RU2752762C1 - Highly soluble triphenylamine-based catholyte and electrochemical current source based on it - Google Patents

Abstract

FIELD: electrochemistry.

SUBSTANCE: invention relates to the use of a triphenylamine derivative of the general formula F1 as a soluble cathode material in the composition of a catholite for an electrochemical current source. In formula F1, the substituent R is selected independently and is a halogen atom -F,- Cl or -Br; a nitrile group -CN; a hydrocarbon radical -CnH2n+1, where n=1-20; an ether residue -O-СпН2п+1, where n=1-20; an ether substituent based on oligoethylene glycol -O(CH2CH2O)nH, where n=1-10; an ether substituent based on oligoethylene glycol -O(CH2CH2O)nCH3, where n=1-10; or an ether substituent based on oligoethylene glycol -O(CH2CH2O)nCmH2m+1, where n=1-10, m=1-12; the substituent R1 is selected independently and is a) a fragment of substituted diphenylamine

,

in which the substituents R3 and R4 are selected independently and represent a halogen atom -F, -Cl or -Br; a hydrocarbon radical -CnH2n+1, where n=1-20; an ether residue -О-CnH2n+1, where n=1-20; an ether substituent based on oligoethylene glycol -O(CH2CH2O)nH, where n=1-10; an ether substituent based on oligoethylene glycol -O(CH2CH2O)nCH3, where n=1-10; an ether substituent based on oligoethylene glycol-O(CH2CH2O)nCmH2m+1, where n=1-10, m=1-12; b) one of the following substituents: a halogen atom -F, -Cl or -Br; a nitrile group -CN; a hydrocarbon radical -CnH2n+1, where n=1-20; the ether residue is -О-CnH2n+1, where n=1-20; the ether substituent based on oligoethylene glycol is O(CH2CH2O)nH, where n=1-10; the ether substituent based on oligoethylene glycol is O(CH2CH2O)nCH3, where n=1-10; the ether substituent based on oligoethylene glycol is O(CH2CH2O)nCmH2m+1, where n=1-10, m=1-12; the R2 substituent is selected independently and is: a) a fragment of substituted diphenylamine

,

in which the substituents R5 and R6 are selected independently and represent a halogen atom -F, -Cl or-Br; a hydrocarbon radical -CnH2n+1, where n=1-20; an ether residue -О-CnH2n+1, where n=1-20; an ether substituent based on oligoethylene glycol -O(CH2CH2O)nH, where n=1-10; an ether substituent based on oligoethylene glycol -O(CH2CH2O)nCH3, where n=1-10; ether substituent based on oligoethylene glycol -O(CH2CH2O)nCmH2m+1, where n=1-10, m=1-12; b) one of the following substituents: hydrocarbon radical -CnH2n+1, where n=1-20; ether residue -O-CnH2n+1, where n=1-20; the ether substituent based on oligoethylene glycol is -O(CH2CH2O)nH, where n=1-10; the ether substituent based on oligoethylene glycol is -O(CH2CH2O)nCH3, where n=1-10; the ether substituent based on oligoethylene glycol is -O(CH2CH2O)nCmH2m+1, where n=1-10, m=1-12.

EFFECT: improvement of the properties of electrochemical current sources and their stability during charge-discharge cycling.

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Description

Technology area

The invention relates to the fields of electrochemistry and energy, namely to organic redox-active materials for electrochemical power sources. This invention discloses the composition of promising highly soluble cathode materials (catholytes) based on arylamines for hybrid and flow batteries.

State of the art

The massive introduction of alternative sources of electricity, such as solar and wind power plants, leads to an imbalance in the generation and consumption of electricity, since the performance of these sources is unstable over time and is highly dependent on changing weather conditions. The use of electrochemical storage devices can be an optimal solution to this problem. Indeed, electrochemical current sources can easily accumulate energy during periods of its excessive generation and, conversely, quickly release it into the network with an increase in power consumption.

The most promising technology for storing large amounts of electricity today is considered to be flow-through accumulators. Unlike other types of batteries (for example, lithium-ion), in these devices, energy storage substances are not in the structure of the electrode, but in separate reservoirs in a dissolved form and are pumped through the electrochemical cell using pumps. Thus, the main advantage of flow-through batteries is that the storage system for active substances (reservoirs) and the device in which the current is generated (electrochemical cell) are isolated from each other. This design allows the battery capacity to be easily scaled by increasing the volume of electrolytes, while the power output is independently controlled by the size and number of electrochemical cells.

Today, vanadium flow accumulators are widely known, as well as other systems based on inorganic compounds, for example, zinc bromide or polysulfide bromide cells. Nevertheless, the widespread introduction of inorganic flow batteries is difficult due to the availability and unstable price of active materials (for example, the price of vanadium has changed 10 times over the past 5 years https://www.vanadiumprice.com), low specific capacity, and other problems associated with their operation. A narrow window of stability of the potentials of aqueous electrolytes limits the maximum attainable battery voltages, and the low solubility of inorganic ions does not allow achieving high specific energy capacities. Moreover, the chemical activity and toxicity of the electrolytes used, the potential risk to the environment and human health of vanadium salts, liquid bromine, concentrated acid solutions or other inorganic active materials further limit the application of this technology.

Taking into account the disadvantages of inorganic flow batteries, new active compounds based on organic molecules are being developed. The introduction of organic active materials makes it possible to abandon the use of heavy metals, concentrated acids, liquid bromine. In addition, the use of organic redox-active materials makes it possible to switch from the use of aqueous electrolytes to electrolytes based on organic solvents. Organic polar solvents such as acetonitrile, dimethylformamide or sulfolane have a wide potential stability window up to 6 Volts [O.R. Luca, J.L. Gustafson, S.M. Maddox, A.Q. Fenwick, D.C. Smith, Org. Chem. Front. 2 (2015) 823-848.], Which will allow the creation of high voltage batteries.

Compounds that undergo a redox reaction during battery charging and discharging are called redox-active compounds. Redox-active compounds used in flow accumulators are divided into two classes - catholytes and anolytes.

The term "anolyte" refers to a compound found in the anode space of a battery that undergoes a transition to a lower oxidation state as the battery is charged. The reaction that occurs with the anolyte at the anode during battery charging can be described by the following elementary equation:

A + e ^- → A ^- or A ^- + e ^- → A ^2- or A ^{n +} + x e ^- → A ^{(nx) +} or A ^n- + x e ^- → A ^{(n + x) -}

The term "catholyte" refers to a compound found in the cathode space of a battery that undergoes a transition to a higher oxidation state as the battery is charged. The reaction taking place with the catholyte at the cathode during battery charging can be described by the following elementary equation:

К - e ^- → К ⁺ or К ^- - e ^- → К or К ^{n +} - y e ^- → A ^{(n + y) +} or K ^n- - y e ^- → A ^{(ny) -}

To date, a large number of organic redox-active compounds have been developed for non-aqueous flow batteries, but the main problems remain the stability and specific energy intensity of such systems. Among anolytes, the most well-proven compounds based on viologen [J. Chai, A. Lashgari, Z. Cao, CK Williams, X. Wang, J. Dong, J. Jiang, ACS Appl. Mater. Interfaces. 12 (2020) 15262-15270; A. Shrestha, KH Hendriks, MS Sigman, SD Minteer, MS Sanford, Chem. - A Eur. J. 26 (2020) 5369-5373), benzothiadiazole [J. Yuan, C. Zhang, Y. Zhen, Y. Zhao, Y. Li, J. Power Sources. 443 (2019); J. Huang, W. Duan, J. Zhang, IA Shkrob, RS Assary, B. Pan, C. Liao, Z. Zhang, X. Wei, L. Zhang, J. Mater. Chem. A. 6 (2018) 6251-6254], quinones [X. Xing, Q. Liu, B. Wang, JP Lemmon, WQ Xu, J. Power Sources. 445 (2020) 227330; P. Geysens, Y. Li, I. Vankelecom, J. Fransaer, K. Binnemans, ACS Sustain. Chem. Eng. 8 (2020) 3832-3843; X. Xing, Q. Liu, W. Xu, W. Liang, J. Liu, B. Wang, JP Lemmon, ACS Appl. Energy Mater. 2 (2019) 2364-2369; Y. Huo, X. Xing, C. Zhang, X. Wang, Y. Li, RSC Adv. 9 (2019) 13128-13132; WO 2018/007991 A1, US 10079401 B2, US 2013/0266836 A1] and some other compounds [C. Zhang, Y. Qian, Y. Ding, L. Zhang, X. Guo, Y. Zhao, G. Yu, Angew. Chemie - Int. Ed. 58 (2019) 7045-7050; CG Armstrong, RW Hogue, KE Toghill, J. Power Sources. 440 (2019) 227037]. Among the described anolytes, there are compounds that meet all the requirements for their successful use in industrial flow batteries - the compounds have a high solubility in organic solvents and a reversible and stable redox transition at low potentials (about -2 V against the Ag / AgNO ₃ reference electrode) ...

, J.S. Moore, J.

