rates, wherein the sweep rates are 25mV/s,100mV/s,225mV/s,625mV/s and 900mV/s;
FIG. 5 is
Figure GDA0003838664340000045
(the molar ratio is 3:1) performing inclusion, and performing linear fitting on peak current of the formed electrolyte and square root of sweep rate in cyclic voltammetry tests at different sweep rates, wherein the sweep rates are 25mV/s,100mV/s,225mV/s,625mV/s and 900mV/s;
FIG. 6 is
Figure GDA0003838664340000051
(molar ratio 3:1)/sulfonic acid group viologen system neutral organic flow battery in the first cycle of charge and discharge under the current of 30mAA time-voltage curve;
FIG. 7 is
Figure GDA0003838664340000052
(the molar ratio is 1:3) and the formed electrolyte is subjected to cyclic voltammetry curves at different sweep rates, wherein the sweep rates are 25mV/s,100mV/s,225mV/s,625mV/s and 900mV/s;
FIG. 8 is
Figure GDA0003838664340000053
(the molar ratio is 1:3) performing inclusion, and performing linear fitting on peak current and square root of sweep rate of the formed electrolyte at different sweep rates in cyclic voltammetry tests, wherein the sweep rates are 25mV/s,100mV/s,225mV/s,625mV/s and 900mV/s;
FIG. 9 is
Figure GDA0003838664340000054
(molar ratio 1:3)/first-turn time-voltage curve of charging and discharging of the sulfonic acid group viologen system neutral organic flow battery under the current of 30 mA;
FIG. 10 is
Figure GDA0003838664340000055
(molar ratio 1:3)/cycle number-capacity-coulombic efficiency-energy efficiency graph under different current discharge conditions of sulfonic violet aqueous neutral organic flow battery
Detailed Description
The invention will be described in further detail below:
aiming at the problem that the organic electrolyte in a water-based organic flow battery needs to be modified to obtain good water solubility in the prior art, the invention provides the water-based neutral piperidine nitroxide free radical flow battery electrolyte, which can improve the solubility of the organic electrolyte without being modified by chemical modification, and finally improves the stability and energy density of the flow battery.
The water system neutral piperidine nitrogen-oxygen free radical type organic flow battery electrolyte consists of an inclusion compound and a supporting electrolyte solution, wherein the inclusion compound consists of an organic electrolyte object and an inclusion compound host for including the organic electrolyte object, the inclusion compound host is an external hydrophilic annular polymer which is formed by connecting a plurality of glucose units, the interior of the annular polymer is hydrophobic, and the annular polymer is provided with a cavity, and the organic electrolyte object is an organic electrolyte which is low in solubility in water or almost insoluble and provided with a negative charge group.
Wherein the clathrate comprises cyclodextrin and its derivatives, and the cyclodextrin and its derivatives are one of gamma-cyclodextrin (gamma-CD) and gamma-cyclodextrin derivatives; the organic electrolyte object is piperidine nitroxide free radical (2,2,6,6-tetramethyl-1-piperidine carbonyl radial) and its derivative, and the piperidine nitroxide free radical derivative is 4-OPO 3 Na-TEMPO、4-NHCOCH 2 SO 3 Na-TEMPO、4-OSO 3 Na-TEMPO、4-NHSO 2 CF 3 Na-TEMPO、4-OSO 2 CF 3 Na-TEMPO、4-OPO 3 K-TEMPO、4-NHCOCH 2 SO 3 K-TEMPO、4-OSO 3 K-TEMPO、4-NHSO 2 CF 3 K-TEMPO、4-OSO 2 CF 3 One of K-TEMPO; the supporting electrolyte solution is an aqueous solution of sodium chloride or potassium chloride, and the concentration of the supporting electrolyte solution is 1mol/L; the molar ratio of the organic electrolyte guest to the inclusion compound host is 1: (0.3-3), and the concentration of the inclusion compound in the supporting electrolyte solution is 0.05-0.5 mol/L.
Wherein the TEMPO has a structural formula:
Figure GDA0003838664340000061
the formula of the TEMPO derivative is:
Figure GDA0003838664340000062
wherein R is-OPO 3 Na、-NHCOCH 2 SO 3 Na、-OSO 3 Na、-NHSO 2 CF 3 Na、-OSO 2 CF 3 Na、-OPO 3 K、-NHCOCH 2 SO 3 K、-OSO 3 K、-NHSO 2 CF 3 K、-OSO 2 CF 3 K。
A preparation method of an aqueous neutral piperidine nitrogen-oxygen free radical type organic flow battery electrolyte comprises the steps of adding an organic electrolyte object and an inclusion compound host for including the organic electrolyte object into a supporting electrolyte solution, carrying out ultrasonic treatment for 60min, and stirring for more than 24h to obtain the electrolyte containing the inclusion compound, wherein the inclusion compound host is cyclic polymer cyclodextrin which is formed by connecting a plurality of glucose units and has hydrophilic outside and hydrophobic inside and a cavity, and the organic electrolyte object is an organic electrolyte which is poor in solubility in water or is almost insoluble and has a negative charge group.
The water system neutral piperidine nitrogen oxygen free radical type organic flow battery has positive electrolyte selected from the electrolyte, negative electrolyte comprising water soluble organic viologen or anthraquinone electrolyte and supporting electrolyte solution, sodium chloride or potassium chloride water solution as the supporting electrolyte solution, cation exchange membrane as ion exchange diaphragm, graphite plate with flow channel as the flow field plate of positive and negative electrodes, and two pieces of graphite felt or carbon paper treated through high temperature oxidation or dilute acid as electrodes.
An assembly method of an aqueous neutral piperidine nitrogen oxygen free radical type organic flow battery comprises the steps that a positive electrode electrolyte consists of a piperidine nitrogen oxygen free radical type organic electrolyte and a supporting electrolyte solution, the organic electrolyte consists of an anion-substituted piperidine nitrogen oxygen free radical type object and a host for including the piperidine nitrogen oxygen free radical object, the host is annular polymer cyclodextrin which is formed by connecting a plurality of glucose units and is hydrophilic on the outside and hydrophobic on the inside and provided with a cavity, and the object is the organic electrolyte which is poor in solubility in water or is hardly dissolved in the electrolyte and provided with a negative charge group; the cathode electrolyte consists of a viologen or anthracene organic electrolyte with high water solubility and a supporting electrolyte solution, and the supporting electrolyte of the cathode and the anode is a potassium chloride or sodium chloride aqueous solution; taking a cation exchange membrane as an ion exchange diaphragm; graphite felt or carbon paper is used as an electrode; the battery assembly sequence is positive electrolyte, graphite plate runner, graphite felt electrode, cation exchange diaphragm, graphite felt electrode, graphite plate runner, negative electrolyte.
The working principle of the water system neutral piperidine nitrogen oxygen free radical type organic flow battery is as follows: the preparation method is characterized in that a piperidine nitroxide free radical organic electrolyte is taken as an object, cyclodextrin is taken as a main body, and based on ion recognition inclusion, active molecules are anion-substituted piperidine nitroxide free radical organic electrolytes and undergo redox reaction in an aqueous solution of neutral potassium chloride or sodium chloride so as to realize charging and discharging.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is illustrative of the embodiments and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
Example 1
Weighing 0.412g 4-OSO 3 Na-TEMPO and 1.946g gamma-CD are added into 15mL of 1mol/L potassium chloride solution, ultrasonic treatment is carried out for 60min, then magnetic stirring is carried out for more than 24h, and the needed clathrate compound solution (1) (1:1) is obtained, wherein the concentration of the subject and the object is 0.1mol/L. The resulting clathrate solution (0.5 mL of 1) was added to 14.5mL of 1M potassium chloride solution to obtain a diluted solution (2) having a subject-guest concentration of 0.003mol/L. And (3) carrying out cyclic voltammetry test on the solution (2) by using a three-electrode system, wherein the used reference electrode is a silver/silver chloride electrode, the working electrode is a glassy carbon electrode, and the counter electrode is a graphite electrode. The sweep rates selected were 25mV/s,100mV/s,225mV/s,625mV/s, and 900mV/s, to obtain the cyclic voltammograms shown in FIG. 1.