, B.A. Helms, Chem. Mater. 30 (2018) 3861-3866; X. Wang, X. Xing, Y. Huo, Y. Zhao, Y. Li, H. Chen, Int. J. Electrochem. Sci. 13 (2018) 6676-6683; J. Huang, Z. Yang, M. Vijayakumar, W. Duan, A. Hollas, B. Pan, W. Wang, X. Wei, L. Zhang, Adv. Sustain. Syst. 2 (2018) 1700131]. Помимо этого, нерешенной остается проблема стабильности и доступности органических католитов.At the same time, the range of studied catholytes is noticeably narrower. Among them, it is worth noting compounds based on cyclopropane [S.G. Robinson, Y. Yan, K.H. Hendriks, M.S. Sanford, M.S. Sigman, J. Am. Chem. Soc. 141 (2019) 10171-10176; Y. Yan, S.G. Robinson, M.S. Sigman, M.S. Sanford, J. Am. Chem. Soc. 141 (2019) 15301-15306], phenothiazine [X. Xing, Q. Liu, J. Li, Z. Han, B. Wang, J.P. Lemmon, Chem. Commun. 55 (2019) 14214-14217], diodrophenazine [G. Kwon, K. Lee, M.H. Lee, B. Lee, S. Lee, S.K. Jung, K. Ku, J. Kim, S.Y. Park, J.E. Kwon, K. Kang, Chem. 5 (2019) 2642-2656], TEMPO (2,2,6,6-tetramethylpiperidine-1-oxide) [Y.Y. Liu, M.A. Goulet, L. Tong, Y.Y. Liu, Y. Ji, L. Wu, R.G. Gordon, M.J. Aziz, Z. Yang, T. Xu, Chem. 5 (2019) 1861-1870; B. Ok, W. Na, T.H. Kwon, Y.W. Kwon, S. Cho, S.M. Hong, A.S. Lee, J.H. Lee, C.M. Koo, J. Ind. Eng. Chem. 80 (2019) 545-550], and tetramorpholine dihydroquinone [E. Drazevic, C. Szabo, D. Konya, T. Lund, K. Wedege, A. Bentien, ACS Appl. Energy Mater. 2 (2019) 4745-4754]. Most of the described compounds show low half-wave potentials of about 0-0.5 V against the reference electrode. Ag / AgNO₃, which does not allow the full use of the wide electrochemical window of stability of organic solvents [P. Geysens, Y. Li, I. Vankelecom, J. Fransaer, K. Binnemans, ACS Sustain. Chem. Eng. 8 (2020) 3832-3843; C.G. Armstrong, R.W. Hogue, K.E. Toghill, J. Power Sources. 440 (2019) 227037; H. Chen, Y. Zhou, Y.C. Lu, ACS Energy Lett. 3 (2018) 1991-1997]. Compounds showing higher potentials up to 1.1 V versus Ag / AgNO reference electrode₃, have low solubility in organic solvents [J. Yuan, C. Zhang, Y. Zhen, Y. Zhao, Y. Li, J. Power Sources. 443 (2019) 227283; M.J. Baran, M.N. Braten, E.C. Montoto, Z.T. Gossage, L. Ma, E.

, J.S. Moore, J.

, B.A. Helms, Chem. Mater. 30 (2018) 3861-3866; X. Wang, X. Xing, Y. Huo, Y. Zhao, Y. Li, H. Chen, Int. J. Electrochem. Sci. 13 (2018) 6676-6683; J. Huang, Z. Yang, M. Vijayakumar, W. Duan, A. Hollas, B. Pan, W. Wang, X. Wei, L. Zhang, Adv. Sustain. Syst. 2 (2018) 1700131]. In addition, the problem of stability and availability of organic catholytes remains unresolved.

So, as an analogue of the described invention, you can cite the compounds based on cyclopropane, investigated in the works [A. Shrestha, K.H. Hendriks, M.S. Sigman, S.D. Minteer, M.S. Sanford, Chem. - A Eur. J. 26 (2020) 5369-5373; S.G. Robinson, Y. Yan, K.H. Hendriks, M.S. Sanford, M.S. Sigman, J. Am. Chem. Soc. 141 (2019) 10171-10176; Y. Yan, S.G. Robinson, M.S. Sigman, M.S. Sanford, J. Am. Chem. Soc. 141 (2019) 15301-15306]. Despite the high solubility (> 1.7 mol / L) and reversibility of the redox process of hexapropylcyclopropanetriamine, this compound undergoes rapid degradation during battery cycling. The binding of several cyclopropanetriaryl fragments into oligomeric compounds allows an increase in the size of molecules, thereby increasing the stability of the battery, as well as suppressing crossover through the membrane, but significantly complicates the synthesis process, and thus the availability of compounds.

Another analogue should be considered 1,4-di- tert -butyl-2,5-bis (2-methoxyethoxy) benzene [US 2014/0370405 A1]. This compound is liquid at room temperature, has a half-wave potential of 0.71 V against the Ag / AgNO ₃ reference electrode, however, the stability of this compound under battery charge-discharge conditions remains controversial. With a small number of cycles, satisfactory stability of systems with benzothiadiazole is observed [J. Yuan, C. Zhang, Y. Zhen, Y. Zhao, Y. Li, J. Power Sources. 443 (2019); J. Huang, W. Duan, J. Zhang, IA Shkrob, RS Assary, B. Pan, C. Liao, Z. Zhang, X. Wei, L. Zhang, J. Mater. Chem. A. 6 (2018) 6251-6254; W. Duan, J. Huang, JA Kowalski, IA Shkrob, M. Vijayakumar, E. Walter, B. Pan, Z. Yang, JD Milshtein, B. Li, C. Liao, Z. Zhang, W. Wang, J. Liu , JS Moore, FR Brushett, L. Zhang, X. Wei, ACS Energy Lett. 2 (2017) 1156-1161], 3-methylbenzoquinone [X. Xing, Q. Liu, B. Wang, JP Lemmon, WQ Xu, J. Power Sources. 445 (2020) 227330; P. Geysens, Y. Li, I. Vankelecom, J. Fransaer, K. Binnemans, ACS Sustain. Chem. Eng. 8 (2020) 3832-3843; X. Xing, Q. Liu, W. Xu, W. Liang, J. Liu, B. Wang, JP Lemmon, ACS Appl. Energy Mater. 2 (2019) 2364-2369], however, as the number of cycles increases, there is a significant decrease in battery capacity over time [Y. Huo, X. Xing, C. Zhang, X. Wang, Y. Li, RSC Adv. 9 (2019) 13128-13132].

The closest analogue of the present invention is a phenothiazine-based compound described in [NH Attanayake, JA Kowalski, KV Greco, MD Casselman, JD Milshtein, SJ Chapman, SR Parkin, FR Brushett, SA Odom, Chem. Mater. 31 (2019) 4353-4363] and having a half-wave potential of the second electron transition of about 0.6 V against the Ag / AgNO ₃ reference electrode. However, as the authors of the work note, despite the fact that an uncharged compound is mixed with acetonitrile in any proportions, the solubility of ionic forms is lower, and amounts to 0.55 mol / L in pure acetonitrile, which may be a limitation when creating electrolytes with high concentrations of redox-active substances and additives of supporting salts. Also, during the operation of a symmetric cell, a 2-fold decrease in battery capacity in 140 cycles was observed, which indicates a low stability of the redox process taking place in this compound.

The examples described above illustrate that the problem of creating highly soluble and stable catholytes for flow batteries has not been solved to date.

The novelty of the claimed invention can be emphasized by several examples below. It is known from the current state of science and technology that triphenylamine (TPA) is a compound prone to oxidative polymerization. (Measurements of all cyclic voltammograms presented in this work, unless otherwise indicated, were carried out in a three-electrode cell with a glassy carbon working electrode (d = 5 mm), an Ag / AgNO ₃ reference electrode and a platinum wire counter electrode in an inert argon atmosphere and using anhydrous acetonitrile as solvent.) As seen from the cyclic voltammogram of triphenylamine shown in FIG. 1, already in the first cycle, the appearance of peaks corresponding to the products of side reactions is observed. On the fifth cycle, a symmetric curve of the cyclic voltammogram with two cathodic and two anode signals is observed. The observed processes have previously been described in the literature [ET Seo, RF Nelson, JM Fritsch, LS Marcoux, DW Leedy, RN Adams, J. Am. Chem. Soc. 178 (1966) 3498-3503]. Triphenylamine undergoes oxidation to form the TPA ^{+ •} radical cation, which either undergoes a dimerization reaction or reacts with a neutral triphenylamine molecule to form tetraphenylbenzidine. The product of the chemical reaction, tetraphenylbenzidine, is oxidized more readily than the starting triphenylamine, resulting in the formation of polytriphenylamine polymer chains. A schematic diagram of the triphenylamine dimerization process is shown in FIG. 2. From the presented data, it seems obvious that triphenylamine and its derivatives are unsuitable for use as catholytes in flow batteries due to their low electrochemical stability and tendency to oxidative polymerization.

From the current state of science and technology, it could be assumed that the chemical modification of the triphenylamine molecule can suppress the polymerization processes and increase the electrochemical stability of the material. However, the introduction of substituents into the triphenylamine structure can lead to an unpredictable change in the electrochemical properties of the resulting molecules, which is the main reason why this class of compounds is not yet used as catholytes in flow batteries.

For example, the modification of a triphenylamine molecule by introducing an aldehyde group into the para-position of one of the phenyl rings leads to an increase in the reversibility of the redox process. As seen in FIG. 3, in the first cycles, one peak is observed each corresponding to the oxidation and reduction of 4- (diphenylamine) benzaldehyde; however, with a larger number of cycles, the appearance of new peaks corresponding to the products of side reactions of dimerization and polymerization is observed.

Cycling stability of 4- (diphenylamine) benzoic acid (FIG. 4) is similar to that of unsubstituted triphenylamine. Already in the first cycles, a noticeable decrease in the cathodic peak is observed in comparison with the anodic one, and by the 50th cycle, the observed signal completely disappears.

According to the previously described mechanism of polymerization, it can be assumed that the substitution of all three protons in the para-positions of the phenyl rings of triphenylamine should lead to a sharp increase in the stability of the redox process. However, as can be seen from the cyclic voltammograms shown in Figs. 5 and FIG. 6, not every combination of substituents leads to the desired result. During cycling of 4- (bis (4-bromophenyl) amino) benzaldehyde, a significant decrease in the height of the peaks and their shift during the first 10 cycles is observed, which indicates the electrochemical degradation of the material. 4- (bis (4-bromophenyl) amino) benzoic acid, on the contrary, has shown itself to be stable in a multiple redox process. However, this compound has a low solubility in organic solvents (solubility in acetonitrile is ~ 0.015 mol / L), which makes this compound unsuitable for use in flow batteries.

In previous scientific publications [Y.G. Zhu, X. Wang, C. Jia, J. Yang, Q. Wang, ACS Catal. 6 (2016) 6191-6197] and patents [JP 3635884 B2; JP 11086903; WO 2007/097912 A2], the authors noted that compounds based on low molecular weight triphenylamines and polytriphenylamines can be used as molecules for charge transfer and / or compounds - protectors that prevent overcharging and overdischarging of lithium-ion batteries. However, from the published materials, it is impossible to draw a conclusion about the applicability of the described compounds as liquid catholytes for electrochemical power sources.

It should be noted that the only triphenylamine-based compound studied in a liquid electrochemical cell is tris (4-bromophenyl) amine [V. Pasala, C. Ramachandra, S. Sethuraman, K. Ramanujam, J. Electrochem. Soc. 165 (2018) A2696-A2702]. A good stability of this compound was shown when used as a catholyte in a static non-aqueous cell against an oxygen-containing anolyte. However, the very low solubility of tris (4-bromophenyl) amine in acetonitrile (~ 0.013 mol / l) does not make it possible to effectively use it in flow accumulators.

Thus, based on the data presented in the literature, it is impossible to make an unambiguous conclusion about the possibility of obtaining stable and highly soluble derivatives of triphenylamine, which could be successfully used as catholytes in flow batteries.

Disclosure of invention

An unexpected result, which is disclosed in this invention, was the potent stabilizing effect of ether substituents, in particular those based on oligomers of oligoethylene glycol, on the electrochemical behavior of the substituted triarylamines, established by the present inventors. In combination with an increase in the solubility of compounds due to the introduction of substituents, a set of properties is provided that are necessary for their successful use as catholytes in flow batteries.

In the course of work on this invention, the authors have obtained, in particular, a number of compounds based on triphenylamine and N ¹ , N ¹ , N ⁴ , N ⁴ -tetraphenylbenzyl-1,4-diamine with different amounts of ether (oligoethylene glycol) substituents. FIG. 7 shows the cyclic voltammogram of 4- (2- (2-methoxy) ethoxy) - N , N- diphenylamine. It should be noted that, despite the presence of two unsubstituted para-positions of the phenyl rings, this compound demonstrates a reversible redox process within 10 cycles. And a compound with two ethylene glycol substituents, the structure and cyclic voltammogram of which are shown in FIG. 8 demonstrates the stability of the redox process for more than 100 cycles. FIG. 9 shows a cyclic voltammogram of a derivative of N ¹ , N ¹ , N ⁴ , N ⁴ -tetraphenylbenzyl-1,4-diamine with two ethylene glycol substituents. For this compound, suppression of oxidative polymerization processes and high reversibility of redox processes during 20 cycles are also observed. Let us emphasize that ether substituents are electron-donating in nature. Their introduction into the structure of the triphenylamine derivative should facilitate its electrochemical oxidation and, consequently, the occurrence of undesirable oxidative polymerization. The opposite effect of the introduction of ether substituents was experimentally found, which is an unexpected result that could not be expected given the current state of science and technology. Presumably, we can talk about the appearance of steric obstacles for the condensation of two or more molecules of substituted triphenylamines.

We emphasize once again that an increase in the stability of the redox process of triphenylamine derivatives with the introduction of ether (ethylene glycol) substituents is an unexpected, but practically very important result that provides a solution to the problem of the present invention.

The objective of this invention is the development and creation of a new catholyte for electrochemical power sources based on electrochemically stable and readily soluble derivatives of triphenylamine - promising cathode materials for electrochemical power sources.

The technical results of the claimed invention is to improve the electrochemical properties of electrochemical power sources, in particular, their stability during charge-discharge cycling.

In addition, another technical result of the present invention is the development of a new cathode material for electrochemical power sources based on electrochemically stable and highly soluble triphenylamine derivatives. These triphenylamine derivatives according to the invention have optimal electrochemical properties and high solubility in polar organic solvents.

The specified technical result is achieved through the use of compounds based on triphenylamine of the general formula F1 as the only or one of the components in the catholyte for an electrochemical current source, in which a rational set of substituents R, R ¹ and R ² ensures their high solubility in polar organic solvents, reversibility and stability of redox processes:

,

,

where in the general formula F1 the substituent R is selected independently and represents:

- a halogen atom -F, -Cl or -Br;

- nitrile group -CN;

- hydrocarbon radical -C _n H _{2n + 1} , where n = 1 - 20;

- ester group -COOC _n H _{2n + 1} , where n = 1 - 20;

- ester group -COO (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ester group -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

- the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1 - 20;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10; or

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

substituent R ¹ is selected independently and represents:

a) a fragment of a substituted diphenylamine:

in which the substituents R ³ and R ⁴ are independently selected and represent:

- a halogen atom -F, -Cl or -Br;

- hydrocarbon radical -C _n H _{2n + 1} , where n = 1 - 20;

- ester group -COOC _n H _{2n + 1} , where n = 1 - 20;

- the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1 - 20;

- ester group -COO (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

b) one of the following substituents:

- a halogen atom -F, -Cl or -Br;

- nitrile group -CN;

- hydrocarbon radical -C _n H _{2n + 1} , where n = 1 - 20;

- ester group -COOC _n H _{2n + 1} , where n = 1 - 20;

- ester group -COO (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ester group -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

- the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1 - 20;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12.

substituent R ² is selected independently and represents:

a) a fragment of a substituted diphenylamine:

in which the substituents R ⁵ and R ⁶ are independently selected and represent:

- a halogen atom -F, -Cl or -Br;

- hydrocarbon radical -C _n H _{2n + 1} , where n = 1 - 20;

- ester group -COOC _n H _{2n + 1} , where n = 1 - 20;

- the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1 - 20;

- ester group -COO (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

b) one of the following substituents:

- hydrocarbon radical -C _n H _{2n + 1} , where n = 1 - 20;

- ester group -COOC _n H _{2n + 1} , where n = 1 - 20;

- ester group -COO (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ester group -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

- the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1 - 20;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12.

In particular embodiments of the invention, the electrochemical power source is a flow-through accumulator, consisting of the following main components:

- an electrochemical cell, with a membrane or separator dividing the electrochemical cell into zones for catholyte and anolyte, in which an electrochemical reaction occurs at the cathode and at the anode;

- at least one container with charged and / or uncharged catholyte and at least one container with charged and / or uncharged anolyte;

- at least one pump providing pumping of catholyte and anolyte between the indicated containers and the electrochemical cell;

- hoses or pipelines for supplying catholyte and anolyte from the indicated containers to the electrochemical cell in the zones for catholyte and anolyte;

- cathode and anode, located in the areas for catholyte and anolyte, respectively.

In particular embodiments of the invention, the electrochemical power source is a hybrid battery, consisting of the following main components:

- an electrochemical cell, with a membrane or separator, dividing the electrochemical cell into zones for catholyte and anolyte, in which an electrochemical reaction occurs at the cathode and at the anode;

- at least one container for charged and / or uncharged catholyte;

- at least one pump providing pumping of the catholyte between the indicated containers and the electrochemical cell;

- hoses or pipelines for supplying the catholyte from the indicated containers to the electrochemical cell in the area for the catholyte;

- a cathode located in the catholyte zone;

- anode located in the anolyte zone.

In particular embodiments of the invention, the catholyte contains a mixture of at least two different compounds of formula F1.

In particular embodiments of the invention, the catholyte additionally contains a solvent in the form of water and / or at least one organic solvent selected from the group: organic carbonates, organic ethers, nitriles, sulfones, sulfoxides, amides, in the following ratio of components in wt. %:

- redox-active compound of general formula F1 - 0.1-99.9999;

- solvent - 0.0001-99.9.

In particular embodiments of the invention, the organic carbonate is independently selected and is ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate.

In particular embodiments, the organic ether is independently selected and is dibutyl ether, tetrahydrofuran, or dimethoxyethane.

In particular embodiments, the nitrile is independently selected and is acetonitrile or propionitrile.

In particular embodiments, the sulfone is independently selected and is sulfolane or dimethyl sulfone.

In particular embodiments, the sulfoxide is independently selected and is dimethyl sulfoxide or methylethyl sulfoxide.

In particular embodiments, the amide is independently selected and is dimethylformamide or N- methyl-2-pyrrolidone.

In particular embodiments of the invention, the catholyte additionally contains an electrochemically stable salt, with the following ratio of components in wt. %:

- redox-active compound of general formula F1 - 0.1-99.9999;

- electrochemically stable salt - 0.0001-99.9.

In particular embodiments of the invention, the electrochemically stable salt comprises:

- one of the following cations: Li ⁺ , Na ⁺ , K ⁺ , R ' ₄ N ⁺ , where R' is independently selected and represents alkyl -C _n H _{2n + 1} , where n = 1-8, N -butyl- N -methylpyrrolidinium, tris (hexyltetradecyl) phosphonium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-3-methylimidazolium;

- one of the following anions: F ^- , Cl ^- , PF ₆ ^- , ClO ₄ ^- , bis (trifluoromethylsulfonyl) imide anion, CF ₃ SO ₃ ^- , [B (CN) ₄ ] ^- , BF ₄ ^- , [F ₃ P (C ₂ F ₅ ) ₃ ] ^- , [F ₃ P (CF ₃ ) ₃ ] ^- , CF ₃ COO ^- .

In particular embodiments of the invention, the anolyte contains a phenazine derivative of general formula A3:

,

,

in which the substituents R ⁷ and R ⁸ are independently selected and represents:

- the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1 - 20;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12.

The present invention also includes a catholyte for an electrochemical power source comprising at least one triphenylamine derivative of general formula F1:

where in the general formula F1 the substituent R is selected independently and represents:

- a halogen atom -F, -Cl or -Br;

- nitrile group -CN;

- hydrocarbon radical -C _n H _{2n + 1} , where n = 1 - 20;

- ester group -COOC _n H _{2n + 1} , where n = 1 - 20;

- ester group -COO (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ester group -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

- the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1 - 20;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10; or

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

substituent R ¹ is selected independently and represents:

a) a fragment of a substituted diphenylamine:

in which the substituents R ³ and R ⁴ are independently selected and represent:

- a halogen atom -F, -Cl or -Br;

- hydrocarbon radical -C _n H _{2n + 1} , where n = 1 - 20;

- ester group -COOC _n H _{2n + 1} , where n = 1 - 20;

- the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1 - 20;

- ester group -COO (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

b) one of the following substituents:

- a halogen atom -F, -Cl or -Br;

- nitrile group -CN;

- hydrocarbon radical -C _n H _{2n + 1} , where n = 1 - 20;

- ester group -COOC _n H _{2n + 1} , where n = 1 - 20;

- ester group -COO (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ester group -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

- the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1 - 20;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12.

substituent R ² is selected independently and represents:

a) a fragment of a substituted diphenylamine:

in which the substituents R ⁵ and R ⁶ are independently selected and represent:

- a halogen atom -F, -Cl or -Br;

- hydrocarbon radical -C _n H _{2n + 1} , where n = 1 - 20;

- ester group -COOC _n H _{2n + 1} , where n = 1 - 20;

- the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1 - 20;

- ester group -COO (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

b) one of the following substituents:

- hydrocarbon radical -C _n H _{2n + 1} , where n = 1 - 20;

- ester group -COOC _n H _{2n + 1} , where n = 1 - 20;

- ester group -COO (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ester group -COO (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ester group -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12;

- the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1 - 20;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10;

- ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12.