As can be seen from the figure 1, it is,
Figure GDA0003838664340000081
(1:1) inclusion compound in neutral supporting electrolyte solution environmentThe anode material has a pair of obviously reversible oxidation-reduction peaks, has good electrochemical reversibility, has an average potential of more than 0.61V, and shows a positive oxidation-reduction potential as a positive electrode material.
In FIG. 2, the peak of the oxidation-reduction potential and the square root of the sweep rate were linearly fitted, and it was found that the slopes of the two straight lines were substantially the same, which proved that
Figure GDA0003838664340000082
The (1:1) inclusion compound has reversible electrochemical performance in a neutral supporting electrolyte solution environment, and the diffusion coefficients of the oxidation reaction and the reduction reaction are approximately the same.
The resulting clathrate solution (1). Sup.0mL was taken as a positive electrode electrolyte. And the sulfonic group viologen electrolyte is used as a negative electrode electrolyte. 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 battery is assembled by the sequence and the position of positive electrolyte, graphite plate flow channel, graphite felt electrode, cation exchange membrane, graphite felt electrode, graphite plate flow channel and negative electrolyte, and the liquid is driven by a peristaltic pump.
Fig. 3 shows a first cycle charge and discharge capacity-voltage curve of the battery, which shows that the battery can work normally and stably and has higher coulombic efficiency.
Example 2
Weighing 0.618g 4-OSO 3 Adding Na-TEMPO and 0.973g gamma-CD into 15mL1mol/L potassium chloride solution, performing ultrasonic treatment for 60min, and magnetically stirring for more than 24h to obtain the required clathrate solution (1) (3:1) and guest 4-OSO 3 The Na-TEMPO concentration is 0.15mol/L, and the main body gamma-CD concentration is 0.05mol/L. Taking 0.5mL of the obtained clathrate solution (1), adding 14.5mL of 1M potassium chloride solution to obtain a diluted solution (2), guest 4-OSO 3 The Na-TEMPO concentration is 0.005mol/L, and the main body gamma-CD concentration is 0.0016mol/L. And (3) carrying out cyclic voltammetry on the solution (2) by using a three-electrode system, wherein the used reference electrode is a silver/silver chloride electrode, the working electrode is a glassy carbon electrode, and the counter electrode is a graphite electrode. The sweep rates selected were 25mV/s,100mV/s,225mV/s,625mV/s, and 900mV/s, to provide the cyclic voltammograms shown in FIG. 4.
As can be seen from the view of figure 4,
Figure GDA0003838664340000091
the (3:1) inclusion compound has a pair of obviously reversible redox peaks in a neutral supporting electrolyte solution environment, has good electrochemical reversibility, has an average potential of more than 0.60V, and shows a positive redox potential when used as a positive electrode material.
In FIG. 5, the peak of the oxidation-reduction potential and the square root of the sweep rate were linearly fitted, and it was found that the slopes of the two straight lines were substantially the same, which proved that
Figure GDA0003838664340000092
The (3:1) inclusion compound has reversible electrochemical performance in a neutral supporting electrolyte solution environment, and the diffusion coefficients of the oxidation reaction and the reduction reaction are approximately the same.
The resulting clathrate solution (1) was collected and used as a positive electrode electrolyte in a volume of 10mL. And the sulfonic group viologen electrolyte is used as the negative electrolyte. 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 battery is assembled by the sequence and the position of positive electrolyte, graphite plate flow channel, graphite felt electrode, cation exchange membrane, graphite felt electrode, graphite plate flow channel and negative electrolyte, and the liquid is driven by a peristaltic pump.
Fig. 6 shows a first cycle charge-discharge capacity-voltage curve of the battery, which shows that the battery can work normally and stably and has high coulombic efficiency.