In particular embodiments of the invention, the catholyte contains a mixture of at least two different compounds of formula F1.

In particular embodiments of the invention, the catholyte additionally contains a solvent in the form of water and / or at least one organic solvent selected from the group: organic carbonates, organic ethers, nitriles, sulfones, sulfoxides, amides, in the following ratio of components in wt. %:

- redox-active compound of general formula F1 - 0.1-99.9999;

- solvent - 0.0001-99.9.

In particular embodiments of the invention, the organic carbonate is independently selected and is ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate.

In particular embodiments, the organic ether is independently selected and is dibutyl ether, tetrahydrofuran, or dimethoxyethane.

In particular embodiments, the nitrile is independently selected and is acetonitrile or propionitrile.

In particular embodiments, the sulfone is independently selected and is sulfolane or dimethyl sulfone.

In particular embodiments, the sulfoxide is independently selected and is dimethyl sulfoxide or methylethyl sulfoxide.

In particular embodiments, the amide is independently selected and is dimethylformamide or N- methyl-2-pyrrolidone.

In particular embodiments of the invention, the catholyte additionally contains an electrochemically stable salt, with the following ratio of components in wt. %:

- redox-active compound of general formula F1 - 0.1-99.9999;

- electrochemically stable salt - 0.0001-99.9.

In particular embodiments of the invention, the catholyte is characterized in that the electrochemically stable salt contains:

- one of the following cations: Li ⁺ , Na ⁺ , K ⁺ , R ' ₄ N ⁺ , where R' is independently selected and represents alkyl -C _n H _{2n + 1} , where n = 1-8, N -butyl- N -methylpyrrolidinium, tris (hexyltetradecyl) phosphonium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-3-methylimidazolium;

- one of the following anions: F ^- , Cl ^- , PF ₆ ^- , ClO ₄ ^- , bis (trifluoromethylsulfonyl) imide anion, CF ₃ SO ₃ ^- , [B (CN) ₄ ] ^- , BF ₄ ^- , [F ₃ P (C ₂ F ₅ ) ₃ ] ^- , [F ₃ P (CF ₃ ) ₃ ] ^- , CF ₃ COO ^- .

The invention also includes the preparation of compounds of general formula F1.

Brief Description of Drawings

Figure 1. Cyclic voltammogram of triphenylamine.

Figure 2. The described mechanism of triphenylamine polymerization [E.T. Seo, R.F. Nelson, J.M. Fritsch, L.S. Marcoux, D.W. Leedy, R.N. Adams, J. Am. Chem. Soc. 178 (1966) 3498-3503].

Figure 3. Cyclic voltammograms of 4 (diphenylamine) benzaldehyde.

Figure 4. Cyclic voltammograms of 4 (diphenylamine) benzoic acid.

Figure 5. Cyclic voltammograms of 4- (bis (4-bromophenyl) amino) benzaldehyde.

Figure 6. Cyclic voltammograms of 4 (bis (4-bromophenyl) amino) benzoic acid.

Figure 7. Cyclic voltammograms of 4- (2- (2-methoxy) ethoxy) -N, N-diphenylamine.

Figure 8. Cyclic voltammograms of 4- (2- (2-methoxyethoxy) ethoxy) - N - (4- (2- (2methoxyethoxy) ethoxy) phenyl) - N- phenylaniline.

Figure 9. Cyclic voltammograms of N ¹ , N ⁴ -bis (4- (2- (2-methoxyethoxy) ethoxy) phenyl) - N ¹ , N ⁴ diphenylbenzyl-1,4-diamine.

Figure 10. Scheme of the synthesis of ethylene glycol derivatives of triphenylamines and N ¹ , N ¹ , N ⁴ , N ⁴ -tetraarylbenzyl-1,4-diamines M1 - M4.

Figure 11. Cyclic voltammograms of compounds M1 and M2 in the potential range from - 2.0 V to +1.0 V.

Figure 12. Cyclic voltammograms of compounds M3 and M4 in the potential range from - 2.0 V to +1.0 V.

Figure 13. Cyclic voltammograms of compound M1.

Figure 14. Cyclic voltammograms of compound M2.

Figure 15. Cyclic voltammograms of compound M3.

Figure 16. Cyclic voltammograms of compound M4.

Figure 17. Structures of flow-through accumulators of two types: with two reservoirs for electrolytes and with four reservoirs for electrolytes. The following components are numbered in the figure: 1 - Tank with catholyte for a cell with two tanks; 1 ' - Tank with anolyte for a cell with two tanks; 1 ^{a -} Reservoir for uncharged catholyte; 1 ^b - Reservoir for charged catholyte; 1 ^{' a} - Tank for uncharged anolyte; 1 ^{' b} - Reservoir for charged anolyte; 2 , 2 ' - Pumps for pumping catholyte and anolyte to the electrochemical cell; 3 , 3 ' - Hoses or pipelines for supplying electrolytes to the electrochemical cell; 4 - Cathode; 4 ' - Anode; 5 - Zone of the electrochemical reaction at the cathode; 5 ' - Zone of the electrochemical reaction at the anode; 6 - Separator.

Figure 18. Structures of hybrid flow-through accumulators of two types: with one reservoir for catholyte and with two reservoirs for catholyte. The following components are numbered in the figure: 1 - Tank with catholyte for a cell with one tank; 1 ^a - Reservoir for uncharged catholyte; 1 ^b - Reservoir for charged catholyte; 2 - Pumps for pumping catholyte to the electrochemical cell; 3,3 ' - Hoses or pipelines for supplying the catholyte to the electrochemical cell; 4 - Cathode; 4 ' - Anode; 5 - zone for catholyte, in which the course of the electrochemical reaction at the cathode is carried out (Zone of the flow of the electrochemical reaction at the cathode); 5 ' - zone for anolyte, in which the course of the electrochemical reaction at the anode is carried out (Zone of the course of the electrochemical reaction at the anode); 6 - Separator.

Figure 19. The structure of the flow accumulator. In the figure, the following components are indicated by numbers: 1 - Tank with catholyte; 1 ' - Container with anolyte; 2 , 2 ' - Peristaltic pumps; 3 , 3 ' - Hoses for supplying electrolytes to the electrochemical cell; 4 - Cathode; 4 ' - Anode; 5 - zone for catholyte, in which the course of the electrochemical reaction at the cathode is carried out (Zone of the flow of the electrochemical reaction at the cathode); 5 ' - zone for anolyte, in which the course of the electrochemical reaction at the anode is carried out (Zone of the course of the electrochemical reaction at the anode); 6 - Neosepta AHA membrane.

Figure 20. The structure of the electrochemical cell of the flow accumulator. The following components are numbered in the figure: 1 - Metal retaining plates; 2 - teflon insulating plates; 3 - graphite current-supplying electrode plates; 4 - teflon distribution plates; 5 - electrodes made of graphite felt 6 mm thick, 2 × 2 cm in size; 6 - Neosepta AHA membrane.

Figure 21. Charge-discharge characteristics; dependences of charging and discharging capacity and Coulomb efficiency on the cycle number for a flow-through accumulator with a catholyte based on the M1 compound.

Figure 22. Charge-discharge characteristics; dependences of the charging and discharging capacity and the Coulomb efficiency on the cycle number for a flow-through accumulator with a catholyte based on the M2 compound.

Figure 23. Charge-discharge characteristics; dependences of charging and discharging capacity and Coulomb efficiency on the cycle number for a flow-through accumulator with a catholyte based on the M3 compound.

Figure 24. Charge-discharge characteristics; dependences of charging and discharging capacity and Coulomb efficiency on the cycle number for a flow-through battery with a catholyte based on the M4 compound.

Figure 25. Charge-discharge characteristics; dependence of charging and discharging capacity and Coulomb efficiency on the cycle number for flow-through batteries with catholyte based on compound M1 at a concentration of 50 mmol / L.

Figure 26. Charge-discharge characteristics; the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number for a flow-through battery with a catholyte based on compound M1 and NaClO ₄ salt that maintains conductivity.

Figure 27. Charge-discharge characteristics; dependences of charging and discharging capacity and Coulomb efficiency on the cycle number for a flow-through accumulator with a catholyte based on the M1 compound and a TBAPF ₆ salt maintaining conductivity.

Figure 28. Charge-discharge characteristics; the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number for a flow-through battery with a catholyte based on compound M1 and a conductivity-maintaining salt LiClO ₄ .

Figure 29. Charge-discharge characteristics; dependences of the charging and discharging capacity and Coulomb efficiency on the cycle number for flow-through batteries with a catholyte based on the M1 compound and a conductive LiPF ₆ salt.

Figure 30. Structure of compound A2 (2,3-bis (2- (2-methoxyethoxy) ethoxy) phenazine).

Figure 31. Charge-discharge characteristics; the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number for a flow-through accumulator with a catholyte based on the M1 compound and an anolyte based on the A2 compound.

Figure 32. Charge-discharge characteristics; the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number for a flow-through battery with a catholyte based on the M3 compound and an anolyte based on the A2 compound.

Figure 33. Charge-discharge characteristics; dependences of charging and discharging capacity and Coulomb efficiency on the cycle number for a flow-through battery with unmixed electrolytes: catholyte based on compound M1, anolyte based on compound A2.

Figure 34. Structure of an electrochemical cell (h-cell). In the figure, the following components are indicated by numbers: 1 - Tank with catholyte; 1 ' - Container with anolyte; 2 - Cation-exchange composite membrane Li1.4Al _0.4 Ge0.2Ti _1.4 (PO ₄ ) ₃ ; 3 - Cathode made of graphite felt; 3 ' - Graphite felt anode; 4 - Current collectors.

Figure 35. Charge-discharge characteristics; dependences of the charging and discharging capacity and Coulomb efficiency on the cycle number for an electrochemical cell (h-cell) with a catholyte based on the M1 compound.

Figure 36. Structure of an electrochemical cell (coin-type cell). In the figure, the following components are indicated by numbers: 1 - Cell cover; 2 - Carbon paper impregnated with soluble catholyte; 3 - Ceramic membrane; 4 -Lithium anode; 5 - Metal disk - spacer; 6 - Spring; 7 -Bottom of the cell.

Figure 37. Cyclic voltammogram of an electrochemical cell based on compound M3 using a lithium anode.

Figure 38. Charge-discharge characteristics; dependences of charging and discharging capacity and Coulomb efficiency on the cycle number for an electrochemical cell based on compound M3 using a lithium anode.

Definition and terms

For a better understanding of the present invention, below are some of the terms used in the present description of the invention. Unless otherwise specified, technical and scientific terms in this application have the standard meanings generally accepted in the scientific and technical literature.

In the present description and in the claims, the terms "includes", "including" and "includes", "having", "containing" and their other grammatical forms are not intended to be construed in an exclusive sense, but, on the contrary, are used in a non-exclusive sense (ie, in the sense of "having in its composition"). Only expressions of the type “consisting of” should be considered as an exhaustive list.

As used herein, the term “—C _n H _{2n + 1} ” or “C _m H _{2m + 1} ” hydrocarbon radical refers to both straight and branched alkyl, usually having from one to twenty carbon atoms or from one to twelve carbon atoms. In some particular embodiments of the invention, this radical is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and others.

Detailed disclosure of the invention

The compounds of the present invention can be prepared using the synthetic methods described below. The methods listed are not exhaustive and can be reasonably modified. These reactions must be carried out using suitable solvents and materials. When implementing these methods for the synthesis of specific substances, it is necessary to take into account the functional groups present in the substances and their influence on the course of the reaction. To obtain some substances, it is necessary to change the order of the steps or to give preference to one of several alternative synthesis schemes. It should be understood that these and all examples given in the application materials are not limiting and are given only to illustrate the present invention.

The chemistry of triarylamines and N ¹ , N ¹ , N ⁴ , N ⁴ -tetraarylbenzyl-1,4-diamines is well studied. The presented derivatives can be synthesized by various methods, for example: from derivatives of aniline and / or diphenylamine by reactions with aryl bromides in the presence of a copper catalyst according to the Ulman reaction [K. Willinger, K. Fischer, R. Kisselev, M. Thelakkat, J. Mater. Chem. 19 (2009) 5364-5376]; in the presence of a palladium catalyst according to the Buchwald-Hartwig reaction [YJ Cheng, J. Luo, S. Hau, DH Bale, TD Kim, Z. Shi, DB Lao, NM Tucker, Y. Tian, LR Dalton, PJ Reid, AKY Jen, Chem. Mater. 19 (2007) 1154-1163]; by introducing various substituents into the structure of triphenylamine by bromination methods [Y. Liu, R. Sakamoto, CL Ho, H. Nishihara, WY Wong, J. Mater. Chem. C. 7 (2019) 9159-9166], acylation [K. Willinger, K. Fischer, R. Kisselev, M. Thelakkat, J. Mater. Chem. 19 (2009) 5364-5376] or substitution of halogen atoms in the benzene ring [K. Willinger, K. Fischer, R. Kisselev, M. Thelakkat, J. Mater. Chem. 19 (2009) 5364-5376].

Compounds M1-M4, which are particular examples corresponding to the general formula F1, were synthesized according to the scheme shown in FIG. 10. Compound (1) was obtained according to the previously described methods [K. Willinger, K. Fischer, R. Kisselev, M. Thelakkat, J. Mater. Chem. 19 (2009) 5364-5376; Y. Kim, J. Choi, C. Lee, Y. Kim, C. Kim, T.L. Nguyen, B. Gautam, K. Gundogdu, H.Y. Woo, B.J. Kim, Chem. Mater. 30 (2018) 5663-5672], and compound (2) - according to the method [W. Liu, L. Liang, P.K. Lo, X.J. Gou, X.H. Sun, Tetrahedron Lett. 57 (2016) 959-963]. To illustrate the feasibility shown in FIG. 10 approaches below are the methods for the synthesis of compounds M1 - M4.

Synthesis of 4-bromo-N- (4-bromophenyl) -N- (4- (2- (2-methoxyethoxy) ethoxy) phenyl) aniline (M1)

Diphenylamine (0.61 g; 3.60 mmol), 1-bromo-4- (2- (2-methoxyethoxy) ethoxy) benzene (0.99 g; 3.60 mmol), bis (dibenzalideneacetone) palladium (0) (100 mg; 0.17 mmol), sodium tert- butylate (0.69 g; 7.20 mmol), tributylphosphine (14 mg; 0.7 mmol) and 60 ml of toluene were placed in a round bottom flask with a reflux condenser. The reaction mixture was purged with argon for 15 minutes, then refluxed for 5 hours. The progress of the reaction was monitored by high performance liquid chromatography. Then the reaction mixture was cooled, washed with 30 ml of ice-cold distilled water, the product was extracted with toluene, the organic fraction was separated, dried over Na ₂ SO ₄ and evaporated.

Next, the resulting dark yellow liquid (1.12 g; 3.05 mmol) was dissolved in 20 ml of dimethylformamide (DMF). To the resulting solution was added N- bromosuccinimide (NBS) (1.11 g; 6.25 mmol) in small portions over 30 minutes, after which the reaction mixture was stirred for 1 hour. The resulting solution was washed with a saturated aqueous solution of NaHCO ₃ , the product was extracted with toluene, the organic extract was dried over Na ₂ SO ₄ and evaporated. The pure product was obtained with a yield of 1.46 g, 78%.

Synthesis of 4-bromo-N, N-bis (4- (2- (2-methoxyethoxy) ethoxy) phenyl) aniline (M2)

Compound M2 was prepared analogously to compound M1. The following reagents were used: aniline (2.0 g; 21.5 mmol), 1-bromo-4- (2- (2-methoxyethoxy) ethoxy) benzene (11.83 g; 43.0 mmol), bis (dibenzalideneacetone ) palladium (0) (100 mg; 0.17 mmol), sodium tert- butylate (8.26 g; 86.0 mmol), tributylphosphine (14 mg; 0.7 mmol) and 100 ml of toluene. In the second stage, the product obtained in the first stage (8.90 g; 18.5 mmol), NBS (3.45 g; 19.42 mmol) and 30 ml of DMF were used. The pure product was obtained in 77% yield (9.28 g).

Synthesis of N ¹ , N ⁴ -bis (4-bromophenyl) -N ¹ , N ⁴ -bis (4- (2- (2-methoxyethoxy) ethoxy) phenyl) benzene-1,4-diamine (M3)

Compound M3 was prepared analogously to compound M1. The following reagents were used: N ¹ , N ⁴ -diphenylbenzene-1,4-diamine (0.50 g; 1.92 mmol), 1-bromo-4- (2- (2-methoxyethoxy) ethoxy) benzene (1, 05 g; 3.84 mmol), bis (dibenzalideneacetone) palladium (0) (100 mg; 0.17 mmol), sodium tert- butylate (0.74 g; 7.68 mmol), tributylphosphine (14 mg; 0, 7 mmol) and 100 ml of toluene. In the second stage, the product obtained in the first stage (1.00 g; 1.55 mmol), NBS (0.58 g; 3.25 mmol) and 30 ml of DMF were used. The pure product was obtained in 94% yield (1.17 g).

Synthesis of N ¹ , N ¹ , N ⁴ , N ⁴ -tetrakis (4- (2- (2-methoxyethoxy) ethoxy) phenyl) benzene-1,4-diamine (M4)

Compound M4 was prepared analogously to compound M1. The following reagents were used: 1,4-diaminobenzene (0.33 g; 3.05 mmol), 1-bromo-4- (2- (2-methoxyethoxy) ethoxy) benzene (3.35 g; 12.2 mmol) , bis (dibenzalideneacetone) palladium (0) (100 mg; 0.17 mmol), sodium tert- butylate (2.34 g; 24.4 mmol), tributylphosphine (14 mg; 0.7 mmol) and 100 ml of toluene. The pure product was obtained in 77% yield (2.08 g).

Physical state and solubility

An important feature of compounds M1 and M2 is their liquid state of aggregation at room temperature, which allows mixing these compounds with acetonitrile in any proportions, and also using M1 and M2 as liquid cathode materials without adding a solvent. For compounds M3 and M4, the melting points were measured by thermogravimetry and amounted to 51 ° C and 73 ° C, respectively, which allows them to be classified as low-melting materials. Compounds M3 and M4 also have a high solubility in acetonitrile, equal to 2.2 mol / L. It should be emphasized that the low melting point and high solubility of the investigated compounds is an unexpected result that does not follow from the current level of science and technology.

Electrochemical properties

To use new compounds in electrochemical current sources, it is necessary to know the oxidation-reduction potentials of the molecules under study. This parameter determines the range of operating potentials of the battery, and is also necessary for the selection of the optimal anolyte. The simplest way to determine the half-wave potential is to measure the cyclic voltammograms of the compounds. These measurements for M1-M4 compounds were carried out in a three-electrode cell with a glassy carbon working electrode (d = 5 mm), an Ag / Ag ⁺ (Basi) reference electrode, and a platinum wire counter electrode in an inert argon atmosphere (before the start of the experiment, the electrochemical cell was purged by an agronomist within 15 minutes). The concentration of active substances was 3 mmol / L, the concentration of the supporting electrolyte TBABF _{4 was} 0.10 mol / L. The measurements were carried out at a sweep rate of 200 mV / s on a Metrohm Autolab potentiostat.

Cyclic voltammograms were measured for each of the compounds over a wide potential range from -2.0 V to +1.0 V. The measurement results are shown in FIG. 11 and FIG. 12. The values of the potentials of the investigated compounds were: M1 - +0.57 V; M2 - +0.41 V; M3 - +0.22 V and +0.61 V; M4 - +0.03 V and +0.45 V against the Ag / AgNO ₃ reference electrode. It should be noted that there are no side signals indicating the occurrence of unwanted side reactions in a wide range of potentials from -2.0 V to more than -0.3 V. The absence of side reactions in this range allows the selection of anolyte with a half-wave potential of up to -2.0 B against the reference electrode Ag / AgNO ₃ .

Stability on electrochemical redox cycling

By the method of cyclic voltammetry, it is possible not only to determine the half-wave potential of the compounds under study, but also to investigate the stability and reversibility of the redox process. For this, a series of cyclic voltammograms is taken from the system under study. With complete coincidence of the curves obtained at the very beginning and at the end of cycling, it can be concluded that the oxidation-reduction process is stable and reversible in time under these conditions, which suggests that the redox process will also be reversible and stable under flow-flow conditions. battery.