Example 3
Weighing 0.206g of 4-OSO 3 Na-TEMPO and 2.919g gamma-CD are added into 15mL1mol/L potassium chloride solution, ultrasonic treatment is carried out for 60min, then magnetic stirring is carried out for more than 24h, and the needed clathrate compound solution (1) (1:3) and object 4-OSO are obtained 3 The Na-TEMPO concentration is 0.05mol/L, and the main body gamma-CD concentration is 0.15mol/L. Taking 0.5mL of the obtained clathrate solution (1), adding 14.5mL of 1M potassium chloride solution to obtain a diluted solution (2), guest 4-OSO 3 The Na-TEMPO concentration is 0.0016mol/L, and the main gamma-CD concentration is 0.0050mol/L. The solution (2) is subjected to cyclic voltammetry by using a three-electrode system, and the used reference electrode isThe silver/silver chloride electrode, the working electrode is a glassy carbon electrode, and the counter electrode is a graphite electrode. The sweep rates selected were 25mV/s,100mV/s,225mV/s,625mV/s, and 900mV/s, to provide the cyclic voltammograms shown in FIG. 7.
As can be seen from the figure 7 of the drawings,
Figure GDA0003838664340000101
the (1:3) inclusion compound has a pair of obviously reversible redox peaks in a neutral supporting electrolyte solution environment, has good electrochemical reversibility, has an average potential of more than 0.62V, and shows a positive redox potential when used as a positive electrode material.
In FIG. 8, the peak of the oxidation-reduction potential and the square root of the sweep rate were linearly fitted, and it was found that the slopes of the two straight lines were substantially the same, which proved that
Figure GDA0003838664340000111
The (1:3) inclusion compound has reversible electrochemical performance in a neutral supporting electrolyte solution environment, and the diffusion coefficients of the oxidation reaction and the reduction reaction are approximately the same.
The resulting clathrate solution (1). Sup.0mL was taken as a positive electrode electrolyte. And the sulfonic group viologen electrolyte is used as the negative electrolyte. 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 battery is assembled by the sequence and the position of positive electrolyte, graphite plate flow channel, graphite felt electrode, cation exchange membrane, graphite felt electrode, graphite plate flow channel and negative electrolyte, and the liquid is driven by a peristaltic pump.
Fig. 9 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 4
Weighing 0.206g of 4-OSO 3 Na-TEMPO and 2.919g gamma-CD are added into 15mL1mol/L potassium chloride solution, ultrasonic treatment is carried out for 60min, then magnetic stirring is carried out for more than 24h, and the needed clathrate compound solution (1) (1:3) and object 4-OSO are obtained 3 The Na-TEMPO concentration is 0.05mol/L, and the main body gamma-CD concentration is 0.15mol/L. The resulting clathrate solution (1): 10mL was used as a positive electrode electrolyte,taking sulfonic group viologen electrolyte as cathode electrolyte, carrying out heat treatment on the graphite felt, specifically putting the graphite felt into Ma Feilu, carrying out heat treatment at 500 ℃ for 10h, taking out after cooling to room temperature, and then directly using. The battery is assembled by the sequence and the position of positive electrolyte, graphite plate flow channel, graphite felt electrode, cation exchange membrane, graphite felt electrode, graphite plate flow channel and negative electrolyte, and the liquid is driven by a peristaltic pump. The battery is subjected to charge and discharge performance tests, different currents are adopted for the charge and discharge tests, currents of 30mA,40mA,50mA,60mA and 70mA are respectively selected, and coulomb and energy efficiency-cycle number and charge and discharge capacity-cycle number graphs can be obtained.
As shown in fig. 10, 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 exhibits good rate performance.