Each of the compounds M1-M4 was investigated by multiple cyclic voltammetry. For measurements, an electrochemical cell and the experimental conditions described above were used. The resulting volt-ampere curves are shown in FIG. 13 to FIG. 16. It should be emphasized that there is a complete coincidence of the 5th, 20th and 100th cycles for all the presented compounds, which indicates the complete reversibility and high stability of the redox process.

Use of compounds of general formula F1 as catholytes in flow and hybrid batteries

This invention discloses the use of compounds of general formula F1 as liquid cathode materials in flow-through and hybrid electrochemical cells.

FIG. 17 shows a typical diagram of a flow-through accumulator. The described device may consist of the following components:

- Containers with catholyte (liquid cathode material) and anolyte (liquid anode material). It is possible to have one reservoir for the catholyte (Fig. 17, 1 ) and one reservoir for the anolyte (Fig. 17, 1 ' ), in the case of using a battery design in which charged and uncharged electrolytes are mixed. In another technical design, the flow accumulator can be equipped with 4 reservoirs: a reservoir for uncharged catholyte (Fig. 17, 1 ^a ), a reservoir for charged catholyte (Fig. 17, 1 ^b ), a reservoir for uncharged anolyte (Fig. 17, 1 ' ^a ) and a reservoir for a charged anolyte (Fig. 17, 1 ' ^b ).

- Pump (s) providing pumping of electrolyte (catholyte and / or anolyte) through the electrochemical cell. The choice of a pump is determined by its chemical resistance to the electrolyte solutions used. (Fig. 17, 2 and 2 ' )

- Hoses or pipelines for supplying electrolytes to the electrochemical cell (Fig. 17, 3 and 3 ' )

- Electrodes (cathode and anode), which can be made of metal (platinum, copper, steel, etc.), carbon materials (graphite, composites based on graphite with polymer materials, graphite felt, carbon paper, etc.), inorganic composites or a combination of these materials. (Fig. 17, 4 and 4 ' )

- The zone of the flow of the electrochemical reaction at the cathode and the zone of the flow of the electrochemical reaction at the anode (Fig. 17, 5 and 5 ' )

- Membrane or separator (Fig. 17, 6 ), located between the cathode and anode region. The separator is designed for the selective transport of positive or negative ions to the electrodes during the charging or discharging of the flow battery. The separator can be a polymeric anion or cation exchange membrane (for example, a Nafion® cation exchange membrane or a Neosepta anion exchange membrane, etc.); ion-conducting ceramic membrane (for example, LISICON, etc.); zeolite-based compounds; porous, ceramic or other type of separator. In the simplest case, the separator can be a porous polymeric membrane with an optimal pore size that provides the transport of small ions and blocks the transfer of redox-active compounds in any of the charge states (examples are dialysis membranes, Celgard separators used in metal-ion batteries ).

We emphasize that flow accumulators can also be manufactured in other designs, which in no way imposes restrictions on the possibility of using compounds of the general formula F1 in them as catholytes.

FIG. 18 shows a diagram of a hybrid battery. The described device will consist of the following components:

- One container in which charged and uncharged catholyte is mixed. (Fig. 18, 1 ). In another technical solution, the battery is equipped with two separate containers for discharged (Fig. 18, 1 ^a ) and charged (Fig. 18, 1 ^b ) catholyte.

- Pump (s) providing pumping of electrolyte (catholyte) through the electrochemical cell. The choice of a pump is determined by its chemical resistance to the electrolyte solutions used. (Fig. 18, 2 )

- Hoses or pipelines for supplying electrolytes to the electrochemical cell (Fig. 18, 3 )

- Positive electrode (cathode), which can be made of metal (platinum, copper, steel, etc.), carbon materials (graphite, composites based on graphite with polymer materials, graphite felt, carbon paper, etc.), inorganic composites or combinations of these materials. (Fig. 18, 4 )

- Negative electrode (anode), which can be made of alkali metal (for example, lithium, sodium, potassium or their alloys), alkaline earth metal (calcium, magnesium), zinc, aluminum or other inorganic or organic redox-active material. (Fig. 18, 4 ' )

- The zone of the flow of the electrochemical reaction at the cathode and the zone of the flow of the electrochemical reaction at the anode (Fig. 18, 5 and 5 ', respectively)

- Membrane or separator (Fig. 18, 6 ), located between the cathode and anode region. The separator is designed for the selective transport of positive or negative ions to the electrodes during the charging or discharging of the flow battery. The separator can be a polymeric anion or cation exchange membrane (for example, a Nafion® cation exchange membrane or a Neosepta anion exchange membrane, etc.); ion-conducting ceramic membrane (for example, LISICON, etc.); zeolite-based compounds; porous, ceramic or other type of separator. In the simplest case, the separator can be a porous polymeric membrane with an optimal pore size that provides the transport of small ions and blocks the transfer of redox-active compounds in any of the charge states (examples are dialysis membranes, Celgard separators used in metal-ion batteries ).

We emphasize that hybrid batteries can be manufactured in other designs, which in no way imposes restrictions on the possibility of using compounds of general formula F1 in them as catholytes.

The catholyte and / or anolyte used in the batteries described above can be:

a) Liquid redox-active compound used without additional additives.

b) A mixture of two or more redox-active compounds.

c) A solution of the redox active compound in a suitable solvent at a concentration of 0.1 to 99.99 weight percent. The solvent can be water, or a pure organic compound, or a mixture of two or more compounds. It can be used as one common solvent for catholyte and anolyte, as well as different ones. Solvents such as organic carbonates (eg ethylene carbonate), ethers (eg dibutyl ether, dimethoxyethane), nitriles (eg acetonitrile), and others can be used.

d) A solution of a redox active compound at a concentration of 0.1 to 99.99 mass percent in a solvent (s) with the addition of a conductivity-maintaining salt. The solvent can be water, or a pure organic compound, or a mixture of two or more compounds. As support salts, inorganic salts (for example, NaClO ₄ , LiPF ₆ ), salts containing an inorganic cation and an organic anion (for example, lithium bis (trifluoromethanesulfonyl) imide LiTFSI, LiB (CN) ₄ ), salts containing an organic cation and inorganic anion (for example, tetrabutylammonium fluoride TBAF, tetrabutylammonium tetrafluoroborate TBABF ₄ , tetrabutylammonium hexafluorophosphate, etc.)

e) A suspension of a redox active compound in a solvent at a concentration of 0.1 to 99.99 mass percent. The solvent can be water, or a pure organic compound, or a mixture of two or more compounds.

c) A suspension of a redox active compound in a solvent at a concentration of 0.1 to 99.99 weight percent, with the addition of a supporting salt from those described in paragraph (d) The solvent can be water, or a pure organic compound, or a mixture of two or more connections.

We emphasize that the above options for the preparation of catholytes and anolytes for flowing and hybrid batteries should be considered as particular examples. From the current state of science and technology, other options for the manufacture of catholytes for flowing and hybrid batteries are known, in which triphenylamine derivatives of the general formula F1 can be used as redox-active compounds.

The use of compounds of the general formula F1 as cathode materials (catholytes) for electrochemical power sources provides a number of practically significant advantages :

1. The ability to use concentrated solutions of cathode materials for electrochemical power sources with a high specific capacity. Compounds M1 and M2, which are special cases corresponding to the general formula F1, have high solubility in acetonitrile, which makes it possible to obtain solutions of catholytes with concentrations of active substances up to 5 mol / l, which corresponds to high specific capacities of catholyte, reaching 134 Ah / l ... In addition, due to the liquid state of aggregation of compounds M1 and M2, they can be used for the preparation of catholytes without a solvent. Compounds corresponding to particular formulas M3 and M4 have a solubility in acetonitrile of 2.2 mol / l, which corresponds to the specific capacities of catholytes up to 117 Ah / l. For comparison, the specific capacities of electrolytes based on vanadium salts currently used in industry are ~ 53 Ah / l [C. Choi, S. Kim, R. Kim, Y. Choi, S. Kim, H. young Jung, J.H. Yang, H.T. Kim, Renew. Sustain. Energy Rev. 69 (2017) 263-274].

2. Create cathode materials with high stability. Compounds M1-M4, which are special cases of the general formula F1, exhibit high stability of redox reactions without any signs of decomposition after several hundred charge-discharge cycles (according to cyclic voltammetry data).

3. Combine the developed cathode materials based on compounds of the general formula F1 with any types of anode materials: liquid organic, liquid inorganic, solid inorganic (including lithium, sodium, potassium, etc.)

4. To create organic flow batteries using cathode materials based on compounds of the general formula F1 with an energy capacity of up to 340 Wh / l. For comparison, the energy intensity of modern industrial flow batteries based on vanadium salts is ~ 19-38 Wh / l [J. Noack, N. Roznyatovskaya, T. Herr, P. Fischer, Angew. Chemie - Int. Ed. 54 (2015) 9776-9809].

5. To create hybrid cells with an alkali metal anode and a cathode based on compounds of the general formula F1 with an energy capacity of up to 540 Wh / l.

Thus, the presented examples fully illustrate the high practical significance and industrial applicability of the disclosed invention.

The present invention is illustrated but not limited by the examples below.

Example 1-A. Use of the M1 compound as a component of the catholyte in the flow accumulator.

The flow accumulator consisted of the following components:

- container with catholyte (Fig. 19, 1 );

- a container with anolyte (Fig. 19, 1 ' );

- peristaltic pumps for pumping catholyte and anolyte to the electrochemical cell (Fig. 19, 2 and 2 ' );

- hoses for supplying catholyte and anolyte to the electrochemical cell (Fig. 19, 3 and 3 ') ;

- electrochemical cell

The electrochemical cell of the flow accumulator consisted of the following components:

- two metal retaining plates (Fig. 20, 1 );

- two Teflon insulating plates (Fig. 20, 2 );

- two graphite current-supplying electrode plates (Fig. 19, 4 and 4 ' ; Fig. 20, 3 );

- two Teflon distribution plates (Fig. 20, 4 ) with graphite felt electrodes (Fig. 20, 5 ) 6 mm thick, 2 × 2 cm in size, which corresponds to a geometrical active area of 4 cm ² ;

- anion-exchange membrane Neosepta AHA (Astom corp) (Fig. 19,6; FIG. twenty,6);

The solutions of catholyte and anolyte were fed to the electrochemical cell through hoses using a peristaltic pump; the solvent pumping rate was 10 ml / min. The flow accumulators were assembled in an argon atmosphere in a glove box.