Example 5
Weighing 0.206g of 4-OSO 3 Na-TEMPO and 1.946g gamma-CD are added into 15mL1mol/L potassium chloride solution, ultrasonic treatment is carried out for 60min, and then magnetic stirring is carried out for more than 24h, thus obtaining the needed clathrate compound solution (1) (1:2) and object 4-OSO 3 The Na-TEMPO concentration is 0.05mol/L, and the main body gamma-CD concentration is 0.10mol/L. Taking 10mL of the obtained inclusion compound solution (1) as an anode electrolyte, taking a sulfonic group viologen electrolyte as a cathode electrolyte, carrying out heat treatment on a graphite felt, specifically putting the graphite felt into Ma Feilu, carrying out heat treatment at 500 ℃ for 10h, taking out after cooling to room temperature, directly using the graphite felt, assembling the battery by the sequence and the position of the anode electrolyte, the graphite plate flow channel, the graphite felt electrode, the cation exchange membrane, the graphite felt electrode, the graphite plate flow channel and the cathode electrolyte, and driving the liquid by a peristaltic pump.
Example 6
Weighing 0.412g 4-OSO 3 Adding Na-TEMPO and 0.973g gamma-CD into 15mL1mol/L potassium chloride solution, performing ultrasonic treatment for 60min, and magnetically stirring for more than 24h to obtain the required clathrate solution (1) (2:1) and guest 4-OSO 3 The Na-TEMPO concentration is 0.10mol/L, and the main body gamma-CD concentration is 0.05mol/L. The resulting clathrate solution (1): 10mL was used as a positive electrode electrolyte, and a sulfonic acid viologen electrolyte was usedAnd (3) performing heat treatment on the graphite felt as a cathode electrolyte, specifically putting the graphite felt into Ma Feilu, heating at 500 ℃ for 10 hours, cooling to room temperature, taking out, and then directly using. The battery is assembled in the order and position of positive electrolyte-graphite plate flow channel-graphite felt electrode-cation exchange membrane-graphite felt electrode-graphite plate flow channel-negative electrolyte, and the liquid is driven by a peristaltic pump.
Example 7
Weighing 0.412g 4-OSO 3 Na-TEMPO and 2.919g gamma-CD are added into 15mL1mol/L potassium chloride solution, ultrasonic treatment is carried out for 60min, then magnetic stirring is carried out for more than 24h, and the needed clathrate compound solution (1) (2:3) and object 4-OSO are obtained 3 The Na-TEMPO concentration is 0.10mol/L, and the main body gamma-CD concentration is 0.15mol/L. Taking 10mL of the obtained inclusion compound solution (1) as an anode electrolyte, taking a sulfonic violet electrolyte as a cathode electrolyte, carrying out heat treatment on a graphite felt, specifically putting the graphite felt into Ma Feilu, carrying out heat treatment at 500 ℃ for 10 hours, taking out after cooling to room temperature, directly using the graphite felt, assembling the battery by the sequence and the position of the anode electrolyte, a graphite plate flow channel, a graphite felt electrode, a cation exchange membrane, a graphite felt electrode, a graphite plate flow channel and the cathode electrolyte, and driving the liquid by a peristaltic pump.
Example 8
Weighing 0.618g 4-OSO 3 Adding Na-TEMPO and 1.946g gamma-CD into 15mL1mol/L potassium chloride solution, performing ultrasonic treatment for 60min, and magnetically stirring for more than 24h to obtain the required clathrate compound solution (1) (3:2) and guest 4-OSO 3 The Na-TEMPO concentration is 0.15mol/L, and the main body gamma-CD concentration is 0.10mol/L. Taking 10mL of the obtained clathrate compound solution (1) as an anode electrolyte, taking a sulfonic group viologen electrolyte as a cathode electrolyte, and carrying out heat treatment on the graphite felt, wherein the specific operation is to place the graphite felt into Ma Feilu, heat-treat the graphite felt for 10 hours at 500 ℃, take out the graphite felt after cooling to room temperature, and then directly use the graphite felt. The battery is assembled in the order and position of positive electrolyte-graphite plate flow channel-graphite felt electrode-cation exchange membrane-graphite felt electrode-graphite plate flow channel-negative electrolyte, and the liquid is driven by a peristaltic pump.