The Neosepta AHA membrane was preconditioned according to the following scheme: first in a mixture of acetonitrile / water (1: 1 by volume) for 1 hour at a temperature of 60 ° C, then in pure acetonitrile for 1 hour at a temperature of 60 ° C, then in an electrolyte solution with a concentration salts 0.05 mol / l in anhydrous acetonitrile for 24 hours at a temperature of 25 ° C.

The flow accumulator was cycled in a combined mode, combining galvanostatic and potentiostatic stages. The cell was charged at a current of 2 mA (0.5 mA / cm ² ) to the upper limit of the potential, then discharged at the same current to the lower limit of the potential and held at the lower limit of the potential for 1000-3000 seconds for the most complete discharge of the battery.

The catholyte was a solution of tetrabutylammonium tetrafluoroborate (TBABF ₄ ) (concentration 0.1 mol / L), 1,1'-dibutyl-4,4'-bipyridine diperchlorate (A1) (concentration 10 mmol / L), compound M1 (concentration 10 mmol / L) in anhydrous acetonitrile (water content 20 ppm).

Anolyte was also a solution of tetrabutylammonium tetrafluoroborate (TBABF ₄ ) (concentration 0.1 mol / L), 1,1'-dibutyl-4,4'-bipyridine dipyrchlorate (A1) (concentration 10 mmol / L), compound M1 (concentration 10 mmol / L) in anhydrous acetonitrile (water content 20 ppm).

The volume of the catholyte was 10 ml, the volume of the anolyte was 10 ml, and the maximum capacity of the flow accumulator was 268 mAh / L.

FIG. 21 shows the charge-discharge characteristics of a flow-through battery with a catholyte based on compound M1: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number.

Based on the results of cycling, the highest discharge capacity was reached on the 12th cycle and amounted to 192 mAh / L (72% of the maximum). After 50 cycles, the discharge capacity was 172 mAh / L. The highest Coulomb efficiency was 80%.

Example 1-B. Use of the M2 compound as a component of the catholyte in the flow accumulator.

The study of the M2 compound as a component of the catholyte in the flow accumulator was carried out according to the procedure described in example 1-A, except that the M2 compound was used instead of the M1 compound.

FIG. 22 shows the charge-discharge characteristics of a flow-through battery with a catholyte based on the M2 compound: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was reached on the 1st cycle and amounted to 209 mAh / l (78% of the maximum). After 50 cycles, the discharge capacity was 156 mAh / L. The highest Coulomb efficiency was 90%.

Example 1-B. Use of the M3 compound as a component of the catholyte in the flow accumulator.

The study of compound M3 as a component of catholyte in a flow battery was carried out according to the method described in example 1-A, except that instead of compound M1, compound M3 was used and, since compound M3 is capable of transferring two electrons, then for the experiment, the concentration of the compound M3 was reduced by 2 times and amounted to 5 mmol / L.

FIG. 23 shows the charge-discharge characteristics of a flow-through battery with a catholyte based on the M3 compound: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was reached on the 15th cycle and amounted to 152 mAh / l (57% of the maximum). After 50 cycles, the discharge capacity was 111 mAh / L. The highest Coulomb efficiency was 96%.

Example 1-D. Use of the M4 compound as a component of the catholyte in the flow accumulator.

The study of compound M4 as a component of the catholyte in a flow accumulator was carried out according to the method described in example 1-B, except that compound M4 was used instead of compound M3.

FIG. 24 shows the charge-discharge characteristics of a flow-through battery with a catholyte based on the M4 compound: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was reached on the 1st cycle and amounted to 133 mAh / l (49% of the maximum). After 50 cycles, the discharge capacity was 98 mAh / L. The highest Coulomb efficiency was 84%.

Example 2-A. An illustration of the possibility of varying the concentration of the active compound and maintaining the conductivity of the salt when using M1 as a component of the catholyte in the flow accumulator.

The study was carried out according to the method described in example 1-A, with the exception of the following parameters:

1) the concentrations of compounds M1 and A1 in the catholyte and anolyte were increased to 50 mmol / l;

2) the concentration of the added maintenance salt (TBABF ₄ ) was increased to 0.5 mol / L.

The maximum capacity of the flowing battery was 1340 mAh / L.

FIG. 25 shows the charge-discharge characteristics of the manufactured flow-through accumulator: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was reached on the 3rd cycle and amounted to 518 mAh / l (38% of the maximum). After 10 cycles, the capacity was 433 mAh / L. The highest Coulomb efficiency was 88%.

Thus, this example illustrates the possibility of changing the concentration of the active substance and maintaining the conductivity of the salt while maintaining the practically important result that is provided by the implementation of the present invention.

Example 3-A. An illustration of the possibility of varying the conductivity-maintaining salt (NaClO ₄ ) when using M1 as a catholyte component in a flow-through accumulator.

The study of a flow battery based on compound M1 as a catholyte component using a different conductivity-maintaining salt was carried out as described in Example 1-A, except that _{sodium perchlorate (NaClO 4} ) was used _{instead of tetrabutylammonium tetrafluoroborate (TBABF 4} ).

FIG. 26 shows the charge-discharge characteristics of a flow-through battery with a catholyte based on compound M1 using NaClO ₄ as a salt maintaining conductivity: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was achieved on the 3rd cycle and amounted to 144 mAh / l (53% of the maximum). After 50 cycles, the capacity was 106 mAh / L. The highest Coulomb efficiency was 98%.

Example 3-B. An illustration of the possibility of varying the conductivity-maintaining salt (TBAPF ₆ ) when using M1 as a catholyte component in a flow accumulator.

The study of a flow battery based on compound M1 as a catholyte component using a different conductivity-maintaining salt was carried out as described in Example 1-A, except that tetrabutylammonium hexafluorophosphate (TBAPF _{6 ) was used instead of tetrabutylammonium tetrafluoroborate (TBABF 4} ).

FIG. 27 shows the charge-discharge characteristics of a flow-through battery with a catholyte based on compound M1 using TBAPF ₆ as a salt maintaining conductivity: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was reached on the 5th cycle and amounted to 153 mAh / l (57% of the maximum). After 50 cycles, the capacity was 79 mAh / L. The highest Coulomb efficiency was 93%.

Example 3-B. An illustration of the possibility of varying the maintaining conductivity of the salt (LiClO ₄ ) when using M1 as a component of the catholyte in the flow accumulator.

The study of a flow battery based on compound M1 as a catholyte component using a different conductivity-maintaining salt was carried out as described in Example 1-A, except that _{lithium perchlorate (LiClO 4} ) was used _{instead of tetrabutylammonium tetrafluoroborate (TBABF 4} ).

FIG. 28 shows the charge-discharge characteristics of a flow-through battery with a catholyte based on compound M1 using LiClO ₄ as a salt maintaining conductivity: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was reached on the 6th cycle and amounted to 140 mAh / l (52% of the maximum). After 50 cycles, the capacity was 27 mAh / L. The highest Coulomb efficiency was 96%.

Example 3-D. An illustration of the possibility of varying the conductivity-maintaining salt (LiPF ₆ ) when using M1 as a catholyte component in a flow-through accumulator.

The study of a flow battery based on compound M1 as a catholyte component using a different conductivity-maintaining salt was carried out as described in Example 1-A, except that lithium hexafluorophosphate (LiPF _{6 ) was used instead of tetrabutylammonium tetrafluoroborate (TBABF 4} ).

FIG. 29 shows the charge-discharge characteristics of a flow-through battery with a catholyte based on compound M1 using LiPF ₆ as a salt maintaining conductivity: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was reached on the 6th cycle and amounted to 71 mAh / l (26% of the maximum). After 50 cycles, the capacity was 25 mAh / L. The highest Coulomb efficiency was 70%.

Example 4-A. An illustration of the possibility of varying the anolyte when using M1 as a component of the catholyte in a flow accumulator.

The study of compound M1 as a component of catholyte and 2,3-bis (2- (2-methoxyethoxy) ethoxy) phenazine (compound A2, Fig. 30) as anolyte component in a flow accumulator was carried out according to the method described in example 1-A, except that compound A2 was used in place of compound A1.

FIG. 30. Structure of compound A2 (2,3-bis (2- (2-methoxyethoxy) ethoxy) phenazine).

FIG. 31 shows the charge-discharge characteristics of a flow-through battery with a catholyte based on the M1 compound and an anolyte based on the A2 compound: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was reached on the 1st cycle and amounted to 201 mAh / l (75% of the maximum). After 50 cycles, the capacity was 165 mAh / L. The highest Coulomb efficiency was 97%.

Example 4-B. An illustration of the possibility of varying the anolyte when using M3 as a catholyte component in a flow accumulator.

The study of compound M3 as a component of catholyte and compound A2 as a component of anolyte in a flow battery was carried out according to the method described in example 1-B, except that compound A2 was used instead of compound A1.

FIG. 32 shows the charge-discharge characteristics of a flow-through battery with a catholyte based on the M1 compound and an anolyte based on the A2 compound: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was achieved on the 1st cycle and amounted to 241 mAh / l (90% of the maximum). After 50 cycles, the capacity was 136 mAh / L. The highest Coulomb efficiency was 99%.

Example 5-A. An illustration of the possibility of using unmixed electrolytes when using М1 as a component of a catholyte in a flow battery.

The study of the flow battery based on the M1 compound as a component of the catholyte using unmixed electrolytes was carried out according to the method described in example 1-A, with the exception of the electrolyte compositions, which are given below.

The catholyte was a solution of sodium perchlorate (NaClO ₄ ) (concentration 0.1 mol / L) and compound M1 (concentration 20 mmol / L) in anhydrous acetonitrile (water content 20 ppm).

Anolyte was a solution of sodium perchlorate (NaClO ₄ ) (concentration 0.1 mol / L) and 1,1'-dibutyl-4,4'-bipyridine dipyridine (A1) (concentration 20 mmol / L) in anhydrous acetonitrile (water content 20 ppm).

The volume of the catholyte was 10 ml, the volume of the anolyte was 10 ml, and the maximum capacity of the flow accumulator was 356 mAh / L.

FIG. 33 shows the charge-discharge characteristics of a flow-through battery with a catholyte based on compound M1: the dependence of the potential on time for the first 5 cycles, the dependence of the charging and discharging capacity and the Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was reached on the 1st cycle and amounted to 211 mAh / l (39% of the maximum). After 50 cycles, the discharge capacity was 148 mAh / L. The highest Coulomb efficiency was 68%.