Example 9
0.0586g of TEMPO and 0.4864g of gamma-CD are weighed and added into 15mL of 1mol/L potassium chloride solution, ultrasonic treatment is carried out for 60min, then magnetic stirring is carried out for more than 24h, and the needed clathrate compound solution (1) (1:1) is obtained, wherein the TEMPO concentration of the object is 0.025mol/L, and the gamma-CD concentration of the main body is 0.025mol/L. Taking 10mL of the obtained clathrate compound solution (1) as an anode electrolyte, taking a sulfonic group viologen electrolyte as a cathode electrolyte, and carrying out heat treatment on the graphite felt, wherein the specific operation is to place the graphite felt into Ma Feilu, heat-treat the graphite felt for 10 hours at 500 ℃, take out the graphite felt after cooling to room temperature, and then directly use the graphite felt. The battery is assembled by the sequence and the position of positive electrolyte, graphite plate flow channel, graphite felt electrode, cation exchange membrane, graphite felt electrode, graphite plate flow channel and negative electrolyte, and the liquid is driven by a peristaltic pump.
Example 10
0.4688g TEMPO and 5.8370g gamma-CD are weighed and added into 15mL1mol/L potassium chloride solution, ultrasonic treatment is carried out for 60min, then magnetic stirring is carried out for more than 24h, and the needed clathrate compound solution (1) (1:1) is obtained, wherein the TEMPO concentration of an object is 0.2mol/L, and the gamma-CD concentration of a host is 0.3mol/L. Taking 10mL of the obtained inclusion compound solution as a positive electrode electrolyte, taking sulfonic group viologen electrolyte as a negative electrode electrolyte, and carrying out heat treatment on the graphite felt, wherein the specific operation is to place the graphite felt into Ma Feilu, heat-treat the graphite felt for 10 hours at 500 ℃, take out the graphite felt after cooling to room temperature, and then directly use the graphite felt. The battery is assembled by the sequence and the position of positive electrolyte, graphite plate flow channel, graphite felt electrode, cation exchange membrane, graphite felt electrode, graphite plate flow channel and negative electrolyte, and the liquid is driven by a peristaltic pump.
Example 11
Weighing 0.4369g 4-OSO 3 K-TEMPO and 5.8370g gamma-CD are added into 15mL1mol/L potassium chloride solution, ultrasonic treatment is carried out for 60min, then magnetic stirring is carried out for more than 24h, and the needed clathrate compound solution (1) (1:1) and object 4-OSO are obtained 3 The concentration of K-TEMPO is 0.1mol/L, and the concentration of main gamma-CD is 0.3mol/L. Taking 10mL of the obtained clathrate compound solution as a positive electrode electrolyte, taking a sulfonic group viologen electrolyte as a negative electrode electrolyte, carrying out heat treatment on a graphite felt, specifically, putting the graphite felt into Ma Feilu, heating at 500 ℃ for 10h, taking out after cooling to room temperature, and then directly using the graphite felt. The battery is assembled by the sequence and the position of positive electrolyte, graphite plate flow channel, graphite felt electrode, cation exchange membrane, graphite felt electrode, graphite plate flow channel and negative electrolyte, and the liquid is driven by a peristaltic pump.
Example 12
Weighing 0.8738g of 4-OSO 3 K-TEMPO and 5.8370g gamma-CD are added into 15mL1mol/L potassium chloride solution, ultrasonic treatment is carried out for 60min, then magnetic stirring is carried out for more than 24h, and needed clathrate compound solution (1) (1:1) and object 4-OSO are obtained 3 The concentration of K-TEMPO is 0.2mol/L, and the concentration of main gamma-CD is 0.3mol/L. Taking 10mL of the obtained clathrate compound solution (1) as an anode electrolyte, taking a sulfonic group viologen electrolyte as a cathode electrolyte, and carrying out heat treatment on the graphite felt, wherein the specific operation is to place the graphite felt into Ma Feilu, heat-treat the graphite felt for 10 hours at 500 ℃, take out the graphite felt after cooling to room temperature, and then directly use the graphite felt. The battery is assembled by the sequence and the position of positive electrolyte, graphite plate flow channel, graphite felt electrode, cation exchange membrane, graphite felt electrode, graphite plate flow channel and negative electrolyte, and the liquid is driven by a peristaltic pump.