Example 6-A. An illustration of the possibility of using a composite membrane when using M1 as a catholyte component in an h-cell electrochemical cell.

The study of the cycling of an electrochemical cell based on compound M1 as a component of the catholyte was carried out according to the procedure given below.

The electrochemical cell (h-cell) used in this experiment consisted of the following components (diagram of the representation cell in Fig. 34):

- container with catholyte (Fig. 34, 1 );

- a container with anolyte (Fig. 34, 1 ' );

- cation-exchange composite membrane Li _1.4 Al _0.4 Ge _0.2 Ti _1.4 (PO ₄ ) ₃ (Fig. 34, 2 ' );

- electrodes made of graphite felt (Fig. 34, 3 and 3 ' ) with a thickness of 6 mm, dimensions of 1 × 1 cm;

- current collectors (Fig. 34, 4 and 4 ' ), made of metal wire

The electrochemical cell was assembled in an argon atmosphere in a glove box. The cation exchange composite membrane used was not preconditioned. Cycling of the electrochemical cell was carried out in a combined mode, combining galvanostatic and potentiostatic stages. The cell was charged at a current of 0.4 mA to the upper potential limit, then discharged at the same current to the lower potential limit and held at the lower potential limit for 1000 seconds to fully discharge the battery.

The catholyte was a solution of lithium perchlorate (LiClO ₄ ) (concentration 20 mmol / L), 1,1'-dibutyl-4,4'-bipyridine dipyridine (A1) (concentration 2 mmol / L), compound M1 (concentration 2 mmol / l) in anhydrous acetonitrile (water content 20 ppm).

The anolyte was a solution of lithium perchlorate (LiClO ₄ ) (concentration 20 mmol / L), 1,1'-dibutyl-4,4'-bipyridine dipyrchlorate (A1) (concentration 2 mmol / L), compound M1 (concentration 2 mmol / l) in anhydrous acetonitrile (water content 20 ppm).

The volume of the catholyte was 5 ml, the volume of the anolyte was 5 ml, and the maximum capacity of the electrochemical cell was 53.6 mAh / l.

FIG. 35 shows a charge-discharge electrochemical cell with a catholyte based on compound M1: the dependence of the potential on time for the first 5 cycles, the dependence of the charge and discharge capacity and Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was achieved on the 1st cycle and amounted to 42 mAh / l (78% of the maximum). After 50 cycles, the capacity was 32 mAh / L. The highest Coulomb efficiency was 95%.

Example 7-A. An illustration of the possibility of using compound M3 as a cathode material in a hybrid battery in combination with a lithium anode.

The electrochemical cell used in this experiment (coin-type cell CR2032) consisted of the following components (the cell diagram is shown in Fig. 36):

- Cell cover (Fig. 36, 1 );

- Carbon paper impregnated with soluble catholyte (Fig. 36, 2 )

- Ceramic membrane (Fig. 36, 3 )

- Lithium anode (Fig. 36, 4 )

- Metal disk - spacer (Fig. 36, 5 );

- Spring (Fig. 36, 6 );

- The bottom of the cell (Fig. 36, 7 )

The electrochemical cell was assembled in an argon atmosphere in a glove box. Cycling was carried out in a galvanostatic mode: the cell was charged at a current of 0.3 mA to the upper limit of the potential, then discharged at a current of -0.3 mA to the lower limit of the potential.

The catholyte was a solution of lithium bis (trifluoromethanesulfonyl) imide (concentration 0.5 mol / l) and compound M3 (concentration 0.2 mol / l) in diglyme. The volume of the catholyte was 20 μL, the maximum capacity of the electrochemical cell was 10.72 Ah / L.

To determine the optimal upper and lower charge and discharge potential of the cell and to study the reversibility of the system, we measured the cyclic voltammograms for a battery with a catholyte based on the M3 compound and a lithium anode. FIG. 37 shows the volt-ampere characteristics of the electrochemical cell, the half-wave potential of the first electron transfer was 3.66 V against Li / Li⁺, the second electron 4.05 V against Li / Li⁺...

FIG. 38 shows the charge-discharge characteristics of an electrochemical cell with a catholyte based on the M3 compound and a lithium anode: the dependence of the potential on time for the first 5 cycles, the dependence of the charge and discharge capacity and Coulomb efficiency on the cycle number.

According to the results of cycling, the highest discharge capacity was reached on the 3rd cycle and amounted to 6.13 Ah / l (57% of the maximum). After 100 cycles, the capacity was 5.50 Ah / l. The highest Coulomb efficiency was 87%.

Although the invention has been described with reference to the disclosed embodiments, it should be apparent to those skilled in the art that the specific experiments described in detail are provided for the purpose of illustrating the present invention only and should not be construed as in any way limiting the scope of the invention. It should be understood that various modifications are possible without departing from the spirit of the present invention.

Claims (79)

1. The use of a triphenylamine derivative of general formula F1 as a soluble cathode material in the composition of a catholyte for an electrochemical power source

, where in the general formula F1 the substituent R is selected independently and represents - a halogen atom -F, -Cl or -Br; - nitrile group -CN; - hydrocarbon radical -C _n H _{2n + 1} , where n = 1-20; - the remainder of the simple ether -O-C _p H _{2p + 1} , where n = 1-20; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10; or - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12; substituent R ¹ is selected independently and represents a) a fragment of substituted diphenylamine

, in which the substituents R ³ and R ⁴ are independently selected and represent - a halogen atom -F, -Cl or -Br; - hydrocarbon radical -C _n H _{2n + 1} , where n = 1-20; - the remainder of the simple ether -O-C _n H _{2n + 1} , where n = 1-20; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12; b) one of the following substituents: - a halogen atom -F, -Cl or -Br; - nitrile group -CN; - hydrocarbon radical -C _n H _{2n + 1} , where n = 1-20; - the remainder of the simple ether -O-C _n H _{2n + 1} , where n = 1-20; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12; substituent R ² is selected independently and represents: a) a fragment of substituted diphenylamine

, in which the substituents R ⁵ and R ⁶ are independently selected and represent - a halogen atom -F, -Cl or -Br; - hydrocarbon radical -C _n H _{2n + 1} , where n = 1-20; - the remainder of the simple ether -O-C _n H _{2n + 1} , where n = 1-20; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12; b) one of the following substituents - hydrocarbon radical -C _n H _{2n + 1} , where n = 1-20; - the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1-20; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{2m + 1} , where n = 1-10, m = 1-12. 2. The use according to claim 1, where the electrochemical power source is a flow-through accumulator, consisting of the following main components: - an electrochemical cell with a membrane or separator (6) dividing the electrochemical cell into zones (5 and 5 ') for catholyte and anolyte, in which an electrochemical reaction occurs at the cathode and at the anode; - at least one container (1, 1 ^a , 1 ^b ) with a charged and / or uncharged catholyte and at least one container (1 ', 1' ^a , 1 ' ^b ) with a charged and / or uncharged anolyte; - at least one pump (2 and 2 '), providing pumping of the catholyte and anolyte between the indicated containers and the electrochemical cell; - hoses or pipelines (3 and 3 ') for supplying catholyte and anolyte from the indicated containers to the electrochemical cell in zones (5 and 5'); - cathode (4) and anode (4 '), located in zones 5 and 5', respectively. 3. Use according to claim 1, wherein the electrochemical power source is a hybrid battery consisting of the following main components: - an electrochemical cell with a membrane or separator (6), dividing the electrochemical cell into zones for catholyte (5) and electrolyte at the anode (5 '); - at least one container (1, 1 ^a , 1 ^b ) for charged and / or uncharged catholyte; - at least one pump (2), providing pumping of the catholyte between the indicated containers and the electrochemical cell; - hoses or pipelines (3) for supplying the catholyte from the indicated containers to the electrochemical cell in the zone (5); - cathode (4) located in zone (5); - anode (4 ') located in zone (5'). 4. Use according to claim 1, wherein the catholyte comprises a mixture of at least two different compounds of formula F1. 5. Use according to any one of claims 1 to 4, in which the catholyte contains a solvent in the form of water and / or at least one organic solvent selected from the group: organic carbonates, organic ethers, nitriles, sulfones, sulfoxides, amides, in the following the ratio of the components in wt%: - redox-active compound of general formula F1 - 0.1-99.9999; - solvent - 0.0001-99.9. 6. Use according to claim 5, wherein: - the organic carbonate is selected independently and is ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate; - the organic ether is selected independently and is dibutyl ether, tetrahydrofuran or dimethoxyethane; - the nitrile is selected independently and is acetonitrile or propionitrile; - the sulfone is independently selected and is sulfolane or dimethyl sulfone; - the amide is selected independently and is dimethylformamide or N-methyl-2-pyrrolidone. 7. Use according to any one of claims 1 to 4, characterized in that the catholyte contains an electrochemically stable salt in the following ratio of components in wt%: - redox-active compound of general formula F1 - 0.1-99.9999; - electrochemically stable salt - 0.0001-99.9. 8. Use according to claim 7, wherein the electrochemically stable salt comprises - one of the following cations: Li ⁺ , Na ⁺ , K ⁺ , R ' ₄ N ₊ , where R' is independently selected and represents alkyl -C _n H _{2n + 1} , where n = 1-8, N-butyl-N -methylpyrrolidinium, tris (hexyltetradecyl) phosphonium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-3-methylimidazolium; - one of the following anions: F ^- , Cl ^- , PF ₆ ^- , ClO ₄ ^- , bis (trifluoromethylsulfonyl) imide anion, CF ₃ SO ₃ ^- , [B (CN) ₄ ] ^- , BF ₄ ^- , [F ₃ P (C ₂ F ₅ ) ₃ ] ^- , [F ₃ P (CF ₃ ) ₃ ] ^- , CF ₃ COO ^- . 9. Use according to any one of claims 2 or 3, in which the anolyte contains a phenazine derivative of general formula A3

in which the substituents R ⁷ and R ⁸ are independently selected and represent - the remainder of the simple ether -OC _n H _{2n + 1} , where n = 1-20; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n H, where n = 1-10; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n CH ₃ , where n = 1-10; - ether substituent based on oligoethylene glycol -O (CH ₂ CH ₂ O) _n C _m H _{3m + 1} , where n = 1-10, m = 1-12.

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