Example 13
Weighing 0.2057g of 4-OPO 3 Na-TEMPO and 1.9457g gamma-CD are added into 15mL1mol/L potassium chloride solution, ultrasonic treatment is carried out for 60min, then magnetic stirring is carried out for more than 24h, and the needed clathrate compound solution (1) (1:1) and object 4-OPO are obtained 3 The Na-TEMPO concentration is 0.05mol/L, and the main body gamma-CD concentration is 0.1mol/L. Taking 10mL of the obtained clathrate compound solution (1) as an anode electrolyte, taking a sulfonic group viologen electrolyte as a cathode electrolyte, and carrying out heat treatment on the graphite felt, wherein the specific operation is to place the graphite felt into Ma Feilu, heat-treat the graphite felt for 10 hours at 500 ℃, take out the graphite felt after cooling to room temperature, and then directly use the graphite felt. The battery is assembled by the sequence and the position of positive electrolyte, graphite plate flow channel, graphite felt electrode, cation exchange membrane, graphite felt electrode, graphite plate flow channel and negative electrolyte, and the liquid is driven by a peristaltic pump.
Example 14
Weighing 0.2057g of 4-OPO 3 Adding Na-TEMPO and 0.9729g gamma-CD into 15mL1mol/L potassium chloride solution, performing ultrasonic treatment for 60min, and magnetically stirring for more than 24h to obtain the required clathrate compound solutionLiquid (1) (1:1), guest 4-OPO 3 The Na-TEMPO concentration is 0.05mol/L, and the main body gamma-CD concentration is 0.05mol/L. Taking 10mL of the obtained clathrate compound solution (1) as an anode electrolyte, taking a sulfonic group viologen electrolyte as a cathode electrolyte, and carrying out heat treatment on the graphite felt, wherein the specific operation is to place the graphite felt into Ma Feilu, heat-treat the graphite felt for 10 hours at 500 ℃, take out the graphite felt after cooling to room temperature, and then directly use the graphite felt. The battery is assembled by the sequence and the position of positive electrolyte, graphite plate flow channel, graphite felt electrode, cation exchange membrane, graphite felt electrode, graphite plate flow channel and negative electrolyte, and the liquid is driven by a peristaltic pump.
Example 15
0.24584g 4-NHSO was weighed 2 CF 3 Adding Na-TEMPO and 2.9187g gamma-CD into 15mL of 1mol/L potassium chloride solution, performing ultrasonic treatment for 60min, and magnetically stirring for more than 24h to obtain the required clathrate compound solution (1) (1:1) and guest 4-NHSO 2 CF 3 The Na-TEMPO concentration is 0.05mol/L, and the main body gamma-CD concentration is 0.15mol/L. Taking 10mL of the obtained inclusion compound solution as a positive electrode electrolyte, taking sulfonic group viologen electrolyte as a negative electrode electrolyte, and carrying out heat treatment on the graphite felt, wherein the specific operation is to place the graphite felt into Ma Feilu, heat-treat the graphite felt for 10 hours at 500 ℃, take out the graphite felt after cooling to room temperature, and then directly use the graphite felt. The battery is assembled by the sequence and the position of positive electrolyte, graphite plate flow channel, graphite felt electrode, cation exchange membrane, graphite felt electrode, graphite plate flow channel and negative electrolyte, and the liquid is driven by a peristaltic pump.
Example 16
Weighing 0.2372g of 4-NHCOCH 2 SO 3 Na-TEMPO and 2.9187g gamma-CD are added into 15mL1mol/L potassium chloride solution, ultrasonic treatment is carried out for 60min, then magnetic stirring is carried out for more than 24h, and the needed clathrate compound solution (1) (1:1) and object 4-NHCOCH are obtained 2 SO 3 The Na-TEMPO concentration is 0.05mol/L, and the main body gamma-CD concentration is 0.15mol/L. Taking 10mL of the obtained clathrate compound solution (1) as an anode electrolyte, taking a sulfonic group viologen electrolyte as a cathode electrolyte, and carrying out heat treatment on the graphite felt, wherein the specific operation is to place the graphite felt into Ma Feilu, heat-treat the graphite felt for 10 hours at 500 ℃, take out the graphite felt after cooling to room temperature, and then directly use the graphite felt. With positive electrolyte-stoneThe battery is assembled by the sequence and the position of the ink plate flow channel, the graphite felt electrode, the cation exchange membrane, the graphite felt electrode, the graphite plate flow channel and the negative electrode electrolyte, and the liquid is driven by a peristaltic pump.
The embodiments described above are merely preferred embodiments of the present invention, and should not be considered as limitations of the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.

Claims (5)

1. The electrolyte of the aqueous neutral piperidine nitrogen-oxygen free radical type organic flow battery is characterized by comprising an inclusion compound and a first supporting electrolyte solution, wherein the inclusion compound comprises an organic electrolyte object and an inclusion compound body for including the organic electrolyte object, and the inclusion compound body is a cyclic polymer which is formed by connecting a plurality of glucose units, is hydrophilic outside and hydrophobic inside and is provided with a cavity;
the clathrate compound main body is cyclodextrin and derivatives thereof, and the cyclodextrin and the derivatives thereof are gamma-cyclodextrin or gamma-cyclodextrin derivatives;
the organic electrolyte object is a piperidine nitroxide free radical derivative, and the piperidine nitroxide free radical derivative is 4-OPO 3 Na-TEMPO、4-NHCOCH 2 SO 3 Na-TEMPO、4-OSO 3 Na-TEMPO、4-NHSO 2 CF 3 Na-TEMPO、4-OSO 2 CF 3 Na-TEMPO、4-OPO 3 K-TEMPO、4-NHCOCH 2 SO 3 K-TEMPO、4-OSO 3 K-TEMPO、4-NHSO 2 CF 3 K-TEMPO and 4-OSO 2 CF 3 One of K-TEMPO;
the molar ratio of the organic electrolyte guest to the inclusion compound host is 1: (0.3-3), and the concentration of the inclusion compound in the first supporting electrolyte solution is 0.05-0.5 mol/L.
2. The aqueous neutral piperidine nitroxide radical organic flow battery electrolyte solution of claim 1, wherein the first supporting electrolyte solution is an aqueous solution of sodium chloride or an aqueous solution of potassium chloride, and the concentration of the first supporting electrolyte solution is 1mol/L.
3. The preparation method of the aqueous neutral piperidine nitrogen-oxygen free radical type organic flow battery electrolyte solution as claimed in any one of claims 1-2, characterized in that an organic electrolyte guest and an inclusion compound host including the organic electrolyte guest are added into a supporting electrolyte solution, and the aqueous neutral piperidine nitrogen-oxygen free radical type organic flow battery electrolyte solution is obtained after ultrasonic agitation.
4. An aqueous neutral piperidine nitrogen oxygen free radical type organic flow battery is characterized by comprising a single battery and a galvanic pile consisting of more than two single batteries, wherein each single battery comprises a positive electrolyte, a positive flow field plate, a positive electrode, an ionic membrane, a negative electrode, a negative flow field plate and a negative electrolyte which are sequentially assembled, and the positive electrolyte adopts the aqueous neutral piperidine nitrogen oxygen free radical type organic flow battery electrolyte according to any one of claims 1-2.
5. The aqueous neutral piperidine nitroxide radical organic flow battery of claim 4, wherein the negative electrode electrolyte is composed of a highly water-soluble viologen or anthraquinone organic electrolyte and a second supporting electrolyte solution; the second supporting electrolyte solution is an aqueous solution of sodium chloride or potassium chloride; the anode flow field plate and the cathode flow field plate are both graphite plates engraved with flow channels; the positive electrode and the negative electrode are both graphite felt or carbon electrodes, and the ion diaphragm is a cation exchange membrane.
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